WO2013153648A1

WO2013153648A1 - Transparent resin laminate

Info

Publication number: WO2013153648A1
Application number: PCT/JP2012/059984
Authority: WO
Inventors: 昌宏斉藤; 秀人橋口; 哲平板本
Original assignee: フクビ化学工業株式会社
Priority date: 2012-04-12
Filing date: 2012-04-12
Publication date: 2013-10-17
Also published as: JP5973555B2; JPWO2013153648A1; CN104220903B; CN104220903A

Abstract

Provided is a transparent resin laminate which, in addition to advanced anti-reflection functions, exhibits excellent mechanical properties such as scratch resistance and hardness and which, in particular, can attain a surface hardness which is 'scratch resistant to 7H'. A double hard-coat layer is disposed between a transparent resin substrate of PC and PMMA or the like and an anti-reflection layer constituted by a low refractive index layer which is formed on the substrate so as to have a refractive index of less than 1.50 and a thickness of between 50 nm and 200 nm. A hard-coat single layer, which is located on the substrate side, contains surface-treated silica sol so as to achieve high surface hardness.

Description

Transparent resin laminate

The present invention relates to a transparent resin laminate having high antireflection performance and excellent scratch resistance, particularly surface hardness.

Conventionally, an antireflection film has been widely used on front panels of display devices such as CRTs, LCDs, and plasma displays in order to prevent reflection on the surface and make the screen easier to see.
A transparent resin laminate having antireflection ability in which a multilayer film is formed on a plastic substrate is also known, for example, on a plastic substrate having translucency, a high refractive index layer, an antireflection layer, a coating layer, A transparent resin laminate having excellent wear resistance, scratch resistance, adhesion, and translucency, which are sequentially laminated, is known (Patent Document 1).
In recent years, electronic devices such as mobile phones and digital cameras have been remarkably advanced, and a display such as a small liquid crystal or organic EL is provided as a display device. For the purpose of protection, the display is usually provided with a transparent resin laminate, and the transparent resin laminate is required to have various characteristics as described below. For example, in order to ensure visibility, it is necessary that transparency and antireflection performance are high. From the viewpoint of mechanical strength, impact resistance, scratch resistance, and high hardness are required. Furthermore, an antistatic ability is required to prevent adverse effects on the equipment due to dust adhesion and charging.
Among the above properties, the properties of impact resistance, scratch resistance, and high hardness related to mechanical strength are not necessarily side by side, for example, those having high impact resistance and being hard to break may have surface hardness, There was a problem that the scratch resistance was insufficient and the film was easily damaged. Under such circumstances, development of an impact-resistant transparent resin laminate having high hardness and excellent scratch resistance has been made (Patent Documents 2 and 3). However, in these existing technologies, the surface hardness of the grade that satisfies “4H and no scratch” can be achieved in the pencil hardness test. On the other hand, mobile terminals such as mobile phones, smart (future) phones, tablets, etc. may be subjected to harsh usage environments such as dropping, stepping on, rubbing, etc., having higher surface hardness and anti-reflection ability Transparent resin laminates that are superior to the above have become necessary.

JP-A-9-288202 JP 2006-35778 A JP2007-216525A

An object of the present invention is to solve the above-mentioned problems and to provide a transparent resin laminate having excellent scratch resistance and surface hardness in addition to high impact resistance and antireflection ability.
As a result of various investigations to improve the above-mentioned physical properties while maintaining a high degree of antireflection ability, the present inventors have provided a multilayer hard coat layer between the resin substrate and the antireflection layer, and the substrate. By including a specific silica sol in the hard coat monolayer located on the side, it was found that the pencil hardness test expressed a surface hardness of “no scratch at 7H” and other characteristics could be satisfied, The present invention has been completed.

