JP7049447B2 - Laminated film and foldable device - Google Patents

Description

The present invention relates to a laminated film having high surface hardness and excellent bending durability, and a foldable device provided with the laminated film.

Demand for foldable devices such as foldable displays and touch panels is increasing in order to further enhance the portability of mobile information terminals such as smartphones and tablets. The foldable device needs to be bent at 180 ° with a small bending radius (for example, a bending radius of about 2.5 mm) in order to improve portability, and extremely high flexibility (flexibility) is required. In addition, since the foldable device is carried in a folded state, opened at the time of use, and then folded again after use, it is required to have high bending durability, that is, durability that does not cause cracks even when repeatedly folded. ..

A highly flexible image display device such as an organic EL is used for the foldable device, but a hard coat layer is provided on the support film in order to impart scratch resistance so that the image display surface is not scratched during handling. It is generally practiced to improve the scratch resistance of the image display surface of an image display device by protecting it with the formed laminated film (hard coat film) (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2014-186210

However, although the conventional hardcoat film has excellent surface hardness and flexibility, cracks occur in the hardcoat layer when it is repeatedly folded, and the bending durability is low, so that it cannot be used as a member for protecting the surface of a foldable device. There was a problem.

Therefore, an object of the present invention is to provide a laminated film which has high surface hardness and excellent bending durability and is suitable as a surface protective material for a foldable device.
Another object of the present invention is to provide a foldable device provided with the laminated film.

That is, the present invention includes a support and
A laminated film having a resin layer laminated on at least one surface of the support.
A laminated film (1) characterized in that the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (Condition 1) and (Condition 2). I will provide a.
(Condition 1) The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer of the laminated film is F or more.
(Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more.
Bending durability test (1):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius is 2.5 mm in the direction in which the surface of the resin layer becomes concave, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (1).

Further, the present invention includes a support and a support.
A laminated film having a resin layer laminated on at least one surface of the support.
A laminated film (2) characterized in that the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (Condition 1) and (Condition 3). I will provide a.
(Condition 1) The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer of the laminated film is F or more.
(Condition 3) The bending durability (2) in the following bending durability test (2) is 10,000 times or more.
Bending durability test (2):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius becomes 4.0 mm in the direction in which the surface of the resin layer becomes convex, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (2).

In the laminated films (1) and (2), the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) further satisfies the following (condition 4). Is preferable.
(Condition 4) In the cylindrical mandrel test specified in JIS K5600-5-1 (1999) in which the surface of the resin layer of the laminated film is convex, the bending radius is 5 mm and the surface of the resin layer is not cracked.

In the laminated films (1) and (2), the water contact angle of the surface of the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) is 95 ° or more. Is preferable.

In the laminated films (1) and (2), it is preferable that the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (condition 5). ..
(Condition 5) No visual scratches occur in the steel wool resistance test in which the surface of the resin layer is rubbed back and forth 30 times while applying a load of 1 kg / cm ² with # 0000 steel wool.

In the laminated films (1) and (2), the haze of the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) may be 1.0% or less. preferable.

In the laminated films (1) and (2), the resin layer is a cured product of a curable composition further containing one or more curable compounds, and at least one of the curable compounds is polyorganosilsesqui. It is preferably oxane.

In the laminated films (1) and (2), the curable composition preferably contains a compound having one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups in the molecule.

In the laminated films (1) and (2), it is preferable that the curable composition further contains a curing catalyst.
The curing catalyst may be a photocationic polymerization initiator.
The curing catalyst may be a thermal cationic polymerization initiator.

In the laminated films (1) and (2), it is preferable that the curable composition further contains a fluorine-containing photopolymerizable resin.

In the laminated films (1) and (2), the support is preferably a transparent support.

The present invention also provides a foldable device including the laminated film (1) or (2).

The foldable device may be an image display device.
In the foldable device, the image display device may be an organic electroluminescence display device.

The laminated film of the present invention has high surface hardness and excellent bending durability. Therefore, the laminated film of the present invention can be suitably used as a surface protective material for a foldable device such as a foldable image display device.

Bending durability test method (R bending method) in the present invention (Bending of the laminated film by 180 ° so that the bending radius (R) is 2.5 mm or 4.0 mm in the direction in which the surface of the resin layer becomes concave or convex. It is a schematic diagram (side view) showing (one operation of stretching). It is a figure which showed the enlargement of (4) of FIG. 6 is a ¹ H-NMR chart of the epoxy group-containing low molecular weight polyorganosyl sesquioxane obtained in Production Example 1. 6 is a ²⁹ Si-NMR chart of the epoxy group-containing low molecular weight polyorganosyl sesquioxane obtained in Production Example 1. 6 is a ¹ H-NMR chart of the epoxy group-containing high molecular weight polyorganosyl sesquioxane obtained in Production Example 2. 9 is a ²⁹ Si-NMR chart of the epoxy group-containing high molecular weight polyorganosyl sesquioxane obtained in Production Example 2.

[Laminated film]
One aspect of the laminated film of the present invention (hereinafter, may be referred to as "laminated film (1)") is a laminated film having a support and a resin layer laminated on at least one surface of the support. The resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (Condition 1) and (Condition 2).
(Condition 1) The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer of the laminated film is F or more.
(Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more.
Bending durability test (1):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius is 2.5 mm in the direction in which the surface of the resin layer becomes concave, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (1).

The laminated film (1) of the present invention has extremely excellent surface hardness and bending durability, and can be suitably used as a surface protective material for foldable devices such as organic EL display devices.
That is, in the laminated film (1) of the present invention, the resin layer satisfies the above-mentioned (Condition 1) and (Condition 2).
In the laminated film (1) of the present invention, when the resin layer is laminated on both sides of the support, if either resin layer satisfies (Condition 1) and (Condition 2). Often, the other resin layer may or may not satisfy (Condition 1) and / or (Condition 2).

The above condition 1 is a condition showing that the surface of the resin layer of the laminated film (1) of the present invention has excellent surface hardness. The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer is F or more, preferably 1H or more, more preferably 2H or more, and more preferably 3H or more. , More preferably 4H or more, more preferably 5H or more, more preferably 6H or more, more preferably 7H or more, still more preferably 8H or more, and particularly preferably 9H. If the pencil hardness of the surface of the resin layer is less than F, the surface hardness of the laminated film (1) of the present invention becomes insufficient, and it may be difficult to use it as a surface protective material for a foldable device.

The above condition 2 is a condition showing that the laminated film (1) of the present invention has excellent bending durability, that is, it has a property that defects such as cracks are unlikely to occur in the resin layer even if it is repeatedly folded. It is a condition indicating that the resin layer has durability (hereinafter, may be referred to as "bending durability (1)") when it is repeatedly folded so that the surface of the resin layer becomes concave (inside).

In FIG. 1, the surface of the resin layer is concave (inside) from the stretched state (FIG. 1 (1)) of the laminated film (1) (FIG. 1) in the bending durability test (1) shown in the above condition 2. ) Is a schematic view (side view) showing one operation of bending 180 ° so that the bending radius (R) is 2.5 mm and extending it again in the direction (not shown). FIG. 2 is an enlarged view of FIG. 1 (4), where R indicates a bending radius. In the bending durability test (1), a cylindrical mandrel having a radius of 2.5 mm can be wound around the bent portion of the resin layer surface of the laminated film (1) so that the bending radius becomes 2.5 mm. In the bending durability test (1), the number of times until the resin layer of the laminated film (1) is cracked when the operation is performed at a speed of 30 to 60 times per minute is defined as the bending durability (1). ) Is used as an index.

The bending durability (1) in the bending durability test (1) of the laminated film (1) of the present invention is 50,000 times or more, preferably 60,000 times or more, more preferably 70,000 times or more, and more preferably 8 times. It is 10,000 times or more, more preferably 90,000 times or more, more preferably 100,000 times or more, further preferably 150,000 times or more, and particularly preferably 200,000 times or more. If the bending durability (1) is less than 50,000 times, the bending durability (1) of the laminated film (1) of the present invention becomes insufficient, and the surface protective material of the foldable device (particularly, a display device that bends inward) It may be difficult to use as.

As another aspect of the laminated film of the present invention (hereinafter, may be referred to as "laminated film (2)"), any one of the resin layers (when the resin layers are laminated on both sides of the support). It is also preferable that the resin layer) satisfies the above (condition 1) and the following (condition 3).
(Condition 3) The bending durability (2) in the following bending durability test (2) is 10,000 times or more.
Bending durability test (2):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius becomes 4.0 mm in the direction in which the surface of the resin layer becomes convex, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (2).

In the laminated film (2) of the present invention, when the resin layer is laminated on both sides of the support, if either resin layer satisfies (Condition 1) and (Condition 3). Often, the other resin layer may or may not satisfy (Condition 1) and / or (Condition 3).

The measuring method of the pencil hardness test under the condition 1 of the laminated film (2) of the present invention and the preferable pencil hardness are the same as those of the laminated film (1).

The above condition 3 is the bending durability of the laminated film (2) of the present invention when the resin layer is repeatedly folded so as to be convex (outside) (hereinafter, "bending durability (2)". ) ”). In the bending durability test (2) for bending durability (2), the above-mentioned bending is performed except that the surface of the resin layer is oriented to be convex (outside) and the bending radius (R) is 4.0 mm. It can be measured under the same conditions as the durability test (1).

The bending durability (2) in the bending durability test (2) of the laminated film (2) of the present invention is 10,000 times or more, more preferably 20,000 times or more, more preferably 30,000 times or more, and more preferably. 40,000 times or more, more preferably 50,000 times or more, more preferably 60,000 times or more, more preferably 70,000 times or more, more preferably 80,000 times or more, more preferably 90,000 times or more, more preferably 100,000 times or more. It is more than once, more preferably 150,000 times or more, and particularly preferably 200,000 times or more. If the bending durability (2) is less than 10,000 times, the bending durability (2) of the laminated film (2) of the present invention becomes insufficient, and the surface protective material of the foldable device (particularly, a display device that bends outward). It may be difficult to use as.

The laminated film (1) and the laminated film (2) of the present invention (hereinafter, may be collectively referred to simply as "laminated film of the present invention") have the resin layer (resin layers on both sides of the support). It is more preferable that (in the case of being laminated, one of the resin layers) satisfies all of the above-mentioned (Condition 1) to (Condition 3).

The laminated film of the present invention (including the laminated film (1) and the laminated film (2); the same applies hereinafter) is further any of the resin layers (when the resin layers are laminated on both sides of the support). One resin layer) preferably satisfies the following (condition 4).
(Condition 4) In the cylindrical mandrel test specified in JIS K5600-5-1 (1999) in which the surface of the resin layer of the laminated film is convex, the bending radius is 5 mm and cracks do not occur on the surface of the resin layer (hereinafter,). For example, it may be referred to as "flexibility of 5 mm or less")

In the laminated film of the present invention, when the resin layer is laminated on both sides of the support, it is sufficient that one of the resin layers satisfies (Condition 4) and the other resin layer is (Condition 4). Condition 4) may or may not be satisfied.

The above condition 4 is a condition showing that the laminated film of the present invention has excellent flexibility. The flexibility of the laminated film of the present invention is 5 mm or less, preferably 4.5 mm or less, more preferably 4.0 mm or less, more preferably 3.5 mm or less, more preferably 3.0 mm or less, still more preferably 2. It is 5.5 mm or less, particularly preferably 2.0 mm or less. If the flexibility exceeds 5 mm, the flexibility of the laminated film of the present invention becomes insufficient, and it may be difficult to use it as a surface protective material for a foldable device (particularly, a display device that folds outward).

Further, in the laminated film of the present invention, it is preferable that the resin layer (when the resin layers are laminated on both sides of the support, one of the resin layers) satisfies the following (condition 5).
(Condition 5) No scratches are visually observed in the steel wool resistance test in which the surface of the resin layer is rubbed back and forth 30 times while applying a load of 1 kg / cm ² with # 0000 steel wool (hereinafter, for example, "resistant". Scratchability is sometimes referred to as "30 times or more")

In the laminated film of the present invention, when the resin layer is laminated on both sides of the support, it is sufficient that one of the resin layers satisfies (Condition 5), and the other resin layer is (Condition 5). Condition 5) may or may not be satisfied.

The above condition 5 is a condition showing that the laminated film of the present invention has excellent scratch resistance. The scratch resistance of the laminated film of the present invention is 30 times or more, preferably 100 times or more, more preferably 200 times or more, more preferably 300 times or more, more preferably 500 times or more, and more preferably 700 times or more. It is more preferably 1000 times or more, and particularly preferably 2000 times or more. If the scratch resistance is less than 30 times, the scratch resistance of the laminated film of the present invention becomes insufficient, and it may be difficult to use it as a surface protective material for a foldable device.

The laminated film of the present invention includes layers other than the support and the resin layer, for example, an anchor layer, an adhesive layer, a low reflection layer, an antifouling layer, a water repellent layer, an oil repellent layer, an antifog layer, a protective film layer, and a printing layer. It may have a conductive layer, an electromagnetic wave shielding layer, an ultraviolet absorbing layer, an infrared absorbing layer, a blue light cut layer and the like. The resin layer may be formed only partially or on the entire surface of the surface of the support.

The haze of the laminated film of the present invention is, for example, 7% or less, preferably 6% or less, more preferably 5% or less, more preferably 4% or less, still more preferably 3% or less. , Especially preferably 2% or less, and most preferably 1% or less. The lower limit of haze is, for example, 0.1%. By setting the haze to 7% or less, for example, it tends to be suitable for use in applications that require extremely high transparency (for example, a surface protective sheet for a display such as a touch panel). The haze of the present invention can be easily controlled within the above range by using, for example, a transparent substrate described later as a support. In this specification, haze can be measured according to JIS K7136.

The total light transmittance of the laminated film of the present invention is, for example, 85% or more, preferably 90% or more. By setting the total light transmittance to 90% or more, for example, it tends to be suitable for use in applications requiring extremely high transparency (for example, a surface protective sheet for a display such as a touch panel). The total light transmittance of the present invention can be easily controlled in the above range by using, for example, a transparent base material described later as a support. In this specification, the total light transmittance can be measured according to JIS K7361-1.

The thickness of the laminated film of the present invention (total thickness of the support / resin layer) can be appropriately selected from the range of, for example, 1 to 10000 μm, preferably 10 to 1000 μm, and more preferably 15 to 800 μm. It is more preferably 20 to 700 μm, and particularly preferably 30 to 500 μm.

In the laminated film of the present invention, the water contact angle of the surface of the resin layer (when the resin layers are laminated on both sides of the support, one of the resin layers) is preferably 95 ° or more, more preferably. 96 ° or more, more preferably 97 ° or more, more preferably 98 ° or more, more preferably 99 ° or more, more preferably 100 ° or more, more preferably 101 ° or more, more preferably 102 ° or more, more preferably. It is 103 ° or more, more preferably 104 ° or more, and particularly preferably 105 ° or more. If the water contact angle is less than 95 °, the antifouling property of the laminated film of the present invention becomes insufficient, and it may be difficult to use it as a surface protective material for a foldable device.

In the laminated film of the present invention, when the resin layer is laminated on both sides of the support, the water contact angle of either resin layer may be 95 ° or more, and the water of the other resin layer may be used. The contact angle is not limited and may be 95 ° or more or less than 95 °.

The laminated film of the present invention having the above-mentioned performance can be obtained by selecting the material of the support described later, controlling the thickness of the support, and controlling the component and thickness of the resin layer and the method of laminating on the support. Can be done.

(Support)
The support in the laminated film of the present invention includes a plastic base material, a metal base material, a ceramic base material, a semiconductor base material, a glass base material, a paper base material, a wood base material (wooden base material), and a coated surface. A known or conventional support such as a base material can be used, and is not particularly limited. Of these, a plastic base material is preferable. The support may have a single-layer structure or a multi-layer (laminated) structure, and the structure (structure) thereof is not particularly limited.

The plastic material constituting the plastic base material is not particularly limited, but is limited to polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide; polycarbonate; polyamide; polyacetal; polyphenylene oxide; polyphenylene sulfide; polyether sulfone; Polyether ether ketone; homopolymers of norbornene-based monomers (additional polymers, ring-opening polymers, etc.), copolymers of norbornene-based monomers and olefin-based monomers such as copolymers of norbornene and ethylene (additional polymers and open polymers) Cyclic olefin copolymers such as ring polymers), cyclic polyolefins such as derivatives thereof; vinyl polymers (eg, acrylic resins such as polymethylmethacrylate (PMMA), polystyrenes, polyvinyl chlorides, acrylonitrile-styrene-butadiene resins (eg) ABS resin), etc.); Vinylidene-based polymer (for example, polyvinylidene chloride, etc.); Cellulosic resin such as triacetyl cellulose (TAC); Epoxy resin; Phenolic resin; Melamine resin; Julia resin; Maleimide resin; Silicone, etc. Examples include plastic materials. The plastic base material may be made of only one kind of plastic material, or may be made of two or more kinds of plastic materials.

Above all, as the plastic base material, in order to obtain a laminated film having excellent transparency and bending durability, it is preferable to use a support (transparent support) having excellent transparency and bending durability, which is more preferable. Is a polyester film (particularly PET, PEN), a polyimide film, a cyclic polyolefin film, a polycarbonate film, a TAC film, a PMMA film, and more preferably a polyester film (particularly PET, PEN) or a polyimide film.

