KR20140133563A - Photocurable resin composition, image display device, and method for producing image display device - Google Patents

Abstract

(일반식(1) 중, R¹은 수소 원자 또는 메틸기를 나타내고, R²는 수소 원자 또는 탄소수 1∼12의 알킬기를 나타내고, n은 1∼7의 수를 나타낸다.)
(일반식(II) 중의 R³ 및 R⁴는, 각각 독립적으로, 수소 원자 또는 탄소수 1∼5의 알킬기를 나타내고, q는 0∼3의 정수를 나타낸다. *는 결합 부분을 나타낸다.)(A) a compound having a structural unit derived from polybutadiene, (B) a compound represented by the following general formula (1), (C) a thiol compound having a group represented by the following general formula (II) Containing an initiator,
(A1) A photocurable resin composition containing a compound having a (meth) acryloyl group and a structural unit derived from polybutadiene as the component (A) is excellent in curability, has an appropriate viscosity, Is good and can be used as one of constituent materials of an image display device.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents a number of 1 to 7)
(R ³ and R ⁴ in the general formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; q represents an integer of 0 to 3;

Description

TECHNICAL FIELD [0001] The present invention relates to a photocurable resin composition, an image display device, and a method of manufacturing an image display device,

The present invention relates to a photo-curable resin composition which is useful for preventing cracks, relieving stress and impacts of an image display apparatus and having excellent transparency, an image display apparatus using the resin composition, and a method of manufacturing the image display apparatus .

As a typical image display apparatus mounted with an image display panel, a liquid crystal display apparatus is exemplified. The liquid crystal display device has a liquid crystal cell and a liquid crystal display panel including an optical film such as a polarizing plate attached to both sides of the liquid crystal cell. This liquid crystal cell is formed by arranging two glass substrates, each having a thickness of about 1 mm, on the surface of which a transparent electrode, a pixel pattern, and the like are formed with a gap of about several microns with the liquid crystal filled and sealed .

Since the liquid crystal display panel is thin and susceptible to damage, a transparent front plate (protective panel) is formed on the front surface of the liquid crystal display panel with a certain space, in particular, in a cellular phone, a game machine, a digital camera, A liquid crystal display device having a structure in which a liquid crystal display device is provided is generally used.

In recent years, a touch panel is mounted on an image display device such as a mobile phone, a game machine, a digital camera, a vehicle-mounted component, a notebook, a desktop PC, and a PC monitor. Such an image display apparatus equipped with a touch panel has a laminated structure of a protective panel, a touch panel, and an image display unit. The image display apparatus includes a protective panel and an image display unit, a protective panel and a touch panel, Air is interposed between the image display units.

The presence of air in these spaces causes scattering of light, which causes deterioration of contrast, luminance, light transmittance, and image quality due to overlapping of images.

In order to prevent such inconveniences, it has been proposed to fill the space portion with a filling material such as resin instead of air (see, for example, Patent Documents 1 to 4). However, filling the space portion with the packing proposed in Patent Documents 1 to 4 has the following problems.

That is, the oil used in Patent Document 1 is difficult to seal to prevent leakage, and there is a possibility of invading materials used in the liquid crystal panel. Further, there is a problem that oil leaks when a crack occurs in the front plate.

The unsaturated polyester used in Patent Document 2 is easily colored in yellow, so that it is not preferable to apply it to a liquid crystal display device.

The silicone used in Patent Document 3 has a problem in that the process is troublesome and the adhesive force with the pressure-sensitive adhesive is not so large since the adhesive force is small and the pressure-sensitive adhesive is separately required for fixation.

The polymer of acrylic monomer used in Patent Document 4 has a small adhesive force and does not require a pressure-sensitive adhesive separately if it is a small-sized device. However, since a pressure-sensitive adhesive is separately required to support the front plate of a large liquid crystal display device, the process becomes troublesome. Further, since the raw material is composed only of monomers, there is a problem that it is difficult to uniformly produce a large-area film because of low viscosity and large curing shrinkage.

The resin composition for filling the aforementioned space of the image display device (for example, a space between the protective panel and the image display unit, a space between the protective panel and the touch panel, and a space between the touch panel and the image display unit) When a thermosetting resin composition is used, it is restricted by the heat-resistant temperature as a component of the image display device.

Therefore, studies have been made on the use of a photo-curable resin composition as a resin composition for filling the space of the image display device.