Means for Solving the Invention

That is, according to the present invention, in the transparent resin laminate in which the hard coat layer (B) is laminated on the transparent resin substrate (A) and the antireflection layer (C) is further laminated on the hard coat layer (B). ,
The hard coat layer (B) is composed of a hard coat layer I (B1) located on the transparent resin substrate side and a hard coat layer II (B2) located on the antireflection layer side,
The hard coat layer I (B1) has a layer thickness of 5 to 20 μm, and (a) a multifunctional urethane acrylate having 6 or more (meth) acryloyl groups in one molecule, and the multifunctional urethane acrylate 100 (B) a cured product of a curable composition comprising 40 to 200 parts by mass of a surface-treated silica sol with respect to parts by mass,
The hard coat layer II (B2) has a layer thickness of 1 to 10 μm, (a) a multifunctional urethane acrylate having 6 or more (meth) acryloyl groups in one molecule, and the multifunctional urethane acrylate 100 (C) 1 to 50 parts by mass of silica sol having an average particle diameter of 5 to 30 nm and a refractive index of 1.44 to 1.50, and (d) a silane coupling compound or a hydrolyzate 1 thereof with respect to parts by mass A cured product of a curable composition comprising from 30 to 30 parts by mass, and (e) 0.1 to 3.0 parts by mass of a metal chelate compound,
The antireflection layer (C) is composed of a low refractive index layer (C1) having a refractive index of less than 1.50 and a thickness of 50 to 200 nm,
The low refractive index layer (C1) comprises (f) a silica sol having an average particle diameter of 5 to 150 nm and a refractive index of 1.44 or less, (d) a silane coupling compound or a hydrolyzate thereof, and (e) (F) silica sol is compounded in an amount of 10 to 50% by mass, and (d) the compounding ratio of the silane coupling compound or a hydrolyzate thereof and (e) the metal chelate compound is 60 to 50%. 99% by mass: The transparent resin laminate is provided with a cured product of a curable composition of 40 to 1% by mass.

In the invention of the transparent resin laminate,
1) The antireflection layer (C) is composed of two layers of the low refractive index layer (C1) and the middle refractive index layer (C2) located on the transparent resin substrate side, and the middle refractive index layer (C2) The refractive index is 1.50 or more and less than 1.75, and the thickness is 50 to 200 nm. 2) The antireflection layer (C) is composed of the low refractive index layer (C1), the middle refractive index layer (C2 ) And a high refractive index layer (C3) provided between the low refractive index layer and the middle refractive index layer. The high refractive index layer (C3) has a refractive index of 1 .60 or more and less than 2.00, the thickness is 50 to 200 nm, and the refractive index of the high refractive index layer (C3) is larger than the refractive index of the middle refractive index layer (C2). A (meth) acryloyl group-modified silica sol or a vinyl group-modified silica sol is preferred.

The transparent resin laminate of the present invention is excellent in mechanical strength in addition to high antireflection performance, and in particular, the surface hardness can achieve “7H with no scratch”. Therefore, it can be suitably used as a front panel of not only a general display device but also a device requiring high hardness, such as a mobile phone, a smart (future) phone, and a tablet.

It is a schematic diagram which shows the cross-sectional structure of the typical antireflection board of this invention.

The transparent resin laminate of the present invention has a basic structure in which a transparent resin substrate (A), a hard coat layer (B), and an antireflection layer (C) are laminated in this order. Further, these layers (B and C) are characterized by being composed of the specified structure, physical properties and components.

[Transparent resin substrate]
The transparent resin substrate is not particularly limited as long as it is a transparent resin that has excellent impact strength and does not obstruct visual field. From the viewpoint of transparency and impact strength, a substrate made of aromatic polycarbonate resin or polymethyl methacrylate resin is preferred. A laminated substrate of an aromatic polycarbonate resin and a polymethyl methacrylate resin may be used. The thickness of the substrate is designed by appropriately selecting from the required transparency and impact strength, but is usually selected from the range of 0.2 to 2.0 mm.

[Hard coat layer (B)]
A hard coat layer (B) is laminated on a transparent resin substrate, and the layer (B) includes a hard coat layer I (B1) and a hard coat layer II (B2). The hard coat layer I (B1) and the hard coat layer II (B2) are such that the hard coat layer I (B1) is located on the substrate side, and an antireflection layer (C described later) is formed on the hard coat layer II (B2). ) Are stacked.

[Hard coat layer I (B1)]
The hard coat layer I (B1) is a layer mainly contributing to hardness, and its film thickness is 5 to 20 μm, preferably 10 to 20 μm. If it is less than 5 μm, the hardness is insufficient, and if it exceeds 20 μm, appearance defects and post-workability become difficult.
The layer comprises (a) a polyfunctional urethane acrylate having 6 or more (meth) acryloyl groups in one molecule (hereinafter also referred to as polyfunctional urethane acrylate) and 100 parts by mass of the polyfunctional urethane acrylate. On the other hand, it is a layer obtained by curing (b) a curable composition comprising 40 to 200 parts by mass of a surface-treated silica sol (hereinafter also referred to as B1 composition).

<(A) Multifunctional urethane acrylate>
The polyfunctional urethane acrylate is a polymerizable compound obtained by a polyaddition reaction between a diisocyanate compound and a (meth) acrylate compound having a plurality of hydroxyl groups, and particularly has 6 or more (meth) acryloyl groups. It is essential. By using the polyfunctional urethane acrylate, a dense layer having a high surface hardness can be formed. A compound having less than 6 (meth) acryloyl groups has insufficient surface hardness and poor scratch resistance.
Examples of the diisocyanate compound used as a raw material for the polyaddition reaction include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane. The Examples of the (meth) acrylate compound as one raw material include trimethylolpropane (meth) acrylate and pentaerythritol (meth) acrylate.
These both raw materials can be used in a quantitative ratio such that the (meth) acryloyl group is 6-fold mol or more, and reacted by a method known per se to obtain the polyfunctional urethane acrylate.