The support (particularly, a plastic base material) may be an antioxidant, an ultraviolet absorber, a light-resistant stabilizer, a heat stabilizer, a crystal nucleating agent, a flame-retardant agent, a flame-retardant aid, a filler, or a plasticizer, if necessary. , Impact resistance improver, reinforcing agent, dispersant, antistatic agent, foaming agent, antibacterial agent and other other additives may be contained. It should be noted that one type of additive may be used alone, or two or more types may be used in combination.

Part or all of the surface of the support (particularly the plastic base material) is roughened, easily adhered, antistatic, sandblasted (sandmat), corona discharge, plasma, and chemical etching. , Known or conventional surface treatments such as water mat treatment, flame treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, and silane coupling agent treatment may be performed. The plastic base material may be an unstretched film or a stretched film (uniaxially stretched film, biaxially stretched film, etc.). As the support, a commercially available product can also be used.

The thickness of the support is, for example, about 1 to 1000 μm, preferably 5 to 500 μm, more preferably 10 to 400 μm, more preferably 15 to 400 μm, still more preferably 20 to 300 μm, and particularly preferably 25 to 200 μm.

The haze of the support of the present invention is, for example, 7% or less, preferably 6% or less, more preferably 5% or less, more preferably 4% or less, still more preferably 3% or less. , Especially preferably 2% or less, and most preferably 1% or less. The lower limit of haze is, for example, 0.1%. By setting the haze to 7% or less, for example, it tends to be suitable for use in applications that require extremely high transparency (for example, a surface protective sheet for a display such as a touch panel).

The total light transmittance of the support of the present invention is, for example, 85% or more, preferably 90% or more. By setting the total light transmittance to 90% or more, for example, it tends to be suitable for use in applications that require extremely high transparency (for example, a surface protective sheet for a display such as a touch panel).

(Resin layer)
In the present invention, the resin layer is formed of a cured product of a curable composition described later. That is, the resin layer is a layer made of a cured product formed by the curable composition, and satisfies the above (Condition 1) and (Condition 2) or (Condition 3), preferably the above (Condition). 4) and / or a layer that satisfies (Condition 5). The resin layer can be produced from a curable composition by the method for producing a laminated film described later.

The thickness of the resin layer is, for example, 1 to 100 μm, preferably 2 to 80 μm, more preferably 3 to 60 μm, still more preferably 5 to 50 μm, and most preferably 10 to 40 μm from the viewpoint of surface hardness and scratch resistance. .. If the thickness of the resin layer is thinner than 1 μm, it may not be possible to maintain high surface hardness. Further, when the thickness of the resin layer is thicker than 100 μm, problems such as large curl are likely to occur.

The haze of the resin layer is, for example, 1.0 or less, preferably 0.5% or less, and more preferably 0.1% or less. The lower limit of the haze of the resin layer is, for example, 0.1%. By setting the haze of the resin layer to 1.0% or less, for example, it tends to be suitable for use in applications requiring extremely high transparency (for example, a surface protective sheet for a display such as a touch panel). .. The haze of the resin layer can be determined by the difference obtained by subtracting the haze of the support from the haze of the above-mentioned laminated film (support / resin layer).

The total light transmittance of the resin layer is, for example, 85% or more, preferably 90% or more. By setting the total light transmittance to 85% or more, it tends to be suitable for use in, for example, applications requiring extremely high transparency (for example, a surface protective sheet for a display such as a touch panel). For the total light transmittance of the resin layer, for example, the above-mentioned curable composition is applied to a release substrate and cured so that the thickness after curing is the same as the resin layer of the laminated film of the present invention, and the cured film is cured. After peeling off, it can be obtained by measuring in accordance with JIS K7361-1.

The resin layer is also excellent in surface smoothness, and the arithmetic average roughness Ra is, for example, 0.1 to 20 nm, preferably 0.1 to 10 nm in _a method based on JIS B0601. More preferably, it is 0.1 to 5 nm.

The resin layer may be laminated on only one surface of the support, or may be laminated on both sides. When the resin layers are laminated on both sides of the support, they may be the same resin layer or different resin layers. When the resin layers are laminated on both sides of the support, one of the resin layers satisfies the above (Condition 1) and (Condition 2) or (Condition 3), and preferably the above (Condition 4). And / or (Condition 5) may be satisfied, and the other resin layer may or may not satisfy any one or more of (Conditions 1 to 5).

(Curable composition)
The curable composition for forming the resin layer in the laminated film of the present invention is not particularly limited, and those used for the hard coat layer of a known hard coat film can be adopted without particular limitation. Can be formed from a cured product of a curable composition containing one or more curable compounds.

As the curable compound constituting the curable composition, a component for forming a hard coat layer of a known hard coat film can be adopted without particular limitation, and for example, a (meth) acrylate compound or a cationically curable compound can be adopted. Examples thereof include silicone resin, epoxy resin, melamine resin, vinyl ether resin, and oxetane resin. In order to satisfy the above-mentioned performance (conditions 1 to 5) in the laminated film of the present invention, a cationically curable silicone resin is preferable.

［式（１）中、Ｒ¹は、カチオン重合性官能基を含有する基を示す。］ The cationically curable silicone resin preferably contains a polyorganosylsesquioxane, and specifically, a polyorganosylsesquioxane having a structural unit represented by the following formula (1) (hereinafter, "the present invention"). It is preferably formed from a curable composition (hereinafter, may be referred to as "the curable composition of the present invention") containing (sometimes referred to as "polyorganosyl sesquioxane").

[In the formula (1), R ¹ represents a group containing a cationically polymerizable functional group. ]

The curable composition of the present invention is a curable composition (curable resin composition) containing the above-mentioned polyorganosylsesquioxane of the present invention as an essential component, and forms a resin layer in the laminated film of the present invention. Is used as a curable composition for. As will be described later, the curable composition of the present invention further comprises a curing catalyst (particularly a photocationic polymerization initiator, a radical polymerizable initiator), one or more thermopolymerizable functional groups in the molecule, and one or more. It may contain other components such as a compound having a photopolymerizable functional group, a fluorine-containing photopolymerizable resin, a surface modifier or a surface modifier.

(Polyorganosilsesquioxane)
The polyorganosyl sesquioxane of the present invention is characterized by having a structural unit represented by the above formula (1).
Further, the polyorganosyl sesquioxane of the present invention has a structural unit represented by the following formula (I) (sometimes referred to as “T3 body”) and a structural unit represented by the following formula (II) (““ T3 body ”). It may be referred to as "T2 body").
Further, the polyorganosyl sesquioxane of the present invention preferably has a structural unit represented by the formula (4) described later.

The structural unit represented by the above formula (1) is a silsesquioxane structural unit (so-called T unit) generally represented by [RSiO _3/2 ]. In addition, R in the above formula indicates a hydrogen atom or a monovalent organic group, and the same applies to the following. The structural unit represented by the above formula (1) is formed by a hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the formula (a) described later). Will be done.

R ¹ in the formula (1) represents a group (monovalent group) containing a cationically polymerizable functional group. That is, the polyorganosylsesquioxane of the present invention is a cationically curable compound (cationically polymerizable compound) having at least a cationically polymerizable functional group in the molecule.

The "cationically polymerizable functional group" in the group containing the cationically polymerizable functional group is not particularly limited as long as it has a cationically polymerizable property, and is, for example, an epoxy group, an oxetane group, a vinyl ether group, a vinylphenyl group, or the like. Can be mentioned.
As the cationically polymerizable functional group, an epoxy group is particularly preferable from the viewpoint of the surface hardness (for example, F or more) of the resin layer.

Examples of the group containing the cationically polymerizable functional group include known and commonly used groups having an oxylane ring, and the group is not particularly limited, but has curability of the curable composition, surface hardness and heat resistance of the cured product (resin layer). From the viewpoint of sex, a group represented by the following formula (1a), a group represented by the following formula (1b), a group represented by the following formula (1c), and a group represented by the following formula (1d) are preferable. , More preferably a group represented by the following formula (1a), a group represented by the following formula (1c), and further preferably a group represented by the following formula (1a).

In the above formula (1a), R ^1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a decamethylene group and the like. Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms. Among them, as R ^1a , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable from the viewpoint of the surface hardness and curability of the cured product (resin layer). , More preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

In the above formula (1b), R ^1b represents a linear or branched alkylene group, and a group similar to R ^1a is exemplified. Among them, as R ^1b , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable from the viewpoint of the surface hardness and curability of the cured product (resin layer). , More preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

In the above formula (1c), R ^1c represents a linear or branched alkylene group, and a group similar to R ^1a is exemplified. Among them, as R ^1c , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable from the viewpoint of the surface hardness and curability of the cured product (resin layer). , More preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

In the above formula (1d), R ^1d represents a linear or branched alkylene group, and a group similar to R ^1a is exemplified. Among them, as R ^1d , a linear alkylene group having 1 to 4 carbon atoms and a branched alkylene group having 3 or 4 carbon atoms are preferable from the viewpoint of the surface hardness and curability of the cured product (resin layer). , More preferably an ethylene group, a trimethylene group, a propylene group, and even more preferably an ethylene group or a trimethylene group.

The R ¹ in the formula (1) is a group represented by the above formula (1a) in which R ^1a is an ethylene group [among others, 2- (3', 4'-epoxycyclohexyl)). Ethyl group] is preferable.

Examples of the group containing the oxetane group include known and commonly used groups having an oxetane ring, and are not particularly limited. For example, the oxetane group itself and an alkyl group (preferably 1 to 10 carbon atoms, more preferably carbon atoms). Examples thereof include a group formed by substituting a hydrogen atom (usually one or more, preferably one hydrogen atom) of 1 to 5 alkyl groups) with an oxetane group. From the viewpoint of curability of the curable composition and heat resistance of the cured product (resin layer), 3-oxetaneyl group, oxetane-3-ylmethyl group, 3-ethyloxetane-3-ylmethyl group, 2- (oxetane-3-3). Il) ethyl group, 2- (3-ethyloxetane-3-yl) ethyl group, 3- (oxetane-3-ylmethoxy) propyl group, 3- (3-ethyloxetane-3-ylmethoxy) propyl group and the like are preferable.

Examples of the group containing a vinyl ether group include known and commonly used groups having a vinyl ether group, and are not particularly limited. For example, the vinyl ether group itself and an alkyl group (preferably 1 to 10 carbon atoms, more preferably carbon atoms). Examples thereof include a group formed by substituting a hydrogen atom (usually one or more, preferably one hydrogen atom) of 1 to 5 alkyl groups) with a vinyl ether group. From the viewpoint of curability of the curable composition and heat resistance of the cured product (resin layer), a vinyloxymethyl group, a 2- (vinyloxy) ethyl group, a 3- (vinyloxy) propyl group and the like are preferable.

Examples of the group containing a vinyl phenyl group include known and commonly used groups having a vinyl phenyl group, and are not particularly limited. For example, the vinyl phenyl group itself and an alkyl group (preferably 1 to 10 carbon atoms, more preferably). Examples thereof include a group formed by substituting a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group having 1 to 5 carbon atoms with a vinylphenyl group. From the viewpoint of curability of the curable composition and heat resistance of the cured product (resin layer), 4-vinylphenyl group, 3-vinylphenyl group, 2-vinylphenyl group and the like are preferable.

The polyorganosylsesquioxane of the present invention may have only one type of structural unit represented by the above formula (1), or may have two or more types of structural units represented by the above formula (1). It may have.

The polyorganosilsesquioxane of the present invention is a silsesquioxane constituent unit [RSiO]. _3/2], In addition to the structural unit represented by the above formula (1), the structural unit represented by the following formula (2) may be included.

The structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) generally represented by [RSiO _3/2 ]. That is, the structural unit represented by the above formula (2) is a hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the formula (b) described later). Formed by.

R ² in the above formula (2) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. Indicates the alkenyl group of. Examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. Examples of the alkyl group include a linear or branched alkyl such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group and an isopentyl group. The group is mentioned. Examples of the alkenyl group include a linear or branched alkenyl group such as a vinyl group, an allyl group, and an isopropenyl group.

Examples of the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include hydrogen atoms or main ribs in each of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group and alkenyl group. From the group consisting of an ether group, an ester group, a carbonyl group, a siloxane group, a halogen atom (fluorine atom, etc.), an acrylic group, a methacryl group, a mercapto group, an amino group, and a hydroxy group (hydroxyl group). Examples include groups substituted with at least one selected species.

Among them, R ² is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and further preferably a phenyl group. be.

The proportion of each of the above-mentioned silsesquioxane constituent units (the constituent unit represented by the formula (1) and the constituent unit represented by the formula (2)) in the polyorganosilsesquioxane of the present invention is these constituent units. It is possible to appropriately adjust the composition of the raw material (hydrolyzable trifunctional silane) for forming the above.

In addition to the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), the polyorganosylsesquioxane of the present invention is further represented by the above formula (1). And the silsesquioxane structural unit other than the structural unit represented by the formula (2) [RSiO _3/2 ], the structural unit represented by [R ₃ SiO _1/2 ] (so-called M unit), [R ₂ SiO]. It has at least one siloxane structural unit selected from the group consisting of the structural unit represented by [ _2/2 ] (so-called D unit) and the structural unit represented by [SiO _4/2 ] (so-called Q unit). You may be doing it. Examples of the silsesquioxane structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the formula (2) include the structural unit represented by the following formula (3). Can be mentioned.

When the polyorganosylsesquioxane of the present invention has a structural unit (T3 body) represented by the above formula (I) and a structural unit (T2 body) represented by the above formula (II), the ratio thereof. [T3 body / T2 body] is not particularly limited, but can be appropriately selected from a range of, for example, 5 or more (for example, 5 or more, 500 or less). The lower limit of the ratio [T3 / T2] of one aspect of the polyorganosylsesquioxane of the present invention is preferably 5, more preferably 6, and even more preferably 7, and the upper limit is preferably 7. It is less than 20, more preferably 18, more preferably 16, and even more preferably 14. By setting the above ratio [T3 body / T2 body] to 5 or more, the surface hardness of the resin layer tends to be improved. By setting the above ratio [T3 / T2] to less than 20 (preferably 18 or less), the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed, so that handling is easy. It becomes easier to apply.

The lower limit of the ratio [T3 / T2] in another aspect of the polyorganosylsesquioxane of the present invention is preferably 20, more preferably 21, more preferably 23, still more preferably 25, and the upper limit. The value is preferably 500, more preferably 100, more preferably 50, and even more preferably 40. By setting the above ratio [T3 body / T2 body] to 20 or more, in addition to improving the surface hardness and adhesion, the surface of the uncured or semi-cured resin layer tends to be tack-free, and blocking resistance is prevented. The property is improved and it becomes easier to wind up on a roll. On the other hand, by setting the above ratio [T3 body / T2 body] to 500 or less, the compatibility with other components in the curable composition is improved, and the viscosity is also suppressed, so that handling becomes easy and coating is performed. It will be easier to do.

If the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Further, if the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). Each of the three oxygen atoms bonded to the silicon atom represented in the structure represented by the following formula (I') is bonded to another silicon atom (silicon atom not represented by the formula (I')). .. On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are each other silicon atom (silicon atom not shown in the formula (II')). It is combined. That is, both the T3 body and the T2 body are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds.

R ^a in the above formula (I) (same as R ^a in the formula (I')) and R ^b in the formula (II) (same as R ^b in the formula (II')) are cationically polymerized, respectively. A group containing a sex functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or Indicates a hydrogen atom. Specific examples of R ^a and R ^b include those similar to R ¹ in the above formula (1) and R ² in the above formula (2). R a in the formula (I) and R ^b in the formula (II ⁾ were each bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosylsesquioxane of the present invention. It is derived from a group (a group other than an alkoxy group and a halogen atom; for example, R ¹ , R ² , hydrogen atom, etc. in the formulas (a) to (c) described later).

R c in the above formula (II) (the same ^{applies to R c in} the formula (II')) indicates a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. .. The alkyl group in R ^c in the formula (II) is generally an alkoxy group in the hydrolyzable silane compound used as a raw material for the polyorganosylsesquioxane of the present invention (for example, X ¹ to X ³ described later). It is derived from an alkyl group that forms an alkoxy group (such as an alkoxy group).

The above ratio [T3 body / T2 body] in the polyorganosyl sesquioxane of the present invention can be determined, for example, by ²⁹ Si-NMR spectrum measurement. ²⁹ In the Si-NMR spectrum, the silicon atom in the structural unit (T3 body) represented by the above formula (I) and the silicon atom in the structural unit (T2 body) represented by the above formula (II) are at different positions. Since a signal (peak) is shown in (chemical shift), the above ratio [T3 / T2] can be obtained by calculating the integration ratio of each of these peaks. Specifically, for example, the polyorganosylsesquioxane of the present invention is represented by the above formula (1) and has a structural unit in which R ¹ is a 2- (3', 4'-epoxycyclohexyl) ethyl group. In this case, the signal of the silicon atom in the structure (T3 body) represented by the above formula (I) appears at −64 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) appears. The signal appears at -54-60 ppm. Therefore, in this case, the above ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) of −64 to −70 ppm and the signal (T2 body) of −54 to -60 ppm. can. When R ¹ is a group containing a cationically polymerizable functional group other than the 2- (3', 4'-epoxycyclohexyl) ethyl group, [T3 body / T2 body] can be obtained in the same manner.