Japanese Patent Application Laid-Open No. 05-011239 Japanese Patent Application Laid-Open No. 03-204616 Japanese Patent Application Laid-Open No. 06-059253 Japanese Patent Application Laid-Open No. 2004-125868

However, in the image display apparatus, for the purpose of improving the contrast of a display image, a frame-type shielding unit is generally provided along a peripheral edge of a protective panel with a predetermined width (see, for example, Figs. 2 shows the liquid crystal display devices 1A and 1B which are one of the image display devices each including the protective panel 40 provided with the light shielding portion 41). The light shielding portion has a function of blocking unnecessary light in the periphery of the image display panel and preventing deterioration of display quality due to light leakage.

However, in the image display device provided with the shielding portion on the protective panel, when the photocurable resin composition is filled in the space, a shade portion (shade portion) similar to the back side portion of the shielding portion And a portion corresponding to P of 2, hereinafter also referred to as " shaded portion "), sufficient light does not reach the photocurable resin composition, which causes a problem of interfering with curing.

For example, when a protective panel is disposed on an image display unit in which a liquid crystal display panel is built in a frame body, a photo-curable resin composition is filled therebetween, and light is irradiated from the protective panel side, (The portion corresponding to Q in Figs. 1 and 2, hereinafter also referred to as a " light transmitting portion ") is transmitted through the inner surface of the frame (light shielding portion) There is a possibility that light is not irradiated and the curing does not proceed sufficiently.

If the curing of the resin composition is insufficient, the quality of the image display device is seriously impaired, which is a great factor for lowering the reliability.

The present invention has an excellent curability (hereinafter also referred to as " curability in a light-shielding portion ") capable of sufficiently accelerating curing even in the case of a shaded portion such as a back side portion of the light- An object of the present invention is to provide a photo-curing resin composition having good viscosity and good compatibility, an image display apparatus using the resin composition, and a method of manufacturing the image display apparatus.

The inventors of the present invention have found that a photo-curing resin composition containing a specific component solves the above-mentioned problems, and accomplished the present invention. That is, the present invention provides the following [1] to [7].

[1] A resin composition comprising (A) a compound having a structural unit derived from polybutadiene,

(B) a compound represented by the following general formula (1)

(C) a thiol compound having a group represented by the following general formula (II), and

(D) a photopolymerization initiator

≪ / RTI >

(A1) a compound having a (meth) acryloyl group and a structural unit derived from polybutadiene, as the component (A).

[Chemical Formula 1]

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents a number of 1 to 7)

(2)

(R ³ and R ⁴ in the general formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; q represents an integer of 0 to 3;

[2] The photocurable resin composition according to Item 1, wherein the component (C) is a thiol compound represented by the following general formula (2).

(3)

(In the general formula (2), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 6, q represents an integer of 0 to 3, And A represents an organic group of p.

[3] The photocurable resin composition according to [1] or [2], wherein R ² in the general formula (1) is an alkyl group having 4 to 12 carbon atoms.

[4] The photo-curing resin composition according to any one of [1] to [3], which contains substantially no organic solvent and has a viscosity at 25 ° C of 500 to 5000 mPa · s.

[5] The photo-curable resin composition according to any one of [1] to [4], wherein the content of the component (C) is 3 to 30 mass% with respect to the total amount of the components (A) to (C).

[6] The photocurable resin composition according to any one of [1] to [5], wherein the content of (A1) is 25 to 100 mass% with respect to the total amount of the component (A).

[7] The positive resist composition according to any one of the above items [1] to [6], which further comprises a compound having a structural unit derived from polybutadiene but not having a (meth) acryloyl group as the component (A) Wherein the photocurable resin composition is a photocurable resin composition.

[8] The photocurable resin composition according to the above-mentioned [7], wherein the mass ratio [A1 / A2] of the component (A1) and the component (A2) is 25/75 to 95/5.

[9] The compound according to any one of [2] to [8], wherein A in the general formula (2) is a group represented by the following formula (C-1) or formula (C- Wherein the photocurable resin composition is a photocurable resin composition.

[Chemical Formula 4]

(In the formula (C-1) or the formula (C-2), * represents a bonding portion and X ^{1 to} X ⁷ each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms Lt; / RTI >

[10] The photocurable resin composition according to any one of the above items [1] to [9], wherein the content of the component (B) is 1 to 40 mass% with respect to the total amount of the components (A) to (C).