<(B) Surface-treated silica sol>
The surface-treated silica sol is a component that imparts extremely high hardness to the transparent resin substrate of the present invention by combining with a polyfunctional urethane acrylate. Therefore, it is important to blend at a ratio of 40 to 200 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate.
In the surface-treated silica sol, the surface of silica particles known per se is treated with a silane coupling agent having an alkoxysilyl group at the terminal, such as 3-methacryloxypropyltriethoxysilane or 3-acryloxypropyltrimethoxysilane (methacrylate). ) An acryloyl group-modified silica sol, or a vinyl group-modified silica sol treated with a silane coupling agent having a vinyl group such as vinyltriethoxysilane or vinylmethyldimethoxysilane.
The surface treatment method is not particularly limited, and a conventionally known method is employed. For example, the silane coupling agent is dissolved in an organic solvent containing water, such as methyl alcohol, toluene, methyl isobutyl ketone, methyl isobutyl butyl ketone, to obtain a solution, and silica sol is added to the solution. Heat to about 150 ° C. and stir for about 5 to 30 hours to react.

<B1 composition>
The B1 composition is a composition that becomes the hard coat layer I by being cured, and is contained in a proportion of 40 to 200 parts by mass of the surface-treated silica sol with respect to 100 parts by mass of the polyfunctional urethane acrylate. In B1 composition, arbitrary additives can be added in the range which does not impair the objective for the purpose of viscosity adjustment or easy coating property. In particular, in order to cure the composition on a transparent resin substrate to obtain a hard coat layer I (B1), the thermal polymerization initiator or the photopolymerization initiator is usually a catalytic amount, usually a solid in the composition. Based on the total amount, 0.01 to 20% by mass is added. This polymerization initiator does not substantially affect the properties of the hard coat layer I obtained by curing the B1 composition.
As the polymerization initiator, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy, which acts by ultraviolet rays or electron beams, from the viewpoint of preventing deformation of the transparent resin substrate due to heat. Photopolymerization initiators such as -cyclohexyl-phenyl-ketone, camphorquinone and benzyl are preferred.

<Formation of hard coat layer I>
Each of the above essential components (a) and (b) and further optional components are dissolved in the following solvent to form a solution of the B1 composition. After applying this solution to the transparent resin substrate, the solvent is dried at 50 ° C. or higher. And then cured by ultraviolet irradiation to form the hard coat layer I. The thickness of the layer is set in the range of 5 to 20 μm, preferably 10 to 20 μm.
Solvents used include alcohol solvents such as ethyl alcohol and (iso) propyl alcohol; aromatic solvents such as toluene and xylene; acetate solvents such as (iso) butyl acetate; methyl ethyl ketone (MEK) and methyl isobutyl ketone A ketone solvent such as (MIBK) is suitable. These solvents are removed by evaporation when the hard coat layer I is formed.

The above components constituting the B1 composition are usually mixed with a solvent in any order at room temperature and stirred to form a solution.
The coating method of this solution on the transparent resin substrate is not particularly limited, and dip coating method, roll coating method, die coating method, flow coating method, spraying method, etc. are adopted, but appearance quality and film thickness control are adopted. In view of the above, the dip coating method is preferable.

[Hard coat layer II (B2)]
The hard coat layer II (B2) is a layer mainly contributing to adhesion with the antireflection layer laminated thereon, and has a film thickness of 1 to 10 μm. If it is less than 1 μm, the adhesion is insufficient, and if it exceeds 10 μm, it is difficult to maintain the appearance.
The layer has (c) an average particle diameter of 5 to 30 nm and a refractive index of 1.44 to 1.50 with respect to (a) the polyfunctional urethane acrylate and 100 parts by mass of the polyfunctional urethane acrylate. A curable composition comprising 1 to 50 parts by weight of silica sol, (d) 1 to 30 parts by weight of a silane coupling compound or a hydrolyzate thereof, and (e) 0.1 to 3.0 parts by weight of a metal chelate compound It is a layer made of a cured product (hereinafter also referred to as B2 composition).
(A) As polyfunctional urethane acrylate, what was mentioned by the term of the hard-coat layer I is used similarly.