The ²⁹ Si-NMR spectrum of the polyorganosyl sesquioxane of the present invention can be measured, for example, by the following devices and conditions.
Measuring device: Product name "JNM-ECA500NMR" (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Number of integrations: 1800 times Measurement temperature: 25 ° C

When the above ratio [T3 body / T2 body] of the polyorganosylsesquioxane of the present invention is within the above range (for example, 5 or more and 500 or less), the polyorganosylsesquioxane of the present invention has a T3 body. It means that a certain amount of T2 bodies are present. Examples of such a T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like. R in the following formula (4)¹And R in the following formula (5)²Are the Rs in the above equation (1), respectively.¹And R in the above formula (2) ²Is the same as. R in the following formulas (4) to (6)^cIs R in equation (II)^cSimilarly, it indicates a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The polyorganosilsesquioxane of the present invention may have any of cage type, incomplete cage type, ladder type, and random type silsesquioxane structures, and two or more of these silsesquioxane structures may be used. You may have them in combination.

When the polyorganosylsesquioxane of the present invention has a structural unit represented by the above formula (4), the total amount of the siloxane structural unit [total siloxane structural unit; total amount of M unit, D unit, T unit, and Q unit. ] (100 mol%), the ratio (total amount) of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) is not particularly limited, but is preferably 55 to 100 mol%. It is more preferably 65 to 100 mol%, still more preferably 80 to 99 mol%. By setting the above ratio to 55 mol% or more, the curability of the curable composition is improved, and the surface hardness and adhesiveness of the cured product (resin layer) are remarkably increased. The ratio of each siloxane constituent unit in the polyorganosyl sesquioxane of the present invention can be calculated, for example, by measuring the composition of the raw material, NMR spectrum, or the like.

Table in the above formula (2) with respect to the total amount of siloxane constituent units in the polyorganosylsesquioxane of the present invention [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the constituent units to be formed and the constituent units represented by the above formula (5) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, and further preferably 0 to 0 to 70 mol%. It is 40 mol%, particularly preferably 1 to 15 mol%. By setting the above ratio to 70 mol% or less, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased, and thus the curable composition. The curability of the cured product (resin layer) tends to be improved, and the surface hardness and adhesiveness of the cured product (resin layer) tend to be higher. On the other hand, when the above ratio is 1 mol% or more, the gas barrier property of the cured product (resin layer) tends to be improved.

Tabled by the above formula (1) with respect to the total amount of siloxane constituent units in the polyorganosylsesquioxane of the present invention [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) is particularly limited. However, it is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%. By setting the above ratio to 60 mol% or more, the surface hardness and adhesiveness of the cured product (resin layer) tend to be higher.

The number average molecular weight (Mn) of the polyorganosilsesquioxane of the present invention in terms of standard polystyrene by gel permeation chromatography is not particularly limited, but can be appropriately selected from the range of 1000 to 50,000, for example. The lower limit of the number average molecular weight of one aspect of the polyorganosylsesquioxane of the present invention is preferably 1000, more preferably 1100, and the upper limit is preferably 3000, more preferably 2800, still more preferably 2600. Is. By setting the number average molecular weight to 1000 or more, the heat resistance, scratch resistance, and adhesiveness of the cured product (resin layer) tend to be further improved. By setting the number average molecular weight to 3000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product (resin layer) tends to be further improved.

The lower limit of the number average molecular weight of another embodiment of the polyorganosilsesquioxane of the present invention is preferably 2500, more preferably 2800, still more preferably 3000, and the upper limit is preferably 50,000, more preferably 10000. , More preferably 8000. By setting the number average molecular weight to 2500 or more, in addition to improving the heat resistance, scratch resistance, and adhesiveness of the cured product (resin layer), the surface of the uncured or semi-cured resin layer becomes tack-free. It is easy to become, the blocking resistance is improved, and it becomes easy to wind up on a roll. By setting the number average molecular weight to 50,000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product (resin layer) tends to be further improved.

The molecular weight dispersion (Mw / Mn) of the polyorganosilsesquioxane of the present invention in terms of standard polystyrene by gel permeation chromatography is not particularly limited, but may be appropriately selected from the range of 1.0 to 4.0. can. The lower limit of the molecular weight dispersion is preferably 1.0, more preferably 1.1, and even more preferably 1.2. By setting the molecular weight dispersion to 1.1 or more, it tends to be liquid and the handleability tends to be improved. On the other hand, the upper limit of the molecular weight dispersion is preferably 4.0, more preferably 3.0, still more preferably 2.5 (for example, preferably 3.0, more preferably 2.0, still more preferably 1. 9). By setting the molecular weight dispersion to 4.0 or less (for example, 3.0 or less), the surface hardness and adhesiveness of the cured product (resin layer) tend to be higher.

The number average molecular weight and the degree of molecular weight dispersion of the polyorganosyl sesquioxane of the present invention can be measured by the following devices and conditions.
Measuring device: Product name "LC-20AD" (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 x 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1-0.2 wt%
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

The 5% weight loss temperature (T _d5 ) of the polyorganosilsesquioxane of the present invention in an air atmosphere is not particularly limited, but is preferably 330 ° C. or higher (for example, 330 to 450 ° C.), and more preferably 340 ° C. or higher. , More preferably 350 ° C. or higher. When the 5% weight loss temperature is 330 ° C. or higher, the heat resistance of the cured product (resin layer) tends to be further improved. In particular, the polyorganosylsesquioxane of the present invention has the above ratio [T3 / T2] of 5 or more and 500 or less, a number average molecular weight of 1000 to 50,000, and a molecular weight dispersion of 1.0 to 4.0. The 5% weight loss temperature is controlled to 330 ° C. or higher. The 5% weight loss temperature is the temperature at which 5% of the weight before heating is reduced when heated at a constant temperature rise rate, and is an index of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere and a heating rate of 5 ° C./min.

The polyorganosylsesquioxane of the present invention can be produced by a known or conventional method for producing a polysiloxane, and is not particularly limited, but for example, one or more hydrolyzable silane compounds are hydrolyzed and used. It can be produced by a method of condensing. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (a)) for forming a structural unit represented by the above formula (1) is indispensable. Must be used as a hydrolyzable silane compound.

More specifically, for example, a compound represented by the following formula (a), which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane of the present invention. Further, if necessary, the polyorganosylsesquioxane of the present invention can be produced by a method of hydrolyzing and condensing a compound represented by the following formula (b) and a compound represented by the following formula (c). ..

The compound represented by the above formula (a) is a compound forming a structural unit represented by the formula (1) in the polyorganosyl sesquioxane of the present invention. R ¹ in the formula (a) represents a group containing a cationically polymerizable functional group as in the case of R ¹ in the above formula (1). That is, as R ¹ in the formula (a), the group represented by the above formula (1a), the group represented by the above formula (1b), the group represented by the above formula (1c), and the above formula (1d). ) Is preferable, a group represented by the above formula (1a) is preferable, a group represented by the above formula (1c) is more preferable, and a group represented by the above formula (1a) is particularly preferable. Is a group represented by the above formula (1a), and is a group in which R ^1a is an ethylene group [among others, a 2- (3', 4'-epoxycyclohexyl) ethyl group].

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. Examples of the alkoxy group in X ¹ include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group and an isobutyloxy group. Further, examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Among them, as X ¹ , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The three X ^1s may be the same or different.

The compound represented by the above formula (b) is a compound forming a structural unit represented by the formula (2) in the polyorganosyl sesquioxane of the present invention. R ² in the formula (b) is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted, as in the case of R ² in the above formula (2). The alkyl group of the above, or the substituted or unsubstituted alkenyl group is shown. That is, as R ² in the formula (b), a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group is preferable, and a substituted or unsubstituted aryl group is more preferable. More preferably, it is a phenyl group.

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified as X ¹ . Among them, as X ² , an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The three X ^2s may be the same or different.

The compound represented by the above formula (c) is a compound forming a structural unit represented by the formula (3) in the polyorganosyl sesquioxane of the present invention. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among them, as X3 ^, an alkoxy group is preferable, and a methoxy group and an ethoxy group are more preferable. The ^three X3s may be the same or different.

As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by the above formulas (a) to (c) may be used in combination. For example, a hydrolyzable trifunctional silane compound other than the compounds represented by the above formulas (a) to (c), a hydrolyzable monofunctional silane compound forming an M unit, and a hydrolyzable bifunctional silane forming a D unit. Examples thereof include compounds, hydrolyzable tetrafunctional silane compounds forming Q units, and the like.

The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted according to the desired structure of the polyorganosylsesquioxane of the present invention. For example, the amount of the compound represented by the above formula (a) is not particularly limited, but is preferably 55 to 100 mol%, more preferably, with respect to the total amount (100 mol%) of the hydrolyzable silane compound used. Is 65 to 100 mol%, more preferably 80 to 99 mol%.

The amount of the compound represented by the above formula (b) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 70 mol%, based on the total amount (100 mol%) of the hydrolyzable silane compound used. Is 0 to 60 mol%, more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol%.

Further, the ratio (ratio of the total amount) of the compound represented by the formula (a) and the compound represented by the formula (b) to the total amount (100 mol%) of the hydrolyzable silane compound used is not particularly limited. It is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%.

Further, when two or more kinds of the above-mentioned hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially. When the above reactions are carried out sequentially, the order in which the reactions are carried out is not particularly limited.

The hydrolysis and condensation reaction of the hydrolyzable silane compound may be carried out in one step or may be carried out in two or more steps. For example, the polyorganosylsesquioxane of the present invention having the above ratio [T3 / T2] of less than 20 and / or the number average molecular weight of less than 2500 may be referred to as "low molecular weight polyorganosylsesquioxane". In order to efficiently produce the above), it is preferable to carry out the hydrolysis and condensation reaction in one step. Further, the polyorganosylsesquioxane of the present invention having the above ratio [T3 / T2] of 20 or more and / or a number average molecular weight of 2500 or more may be referred to as “high molecular weight polyorganosylsesquioxane”. In order to efficiently produce the above-mentioned), the hydrolysis and condensation reaction should be carried out in two or more steps (preferably two steps), that is, the above low molecular weight polyorganosylsesquioxane should be used as a raw material. It is preferable to carry out the hydrolysis and condensation reaction at least once. Hereinafter, the hydrolysis and condensation reaction of the hydrolyzable silane compound is carried out in one step to obtain a low molecular weight polyorganosylsesquioxane, and the low molecular weight polyorganosylsesquioxane is further subjected to the hydrolysis and condensation reaction. The embodiment of obtaining a high-molecular-weight polyorganosylsesquioxane will be described below, but the method for producing the polyorganosylsesquioxane of the present invention is not limited thereto.

When the hydrolysis and condensation reaction of the present invention is carried out in two steps, preferably, in the first step of the hydrolysis and condensation reaction, the above ratio [T3 / T2] is 5 or more and less than 20, and the number average molecular weight. The low molecular weight polyorganosylsesquioxane having a molecular weight of 1000 or more and less than 2500 is obtained, and in the second stage, the low molecular weight polyorganosylsesquioxane is further subjected to hydrolysis and condensation reactions to obtain the above ratio [T3]. Body / T2 body] is 20 or more and 500 or less, and a high molecular weight polyorganosylsesquioxane having a number average molecular weight of 2500 or more and 50,000 or less can be obtained.

The first-stage hydrolysis and condensation reaction can be carried out in the presence or absence of a solvent. Above all, it is preferable to carry out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol. And so on. Of these, ketones and ethers are preferable as the solvent. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination.

The amount of the solvent used in the first-stage hydrolysis and condensation reaction is not particularly limited, and the desired reaction time is in the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the hydrolyzable silane compound. Etc., it can be adjusted as appropriate.

The first stage hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkaline catalyst, but an alkaline catalyst is preferable in order to suppress the decomposition of cationically polymerizable functional groups such as epoxy groups. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid and p. -Sulphonic acid such as toluene sulfonic acid; solid acid such as active clay; Lewis acid such as iron chloride can be mentioned. Examples of the alkaline catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide. Hydroxide; Alkaline metal carbonate such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; Alkaline earth metal carbonate such as magnesium carbonate; Lithium hydrogen carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate , Alkaline metal hydrogen carbonates such as cesium hydrogen carbonate; alkali metal organic acid salts such as lithium acetate, sodium acetate, potassium acetate, cesium acetate (eg acetate); alkaline earth metal organic acids such as magnesium acetate Salts (eg, acetates); alkali metal alkoxides such as lithium methoxyd, sodium methoxyd, sodium ethoxydo, sodium isopropoxide, potassium ethoxydo, potassium t-butoxide; alkali metal phenoxide such as sodium phenoxide; triethylamine , N-Methylpiperidin, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene and other amines (tertiary amines). Etc.); Examples thereof include nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl and 1,10-phenanthroline. It should be noted that one type of catalyst may be used alone, or two or more types may be used in combination. Further, the catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.

The amount of the catalyst used in the first-stage hydrolysis and condensation reaction is not particularly limited, and is appropriately within the range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. Can be adjusted.

The amount of water used in the first-stage hydrolysis and condensation reaction is not particularly limited, and is appropriately adjusted within the range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound. be able to.

The method for adding water in the first-stage hydrolysis and condensation reaction is not particularly limited, and the total amount of water used (total amount used) may be added all at once or sequentially. good. When added sequentially, it may be added continuously or intermittently.

As the reaction conditions for the first-stage hydrolysis and condensation reaction, in particular, reaction conditions are selected such that the above ratio [T3 / T2] in the low molecular weight polyorganosylsesquioxane is 5 or more and less than 20. This is very important. The reaction temperature of the first-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 40 to 100 ° C, more preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the ratio [T3 / T2] tends to be more efficiently controlled to 5 or more and less than 20. The reaction time of the hydrolysis and condensation reaction in the first stage is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours. Further, the first-stage hydrolysis and condensation reaction can be carried out under normal pressure, under pressure or under reduced pressure. The atmosphere for performing the hydrolysis and condensation reaction in the first stage is not particularly limited, and may be, for example, under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as under air. It may be present, but it is preferably in an inert gas atmosphere.

The low molecular weight polyorganosylsesquioxane is obtained by the first-stage hydrolysis and condensation reaction. After the completion of the first-stage hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the decomposition of the cationically polymerizable functional group such as ring opening of the epoxy group. Further, the low molecular weight polyorganosylsesquioxane is separated by, for example, water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and other separation means, or a combination thereof. It may be separated and purified by means or the like.

The low molecular weight polyorganosyl sesquioxane obtained by the first-stage hydrolysis and condensation reaction is subjected to the second-stage hydrolysis and condensation reaction to produce a high-molecular-weight polyorganosyl sesquioxane. be able to.
The second-stage hydrolysis and condensation reaction can be carried out in the presence or absence of a solvent. When the second-stage hydrolysis and condensation reaction is carried out in the presence of a solvent, the solvent mentioned in the first-stage hydrolysis and condensation reaction can be used. As the solvent for the hydrolysis and condensation reaction in the second stage, the low molecular weight polyorganosylsesquioxane containing the reaction solvent for the hydrolysis and condensation reaction in the first stage, the extraction solvent and the like is distilled off as it is or partially. May be used. It should be noted that one type of solvent may be used alone, or two or more types may be used in combination.

When the solvent is used in the hydrolysis and condensation reaction of the second stage, the amount used is not particularly limited and is in the range of 0 to 2000 parts by weight with respect to 100 parts by weight of the low molecular weight polyorganosylsesquioxane. Therefore, it can be appropriately adjusted according to the desired reaction time and the like.

The second stage hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water. As the above-mentioned catalyst, the catalyst mentioned in the first-stage hydrolysis and condensation reaction can be used, and in order to suppress the decomposition of cationically polymerizable functional groups such as epoxy groups, an alkaline catalyst is preferable. More preferably, it is a hydroxide of an alkali metal such as sodium hydroxide, potassium hydroxide and cesium hydroxide; a carbonate of an alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate. It should be noted that one type of catalyst may be used alone, or two or more types may be used in combination. Further, the catalyst can also be used in a state of being dissolved or dispersed in water, a solvent or the like.

The amount of the catalyst used in the second-stage hydrolysis and condensation reaction is not particularly limited, and is preferably 0.01 to 10000 ppm, more preferably 0, with respect to the low molecular weight polyorganosylsesquioxane (1000000 ppm). It can be appropriately adjusted within the range of 1 to 1000 ppm.

The amount of water used in the hydrolysis and condensation reaction of the second stage is not particularly limited, and is preferably 10 to 100,000 ppm, more preferably 100 to 20,000 ppm, based on the low molecular weight polyorganosylsesquioxane (1000000 ppm). It can be adjusted as appropriate within the range of. When the amount of water used is larger than 100,000 ppm, it tends to be difficult to control the ratio of high molecular weight polyorganosylsesquioxane [T3 / T2] and the number average molecular weight within a predetermined range.

The method for adding water in the second-stage hydrolysis and condensation reaction is not particularly limited, and the total amount of water used (total amount used) may be added all at once or sequentially. good. When added sequentially, it may be added continuously or intermittently.

As the reaction conditions for the hydrolysis and condensation reaction in the second stage, the ratio [T3 / T2] in the high molecular weight polyorganosylsesquioxane is 20 or more and 500 or less, and the number average molecular weight is 2500 to 50,000. It is important to select such reaction conditions. The reaction temperature of the hydrolysis and condensation reaction in the second stage varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200 ° C, more preferably 30 to 100 ° C. By controlling the reaction temperature within the above range, the ratio [T3 body / T2 body] and the number average molecular weight tend to be controlled more efficiently within the desired range. The reaction time of the hydrolysis and condensation reaction in the second stage is not particularly limited, but is preferably 0.5 to 1000 hours, more preferably 1 to 500 hours.
Further, the desired ratio is obtained by performing timely sampling while performing hydrolysis and condensation reaction within the above reaction temperature range, and performing the reaction while monitoring the above ratio [T3 body / T2 body] and the number average molecular weight. [T3 / T2], high molecular weight polyorganosylsesquioxane having a number average molecular weight can also be obtained.