[11] The photocurable resin composition according to any one of the above items [1] to [10], wherein the content of the component (A) is 50 to 98 mass% with respect to the total amount of the components (A) to (C).

[12] An image display apparatus having an image display section,

A protective panel having a light-shielding portion along an outer edge,

A protective layer provided between the image display unit and the protection panel,

And an image display device having a stacked structure including a plurality of pixels,

Wherein the resin layer is a cured product of the photo-curable resin composition according to any one of [1] to [11].

[13] An image display apparatus having an image display unit,

A touch panel,

A protective panel having a light-shielding portion along an outer edge,

A protective layer disposed between the touch panel and the protective panel,

And an image display device having a stacked structure including a plurality of pixels,

Wherein the resin layer is a cured product of the photo-curable resin composition according to any one of [1] to [11].

[14] An image display unit or a touch panel having an image display portion and a protective panel having a light shielding portion along an outer peripheral edge are disposed opposite to each other, and the photo-curable resin composition is cured by interposing a photo- A method of manufacturing an image display device,

A method for manufacturing an image display device, comprising the steps of: curing a photo-curable resin composition according to any one of the above items [1] to [11] and irradiating light from at least the protective panel side.

The photo-curable resin composition of the present invention is excellent in curability in a light-shielding portion, has an appropriate viscosity, and is excellent in compatibility. Further, the cured product of the photo-curing resin composition is excellent in transparency and refractive index and has an appropriate dielectric constant.

According to the method of manufacturing an image display apparatus of the present invention, since a photo-curing resin composition having excellent curability in the light shielding portion is used, even when a protective panel having a light shielding portion is used along the peripheral edge, It is possible to sufficiently cure the portion on the back side of the light-shielding portion even when irradiated, and an image display device with excellent quality can be manufactured with good productivity.

1 is a cross-sectional view schematically showing an embodiment of a liquid crystal display device which is an example of an image display device of the present invention.
Fig. 2 is a cross-sectional view schematically showing a liquid crystal display device equipped with a touch panel, which is an embodiment of a liquid crystal display device which is an example of the image display device of the present invention.

Hereinafter, the photocurable resin composition of the present invention, the method for producing an image display apparatus using the same, and the image display apparatus will be described in more detail with reference to the embodiments. The present invention is not limited by these embodiments.

As used herein, "(meth) acrylate" means "acrylate" and the corresponding "methacrylate". Similarly, the term "(meth) acryl" means "acryl" and the corresponding "methacryl", and "(meth) acryloyl" means "acryloyl" and the corresponding "methacryloyl" do.

[Photocurable resin composition]

(A) a compound having a structural unit derived from polybutadiene, (B) a compound represented by the general formula (1), (C) a compound represented by the general formula ) A thiol compound having a group represented by the general formula (II), and (D) a photopolymerization initiator, wherein as the component (A), a structural unit derived from a polybutadiene having a (A1) Branching compounds. Other additives other than the above components (A) to (D) may be contained within a range not to impair the effects of the present invention. Hereinafter, each component will be described.

≪ Component (A): Compound having a structural unit derived from polybutadiene >

The resin composition of the present invention contains, as the component (A), a compound having a structural unit derived from polybutadiene.

(A) is a compound having a structural unit derived from polybutadiene (hereinafter also referred to as " polybutadiene (meth) acrylate ") having (A1) (meth) acryloyl group, (Meth) acryloyl group, and having a structural unit derived from polybutadiene. The resin composition of the present invention includes polybutadiene (meth) acrylate which is a component (A1).

The content of the component (A1) is preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 30% by mass or more based on the total amount of the component (A), from the viewpoint of improving the curing property in the light- , Preferably not less than 40 mass%, and most preferably not less than 52 mass%.

(Component (A1): a compound having a (meth) acryloyl group and having a structural unit derived from polybutadiene)

Examples of the compound having a (meth) acryloyl group as the component (A1) and a structural unit derived from polybutadiene include a compound obtained by reacting a polybutadiene diol and a monoisocyanate compound having a (meth) acryloyl group And the like.

The polybutadiene may have a "1,4-structural unit" or a "1,2-structural unit". The "1,4-structural unit" in the polybutadiene is a structural unit represented by the following formula (1t) or (1c), and the "1,2-structural unit" It is a repeating unit to be displayed.