<(C) Silica sol>
The silica sol contained in the hard coat layer II (B2) is a particle that contributes to the improvement of scratch resistance, and has an average particle size of 5 to 30 nm and a refractive index of 1.44 to 1.50. When the average particle size is out of the above range, the crack resistance is deteriorated.
The silica sol is a single particle, a non-hollow particle having a dense inside and no space inside, and has a density of usually 1.9 g / cm ³ or more. Since the silica sol is known per se and commercially available, a commercially available product satisfying the above average particle diameter and refractive index may be selected and used. Since the silica sol is usually provided in a state of being dispersed in a solvent, this solvent is inevitably mixed in the curable composition solution for forming the hard coat layer II and behaves in the same manner as other solvents. .

<(D) Silane coupling compound or hydrolyzate thereof>
The silane coupling compound or its hydrolyzate itself hydrolyzes to form a dense siliceous film.
As this silane coupling compound, a well-known thing can be used without a restriction | limiting. For example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, γ-glycid Xylpropyltrimethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopro Examples include pyrtriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
Depending on the type of the silane coupling compound, for the purpose of improving the solubility in water or a solvent, it is preferable that the silane coupling compound is a decomposition product that has been previously hydrolyzed with a dilute acid or the like. The method of hydrolyzing in advance is not particularly limited, and a method of hydrolyzing a part using an acid catalyst such as acetic acid is common.

<(E) Metal chelate compound>
The metal chelate compound is contained for the purpose of increasing the denseness and strength of the layer and further the hardness. The metal chelate compound is a compound in which a chelating agent having a bidentate ligand as a representative example is coordinated to a metal such as titanium, zirconium, or aluminum.
Specifically, triethoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethylacetonate) Acetate) titanium, diethoxy bis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis Titanium chelate compounds such as (ethyl acetoacetate) titanium, tris (acetylacetonate) mono (ethyl acetoacetate) titanium;
Triethoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) zirconium, triethoxy mono (ethylacetonato) zirconium, Diethoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetyl) Acetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonate) mono (ethylacetoacetate) zirconium, etc. Hexafluorophosphate chelate compounds;
Diethoxy mono (acetylacetonato) aluminum, monoethoxy bis (acetylacetonato) aluminum, di-i-propoxy mono (acetylacetonato) aluminum, monoethoxy bis (ethylacetoacetate) aluminum, diethoxy mono (Ethylacetoacetate) Aluminum chelate compounds such as aluminum can be mentioned.

<B2 composition>
The B2 composition is a curable composition containing the components (a), (c), (d) and (e) as essential components, and is blended at the following specific ratio.
(C) The silica sol is blended in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate. If the amount is less than 1 part by mass, the scratch resistance does not appear, and if it exceeds 50 parts by mass, the film adhesion deteriorates.
(D) The silane coupling compound or the hydrolyzate thereof is blended in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate. If it is less than 1 part by mass, the film adhesion is poor, and if it exceeds 50 parts by mass, the scratch resistance becomes poor.
(E) The metal chelate compound is blended in an amount of 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate. Outside this range, the adhesion with the antireflection layer C formed on the hard coat film II becomes poor.
In the B2 composition, any additive component can be added in the same manner as the B1 composition. Usually, a polymerization initiator is added for the purpose of accelerating curing, and a solvent is used for the purpose of coating. The preparation method of B2 composition is also performed according to that of B1 composition.

<Formation of hard coat layer II>
The hard coat layer II is directly laminated on the hard coat layer I laminated on the transparent resin substrate to form a two-layer hard coat layer. The hard coat layer II is formed in the same manner as the hard coat layer I in terms of the coating method and the curing method. The thickness of the layer to be formed is set in the range of 1 to 10 μm.

[Antireflection layer (C)]
In the transparent resin laminate of the present invention, the antireflection layer (C) is directly laminated on the hard coat layer laminated on the transparent resin substrate. The antireflection layer (C) is composed of a low refractive index layer (C1) having a refractive index of less than 1.50 and a thickness of 50 to 200 nm. As will be described later, when the antireflection layer (C) is composed of a plurality of antireflection layers, the low refractive index layer is an antireflection layer that becomes the outermost layer (viewing side).
The low refractive index layer (C1) does not exhibit a sufficient antireflection function when the refractive index is 1.50 or more. Further, when the thickness is out of the range of 50 to 200 nm, the antireflection function is not exhibited.
The low refractive index layer (C1) comprises (f) a silica sol having an average particle diameter of 5 to 150 nm and a refractive index of 1.44 or less, (d) a silane coupling compound or a hydrolyzate thereof, and (e) (F) silica sol is compounded in an amount of 10 to 50% by mass, and (d) the compounding ratio of the silane coupling compound or a hydrolyzate thereof and (e) the metal chelate compound is 60 to 50%. 99% by mass: a layer composed of a cured product of a curable composition (C1 composition) of 40 to 1% by mass.