The second-stage hydrolysis and condensation reaction can be carried out under normal pressure, under pressure or under reduced pressure. The atmosphere for performing the hydrolysis and condensation reaction in the second stage is not particularly limited, and may be, for example, under an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as under air. It may be present, but it is preferably in an inert gas atmosphere.

The high molecular weight polyorganosyl sesquioxane is obtained by the hydrolysis and condensation reaction of the second stage. After the completion of the hydrolysis and condensation reaction in the second stage, it is preferable to neutralize the catalyst in order to suppress the decomposition of the cationically polymerizable functional group such as the ring opening of the epoxy group. In addition, separation means for high-molecular-weight polyorganosylsesquioxane, for example, washing with water, washing with acid, washing with alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., and separation by combining these. It may be separated and purified by means or the like.

Since the polyorganosil sesquioxane of the present invention has the above-mentioned structure, the resin layer obtained by curing the curable composition containing the polyorganosil sesquioxane as an essential component has high surface hardness and excellent bending durability. The property is imparted, and it becomes easy to form a resin layer satisfying the above-mentioned (conditions 1 to 5).

In the curable composition of the present invention, the polyorganosylsesquioxane of the present invention may be used alone or in combination of two or more.

The content (blending amount) of the polyorganosylsesquioxane of the present invention in the curable composition of the present invention is not particularly limited, but is 50 with respect to the total amount (100% by weight) of the curable composition excluding the solvent. It is preferably by weight or more and less than 100% by weight, more preferably 60 to 99% by weight, still more preferably 70 to 95% by weight. By setting the content of the polyorganosylsesquioxane of the present invention to 50% by weight or more, the surface hardness and adhesiveness of the cured product (resin layer) tend to be further improved. On the other hand, by setting the content of the polyorganosylsesquioxane of the present invention to less than 100% by weight (for example, 95% by weight or less), a curing catalyst and one or more heat-polymerizable functional groups in the molecule described later can be obtained. A compound having one or more photopolymerizable functional groups, an epoxy compound, a fluorine-containing photopolymerizable resin, and the like can be contained, whereby the curing of the curable composition can be promoted more efficiently, and the curing can be promoted more efficiently. Surface hardness and bending durability tend to improve.

The ratio of the polyorganosylsesquioxane of the present invention to the total amount (100% by weight) of the cationically curable compound contained in the curable composition of the present invention is not particularly limited, but is preferably 60 to 99% by weight, more preferably. Is 65 to 98% by weight, more preferably 70 to 95% by weight. By setting the content of the polyorganosyl sesquioxane of the present invention to 60% by weight or more, the surface hardness and adhesiveness of the cured product (resin layer) tend to be further improved. On the other hand, by setting the content of the polyorganosylsesquioxane of the present invention to 99% by weight or less, it has one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups in the molecule described later. A compound, an epoxy compound, or the like can be contained, which tends to improve the surface hardness and bending durability.

(Curing catalyst)
The curable composition of the present invention preferably further contains a curing catalyst. Above all, it is particularly preferable to include a cationic polymerization initiator or a radical polymerization initiator as the curing catalyst in that the curing time until it becomes more tack-free can be shortened.

The cationic polymerization initiator is a compound capable of initiating or accelerating the cationic polymerization reaction of a cationically curable compound such as the polyorganosylsesquioxane of the present invention. The cationic polymerization initiator is not particularly limited, and examples thereof include a photocationic polymerization initiator (photoacid generator), a thermal cationic polymerization initiator (thermal acid generator), and the like.

As the photocationic polymerization initiator, a known or commonly used photocationic polymerization initiator can be used, for example, a sulfonium salt (a salt of a sulfonium ion and an anion) and an iodonium salt (a salt of an iodonium ion and an anion). , Selenium salt (salt of selenium ion and anion), ammonium salt (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), salt of transition metal complex ion and anion, etc. .. These can be used alone or in combination of two or more.

Examples of the sulfonium salt include [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, triphenylsulfonium salt, tri-p-tolylsulfonium salt, and the like. Tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, Triaryl such as tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt, etc. Sulfonium salt; Diarylsulfonium salt such as diphenylphenacil sulfonium salt, diphenyl4-nitrophenacil sulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4- Monoarylsulfonium salts such as methoxyphenylmethylbenzylsulfonium salt; trialkylsulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, dimethylbenzylsulfonium salt and the like can be mentioned.

As the diphenyl [4- (phenylthio) phenyl] sulfonium salt, for example, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate and the like can be used. ..

Examples of the iodonium salt include the trade name "UV9380C" (manufactured by Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium = hexafluoroantimonate 45% alkylglycidyl ether solution), and the trade name " RHODORSIL PHOTOINITIOTOR 2074 "(manufactured by Rhodia Japan Co., Ltd., tetrakis (pentafluorophenyl) borate = [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name" WPI-124 "(Wako Pure Chemical Industries, Ltd.) Co., Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt and the like.

Examples of the selenium salt include triaryl selenium salts, tri-p-tolyl selenium salts, tri-o-tolyl selenium salts, tris (4-methoxyphenyl) selenium salts, 1-naphthyldiphenyl selenium salts and the like. Salts; diallyl selenium salts such as diphenylphenacyl selenium salt, diphenylbenzyl selenium salt, diphenylmethyl selenium salt; monoaryl selenium salts such as phenylmethyl benzyl selenium salt; trialkyl selenium salts such as dimethyl phenacyl selenium salt and the like. ..

Examples of the ammonium salt include tetra (tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt and the like). Alkylammonium salt; Pyrrolidium salt such as N, N-dimethylpyrrolidium salt, N-ethyl-N-methylpyrrolidium salt; N, N'-dimethylimidazolinium salt, N, N'-diethylimidazolinium salt, etc. Imidazolinium salt; tetrahydropyrimidium salt such as N, N'-dimethyltetrahydropyrimidium salt, N, N'-diethyltetrahydropyrimidium salt; N, N-dimethylmorpholinium salt, N, N -Morholinium salt such as diethylmorpholinium salt; piperidinium salt such as N, N-dimethylpiperidinium salt, N, N-diethylpiperidinium salt; pyridinium salt such as N-methylpyridinium salt and N-ethylpyridinium salt. Imidazolium salts such as N, N'-dimethylimidazolium salt; quinolium salts such as N-methylquinolium salt; isoquinolium salts such as N-methylisoquinolium salt; thiazonium salts such as benzylbenzothiazonium salt; Examples thereof include acridium salts such as benzyl acridium salts.

Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, and tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salt such as triphenylbenzylphosphonium salt; and triethyl. Examples thereof include tetraalkylphosphonium salts such as benzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt and triethylphenacylphosphonium salt.

Examples of the salt of the transition metal complex ion include salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ and (η5-cyclopentadienyl) (η6-xylene) Cr ⁺ . ; Salts of iron complex cations such as (η5-cyclopentadienyl) (η6-toluene) Fe ⁺ , (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ and the like can be mentioned.

Examples of the anions constituting the above-mentioned salt include SbF _6- ^, PF _6- ^, BF _4- ^, (CF ₃ CF ₂ ) ₃ PF _3- ^, (CF ₃ CF ₂ CF ₂ ) ₃ PF _3- ^, (C). ₆ F ₅ ) ₄ B- ^, (C ₆ F ₅ ) ₄ Ga- ^, Sulfonic acid anion (trifluoromethane sulfonic acid anion, pentafluoroethane sulfonic acid anion, nonafluorobutane sulfonic acid anion, methane sulfonic acid anion, benzene sulfonic acid Anion, p-toluene sulfonic acid anion, etc.), (CF ₃ SO ₂ ) ₃ C- ^, (CF ₃ SO ₂ ) ₂ N- ^, perhalogenate ion, halide sulfonic acid ion, sulfate ion, carbonate ion, aluminic acid Examples thereof include an ion, a hexafluorobismasic acid ion, a carboxylate ion, an arylborate ion, a thiocyanate ion, and a nitrate ion.

Examples of the thermal cationic polymerization initiator include aryl sulfonium salts, aryl iodonium salts, allen-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes and the like.

Examples of the aryl sulfonium salt include hexafluoroantimonate salt and the like. In the curable composition of the present invention, for example, trade names "SP-66" and "SP-77" (all manufactured by ADEKA Corporation); trade names "Sun Aid SI-60L" and "Sun Aid SI-80L". , "Sun Aid SI-100L", "Sun Aid SI-150L" (all manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropyrate and aluminum tris (ethyl acetoacetate). Examples of the boron trifluoride amine complex include a boron trifluoride monoethylamine complex, a boron trifluoride imidazole complex, and a boron trifluoride piperidine complex.

In the curable composition of the present invention, one type of curing catalyst may be used alone, or two or more types may be used in combination.

The content (blending amount) of the curing catalyst in the curable composition of the present invention is not particularly limited, but is 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the polyorganosylsesquioxane of the present invention. Is more preferable, and more preferably 0.05 to 3.0 parts by weight, still more preferably 0.1 to 1.0 part by weight (for example, 0.3 to 1.0 part by weight). By setting the content of the curing catalyst to 0.01 parts by weight or more, the curing reaction can be efficiently and sufficiently proceeded, and the surface hardness and adhesiveness of the cured product (resin layer) tend to be further improved. .. On the other hand, when the content of the curing catalyst is 3.0 parts by weight or less, the storage stability of the curable composition tends to be further improved, and the coloring of the cured product (resin layer) tends to be suppressed.

(A compound having one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups in the molecule)
The curable composition of the present invention contains a compound having one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups in the molecule (hereinafter, may be referred to as "Compound A"). Is preferable. By containing compound A together with the polyorganosylsesquioxane of the present invention, the curable composition of the present invention can effectively increase the crosslink density when made into a cured product, and can be used as a cured product (resin layer). High surface hardness and excellent bending durability are easily imparted.

The "thermopolymerizable functional group" possessed by the compound A is not particularly limited as long as it is a functional group that imparts polymerizable property to the compound A by heat, and examples thereof include a hydroxyl group, an epoxy group, an oxetanyl group, and a vinyl ether group. From the viewpoint of surface hardness and bending durability of the resin layer of the present invention, hydroxyl groups and epoxy groups are preferable. When the compound A has two or more thermopolymerizable functional groups, these thermopolymerizable functional groups may be the same or different from each other.

The "photopolymerizable functional group" possessed by the compound A is not particularly limited as long as it is a functional group that imparts polymerizability to the compound A by light (for example, ultraviolet rays), and examples thereof include a (meth) acryloyl group and a vinyl group. The (meth) acryloyl group is preferable from the viewpoint of the surface hardness and bending durability of the resin layer of the present invention. When the compound A has two or more photopolymerizable functional groups, these photopolymerizable functional groups may be the same or different from each other.

The number of thermopolymerizable functional groups contained in one molecule of compound A may be 1 or more, and is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. One or two. Further, the number of photopolymerizable functional groups contained in one molecule of compound A may be 1 or more, and is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1, for example. Is one or two.

The functional group equivalent of the thermopolymerizable functional group of the compound A is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and further preferably 120 to 450. If the functional group equivalent is less than 50, the bending durability of the cured product (resin layer) may be insufficient. On the other hand, if the functional group equivalent exceeds 500, the surface hardness of the cured product (resin layer) may decrease. The functional group equivalent of the thermopolymerizable functional group of compound A can be calculated by the following formula.
[Functional equivalent of thermopolymerizable functional group] = [Molecular weight of compound A] / [Number of thermopolymerizable functional groups of compound A]

The functional group equivalent of the photopolymerizable functional group of compound A is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. If the functional group equivalent is less than 50, the bending durability of the cured product (resin layer) may be insufficient. On the other hand, if the functional group equivalent exceeds 500, the surface hardness of the cured product (resin layer) may decrease. The functional group equivalent of the photopolymerizable functional group of compound A can be calculated by the following formula.
[Functional equivalent of photopolymerizable functional group] = [Molecular weight of compound A] / [Number of photopolymerizable functional groups of compound A]

Specific examples of the compound A include, for example, both 3,4-epoxide cyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and tripropylene glycol diglycidyl ether di (meth) acrylate (tripropylene glycol diglycidyl ether). (Compound obtained by reacting (meth) acrylic acid with the epoxy group of Tripropylene glycol diglycidyl ether), tripropylene glycol diglycidyl ether half (meth) acrylate (reacting (meth) acrylic acid with one of the epoxy groups of tripropylene glycol diglycidyl ether) (Compound obtained by reacting (meth) acrylic acid with both epoxy groups of bisphenol A epoxide di (meth) acrylate), bisphenol A epoxide half (meth) acrylate (bisphenol A). A compound obtained by reacting one epoxy group of diglycidyl ether with (meth) acrylic acid or a derivative thereof), bisphenol F epoxide di (meth) acrylate, bisphenol F epoxy half (meth) acrylate, bisphenol S epoxide di (meth) acrylate. , Bisphenol S Epoxide Half (meth) acrylate or other compound having an epoxy group and / or a hydroxyl group and a (meth) acryloyl group in one molecule; 3-oxetanylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) ) Oxetanyl group in one molecule such as acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, 3-butyl-3-oxetanylmethyl (meth) acrylate, 3-hexyl-3-oxetanylmethyl (meth) acrylate. And a compound having a (meth) acryloyl group; 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2 (meth) acrylate. -Vinyloxypropyl, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-methyl (meth) acrylate- 3-Vinyloxypropyl, (meth) acrylic acid 1,1-dimethyl-2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxybutyl, (meth) acrylic acid 1-methyl-2-vinyloxypropyl, (meth) acrylic acid 2-Vinyloxybutyl, ( Meta) 4-vinyloxycyclohexyl acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) 2-vinyloxycyclohexylmethyl acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, (meth) ) 2- (Vinyloxyethoxy) ethyl acrylate, 2- (meth) acrylate 2- (vinyloxyisopropoxy) ethyl, (meth) acrylate 2- (vinyloxyethoxy) propyl, (meth) acrylate 2- (bini) Loxyethoxy) isopropyl, (meth) acrylate 2- (vinyloxyisopropoxy) propyl, (meth) acrylate 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylate 2- (vinyloxyethoxyethoxy) ethyl, 2- (Meta) acrylate 2- (vinyloxyethoxyisopropoxy) ethyl, (meth) acrylate 2- (vinyloxyisopropoxyethoxy) ethyl, (meth) acrylate 2- (vinyloxyisopropoxyisopropoxy) ethyl, ( 2- (Vinyloxyethoxyethoxy) propyl (meth) acrylic acid, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylic acid, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylic acid, (meth) acrylic Acid 2- (vinyloxyisopropoxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2 -(Vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (Vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopro) Penoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) Examples thereof include compounds having a vinyl ether group and a (meth) acryloyl group in one molecule such as ethoxy) ethyl, (meth) polyethylene glycol monovinyl ether acrylate, and (meth) polypropylene glycol monovinyl ether acrylate.

From the viewpoint of bending durability and surface hardness of the cured product (resin layer), the compound A contains an epoxy group and / or a hydroxyl group as a thermopolymerizable functional group and (meth) acryloyl as a photopolymerizable functional group in one molecule. Compounds having a group are preferable, and specific examples thereof include 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, tripropylene glycol diglycidyl ether half (meth) acrylate, and bisphenol A epoxy half (meth) acrylate. , Bisphenol F epoxy half (meth) acrylate, bisphenol S epoxy half (meth) acrylate and the like are preferable.

In the curable composition of the present invention, one type of compound A may be used alone, or two or more types may be used in combination. Compound A can be produced by a known method, for example, a part of the heat-polymerizable functional group of a compound having two or more heat-polymerizable functional groups (for example, an epoxy group and a hydroxyl group) in one molecule. Is obtained by a method of reacting with a carboxylic acid having a photopolymerizable functional group (for example, acrylic acid, methacrylic acid, etc.) or a derivative thereof. Examples of the compound A include trade names "light ester G", "epoxy ester 200PA", "epoxy ester 200PA-E5" (all manufactured by Kyoeisha Chemical Co., Ltd.), and trade names "NKOLIGO EA1010N" (above, Kyoeisha Chemical Co., Ltd.). Commercial products such as those manufactured by Shin-Nakamura Chemical Industry Co., Ltd. can also be used.

The content (blending amount) of the compound A in the curable composition of the present invention is not particularly limited, but the solid content is 1 to 100 parts by weight with respect to 100 parts by weight of the polyorganosylsesquioxane of the present invention. Is preferable, more preferably 3 to 75 parts by weight, still more preferably 5 to 50 parts by weight. By setting the content of the compound A to 1 part by weight or more, the bending durability of the cured product (resin layer) tends to be further improved. On the other hand, by setting the content of the compound A to 100 parts by weight or less, the surface hardness of the cured product (resin layer) tends to be maintained.