[Chemical Formula 5]

Examples of polybutadiene diols having mainly 1,4-structural units include polybd R-45HT, Poly bd R-15HT (content ratio of 1,4-structural units: 80%, trade name, manufactured by Idemitsu Kosan Co., ).

Examples of the polybutadiene diol having a 1,2-structural unit mainly include a compound represented by the following general formula (1a), specifically, G-1000 (content ratio of 1,2-structural units: 85% (Content ratio of 1,2-structural units: 85%) and G-3000 (content ratio of 1,2-structural units: 90%) (trade name, manufactured by Japan Soda Co., Ltd.) .

[Chemical Formula 6]

(In the formula (1a), n1 represents an integer of 1 to 60.)

In the component (A1), the content ratio of the 1,2-structural unit and the 1,4-structural unit [1,2-structural unit / 1,4-structural unit] is preferably 10/90 to 98/2 , More preferably 60/40 to 98/2, still more preferably 70/30 to 97/3, and most preferably 80/20 to 95/5.

Examples of the monoisocyanate compound having a (meth) acryloyl group include 2-isocyanatoethyl (meth) acrylate, 2-isocyanate propyl (meth) acrylate and 3-isocyanate propyl (meth) acrylate.

The reaction of the polybutadiene diol with the monoisocyanate compound having a (meth) acryloyl group can be carried out in the presence of, for example, a polymerization inhibitor such as p-methoxyphenol and a catalyst such as dibutyltin dilaurate .

In the present invention, the weight average molecular weight (Mw) of the component (A1) is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and still more preferably 3,000 to 20,000, from the viewpoints of curability, flexibility, 10,000.

In the present specification, the weight average molecular weight (Mw) of the component (A) is measured by gel permeation chromatography (GPC) and converted to a value obtained by using a calibration curve of standard polystyrene. The number average molecular weight, the weight average molecular weight and the degree of dispersion are defined as follows when the number of molecules of the molecular weight Mi in the component (A) is Ni.

(a) Number average molecular weight (Mn)

Mn = Σ (N _i M _i ) / ΣN _i = ΣX _i M _i

(X _i = mole fraction of molecules of molecular weight M _i = N _i / ΣN _i )

(b) Weight average molecular weight (Mw)

Mw = Σ (N _i M _i ² ) / ΣN _i M _i = ΣW _i M _i

(W _i = weight fraction of molecules of molecular weight M _i = N _i M _i / ΣN _i M _i )

(c) Molecular weight distribution (degree of dispersion)

Dispersion degree = Mw / Mn

The content of the component (A1) is preferably from 25 to 100% by mass, more preferably from 30 to 100% by mass, and still more preferably from 30 to 100% by mass, based on the total amount of the component (A), from the viewpoint of improvement in the curing property in the light- Is 40 to 100 mass%, and most preferably 45 to 100 mass%.

(Component (A2): a compound having no (meth) acryloyl group and having a structural unit derived from polybutadiene)

In the resin composition of the present invention, the component (A) may contain only the component (A1), but from the viewpoint of obtaining a resin composition having a curing property, a curing shrinkage ratio and workability, (A2) a compound having a structural unit derived from polybutadiene (hereinafter, also referred to as a "component (A2)") without having a (meth) acryloyl group together with the component (A1).

Examples of the compound of the component (A2) include a polybutadiene diol, polybutadiene dicarboxylic acid, maleated polybutadiene, butadiene homopolymer, a copolymer copolymerizable with butadiene, a compound obtained by reacting a polybutadiene diol and a compound having an isocyanate group A compound obtained by reacting a polybutadiene dicarboxylic acid with a compound having a carboxyl group, a compound obtained by reacting a polybutadiene dicarboxylic acid with a compound having a hydroxyl group, a compound obtained by reacting a polybutadiene dicarboxylic acid with a compound having an epoxy group, .

Examples of the polybutadiene dicarboxylic acid having mainly a 1,2-structural unit include C-1000 (content ratio of 1,2-structural units: not less than 85%, trade name, manufactured by Nippon Soda Co., Ltd.) have.

Examples of the butadiene homopolymer mainly containing a 1,2-structural unit include B-1000 (content ratio of 1,2-structural units: 85%), B-2000 (content ratio of 1,2- structural units: 85% B-3000 (content ratio of 1,2-structural units: 90%) (trade name, manufactured by Japan Soda Co., Ltd.).