<(F) Silica sol>
The silica sol contained in the low refractive index layer (C1) is a particle for controlling the refractive index of the layer, and has an average particle diameter of 5 to 150 nm and a refractive index of 1.44 or less. When the average particle size is out of the above range, the reflection performance is lowered or the haze ratio is increased. When the refractive index exceeds 1.44, the reflection performance decreases.
What is necessary is just to select and use the said silica sol from the commercial item what satisfy | fills the said average particle diameter and refractive index. In particular, from the viewpoint of the antireflection effect, silica sol particles having a hollow interior are suitable. Since the silica sol is also usually provided in a state of being dispersed in a solvent, the solvent behaves in the same manner as in the case of the (c) silica sol.
As the (d) silane coupling compound or a hydrolyzate thereof and the (e) metal chelate compound, those described above can be used in the same manner.

<C1 composition>
The C1 composition is a curable composition containing the components (f), (d), and (e) as essential components, and is blended at the following specific ratio.
(F) Silica sol needs to be contained in the layer in an amount of 10 to 50% by mass. If it is less than 10% by mass, a sufficient antireflection effect cannot be expected. When it exceeds 50% by mass, the scratch resistance and adhesion are deteriorated.
The compounding ratio of (d) the silane coupling compound or its hydrolyzate and (e) the metal chelate compound is 60 to 99% by mass: 40 to 1% by mass. (E) When the compounding ratio of the metal chelate compound exceeds 40% by mass, the film becomes brittle or the chelate compound is precipitated, which is not preferable. If it is less than 1% by mass, the effect is not exhibited.
Arbitrary additional components can be added to the C2 composition in the same manner as the B1 and B2 compositions. Usually, a solvent is used for the purpose of coating. The method for preparing the C2 composition is also performed in accordance with that for the B1 or B2 composition.

<Formation of low refractive index layer (C1)>
The low refractive index layer is laminated on the hard coat layer, specifically, the hard coat II layer laminated on the transparent resin substrate. The low refractive index layer is formed in accordance with the formation of the hard coat layer by applying a solution of the C1 composition onto the hard coat II layer, which is a cured product, and then drying and heating and curing at 70 to 120 ° C. Do it. The thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.
When the antireflection layer is composed of two layers of a medium refractive index layer and a low refractive index layer, which will be described later, the medium refractive index layer is first formed on the hard coat II layer, and then on the layer. A low refractive index layer is formed. Furthermore, when the antireflective layer is composed of three layers of a medium refractive index layer, a high refractive index layer, and a low refractive index layer, the medium refractive index layer is first formed on the hard coat II layer, Next, a high refractive index layer is formed on the layer, and a low refractive index layer is formed thereon.

[Medium refractive index layer (C2)]
The transparent resin laminate of the present invention preferably has a two-layer structure in which an intermediate refractive index layer is laminated on the substrate surface side of the low refractive index layer in order to further enhance the antireflection effect.
The medium refractive index layer is preferably a layer having a refractive index of 1.50 or more and less than 1.75 and a thickness of 50 to 200 nm.
This medium refractive index layer is typically added to the above-mentioned (d) silane coupling compound or its hydrolyzate 20 to 80 parts by mass and (e) 0.1 to 2 parts by mass of a metal chelate compound, (G) Curing containing 20 to 80 parts by mass of metal oxide particles having a refractive index of 1.70 or more and 2.80 or less {with the total amount of (d), (e) and (g) being 100 parts by mass} The adhesive composition is cured to form.
Further, the middle refractive index layer can contain a thermosetting resin as a binder. Examples of thermosetting resins include phenol-formaldehyde resins, silane-modified phenol resins, furan-formaldehyde resins, xylene-formaldehyde resins, ketone-formaldehyde resins, urea formaldehyde resins, melamine-formaldehyde resins, alkyd resins, and unsaturated polyester resins. (Silane modified) epoxy resin, bismaleimide resin, triallyl cyanurate resin, acrylic resin, (silane modified) acrylic resin, silicone resin, urethane resin and the like. These resins may be used alone or in combination of two or more. The said thermosetting resin used as a binder has the advantage that it has tolerance with respect to the oxidation by photoactivity.