(Fluorine-containing photopolymerizable resin)
The curable composition of the present invention preferably contains a fluorine-containing photopolymerizable resin. The fluorine-containing photopolymerizable resin is a resin (oligomer) having a fluorine-containing group such as a fluoroaliphatic hydrocarbon skeleton and a photopolymerizable functional group in the molecule. When the curable composition of the present invention contains a fluorine-containing photopolymerizable resin together with the polyorganosylsesquioxane of the present invention and compound A, the crosslink density of the surface of the resin layer when made into a cured product is effectively increased. It has the property of improving the appearance such as the smoothness of the surface of the cured product (resin layer) and improving the surface hardness, scratch resistance and stain resistance. In particular, the effect of the fluorine-containing photopolymerizable resin becomes remarkable when it is blended with the compound A in the curable composition of the present invention.

Examples of the photopolymerizable functional group possessed by the fluorine-containing photopolymerizable resin include the same as the "photopolymerizable functional group" possessed by the above compound A, and the scratch resistance and antifouling property of the resin layer of the present invention can be mentioned. From the viewpoint of, a (meth) acryloyl group is preferable. When the fluorine-containing photopolymerizable resin has two or more photopolymerizable functional groups, these photopolymerizable functional groups may be the same or different.

The number of photopolymerizable functional groups contained in one molecule of the fluorine-containing photopolymerizable resin is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. Is.

The "fluorine-containing group" contained in the fluorine-containing photopolymerizable resin is not particularly limited as long as it has a fluorine atom, and examples thereof include those having a fluoroaliphatic hydrocarbon skeleton. Examples of the fluoroaliphatic hydrocarbon skeleton include fluoroC _1-10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, and fluorohexane. be able to.

In these fluoroaliphatic hydrocarbon skeletons, at least a part of hydrogen atoms may be replaced with fluorine atoms, but all hydrogens can improve scratch resistance, slipperiness and antifouling property of the resin layer. A perfluoroaliphatic hydrocarbon skeleton in which the atom is replaced with a fluorine atom is preferable.

Further, the fluoroaliphatic hydrocarbon skeleton may form a polyfluoroalkylene ether skeleton which is a repeating unit via an ether bond. The fluoroaliphatic hydrocarbon group as a repeating unit may be at least one selected from the group consisting of _{fluoroC 1-4} alkylene groups such as fluoromethylene, fluoroethylene, fluoropropylene and fluoroisopropylene. The number of repetitions (degree of polymerization) of the polyfluoroalkylene ether unit is, for example, 10 to 3000, preferably 30 to 1000, and more preferably 50 to 500.

The fluorine-containing photopolymerizable resin may have a silicone-containing group in addition to the above-mentioned "photopolymerizable functional group" and "fluorine-containing group". Since the fluorine-containing photopolymerizable resin further has a silicone-containing group, the affinity with the polyorganosylsesquioxane of the present invention is improved, and the surface hardness, scratch resistance, and stain resistance of the cured product (resin layer) are improved. Sex tends to improve further. The silicone-containing group is a group having a polyorganosiloxane skeleton, and may be a polyorganosiloxane formed in M units, D units, T units, or Q units, but usually, a polyorganosiloxane formed in D units is used. It is preferably used. As the organic group of the polyorganosiloxane, a C _1-4 alkyl group and an aryl group are usually used, and a methyl group and a phenyl group (particularly a methyl group) are generally used. The number of repetitions (degree of polymerization) of the siloxane unit is, for example, 2 to 3000, preferably 3 to 2000, and more preferably 5 to 1000.

As the fluorine-containing photopolymerizable resin, a commercially available product can be used, for example, trade names "Megafuck RS-56", "Megafuck RS-75", "Megafuck RS-72-K", "Megafuck RS". -76-E "," Megafuck RS-76-E "," Megafuck RS-76-NS "," Megafuck RS-78 "," Megafuck RS-90 "(all manufactured by DIC Co., Ltd.) ; The trade names "Futagent 601AD", "Futagent 601ADH2", "Futagent 602A", "Futergent 650AC", "Futtergent 681" (all manufactured by Neos Co., Ltd.) and the like can be used.

These fluorine-containing photopolymerizable resins may be used alone or in combination of two or more.

The content (blending amount) of the fluorine-containing photopolymerizable resin in the curable composition of the present invention is not particularly limited, but as a solid content, for example, with respect to 100 parts by weight of the polyorganosylsesquioxane of the present invention. It is 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and further preferably 0.2 to 3 parts by weight. By setting the content of the fluorine-containing photopolymerizable resin to 0.01 parts by weight or more, the scratch resistance and stain resistance of the cured product (resin layer) tend to be further improved.

(Epoxy compound)
The curable composition may contain an epoxy compound other than the polyorganosyl sesquioxane of the present invention (hereinafter, may be simply referred to as an "epoxy compound"). By containing an epoxy compound in addition to the polyorganosyl sesquioxane of the present invention, a cured product (resin layer) having high surface hardness and excellent flexibility, flexibility and processability can be formed.

As the epoxy compound, a known and commonly used compound having one or more epoxy groups (oxylan rings) in the molecule can be used, and the alicyclic epoxy compound (aliphatic epoxy resin) and fragrance are not particularly limited. Examples thereof include a group epoxy compound (aromatic epoxy resin) and an aliphatic epoxy compound (aliphatic epoxy resin). Of these, alicyclic epoxy compounds are preferable.

Examples of the alicyclic epoxy compound include known and commonly used compounds having one or more alicyclics and one or more epoxy groups in the molecule, and are not particularly limited. For example, (1) fat in the molecule. A compound having an epoxy group (referred to as "aliphatic epoxy group") composed of two adjacent carbon atoms and oxygen atoms constituting the ring; (2) The epoxy group is directly bonded to the alicyclic by a single bond. Compounds; (3) Compounds having an alicyclic and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like can be mentioned.

As the compound (1) having an alicyclic epoxy group in the molecule, it can be arbitrarily selected and used from known and commonly used compounds. Among them, the cyclohexene oxide group is preferable as the alicyclic epoxy group, and the compound represented by the following formula (i) is particularly preferable.

In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. Can be mentioned as a group in which a plurality of groups are linked. One or more hydrogen atoms of the cyclohexane ring in the formula (i) may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms.

Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group and the like. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group and the like. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-. Examples thereof include a divalent cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which a part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include a vinylene group, a propenylene group, and a 1-butenylene group. , 2-Butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like can be mentioned as a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, as the epoxidized alkenylene group, an alkenylene group in which the entire carbon-carbon double bond is epoxidized is preferable, and more preferably, the entire carbon-carbon double bond is epoxidized and has 2 to 4 carbon atoms. It is an alkenylene group.

Typical examples of the alicyclic epoxy compound represented by the above formula (i) are (3,4,3', 4'-diepoxy) bicyclohexyl, and the following formulas (i-1) to (i-10). ) Can be mentioned. In addition, l and m in the following formulas (i-5) and (i-7) represent integers of 1 to 30, respectively. R'in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group and an isopropylene group. A chain alkylene group is preferred. N1 to n6 in the following formulas (i-9) and (i-10) represent integers of 1 to 30, respectively. Examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxylane, bis (3,4-epoxycyclohexylmethyl) ether and the like can be mentioned.

Examples of the compound in which the epoxy group is directly bonded to the alicyclic (2) by a single bond include a compound represented by the following formula (ii).

In the formula (ii), R "is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of the p-valent alcohol, and p and n each represent a natural number. Examples of the valent alcohol [R "(OH) _p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (alcohols having 1 to 15 carbon atoms) and the like. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parentheses) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxylanyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol [for example. , Product name "EHPE3150" (manufactured by Daicel Corporation), etc.] and the like can be mentioned.

Examples of the compound having an alicyclic and a glycidyl ether group in the above-mentioned (3) molecule include an alicyclic alcohol (particularly, an alicyclic polyhydric alcohol) glycidyl ether. More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy)). Cyclohexyl] A compound obtained by hydrogenating a bisphenol A type epoxy compound such as propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2,5-dimethylpropoxy) 3-Epoxypropoxy) Cyclohexyl] Hydrogenated bisphenol F type epoxy compound such as methane (hydrogenated bisphenol F type epoxy compound); hydrided biphenol type epoxy compound; hydrided phenol novolak type epoxy compound; hydride cresol Novolak type epoxy compound; bisphenol A hydride cresol novolak type epoxy compound; hydride naphthalene type epoxy compound; hydride epoxy compound of epoxy compound obtained from trisphenol methane; hydrided epoxy compound of the following aromatic epoxy compound and the like. be able to.

Examples of the aromatic epoxy compound include bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and an epibis-type glycidyl ether type epoxy resin obtained by a condensation reaction with epihalohydrin; these epis. High molecular weight epibistype glycidyl ether type epoxy resin obtained by further addition reaction of bistype glycidyl ether type epoxy resin with the above bisphenols; phenols [for example, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehydes [for example, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] and polyhydric alcohols obtained by subjecting them to a condensation reaction with epihalohydrin. Alkyl type glycidyl ether type epoxy resin; Two phenol skeletons are bonded to the 9-position of the fluorene ring, and glycidyl is attached to the oxygen atom obtained by removing the hydrogen atom from the hydroxy group of these phenol skeletons, either directly or via an alkyleneoxy group. Examples thereof include an epoxy compound to which a group is bonded.

Examples of the aliphatic epoxy compound include glycidyl ethers of alcohols having no q-valent cyclic structure (q is a natural number); monovalent or polyvalent carboxylic acids [eg, acetic acid, propionic acid, butyric acid, stearic acid, etc. Glycidyl ester of adipic acid, sebacic acid, maleic acid, itaconic acid, etc .; epoxidized fats and oils having double bonds such as epoxidized flaxseed oil, epoxidized soybean oil, epoxidized ash oil; polyolefin (poly) such as epoxidized polybutadiene. (Including alkaziene) epoxides and the like can be mentioned. Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-Propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and other dihydric alcohols; Examples thereof include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. Further, the q-valent alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol or the like.

The above epoxy compound may be used alone or in combination of two or more. As the epoxy compound, an alicyclic epoxy compound is preferable from the viewpoint of surface hardness, flexibility, bending durability, etc. of the cured product (resin layer), and (2) an epoxy group is directly bonded to the alicyclic by a single bond. The compound is more preferable, and the compound represented by the above formula (ii) [for example, trade name “EHPE3150” (manufactured by Daicel Co., Ltd.)] is particularly preferable.

The content (blending amount) of the epoxy compound is, for example, 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, based on 100 parts by weight of the total amount of the polyorganosylsesquioxane of the present invention. , More preferably 5 to 50 parts by weight. By setting the content of the epoxy compound to 0.5 parts by weight or more, the surface hardness of the cured product (resin layer) becomes higher, and the flexibility, flexibility, processability, and bending durability tend to be superior. .. On the other hand, when the content of the epoxy compound is 100 parts by weight or less, the scratch resistance of the cured product tends to be further improved.

(Silica particles having a group containing a (meth) acryloyl group on the surface)
The curable composition of the present invention may contain "silica particles having a group containing a (meth) acryloyl group on the surface". Silica particles having a group containing a (meth) acryloyl group on the surface have innumerable hydroxyl groups (Si—OH groups) on the surface of the silica particles, and when cured, the hydroxyl groups and the polyorganosylsesquioxane of the present invention are used. Reacts to improve the cross-linking density of polyorganosylsesquioxane after curing. Further, when the (meth) acryloyl groups in the plurality of silica particles are bonded to each other during curing, the crosslink density after curing is improved. By improving the crosslink density after curing in this way, the scratch resistance of the resin layer is improved. Further, if a layer (functional layer) having functions such as antifouling property and low reflectivity is provided on the resin layer, the adhesion between the resin layer and the functional layer is weak, and the functional layer may be peeled off. It may not have so-called recoating properties. However, when the silica particles are used, recoatability can be imparted, and processability (processability) when the functional layer is provided on the surface of the resin layer can also be improved.

Further, it is considered that the silica particles can impart stability in the curable composition by having a (meth) acryloyl group on the surface. The above-mentioned stability means that the silica particles react with polyorganosyl sesquioxane in the stage of preparing the curable composition before curing, and the viscosity of the curable composition is significantly increased (gelled). , Say that it does not solidify. Ordinary silica particles (SiO) having no functional group such as a group containing (meth) acryloyl group on the surface. ₂When particles) are used, the silica particles may aggregate with each other and the curable composition may gel. The silica particles may have a functional group (for example, a silicone-modifying group) other than the (meth) acryloyl group. The (meth) acryloyl group is a general term for an acryloyl group (acrylic group) and a metaacryloyl group (methacrylic group).

As the silica particles, a dispersion liquid (dispersion) in a state of being dispersed in a known or commonly used general dispersion medium such as water or an organic solvent may be used. Further, the silica particles obtained by reacting the silica particles with a silane coupling agent having a group containing a (meth) acryloyl group may be used as the silica particles. As the silica particles, for example, trade names "BYK-LPX 22699", "NANOBYK-3650", "NANOBYK-3651", and "NANOBYK-3652" (all manufactured by Big Chemie Japan Co., Ltd.) can be used. ..

The particle size of the silica particles is, for example, 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 30 nm.

When the curable composition of the present invention contains silica particles having a group containing a (meth) acryloyl group on the surface, the ratio thereof is, for example, 0.01 with respect to 100 parts by weight of the polyorganosylsesquioxane of the present invention. It is about 20 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, and further preferably 0.2 to 5 parts by weight. By setting the ratio of the silica particles to 0.01 parts by weight or more, the appearance of the surface of the resin layer can be improved and sufficient recoatability can be imparted. Further, by setting the ratio of the silica particles to 20 parts by weight or less, the surface hardness of the resin layer can be increased.

(Silicone acrylate)
The curable composition of the present invention may contain "silicon acrylate". Silicon acrylate (silicone acrylate) is a kind of additive having at least a silicon atom and a (meth) acryloyl group. The silicon acrylate may have a functional group (for example, a hydroxyl group) other than the (meth) acryloyl group. The silicon acrylate may be silicon diacrylate, silicon triacrylate, silicon tetra acrylate, silicon penta acrylate, silicon hexa acrylate, silicon hepta acrylate, or silicon octa acrylate. When the silicon acrylate is used in a curable composition together with the polyorganosylsesquioxane, the crosslink density on the surface of the resin layer can be effectively increased when the resin layer is used, and the surface smoothness of the resin layer can be increased. It has the property of improving the appearance such as, and improving the surface hardness, scratch resistance and stain resistance. The (meth) acryloyl group is a general term for an acryloyl group (acrylic group) and a metaacryloyl group (methacrylic group).

As the silicon acrylate, a dispersion liquid (dispersion) in a state of being dispersed in a known or commonly used general dispersion medium such as an organic solvent (for example, acetone, toluene, methanol, ethanol) may be used. As the silicon acrylate, for example, trade names "KRM8479", "EBECRYL 350", and "EBECRYL 1360" (manufactured by Daicel Ornex Co., Ltd.) can be used.

When the curable composition of the present invention contains the silicon acrylate, the ratio thereof is, for example, 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyorganosylsesquioxane. Parts, more preferably 0.01 to 5 parts by weight, still more preferably 0.2 to 3 parts by weight. By setting the ratio of the silicon acrylate to 0.01 parts by weight or more, scratch resistance and stain resistance when the resin layer is used can be improved. Further, by setting the ratio of the silicon acrylate to 15 parts by weight or less, the surface hardness of the resin layer can be further increased.

It is preferable to use both silicon acrylate and silica particles having a group containing a (meth) acryloyl group on the surface in terms of further improving the appearance of the resin layer, increasing the surface hardness, and improving the scratch resistance. .. When both the silicon acrylate and the silica particles are contained, the total ratio of the silicon acrylate and the silica particles is, for example, 0.01 to 20 parts by weight, preferably 0, with respect to 100 parts by weight of the polyorganosylsesquioxane. It is 05 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.2 to 5 parts by weight. By setting the ratio to 0.01 parts by weight or more, scratch resistance when the resin layer is used can be improved. Further, by setting the ratio to 20 parts by weight or less, the surface hardness of the resin layer can be further increased.

(Leveling agent)
The curable composition of the present invention may have a leveling agent. Examples of the leveling agent include a silicone-based leveling agent, a fluorine-based leveling agent, and a silicone-based leveling agent having a hydroxyl group. However, the leveling agent does not contain the above-mentioned fluorine-containing photopolymerizable resin.

As the silicone-based leveling agent, a commercially available silicone-based leveling agent can be used, for example, trade names "BYK-300", "BYK-301 / 302", "BYK-306", "BYK-307", "BYK". -310 "," BYK-315 "," BYK-313 "," BYK-320 "," BYK-322 "," BYK-323 "," BYK-325 "," BYK-330 "," BYK-331 " , "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-345 / 346", "BYK-347", "BYK-348", "BYK-349" , "BYK-370", "BYK-375", "BYK-377", "BYK-378", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (above, manufactured by Big Chemie Japan Co., Ltd.); trade names "AC FS 180", "AC FS 360", "AC S 20" (above, manufactured by Algin Chemie); Product names "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404" (above, Kyoeisha Chemical Co., Ltd. ); Product names "KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112" (above, Shin-Etsu Chemical Industry Co., Ltd.) Made by); Product names "LP-7001", "LP-7002", "8032 ADDITION", "57 ADDITION", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITION", Commercially available products such as "8618 ADDITION", "3 ADDITION", and "56 ADDITION" (all manufactured by Toray Dow Corning Co., Ltd.) can be used.

As the fluorine-based leveling agent, a commercially available fluorine-based leveling agent can be used, for example, trade names "Optur DSX" and "Optur DAC-HP" (all manufactured by Daikin Industries, Ltd.); 242 ”,“ Surflon S-243 ”,“ Surflon S-420 ”,“ Surflon S-611 ”,“ Surflon S-651 ”,“ Surflon S-386 ”(above, manufactured by AGC Seimi Chemical Co., Ltd.); Name "BYK-340" (manufactured by Big Chemie Japan Co., Ltd.); Product names "AC 110a", "AC 100a" (all manufactured by Algin Chemie); Product names "Mega Fuck F-114", "Mega Fuck F-" 410 "," Mega Fuck F-444 "," Mega Fuck EXP TP-2066 "," Mega Fuck F-430 "," Mega Fuck F-472SF "," Mega Fuck F-477 "," Mega Fuck F-552 " , "Mega Fuck F-553", "Mega Fuck F-554", "Mega Fuck F-555", "Mega Fuck R-94", "Mega Fuck RS-72-K", "Mega Fuck RS-75" , "Mega Fuck F-556", "Mega Fuck EXP TF-1637", "Mega Fuck EXP TF-1437", "Mega Fuck F-558", "Mega Fuck EXP TF-1537" (above, DIC Co., Ltd.) ); Product names "FC-4430", "FC-4432" (above, manufactured by Sumitomo 3M Co., Ltd.); "Gent 150", "Futargent 150CH", "Futagent AK", "Futagent 501", "Futagent 250", "Futagent 251", "Futagent 222F", "Futagent 208G", "Futer" "Gento 300", "Futagent 310", "Futagent 400SW" (all manufactured by Neos Co., Ltd.); trade names "PF-136A", "PF-156A", "PF-151N", "PF-636" , "PF-6320", "PF-656", "PF-6520", "PF-651", "PF-652", "PF-3320" (all manufactured by Kitamura Chemical Industry Co., Ltd.) Goods can be used.

Examples of the silicone-based leveling agent having a hydroxyl group include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or a side chain of a polyorganosiloxane skeleton (polydimethylsiloxane, etc.), and a main polyorganosiloxane skeleton. Examples thereof include polyester-modified polyorganosiloxane in which a polyester group is introduced into a chain or a side chain, silicone-modified (meth) acrylic resin in which polyorganosiloxane is introduced into a (meth) acrylic resin, and the like. In these leveling agents, the hydroxyl group may have a polyorganosiloxane skeleton, or may have a polyether group or a polyester group. As a commercially available product of such a leveling agent, for example, trade names "BYK-370", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" and the like can be used.

When the curable composition of the present invention contains the above leveling agent, the ratio thereof is, for example, 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyorganosylsesquioxane of the present invention, preferably 0. It is 05 to 15 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.2 to 5 parts by weight. If the proportion of the leveling agent is too small, the surface smoothness of the resin layer may decrease, and if it is too large, the surface hardness of the resin layer may decrease.

The curable composition of the present invention further comprises, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate. , Carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, inorganic fillers obtained by treating these fillers with organic silicon compounds such as organohalosilane, organoalkoxysilane and organosilazane; silicone resin, epoxy resin Organic resin fine powder such as fluororesin; filler such as conductive metal powder such as silver and copper, curing aid, solvent (organic solvent, etc.), stabilizer (antioxidant, ultraviolet absorber, light-resistant stabilizer) , Heat stabilizers, heavy metal inactivating agents, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nuclei Agent, coupling agent (silane coupling agent, etc.), lubricant, wax, plasticizer, mold release agent, impact resistance improver, hue improver, clearing agent, rhology adjuster (fluidity improver, etc.), processability Improvement agent, colorant (dye, pigment, etc.), antistatic agent, dispersant, defoaming agent, armpit inhibitor, surface modifier (slip agent, etc.), matting agent, defoaming agent, defoaming agent, defoaming It may contain conventional additives such as foaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners, photosensitizers, and foaming agents. These additives can be used alone or in combination of two or more.

(Manufacturing method of curable composition)
The curable composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above components at room temperature or, if necessary, while heating. The curable composition can be used as a one-component composition in which each component is mixed in advance as it is, or for example, two or more components stored separately before use. It can also be used as a multi-liquid system (for example, a two-component system) composition which is used by mixing in a predetermined ratio.

The curable composition of the present invention is not particularly limited, but is preferably liquid at room temperature (about 25 ° C.). More specifically, the curable composition has a viscosity of a solution diluted to 20% of a solvent [particularly, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight] at 25 ° C. of 300. It is preferably about 20000 mPa · s, more preferably 500 to 10000 mPa · s, and even more preferably 1000 to 8000 mPa · s. By setting the viscosity to 300 mPa · s or more, the heat resistance of the resin layer tends to be further improved. On the other hand, when the viscosity is 20000 mPa · s or less, the curable composition is easily prepared and handled, and bubbles tend to be less likely to remain in the resin layer. The viscosity of the curable composition was measured using a viscometer (trade name "MCR301", manufactured by Anton Pearl Co., Ltd.) at a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25 ° C. Measured under conditions.

The resin layer in the present invention can be obtained by advancing the polymerization reaction of the cationically curable compound (polyorganosylsesquioxane of the present invention, etc.) contained in the curable composition and curing the resin layer.

In order to further improve the recoatability of the resin layer, the surface of the resin layer may be subjected to surface treatment such as corona discharge treatment, plasma discharge treatment, ozone exposure treatment, and excima treatment in which the surface is modified by corona discharge irradiation. Above all, the corona discharge treatment is more preferable because the recoatability can be easily improved.

The corona discharge treatment is a treatment for processing the surface of the resin layer by generating a non-uniform electric field around a sharp electrode (needle electrode) and generating a continuous discharge. The plasma discharge treatment is a treatment for processing the surface of the resin layer by generating positive and negative charged particles activated by discharging in the atmosphere. The ozone exposure treatment is, for example, a treatment in which ozone is generated by irradiation with ultraviolet rays using a low-pressure mercury lamp or the like in the presence of oxygen to process the surface of the resin layer. The excimer treatment is a treatment for processing the surface of the resin layer by irradiation with ultraviolet rays or laser using an excimer lamp in a vacuum state.

The functional layer that can be provided on the resin layer includes, for example, a layer having functions such as scratch resistance, abrasion resistance, stain resistance (stain resistance), fingerprint resistance, and antireflection (low reflection resistance). Can be mentioned. The functional layer is a general publicly known or conventional functional layer having the above-mentioned functions used in a resin layer in a display device such as a mobile phone or a smartphone. Examples of the material constituting the functional layer include an acrylic material, a fluorine-based material, and a silicone-based material. Examples of the method of providing the functional layer on the resin layer include a method of coating in the same manner as the laminated film described later, and a method of vapor deposition or sputtering.

(Manufacturing method of laminated film)
The laminated film of the present invention can be produced according to a known or conventional method for producing a hard-coated film, and the production method is not particularly limited, but the curable composition is applied to at least one surface of a support. It can be produced by forming a resin layer by curing the curable composition.

The curing method in the resin layer can be appropriately selected from well-known methods, and examples thereof include a method of irradiating with active energy rays and / or heating. As the active energy ray, for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Of these, ultraviolet rays are preferable because they are easy to handle.

The conditions for curing the resin layer by irradiation with active energy rays can be appropriately adjusted according to the type and energy of the active energy rays to be irradiated, the shape and size of the resin layer, and the like, and are not particularly limited, but are irradiated with ultraviolet rays. In this case, for example, it is preferably about 1 to 1000 mJ / cm ² . For irradiation of the active energy rays, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used. After irradiation with the active energy rays, further heat treatment (annealing, aging) can be performed to further proceed the curing reaction.

The conditions for curing the resin layer by heating are not particularly limited, but are preferably, for example, 30 to 200 ° C, more preferably 50 to 190 ° C. The curing time can be set as appropriate.

Since the laminated film of the present invention is composed of a resin layer having excellent flexibility and workability, it can be manufactured by a roll-to-roll method. By manufacturing the laminated film of the present invention by a roll-to-roll method, it is possible to remarkably increase its productivity. As a method for producing the laminated film of the present invention by a roll-to-roll method, a known or conventional roll-to-roll method can be adopted, and the process is not particularly limited, but is a step of feeding out a support wound in a roll shape. (Step A) and the curable composition are applied to at least one surface of the drawn support, and then the solvent is removed by drying if necessary, and then the curable composition is cured to form a resin layer. (Step B) and then winding the obtained laminate onto a roll (step C) are included as essential steps, and these steps (steps A to C) are continuously carried out. The method and the like can be mentioned. The method may include steps other than steps A to C.

[Foldable device]
Since the laminated film of the present invention has high surface hardness and excellent bending durability, it is suitably used as a surface protective material for a foldable device that is repeatedly folded and used in addition to a surface protective material for a normal image display device. be able to.
Flexible devices include, for example, mobile information terminals such as smartphones, tablets, and wearable terminals. For example, the laminated film of the present invention includes displays for these flexible devices (for example, touch panels, wearable terminals, organic EL displays, etc.). Includes protective films, barrier films, TFT substrates, etc. for displays used in Since the foldable device of the present invention includes the laminated film of the present invention having excellent bending durability, cracks do not occur in the resin layer even after repeated bending and stretching, and the resin layer is excellent in reliability. Further, a foldable device such as a personal digital assistant provided with the laminated film having excellent transparency is excellent in visibility.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The molecular weight of the product was measured by Alliance HPLC System 2695 (manufactured by Waters), Refractometer Electrox Detector 2414 (manufactured by Waters), column: Tskgel GMH _HR -M × 2 (manufactured by Tosoh Corporation), guard column: Tskgel guard. Volume HHR L (manufactured by Tosoh Corporation), column oven: COLUMN _HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C. The ratio of T2 body to T3 body [T3 body / T2 body] in the product was measured by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz).

Production Example 1: Production of low molecular weight polyorganosylsesquioxane containing an epoxy group In a 1000 ml flask (reaction vessel) equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube, 2- (3,4-Epoxide cyclohexyl) Ethyltrimethoxysilane 277.2 mmol (68.30 g), phenyltrimethoxysilane 3.0 mmol (0.56 g), and acetone 275.4 g were charged and heated to 50 ° C. .. To the mixture thus obtained, 7.74 g (2.8 mmol as potassium carbonate) of a 5% aqueous potassium carbonate solution was added in 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. Added. No significant temperature increase occurred during the addition. Then, the polycondensation reaction was carried out under a nitrogen stream for 5 hours at 50 ° C.
Then, at the same time as cooling the reaction solution, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% saline solution were added. This solution was transferred to a 1 L separatory funnel, and 137.70 g of methyl isobutyl ketone was added again and washed with water. After the liquid separation, the aqueous layer is withdrawn, washed with water until the lower layer liquid becomes neutral, and after the upper layer liquid is separated, the solvent is distilled off from the upper layer liquid under the conditions of 1 mmHg and 50 ° C. to remove the methylisobutyl ketone 23. 75.18 g of a colorless transparent liquid product (epoxide group-containing low molecular weight polyorganosylsesquioxane) containing% by weight was obtained.
Analysis of the product revealed a number average molecular weight of 2235 and a molecular weight dispersion of 1.54. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the above product was 11.9.
The ¹ H-NMR chart of the obtained epoxy group-containing low molecular weight polyorganosyl sesquioxane is shown in FIG. 3, and the ²⁹ Si-NMR chart is shown in FIG. 4, respectively.

Production Example 2: Production example of epoxy group-containing high molecular weight polyorganosyl sesquioxane in a 1000 ml flask (reaction vessel) equipped with a thermometer, agitator, a reflux cooler, and a nitrogen introduction tube under a nitrogen stream. The mixture (75 g) containing the epoxy group-containing low molecular weight polyorganosyl sesquioxane obtained in 1 was charged, and 100 ppm (5) of potassium hydroxide was added to the net content of the epoxy group-containing low molecular weight polyorganosyl sesquioxane. .6 mg), 2000 ppm (112 mg) of water was added, and the sample was sampled at 80 ° C. for 18 hours to measure the molecular weight. As a result, the number average molecular weight Mn increased to 6000, and then cooled to room temperature and methyled. When 300 mL of isobutyl ketone is added, 300 mL of water is added, and the alkaline component is removed and concentrated by repeating washing with water, a colorless transparent liquid product containing 25% by weight of methyl isobutyl ketone (epoxide group-containing high molecular weight poly). 74.5 g of organosilsesquioxane 1) was obtained.
Analysis of the product revealed a number average molecular weight of 6176 and a molecular weight dispersion of 2.31. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the above product was 50.2.
The ¹ H-NMR chart of the obtained epoxy group-containing high molecular weight polyorganosyl sesquioxane 1 is shown in FIG. 5, and the ²⁹ Si-NMR chart is shown in FIG. 6, respectively.

Example 1: Production of Hard Coat Film A mixed solution with the compounding ratio shown in Table 1 was prepared and used as a hard coat liquid (curable composition). The surface of a PEN film (trade name "Theonex Q65HWA", manufactured by Teijin Limited) using a wire bar # 14 so that the thickness of the hard coat layer after curing the hard coat liquid obtained above is 10 μm. The film was left in an oven at 150 ° C. for 2 minutes, and then irradiated with ultraviolet rays at an illuminance of 600 mJ / cm ² using a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.). Then, the coating film of the hard coat liquid was cured by heat treatment at 150 ° C. for 60 minutes to prepare a hard coat film having a hard coat layer.

Examples 2 to 5: Production of Hard Court Film A hard coat film was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was changed to 20 to 50 μm.

Example 6: Production of Hard Court Film A hard coat film was produced in the same manner as in Example 1 except that the hard coat liquid having the compounding ratio shown in Table 2 was used and the thickness of the hard coat layer was changed to 40 μm. bottom.

Example 7: Production of Hard Court Film A hard coat film was produced in the same manner as in Example 1 except that the hard coat liquid having the compounding ratio shown in Table 3 was used and the thickness of the hard coat layer was changed to 40 μm. bottom.

Example 8: Production of Hard Court Film A hard coat film was produced in the same manner as in Example 1 except that the hard coat liquid having the compounding ratio shown in Table 4 was used and the thickness of the hard coat layer was changed to 40 μm. bottom.

Comparative Examples 1 to 3: Production of Hard Court Film A hard coat film in the same manner as in Example 1 except that the hard coat liquid having the compounding ratio shown in Table 5 was used and the thickness of the hard coat layer was changed to 40 μm. Was produced.

The hard-coated films obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 6.

<Haze and total light transmittance>
The haze and total light transmittance of the hard-coated film obtained above were measured using a haze meter (NDH-5000W, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

<Surface hardness (pencil hardness)>
The pencil hardness of the surface of the hard coat layer in the hard coat film obtained above was evaluated according to JIS K5600-5-4 (750 g load).

<Scratch resistance>
# 0000 steel wool is reciprocated with a load of 1000 g / cm ² against the surface of the hard coat layer in the hard coat film obtained above, and the presence or absence of scratches on the surface of the hard coat layer is confirmed, and the surface of the hard coat layer is covered. The scratch resistance was evaluated by the number of times until the scratch was confirmed. If no scratches could be confirmed even after reciprocating 1000 times or more, "1K <" was displayed.

<Flexibility (1) (Cylindrical mandrel method)>
The flexibility of the hard coat film obtained above is cracked on the surface of the hard coat layer according to JIS K5600-5-1 using a cylindrical mandrel so that the hard coat surface is concave (inside). Flexibility (1) was evaluated by the bending radius (mm).

<Flexibility (2) (cylindrical mandrel method)>
The flexibility of the hardcoat film obtained above is cracked on the surface of the hardcoat layer according to JIS K5600-5-1 using a cylindrical mandrel so that the hardcourt surface is convex (outside). Flexibility (2) was evaluated by the bending radius (mm).

<Continuous bending durability (1)>
The continuous bending durability of the hard-coated film obtained above was measured using a planar unloaded U-shaped expansion / contraction tester (Z-044 manufactured by Yuasa System Equipment Co., Ltd.). The measurement is performed with the surface of the hard coat layer as concave (inside) at a bending radius of 2.5 mm and a speed of 30 to 60 times / minute, and the number of times until cracks occur in the hard coat layer is defined as bending durability (1). (See Figures 1 and 2). When cracks did not occur even after 100,000 times, "100K <" was displayed.

<Bending durability (2)>
The continuous bending durability of the hard-coated film obtained above was measured using a planar unloaded U-shaped expansion / contraction tester (Z-044 manufactured by Yuasa System Equipment Co., Ltd.). The measurement is performed with the surface of the hard coat layer as convex (outside), with a bending radius of 4.0 mm and a speed of 30 to 60 times / minute, and the number of times until cracks occur in the hard coat layer is defined as bending durability (2). (See Figures 1 and 2). When cracks did not occur even after 100,000 times, "100K <" was displayed.

<Water contact angle>
The water contact angle (°) of the surface of the hard coat film obtained above (the surface of the hard coat layer) was measured by the sessile drop method.