<(G) Metal oxide particles>
(G) The metal oxide particles are contained for the purpose of satisfying that the refractive index of the medium refractive index layer is 1.50 or more and less than 1.75. Typically, the average particle diameter is 10 to 100 nm. Metal oxide particles having a refractive index of 1.70 or more and 2.80 or less.
As the metal oxide particles, zirconium oxide particles (refractive index = 2.40); composite zirconium metal oxide particles in which zirconium oxide and other oxides such as silicon oxide are combined at the molecular level to adjust the refractive index; Titanium oxide particles (refractive index = 2.71); composite titanium metal oxide particles whose refractive index is adjusted by combining titanium oxide with other oxides such as silicon oxide and zirconium oxide; silica particles (refractive Rate = 1.55) or the like is used. It selects from these metal oxide particles, or it combines suitably, and it adjusts so that it may become a layer of the said desired refractive index. Such particles are known per se and are commercially available.

<Formation of Medium Refractive Index Layer (C2)>
The middle refractive index layer is laminated on the hard coat layer, specifically, the hard coat II layer laminated on the transparent resin substrate. The medium refractive index layer is formed in the same manner as the low refractive index layer, and the thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.

[High refractive index layer (C3)]
The transparent resin laminate of the present invention has a three-layer structure in which a high refractive index layer (C3) is laminated between a low refractive index layer (C1) and a middle refractive index layer (C2) in order to exhibit an extremely high antireflection effect. A layer structure is particularly preferable.
The high refractive index layer is preferably a layer having a refractive index of 1.60 or more and less than 2.00 and a thickness of 50 to 200 nm. In addition, it is essential that the refractive index of the high refractive index layer is higher than the refractive index of the medium refractive index layer.
This high refractive index layer is typically composed of the above-mentioned (d) silane coupling compound or its hydrolyzate 10 to 50 parts by mass, and (g) 50 to 90 parts by mass of metal oxide particles {(d) And the total amount of (g) is 100 parts by mass} is formed by curing. (G) The metal oxide particles are selected from the above metal oxide particles or a combination thereof so that the refractive index of the high refractive index layer is 1.60 or more and less than 2.00. The
Further, similarly to the middle refractive index layer, a thermosetting resin can be contained as a binder.

<Formation of high refractive index layer (C3)>
The high refractive index layer is laminated on the medium refractive index layer laminated on the hard coat layer, and then the low refractive index layer is laminated on the high refractive index layer to form a three-layer structure. The high refractive index layer is formed in the same manner as the low refractive index layer, and the thickness of the layer is set in the range of 50 to 200 nm from the viewpoint of antireflection performance.

The transparent resin laminate of the present invention is not limited to the one having the above layer structure. For example, an overcoat layer can be provided for the purpose of protecting the antireflection layer. Examples of such an overcoat layer include organic polysiloxane materials and fluororesin coat layers that impart wear resistance and scratch resistance.
Furthermore, an adhesive layer made of an acrylic, rubber, or silicone adhesive can be provided on the back side of the transparent resin laminate. Furthermore, in the transparent resin laminate of the present invention, a hard coat layer (B) and an antireflection layer (C) may be laminated on both the front and back surfaces of the transparent resin substrate.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited at all by these Examples. In addition, not all combinations of features described in the embodiments are essential to the solution means of the present invention.
Various components and abbreviations used in the following Examples and Comparative Examples, and test methods are as follows.

(A) polyfunctional urethane acrylate a-1; aliphatic organic isocyanate-based hexafunctional acrylate a-2; aromatic organic isocyanate-based hexafunctional acrylate (b) surface-treated silica sol b-1; acrylate group-modified silica sol (3-acryloxy) (Treated with propyltrimethoxysilane) Average particle size: 20nm, MIBK dispersion, solid part: 30wt%
b-2: Vinyl group-modified silica sol (treated with vinyltrimethoxysilane) Average particle diameter: 20 nm, MEK dispersion, solid part: 30 wt%
(C) Silica sol c-1; average particle diameter: 10 nm, refractive index: 1.46, IPA dispersion, solid part: 20 wt%
c-2; average particle diameter: 80 nm, refractive index: 1.46, IPA dispersion, solid part: 30 wt%
(D) Silane coupling agent compound or hydrolyzate thereof d-1; γ-glycidoxypropyltrimethoxysilane d-2; 3-acryloxypropyltrimethoxysilane d-3; 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane (e) metal chelate compound e-1; zirconium dibutoxybis (ethylacetoacetate)
e-2; alkyl acetoacetate aluminum diisopropylate e-3; aluminum trisacetylacetonate e-4; zirconium tetraacetylacetonate (f) silica sol f-1; average particle size: 50 nm, hollow silica sol, refractive index: 1.30 , IPA dispersion, solid part: 20wt%
f-2; average particle diameter: 80 nm, silica sol, refractive index: 1.46, IPA dispersion, solid part: 20 wt%
f-3; average particle diameter: 10 nm, silica sol, refractive index: 1.46, IPA dispersion, solid part: 20 wt%
(G) Metal oxide particles g-1: Average particle diameter: 50 nm, zirconia sol, refractive index: 2.40, PGM dispersion, solid part: 55 wt%
g-2: Average particle diameter: 20 nm, titania sol, refractive index: 2.71, MIBK dispersion, solid part: 20 wt%
(H) Others h-1: IPA (isopropyl alcohol)
h-2; MIBK (methyl isobutyl ketone)
h-3; toluene h-4; photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone)
h-5; 0.05N acetic acid h-6; alkoxy group-containing silane-modified epoxy resin