The components used in Examples and Comparative Examples are as follows.
[resin]
Production Example 1: Epoxy group-containing low molecular weight polyorganosyl sesquioxane obtained in Production Example 1 (polyorganosyl sesquioxane of the present invention)
200PA-E5: Trade name "epoxy ester 200PA-E5", tripropylene glycol diglycidyl ether half (meth) acrylate (having one or more heat-polymerizable functional groups and one or more photopolymerizable functional groups in the molecule. Compound), Light Ester G manufactured by Kyoeisha Chemical Co., Ltd. :: Trade name "Light Ester G", Glycydyl Methacrylate (A compound having one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups in the molecule. ), EA-1010N manufactured by Kyoeisha Chemical Co., Ltd .: trade name "NKOLIGO EA1010N", bisphenol A epoxy half acrylate (has one or more heat-polymerizable functional groups and one or more photopolymerizable functional groups in the molecule. Compound), EHPE3150 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "EHPE3150" (compound in which an epoxy group is directly bonded to the alicyclic by a single bond), celloxide 2021P manufactured by Daicel Co., Ltd .: trade name "cellokiside 2021P" , 3,4-Epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, manufactured by Daicel Co., Ltd. [Polymerization initiator]
CPI-310PG: Trade name "CPI-310PG", Photocationic polymerization initiator, manufactured by San-Apro Co., Ltd. CPI-210S: Product name "CPI-210S", Photo-cationic polymerization initiator, manufactured by San-Apro Co., Ltd. [Fluorine-containing light Polymerizable resin]
FT601ADH2: Product name "Futergent 601ADH2", manufactured by Neos Co., Ltd. RS-76-E: Product name "Megafuck RS-76-E", manufactured by DIC Corporation [Surface conditioner]
Surflon S243: Product name "Surflon S243" (fluorine-based leveling agent), manufactured by AGC Seimi Chemical Co., Ltd. [solvent]
MIBK: Methyl Isobutyl Ketone MEK: Methyl Ethyl Ketone

The variations of the present invention described above are described below.
[1] Support and
A laminated film having a resin layer laminated on at least one surface of the support.
A laminated film characterized in that the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (Condition 1) and (Condition 2).
(Condition 1) The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer of the laminated film is F or more.
(Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more.
Bending durability test (1):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius is 2.5 mm in the direction in which the surface of the resin layer becomes concave, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (1). [2] The pencil hardness is 1H or more (preferably 2H or more, more preferably 2H or more). The laminated film according to the above [1], which is 3H or more, more preferably 4H or more, more preferably 5H or more, more preferably 6H or more, more preferably 7H or more, still more preferably 8H or more, and particularly preferably 9H). ..
[3] The bending durability (1) is 60,000 times or more (preferably 70,000 times or more, more preferably 80,000 times or more, more preferably 90,000 times or more, more preferably 100,000 times or more, still more preferably. The laminated film according to the above [1] or [2], which is 150,000 times or more, particularly preferably 200,000 times or more).
[4] Support and
A laminated film having a resin layer laminated on at least one surface of the support.
A laminated film characterized in that the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (Condition 1) and (Condition 3).
(Condition 1) The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer of the laminated film is F or more.
(Condition 3) The bending durability (2) in the following bending durability test (2) is 10,000 times or more.
Bending durability test (2):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius becomes 4.0 mm in the direction in which the surface of the resin layer becomes convex, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (2). [5] The pencil hardness is 1H or more (preferably 2H or more, more preferably 2H or more). The laminated film according to the above [4], which is 3H or more, more preferably 4H or more, more preferably 5H or more, more preferably 6H or more, more preferably 7H or more, still more preferably 8H or more, and particularly preferably 9H). ..
[6] The bending durability (2) is 20,000 times or more (preferably 30,000 times or more, more preferably 40,000 times or more, more preferably 50,000 times or more, more preferably 60,000 times or more, more preferably. 70,000 times or more, more preferably 80,000 times or more, more preferably 90,000 times or more, more preferably 100,000 times or more, still more preferably 150,000 times or more, particularly preferably 200,000 times or more). 4] or the laminated film according to [5].
[7] Further, the above [1] to [6], wherein the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (condition 4). The laminated film according to any one.
(Condition 4) In the cylindrical mandrel test specified in JIS K5600-5-1 (1999) in which the surface of the resin layer of the laminated film is convex, the bending radius is 5 mm (preferably 4.5 mm, more preferably 4.0 mm). , More preferably 3.5 mm, more preferably 3.0 mm, still more preferably 2.5 mm, particularly preferably 2.0 mm), and cracks do not occur on the surface of the resin layer [8] The resin layer (of the support). The water contact angle of the surface of one of the resin layers when the resin layers are laminated on both sides is 95 ° or more (preferably 96 ° or more, more preferably 97 ° or more, more preferably 98 ° or more, more. It is preferably 99 ° or more, more preferably 100 ° or more, more preferably 101 ° or more, more preferably 102 ° or more, more preferably 103 ° or more, still more preferably 104 ° or more, and particularly preferably 105 ° or more). , The laminated film according to any one of the above [1] to [7].
[9] Further, the above [1] to [8], wherein the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (condition 5). The laminated film according to any one.
(Condition 5) While applying a load of 1 kg / cm ² with # 0000 steel wool, the surface of the resin layer was applied 30 times (preferably 100 times, more preferably 200 times, more preferably 300 times, more preferably 500 times). No scratches are visually observed in the steel wool resistance test in which the material is rubbed back and forth once, more preferably 700 times, still more preferably 1000 times, and particularly preferably 2000 times).
[10] The haze of the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) is 1.0% or less (preferably 0.5% or less, more preferably 0). The laminated film according to any one of the above [1] to [9], which is 1% or less).

[11] Haze is 7% or less (preferably 6% or less, more preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, particularly preferably 2% or less, most preferably 1% or less. ), The laminated film according to any one of the above [1] to [10].
[12] The laminated film according to any one of the above [1] to [11], wherein the total light transmittance is 85% or more (preferably 90% or more).
[13] The thickness (total thickness of the support / resin layer) is 1 to 10000 μm (preferably 10 to 1000 μm, more preferably 15 to 800 μm, still more preferably 20 to 700 μm, particularly preferably 30 to 500 μm). The laminated film according to any one of the above [1] to [12].

[14] The support is a polyester film (particularly PET, PEN), a polyimide film, a cyclic polyolefin film, a polycarbonate film, a TAC film, or a PMMA film (preferably a polyester film (particularly PET, PEN), or a polyimide film. ), The laminated film according to any one of the above [1] to [13].
[15] The thickness of the support is 1 to 1000 μm (preferably 5 to 500 μm, more preferably 10 to 400 μm, more preferably 15 to 400 μm, still more preferably 20 to 300 μm, particularly preferably 25 to 200 μm). The laminated film according to any one of the above [1] to [14].
[16] The haze of the support is 7% or less (preferably 6% or less, more preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, particularly preferably 2% or less, most preferably. Is 1% or less), the laminated film according to any one of the above [1] to [15].
[17] The laminated film according to any one of the above [1] to [16], wherein the total light transmittance of the support is 85% or more (preferably 90% or more).

[18] The thickness of the resin layer is 1 to 100 μm (preferably 2 to 80 μm, more preferably 3 to 60 μm, still more preferably 5 to 50 μm, most preferably 10 to 40 μm). 17] The laminated film according to any one of.
[19] The laminated film according to any one of the above [1] to [18], wherein the total light transmittance of the resin layer is 85% or more (preferably 90% or more).
[20] The arithmetic mean roughness Ra of the resin layer is 0.1 to 20 nm (preferably 0.1 to 10 nm, more preferably 0.1 to 5 nm) in _a method based on JIS B0601. The laminated film according to any one of [1] to [19].

［式（１）中、Ｒ¹は、カチオン重合性官能基を含有する基を示す。］
［２３］前記カチオン重合性官能基が、エポキシ基、オキセタン基、ビニルエーテル基、及びビニルフェニル基からなる群から選ばれる少なくとも１種（好ましくはエポキシ基）である、前記［２２］に記載の積層フィルム。
［２４］前記カチオン重合性官能基を含有する基が、下記式（１ａ）で表される基、下記式（１ｂ）で表される基、下記式（１ｃ）で表される基、及び下記式（１ｄ）で表される基からなる群から選ばれる少なくとも１種（好ましくは下記式（１ａ）で表される基、及び下記式（１ｃ）で表される基からなる群から選ばれる少なくとも１種、さらに好ましくは下記式（１ａ）で表される基）である、前記［２２］又は［２３］に記載の積層フィルム。

［上記式（１ａ）中、Ｒ^1aは、直鎖又は分岐鎖状のアルキレン基を示す。］

［上記式（１ｂ）中、Ｒ^1bは、直鎖又は分岐鎖状のアルキレン基を示す。］

［上記式（１ｃ）中、Ｒ^1cは、直鎖又は分岐鎖状のアルキレン基を示す。］

［上記式（１ｄ）中、Ｒ^1dは、直鎖又は分岐鎖状のアルキレン基を示す。］
［２５］Ｒ¹が、上記式（１ａ）で表される基であって、Ｒ^1aがエチレン基である基［中でも、２－（３’，４’－エポキシシクロヘキシル）エチル基］である、前記［２２］～［２４］のいずれか１つに記載の積層フィルム。 [21] The resin layer is a cured product of a curable composition containing one or more curable compounds, and at least one of the curable compounds is polyorganosyl sesquioxane. 20] The laminated film according to any one of.
[22] The laminated film according to the above [21], wherein the curable composition contains a polyorganosyl sesquioxane having a structural unit represented by the following formula (1).

[In the formula (1), R ¹ represents a group containing a cationically polymerizable functional group. ]
[23] The laminate according to the above [22], wherein the cationically polymerizable functional group is at least one selected from the group consisting of an epoxy group, an oxetane group, a vinyl ether group, and a vinylphenyl group (preferably an epoxy group). the film.
[24] The group containing the cationically polymerizable functional group is a group represented by the following formula (1a), a group represented by the following formula (1b), a group represented by the following formula (1c), and the following. At least one selected from the group consisting of the groups represented by the formula (1d) (preferably at least one selected from the group consisting of the groups represented by the following formula (1a) and the group represented by the following formula (1c). The laminated film according to the above [22] or [23], which is one type, more preferably a group represented by the following formula (1a).

[In the above formula (1a), R ^1a represents a linear or branched alkylene group. ]

[In the above formula (1b), R ^1b represents a linear or branched alkylene group. ]

[In the above formula (1c), R ^1c represents a linear or branched alkylene group. ]

[In the above formula (1d), R ^1d represents a linear or branched alkylene group. ]
[25] R ¹ is a group represented by the above formula (1a), and R ^1a is an ethylene group [among others, a 2- (3', 4'-epoxycyclohexyl) ethyl group]. The laminated film according to any one of [22] to [24].

［上記式（２）中、Ｒ²は、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、又は、置換若しくは無置換のアルケニル基を示す。］
［２７］前記Ｒ²が、置換若しくは無置換のアリール基、置換若しくは無置換のアルキル基、又は置換若しくは無置換のアルケニル基（好ましくは置換若しくは無置換のアリール基、より好ましくはフェニル基）である、前記［２６］に記載の積層フィルム。
［２８］前記ポリオルガノシルセスキオキサンが、下記式（Ｉ）で表される構成単位（「Ｔ３体」と称する場合がある）と、下記式（ＩＩ）で表される構成単位（「Ｔ２体」と称する場合がある）を有する、前記［２２］～［２７］のいずれか１つに記載の積層フィルム。

［上記式（Ｉ）中のＲ^a及び式（ＩＩ）中のＲ^bは、それぞれ、カチオン重合性官能基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。上記式（ＩＩ）中のＲ^cは、水素原子又は炭素数１～４のアルキル基を示す。］
［２９］上記式（Ｉ）で表される構成単位（Ｔ３体）と、上記式（ＩＩ）で表される構成単位（Ｔ２体）の割合［Ｔ３体／Ｔ２体］が５以上（例えば、５以上、５００以下）である、前記［２８］に記載の積層フィルム。
［３０］前記割合［Ｔ３体／Ｔ２体］の下限値が５（好ましくは６、さらに好ましくは７）であり、上限値が２０未満（好ましくは１８、より好ましくは１６、さらに好ましくは１４）である、前記［２９］に記載の積層フィルム。
［３１］前記割合［Ｔ３体／Ｔ２体］の下限値が２０（好ましくは２１、より好ましくは２３、さらに好ましくは２５）であり、上限値が５００（好ましくは１００、より好ましくは５０、さらに好ましくは４０）である、前記［２９］に記載の積層フィルム。
［３２］前記ポリオルガノシルセスキオキサンが、下記式（４）で表される構成単位を有する、前記［２２］～［３１］のいずれか１つに記載の積層フィルム。

［式（４）中、Ｒ¹は、式（１）におけるものと同じ。Ｒ^cは、式（ＩＩ）におけるものと同じ。］
［３３］前記ポリオルガノシルセスキオキサンにおけるシロキサン構成単位の全量（１００モル％）に対する、前記式（１）で表される構成単位及び前記式（４）で表される構成単位の割合（総量）が５５～１００モル％（好ましくは６５～１００モル％、さらに好ましくは８０～９９モル％）である、前記［３２］に記載の積層フィルム。
［３４］前記ポリオルガノシルセスキオキサンが下記式（５）で表される構成単位を有する、前記［２２］～［３３］のいずれか１つに記載の積層フィルム。

［式（５）中、Ｒ²は、式（２）におけるものと同じ。Ｒ^cは、式（ＩＩ）におけるものと同じ。］
［３５］前記ポリオルガノシルセスキオキサンにおけるシロキサン構成単位の全量（１００モル％）に対する、前記式（２）で表される構成単位及び前記式（５）で表される構成単位の割合（総量）が０～７０モル％（好ましくは０～６０モル％、より好ましくは０～４０モル％、特に好ましくは１～１５モル％）である、前記［３４］に記載の積層フィルム。
［３６］前記ポリオルガノシルセスキオキサンにおけるシロキサン構成単位の全量（１００モル％）に対する、前記式（１）で表される構成単位、前記式（２）で表される構成単位、前記式（４）で表される構成単位、及び前記式（５）で表される構成単位の割合（総量）が６０～１００モル％（好ましくは７０～１００モル％、より好ましくは８０～１００モル％）である、前記［３２］～［３５］のいずれか１つに記載の積層フィルム。
［３７］前記ポリオルガノシルセスキオキサンの数平均分子量の下限値が１０００（好ましくは１１００）であり、上限値が３０００（好ましくは２８００、より好ましくは２６００）である、前記［２１］～［３６］のいずれか１つに記載の積層フィルム。
［３８］前記ポリオルガノシルセスキオキサンの数平均分子量の下限値が２５００（好ましくは２８００、より好ましくは３０００）であり、上限値が５００００（好ましくは１００００、より好ましくは８０００）である、前記［２１］～［３６］のいずれか１つに記載の積層フィルム。
［３９］前記ポリオルガノシルセスキオキサンの分子量分散度の下限値が１．０（好ましくは１．１、より好ましくは１．２）である、前記［２１］～［３８］のいずれか１つに記載の積層フィルム。
［４０］前記ポリオルガノシルセスキオキサンの分子量分散度の上限値が３．０（好ましくは２．０、より好ましくは１．９）である、前記［２１］～［３９］のいずれか１つに記載の積層フィルム。
［４１］前記ポリオルガノシルセスキオキサンの分子量分散度の上限値が４．０（好ましくは３．０、より好ましくは２．５）である、前記［２１］～［３９］のいずれか１つに記載の積層フィルム。
［４２］前記ポリオルガノシルセスキオキサンの空気雰囲気下における５％重量減少温度（Ｔ_d5）が３３０℃以上（例えば、３３０～４５０℃、好ましくは３４０℃以上、より好ましくは３５０℃以上）である、前記［２１］～［４１］のいずれか１つに記載の積層フィルム。
［４３］前記硬化性組成物における前記ポリオルガノシルセスキオキサンの含有量（配合量）が、溶媒を除く硬化性組成物の全量（１００重量％）に対して、５０重量％以上、１００重量％未満（好ましくは６０～９９重量％、より好ましくは７０～９５重量％）である、前記［２１］～［４２］のいずれか１つに記載の積層フィルム。
［４４］前記硬化性組成物に含まれるカチオン硬化性化合物の全量（１００重量％）に対する前記ポリオルガノシルセスキオキサンの割合が６０～９９重量％（好ましくは６５～９８重量％、より好ましくは７０～９５重量％）である、前記［２１］～［４３］のいずれか１つに記載の積層フィルム。 [26] The laminated film according to any one of the above [22] to [25], wherein the polyorganosyl sesquioxane further has a structural unit represented by the following formula (2).

[In the above formula (2), R ² is a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group. The substituted alkenyl group is shown. ]
[27] The R ² is a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group (preferably a substituted or unsubstituted aryl group, more preferably a phenyl group). The laminated film according to the above [26].
[28] The polyorganosyl sesquioxane has a structural unit represented by the following formula (I) (sometimes referred to as "T3 body") and a structural unit represented by the following formula (II) ("T2". The laminated film according to any one of the above [22] to [27], which may be referred to as "body").

[R a in the above formula (I) and R ^b in the formula (II ⁾ are a group containing a cationically polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and a substituent, respectively. Alternatively, it indicates an unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. R ^c in the above formula (II) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
[29] The ratio [T3 body / T2 body] of the structural unit (T3 body) represented by the above formula (I) and the structural unit (T2 body) represented by the above formula (II) is 5 or more (for example). The laminated film according to the above [28], which is 5 or more and 500 or less).
[30] The lower limit of the ratio [T3 / T2] is 5 (preferably 6, more preferably 7), and the upper limit is less than 20 (preferably 18, more preferably 16, even more preferably 14). The laminated film according to the above [29].
[31] The lower limit of the ratio [T3 / T2] is 20 (preferably 21, more preferably 23, still more preferably 25), and the upper limit is 500 (preferably 100, more preferably 50, further. The laminated film according to the above [29], preferably 40).
[32] The laminated film according to any one of the above [22] to [31], wherein the polyorganosyl sesquioxane has a structural unit represented by the following formula (4).