[Reflective test]
Using a “V-550” testing machine manufactured by JASCO Corporation, the reflectance at the lowest point (transparent resin laminate surface) was measured at a scanning speed of 1000 nm / min and a wavelength in the range of 380 to 780 nm. It shows that it is excellent in antireflection ability, so that a numerical value is small.
[Abrasion resistance test]
Set a test piece on a rubbing tester, reciprocate 100 mm between 40 mm with 2 kg / cm ² load on steel wool # 0000 (Nippon Steel Wool Co., Ltd. “BONSTER”), measure the number and number of scratches, and evaluate did. The evaluation criteria are as follows, the transmitted light means light transmitted through the transparent resin laminate, and the reflected light means light reflected on the surface of the laminate.
“◎”: No flaws were observed when observed with either transmitted light or reflected light.
“◯”: Several scratches were observed when observed with transmitted light, but not with reflected light.
“Δ”: Several scratches were confirmed when observed with either transmitted light or reflected light.
“×”: Ten or more scratches were confirmed when observed with either transmitted light or reflected light.
[Hardness test]
Using a hardness meter “C-2210” manufactured by Yoshimitsu Seimitsu Co., Ltd., the hardness was measured with a pencil (“Uni” manufactured by Mitsubishi Pencil Co., Ltd.). The hardness is represented by pencil hardness, and the higher the hardness, the better the scratch resistance. The pencil hardness 7H refers to the hardness when a scratch is confirmed with a 7H pencil, but with an 8H pencil.

Example 1
On the PMMA side of a laminated resin substrate (PC layer thickness 0.93 mm, PMMA layer thickness 0.07 mm) of 1 mm thick aromatic polycarbonate resin (PC) and polymethyl methacrylate resin (PMMA), the following method is used. A hard coat layer and an antireflection layer were further formed thereon.
[Solution composition for forming hard coat layer I]
・ A-1; 300g
・ B-1: 450g
・ H-1; 235g
・ H-4; 15g
[Solution composition for forming hard coat layer II]
・ A-1; 175g
・ C-1; 300g
・ D-1; 20g
・ E-3; 1.5g
・ H-1; 198.1g
・ H-2; 274.6g
・ H-3; 17.5g
・ H-4; 8.8g
・ H-5; 4.5g
[Antireflection layer forming solution composition]
・ F-1; 45g
・ D-1; 13g
・ E-3; 3g
・ H-1; 935g
・ H-5; 4g

First, a laminated resin substrate was dip-coated using a hard coat layer I forming solution having the above composition, dried at 60 ° C. for 5 minutes, and UV cured to form a hard coat layer I having a thickness of 12 μm. Next, the substrate having the hard coat layer I was dip coated with the solution for forming the hard coat layer II having the above composition, dried at 60 ° C. for 5 minutes, and UV cured to form a hard coat layer II having a thickness of 3 μm. . Further, the substrate having the hard coat layer was dip-coated with an antireflection layer forming solution and heat-treated at 80 ° C. for 20 minutes to form an antireflection layer (low refractive index layer) having a thickness of 100 nm. Thereafter, a fluorine-based antifouling agent was overcoated with dip coating, followed by heat treatment at 100 ° C. for 120 minutes to cure the film.
The reflectance, hardness, and scratch resistance of the resulting transparent laminate were measured and evaluated according to the above test methods. The results are shown in Table 1.
Examples 2 to 6
A transparent resin laminate was prepared in the same manner as in Example 1 except that the hard coat layer I forming solution, the hard coat layer II forming solution, and the antireflection layer forming solution shown in Table 1 were used. Measurements were performed in the same manner. The results are shown in Tables 1 and 2.

Comparative Examples 1-5
A transparent resin laminate was prepared in the same manner as in Example 1 except that the hard coat layer I forming solution, the hard coat layer II forming solution, and the antireflection layer forming solution shown in Table 2 were used. Measurements were performed in the same manner. The results are shown in Table 3.

As a result of comparison between Example 1 and Comparative Example 1, if the hard coat layer I contains (A) surface-treated silica sol in an amount of less than 50 parts by mass with respect to 100 parts by mass of the polyfunctional urethane acrylate, the hardness performance deteriorates. I understand that. Further, from Comparative Example 2, when the thickness of the hard coat layer I is not 5 μm or more, the hardness performance is poor and the scratch resistance is extremely poor. Furthermore, from Comparative Example 3, when the silane coupling agent is not included in the hard coat layer II, both the hardness performance and the scratch resistance are insufficient. From Comparative Example 4, when no silica sol is contained in the hard coat layer II, the scratch resistance is insufficient. From Comparative Example 5, when the hard coat layer II is not present, the hardness performance is insufficient and the scratch resistance is extremely poor.

Examples 7-9
It consists of two or three layers by the following method using a solution for forming a low refractive index layer, a solution for forming a medium refractive index layer, and a solution for forming a high refractive index layer as necessary, as shown in Table 3. A transparent resin laminate having an antireflection film was prepared and evaluated. The results are shown in Table 4.
In the same manner as in Example 1, after forming the hard coat layer on the laminated resin substrate, the substrate having the hard coat layer was dip coated on the medium refractive index layer forming solution, and heat-treated at 90 ° C. for 30 minutes. A medium refractive index layer having a thickness of 85 nm was formed. Next, the substrate was dip-coated with a solution for forming a low refractive index layer, and heat-treated at 80 ° C. for 20 minutes to form a low refractive index layer having a thickness of 100 nm. However, in Examples 7 and 8, before forming the low refractive index layer, that is, after forming the middle refractive index layer, the substrate was dip coated with the solution for forming the high refractive index layer, and then at 80 ° C. for 20 minutes. Then, heat treatment was performed to form a high refractive index layer having a thickness of 80 nm.

Claims

In the transparent resin laminate in which the hard coat layer (B) is laminated on the transparent resin substrate (A) and the antireflection layer (C) is further laminated on the hard coat layer (B),
The hard coat layer (B) is composed of a hard coat layer I (B1) located on the transparent resin substrate side and a hard coat layer II (B2) located on the antireflection layer side,
The hard coat layer I (B1) has a layer thickness of 5 to 20 μm, and (a) a multifunctional urethane acrylate having 6 or more (meth) acryloyl groups in one molecule, and the multifunctional urethane acrylate 100 (B) a cured product of a curable composition comprising 40 to 200 parts by mass of a surface-treated silica sol with respect to parts by mass,
The hard coat layer II (B2) has a layer thickness of 1 to 10 μm, (a) a multifunctional urethane acrylate having 6 or more (meth) acryloyl groups in one molecule, and the multifunctional urethane acrylate 100 (C) 1 to 50 parts by mass of silica sol having an average particle diameter of 5 to 30 nm and a refractive index of 1.44 to 1.50, and (d) a silane coupling compound or a hydrolyzate 1 thereof with respect to parts by mass A cured product of a curable composition comprising from 30 to 30 parts by mass, and (e) 0.1 to 3.0 parts by mass of a metal chelate compound,
The antireflection layer (C) is composed of a low refractive index layer (C1) having a refractive index of less than 1.50 and a thickness of 50 to 200 nm,
The low refractive index layer (C1) comprises (f) a silica sol having an average particle diameter of 5 to 150 nm and a refractive index of 1.44 or less, (d) a silane coupling compound or a hydrolyzate thereof, and (e) (F) silica sol is compounded in an amount of 10 to 50% by mass, and (d) the compounding ratio of the silane coupling compound or a hydrolyzate thereof and (e) the metal chelate compound is 60 to 50%. 99% by mass: The transparent resin laminate, comprising a cured product of a curable composition in an amount of 40 to 1% by mass.
The antireflection layer (C) is composed of two layers of the low refractive index layer (C1) and the middle refractive index layer (C2) located on the transparent resin substrate side, and the middle refractive index layer (C2) 2. The transparent resin laminated plate according to claim 1, having a refractive index of 1.50 or more and less than 1.75 and a thickness of 50 to 200 nm.
The antireflective layer (C) includes the low refractive index layer (C1), the middle refractive index layer (C2), and a high refractive index layer (between the low refractive index layer and the middle refractive index layer ( C3), the high refractive index layer (C3) has a refractive index of 1.60 or more and less than 2.00, a thickness of 50 to 200 nm, and the high refractive index layer (C3) The transparent resin laminate according to claim 2, wherein the refractive index is larger than the refractive index of the middle refractive index layer (C2).
The transparent resin laminate according to any one of claims 1 to 3, wherein the surface-treated silica sol is (meth) acryloyl group-modified silica sol or vinyl group-modified silica sol.