[In equation (4), R ¹ is the same as in equation (1). R ^c is the same as in equation (II). ]
[33] The ratio (total amount) of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) to the total amount (100 mol%) of the siloxane structural unit in the polyorganosyl sesquioxane. ) Is 55 to 100 mol% (preferably 65 to 100 mol%, more preferably 80 to 99 mol%), according to the above-mentioned [32].
[34] The laminated film according to any one of the above [22] to [33], wherein the polyorganosyl sesquioxane has a structural unit represented by the following formula (5).

[In equation (5), R ² is the same as in equation (2). R ^c is the same as in equation (II). ]
[35] The ratio (total amount) of the structural unit represented by the formula (2) and the structural unit represented by the formula (5) to the total amount (100 mol%) of the siloxane structural unit in the polyorganosyl sesquioxane. ) Is 0 to 70 mol% (preferably 0 to 60 mol%, more preferably 0 to 40 mol%, particularly preferably 1 to 15 mol%), the laminated film according to the above [34].
[36] The structural unit represented by the formula (1), the structural unit represented by the formula (2), the structural unit represented by the formula (2), with respect to the total amount (100 mol%) of the siloxane structural unit in the polyorganosyl sesquioxane. The ratio (total amount) of the structural unit represented by 4) and the structural unit represented by the formula (5) is 60 to 100 mol% (preferably 70 to 100 mol%, more preferably 80 to 100 mol%). The laminated film according to any one of the above [32] to [35].
[37] The lower limit of the number average molecular weight of the polyorganosyl sesquioxane is 1000 (preferably 1100), and the upper limit is 3000 (preferably 2800, more preferably 2600). 36] The laminated film according to any one of.
[38] The lower limit of the number average molecular weight of the polyorganosyl sesquioxane is 2500 (preferably 2800, more preferably 3000), and the upper limit is 50,000 (preferably 10000, more preferably 8000). The laminated film according to any one of [21] to [36].
[39] Any one of the above [21] to [38], wherein the lower limit of the molecular weight dispersion of the polyorganosylsesquioxane is 1.0 (preferably 1.1, more preferably 1.2). The laminated film described in 1.
[40] Any one of the above [21] to [39], wherein the upper limit of the molecular weight dispersion of the polyorganosylsesquioxane is 3.0 (preferably 2.0, more preferably 1.9). The laminated film described in 1.
[41] Any one of the above [21] to [39], wherein the upper limit of the molecular weight dispersion of the polyorganosylsesquioxane is 4.0 (preferably 3.0, more preferably 2.5). The laminated film described in 1.
[42] When the 5% weight loss temperature (T _d5 ) of the polyorganosilsesquioxane in an air atmosphere is 330 ° C. or higher (for example, 330 to 450 ° C., preferably 340 ° C. or higher, more preferably 350 ° C. or higher). The laminated film according to any one of the above [21] to [41].
[43] The content (blending amount) of the polyorganosyl sesquioxane in the curable composition is 50% by weight or more, 100% by weight, based on the total amount (100% by weight) of the curable composition excluding the solvent. The laminated film according to any one of the above [21] to [42], which is less than% (preferably 60 to 99% by weight, more preferably 70 to 95% by weight).
[44] The ratio of the polyorganosylsesquioxane to the total amount (100% by weight) of the cationically curable compound contained in the curable composition is 60 to 99% by weight (preferably 65 to 98% by weight, more preferably 65% by weight). The laminated film according to any one of the above [21] to [43], which is 70 to 95% by weight).

[45] The laminated film according to any one of the above [21] to [44], wherein the curable composition further contains a curing catalyst.
[46] The laminated film according to the above [45], wherein the curing catalyst is a photocationic polymerization initiator.
[47] The laminated film according to the above [45], wherein the curing catalyst is a thermal cationic polymerization initiator.
[48] The content (blending amount) of the curing catalyst is 0.01 to 3.0 parts by weight (preferably 0.05 to 3.0 parts by weight) with respect to 100 parts by weight of the polyorganosylsesquioxane. , More preferably 0.1 to 1.0 parts by weight, still more preferably 0.3 to 1.0 parts by weight), according to any one of the above [45] to [47].

[49] A compound (hereinafter, may be referred to as "Compound A") in which the curable composition has one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups in the molecule. The laminated film according to any one of the above [21] to [48], which comprises.
[50] The "thermopolymerizable functional group" contained in the compound A is selected from at least one selected from the group consisting of a hydroxyl group, an epoxy group, an oxetanyl group, and a vinyl ether group (preferably from the group consisting of a hydroxyl group and an epoxy group). The laminated film according to the above [49], which is at least one of the above-mentioned (49).
[51] The "photopolymerizable functional group" contained in the compound A is at least one selected from the group consisting of a (meth) acryloyl group and a vinyl group (preferably a (meth) acryloyl group). ] Or [50].
[52] The above-mentioned [49] to [52], wherein the compound A has 1 to 5 (preferably 1 to 3, more preferably 1 or 2) thermopolymerizable functional groups in one molecule. 51] The laminated film according to any one of.
[53] The above-mentioned [49] to [53], wherein the compound A has 1 to 5 (preferably 1 to 3, more preferably 1 or 2) photopolymerizable functional groups in one molecule. 52] The laminated film according to any one of.
[54] Any one of the above [49] to [53], wherein the functional group equivalent of the thermopolymerizable functional group of the compound A is 50 to 500 (preferably 80 to 480, more preferably 120 to 450). The laminated film described in.
[55] Any one of the above [49] to [54], wherein the photopolymerizable functional group of the compound A has a functional group equivalent of 50 to 500 (preferably 80 to 480, more preferably 120 to 450). The laminated film described in.
[56] The compound A is a compound having an epoxy group and / or a hydroxyl group as a thermopolymerizable functional group and a (meth) acryloyl group as a photopolymerizable functional group in one molecule. 55] The laminated film according to any one of.
[57] The compound A is 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, tripropylene glycol diglycidyl ether half (meth) acrylate, bisphenol A epoxy half (meth) acrylate, bisphenol F epoxy. The laminated film according to any one of the above [49] to [56], which is at least one selected from the group consisting of a half (meth) acrylate and a bisphenol S epoxy half (meth) acrylate.
[58] The content (blending amount) of the compound A is 1 to 100 parts by weight (preferably 3 to 75 parts by weight, more preferably 3 to 75 parts by weight) with respect to 100 parts by weight of the polyorganosyl sesquioxane as a solid content. 5. The laminated film according to any one of the above [49] to [57], which is 5 to 50 parts by weight).

[59] The laminated film according to any one of the above [21] to [58], wherein the curable composition further contains a fluorine-containing photopolymerizable resin.
[60] The photopolymerizable functional group of the fluorine-containing photopolymerizable resin is at least one (preferably (meth) acryloyl group) selected from the group consisting of a (meth) acryloyl group and a vinyl group. The laminated film according to [59].
[61] The above-mentioned [59] or [60], wherein the fluorine-containing photopolymerizable resin has 1 to 5 (preferably 1 to 3) photopolymerizable functional groups in one molecule. Laminated film.
[62] The laminated film according to any one of [59] to [61], wherein the fluorine-containing group of the fluorine-containing photopolymerizable resin is a group having a fluoroaliphatic hydrocarbon skeleton. [63] The laminated film according to the above [62], wherein the fluoroaliphatic hydrocarbon skeleton forms a polyfluoroalkylene ether skeleton which is a repeating unit via an ether bond. [64] The laminated film according to any one of [59] to [63], wherein the fluorine-containing photopolymerizable resin has a silicone-containing group.
[65] The content (blending amount) of the fluorine-containing photopolymerizable resin is 0.01 to 15 parts by weight (preferably 0.05) with respect to 100 parts by weight of the polyorganosylsesquioxane as a solid content. The laminated film according to any one of the above [59] to [64], which is ~ 10 parts by weight, more preferably 0.01 to 5 parts by weight, still more preferably 0.2 to 3 parts by weight).

［上記式（ｉ）中、Ｙは単結合又は連結基（１以上の原子を有する二価の基）を示す。式（ｉ）中のシクロヘキサン環の水素原子の１個以上は、炭素数１～６のアルキル基などの置換基で置換されていてもよい。］
［７０］前記式（ｉ）で表される脂環式エポキシ化合物が、（３，４，３’，４’－ジエポキシ）ビシクロヘキシル、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、１，２－ビス（３，４－エポキシシクロヘキシル）エタン、２，３－ビス（３，４－エポキシシクロヘキシル）オキシラン、ビス（３，４－エポキシシクロヘキシルメチル）エーテル、及び下記式（ｉ－１）～（ｉ－１０）で表される化合物からなる群から選ばれる少なくとも１種である、前記［６９］に記載の積層フィルム。

［上記式（ｉ－５）、（ｉ－７）中のｌ、ｍは、それぞれ１～３０の整数を表す。上記式（ｉ－５）中のＲ’は炭素数１～８のアルキレン基を示す。上記式（ｉ－９）、（ｉ－１０）中のｎ１～ｎ６は、それぞれ１～３０の整数を示す。］
［７１］前記（２）脂環にエポキシ基が直接単結合で結合している化合物が、下記式（ｉｉ）で表される化合物である、前記［６８］～［７０］のいずれか１つに記載の積層フィルム。

［式（ｉｉ）中、Ｒ”は、ｐ価のアルコールの構造式からｐ個の水酸基（－ＯＨ）を除いた基（ｐ価の有機基）を示す。ｐ、ｎはそれぞれ自然数を表す。ｐが２以上の場合、それぞれの（ ）内（外側の括弧内）の基におけるｎは同一でもよく異なっていてもよい。］［７２］前記エポキシ化合物が、（２）脂環にエポキシ基が直接単結合で結合している化合物（好ましく、上記式（ｉｉ）で表される化合物）である、前記［６８］～［７１］のいずれか１つに記載の積層フィルム。
［７３］前記エポキシ化合物の含有量（配合量）が、前記ポリオルガノシルセスキオキサンの全量１００重量部に対して、０．５～１００重量部（好ましくは１～８０重量部、より好ましくは５～５０重量部）である、前記［６６］～［７２］のいずれか１つに記載の積層フィルム。 [66] Any of the above [21] to [65], wherein the curable composition further contains an epoxy compound other than the polyorganosyl sesquioxane (hereinafter, may be simply referred to as an "epoxy compound"). The laminated film according to one.
[67] In the above [66], the epoxy compound is at least one selected from the group consisting of an alicyclic epoxy compound, an aromatic epoxy compound, and an aliphatic epoxy compound (preferably an alicyclic epoxy compound). The laminated film described.
[68] The alicyclic epoxy compound has (1) an epoxy group (referred to as "alicyclic epoxy group") composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic in the molecule. The compound is selected from the group consisting of (2) a compound in which an epoxy group is directly bonded to the alicyclic by a single bond; and (3) a compound having an alicyclic and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound). The laminated film according to the above [67], which is at least one kind.
[69] The laminated film according to the above [68], wherein the compound having an alicyclic epoxy group in the molecule (1) is a compound represented by the following formula (i).

[In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). One or more hydrogen atoms of the cyclohexane ring in the formula (i) may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms. ]
[70] The alicyclic epoxy compound represented by the formula (i) is (3,4,3', 4'-diepoxy) bicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, and the like. 1,2-Bis (3,4-epoxycyclohexyl) ethane, 2,3-bis (3,4-epoxycyclohexyl) oxylane, bis (3,4-epoxycyclohexylmethyl) ether, and the following formula (i-1) The laminated film according to the above [69], which is at least one selected from the group consisting of the compounds represented by (i-10).

[L and m in the above equations (i-5) and (i-7) represent integers of 1 to 30, respectively. R'in the above formula (i-5) represents an alkylene group having 1 to 8 carbon atoms. N1 to n6 in the above equations (i-9) and (i-10) represent integers of 1 to 30, respectively. ]
[71] Any one of the above [68] to [70], wherein the compound in which the epoxy group is directly bonded to the alicyclic (2) by a single bond is a compound represented by the following formula (ii). The laminated film described in.

[In the formula (ii), R "represents a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of the p-valent alcohol. P and n represent natural numbers, respectively. When p is 2 or more, n in each group in () (inside parentheses on the outside) may be the same or different.] [72] The epoxy compound has an epoxy group in (2) an alicyclic. The laminated film according to any one of the above [68] to [71], which is a compound directly bonded by a single bond (preferably a compound represented by the above formula (ii)).
[73] The content (blending amount) of the epoxy compound is 0.5 to 100 parts by weight (preferably 1 to 80 parts by weight, more preferably 1 to 80 parts by weight) with respect to 100 parts by weight of the total amount of the polyorganosyl sesquioxane. 5. The laminated film according to any one of the above [66] to [72], which is 5 to 50 parts by weight).

[74] The laminated film according to any one of the above [1] to [73], wherein the support is a transparent support.
[75] A foldable device comprising the laminated film according to any one of the above [1] to [74].
[76] The foldable device according to the above [75], which is an image display device.
[77] The foldable device according to the above [76], wherein the image display device is an organic electroluminescence display device.

Since the laminated film of the present invention has high surface hardness and excellent bending durability, it is suitable as a surface protective material for foldable devices such as organic electroluminescence display devices.

Claims (14)

With the support,
A laminated film having a resin layer laminated on at least one surface of the support.
The resin layer is a cured product of a curable composition containing one or more curable compounds, and the curable composition is a polyorganosylsesquioxane having a group containing an epoxy group as the curable compound. In addition, a compound having one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups is contained in the molecule.
The support is a plastic base material, and the plastic materials constituting the plastic base material are polyester, polyimide, polycarbonate, polyamide, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyether sulfone, polyether ether ketone, cyclic polyolefin, and vinyl. It is at least one selected from the group consisting of a system polymer, a vinylidene polymer, a cellulose resin, an epoxy resin, a phenol resin, a melamine resin, a urea resin, a maleimide resin, and a silicone resin.
The support has a thickness of 15 to 200 μm and has a thickness of 15 to 200 μm.
The thickness of the laminated film is 20 to 500 μm, and the thickness is 20 to 500 μm.
A laminated film characterized in that the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (Condition 1) and (Condition 2).
(Condition 1) The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer of the laminated film is F or more.
(Condition 2) The bending durability (1) in the following bending durability test (1) is 50,000 times or more.
Bending durability test (1):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius is 2.5 mm in the direction in which the surface of the resin layer becomes concave, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (1). With the support,
A laminated film having a resin layer laminated on at least one surface of the support.
The resin layer is a cured product of a curable composition containing one or more curable compounds, and the curable composition is a polyorganosylsesquioxane having a group containing an epoxy group as the curable compound. In addition, a compound having one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups is contained in the molecule.
The support is a plastic base material, and the plastic materials constituting the plastic base material are polyester, polyimide, polycarbonate, polyamide, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyether sulfone, polyether ether ketone, cyclic polyolefin, and vinyl. It is at least one selected from the group consisting of a system polymer, a vinylidene polymer, a cellulose resin, an epoxy resin, a phenol resin, a melamine resin, a urea resin, a maleimide resin, and a silicone resin.
The support has a thickness of 15 to 200 μm and has a thickness of 15 to 200 μm.
The thickness of the laminated film is 20 to 500 μm, and the thickness is 20 to 500 μm.
A laminated film characterized in that the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (Condition 1) and (Condition 3).
(Condition 1) The pencil hardness of the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999) on the surface of the resin layer of the laminated film is F or more.
(Condition 3) The bending durability (2) in the following bending durability test (2) is 10,000 times or more.
Bending durability test (2):
From the stretched state of the laminated film, bend it 180 ° so that the bending radius becomes 4.0 mm in the direction in which the surface of the resin layer becomes convex, and stretch it again once, at a speed of 30 to 60 times / minute. The number of times until cracks occur in the resin layer of the laminated film when the above operation is performed is used as an index of bending durability (2). The laminated film according to claim 1 or 2, wherein the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (condition 4).
(Condition 4) In the cylindrical mandrel test specified in JIS K5600-5-1 (1999) in which the surface of the resin layer of the laminated film is convex, the bending radius is 5 mm and cracks do not occur on the surface of the resin layer. The invention according to any one of claims 1 to 3, wherein the water contact angle of the surface of the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) is 95 ° or more. Laminated film. Further, according to any one of claims 1 to 4, the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) satisfies the following (condition 5). Laminated film.
(Condition 5) No visual scratches occur in the steel wool resistance test in which the surface of the resin layer is rubbed back and forth 30 times while applying a load of 1 kg / cm ² with # 0000 steel wool. The lamination according to any one of claims 1 to 5, wherein the haze of the resin layer (one of the resin layers when the resin layers are laminated on both sides of the support) is 1.0% or less. the film. The laminated film according to any one of claims 1 to 6, wherein the curable composition further contains a curing catalyst. The laminated film according to claim 7 , wherein the curing catalyst is a photocationic polymerization initiator. The laminated film according to claim 7 , wherein the curing catalyst is a thermal cationic polymerization initiator. The laminated film according to any one of claims 1 to 9 , wherein the curable composition further contains a fluorine-containing photopolymerizable resin. The laminated film according to any one of claims 1 to 10 , wherein the support is a transparent support. A foldable device comprising the laminated film according to any one of claims 1 to 11 . The foldable device according to claim 12 , which is an image display device. The foldable device according to claim 13 , wherein the image display device is an organic electroluminescence display device.

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