Examples of the compound obtained by reacting the polybutadiene diol with a compound having an isocyanate group include TEA-1000 and TE-2000 (trade name, manufactured by Nippon Soda Co., Ltd.).

Examples of the compound obtained by reacting the polybutadiene dicarboxylic acid with a compound having an epoxy group include EPB13 (trade name, manufactured by Nippon Soda Co., Ltd.).

From the viewpoint of improvement of the curing property at the light shielding portion and from the viewpoint of obtaining a resin composition having an appropriate viscosity, the mass ratio [(A1) / (A2)] of the component (A1) To 95/5, more preferably 30/70 to 90/10, further preferably 40/60 to 80/20, most preferably 45/55 to 70/30. When the mass ratio is 25/75 or more, the curing property of the resultant resin composition in the light shielding portion can be improved. On the other hand, if the mass ratio is 95/5 or less, a resin composition having an appropriate viscosity can be produced.

The content of the component (A) in the resin composition of the present invention is preferably 50 to 98% by mass, more preferably 60 to 94% by mass, More preferably 68 to 92 mass%, and most preferably 80 to 92 mass%.

When the content of the component (A) is 50 mass% or more, the curing property of the obtained resin composition in the light shielding portion can be improved and the dielectric constant can be reduced. On the other hand, when the content is 98% by mass or less, the content of the component (B) and the component (C) can be ensured, so that not only a resin composition having an appropriate viscosity can be obtained but also the transparency of the cured product of the resin composition can be improved.

≪ Component (B): a compound represented by the general formula (1) >

The resin composition of the present invention contains, as the component (B), a compound represented by the following general formula (1).

(7)

R ¹ in the general formula (1) represents a hydrogen atom or a methyl group. R ² in the general formula (1) represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. When the number of carbon atoms in the alkyl group exceeds 12, compatibility with the component (A) is deteriorated and the transparency of the cured product is lowered.

Therefore, as R ² , an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl group having 5 to 10 carbon atoms is preferable from the viewpoint of improving the compatibility with the component (A) and improving the curing property of the resulting resin composition in the light- More preferably an alkyl group having 1 to 11 carbon atoms, and still more preferably an alkyl group having 6 to 10 carbon atoms.

Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, , An octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The alkyl group may be either linear or branched.

At least a part of the hydrogen atoms of these alkyl groups may be substituted with a substituent such as a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a carbonyl group, a formyl group, an ester group, an amide group, An alkylthio group, an arylthio group, an amino group, a silyl group, a silyloxy group and the like.

N in the general formula (1) represents a number of 1 to 7, but from the viewpoint of compatibility with the component (A) and the component (C), it is preferably 1 to 6, more preferably 1 to 5, More preferably 3 to 5.

When n exceeds 7, the compatibility with the component (A) and the component (C) is lowered, and the transparency of the cured product tends to deteriorate. In addition, the curing property of the resultant resin composition in a light mineral decreases, which is not preferable.

In the present invention, n represents the average value of the number of ethylene oxide chains of the compound represented by the general formula (1).

Examples of the compound represented by the general formula (1) include phenoxyethyl (meth) acrylate, butylphenoxypolyethylene glycol (meth) acrylate, pentylphenoxypolyethylene glycol (meth) acrylate, hexylphenoxy (Meth) acrylate, decylphenoxypolyethylene glycol (meth) acrylate, octylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, decylphenoxypolyethylene glycol And the like.

These compounds may be used alone or in combination of two or more.

Preferred examples of commercially available products of the compound represented by the above general formula (1) include FA-310A (R ¹ : hydrogen atom, R ² : hydrogen atom, n in the formula (1), trade name, manufactured by Hitachi Chemical Co., (Compound having an average value of n: 4), FA-314A (trade name, product of Hitachi Chemical Co., Ltd., R ¹ : hydrogen atom, R ² : nonyl group, n: average value: 4)

The weight average molecular weight (Mw) of the component (B) is preferably 3,000 or less, more preferably 100 to 2,800, further preferably 150 to 2,000, and most preferably 200 to 1,500.

The content of the component (B) in the resin composition of the present invention is preferably from 1 to 40 mass%, more preferably from 3 to 30 mass%, more preferably from 3 to 30 mass%, based on the total amount of the components (A) And more preferably 4 to 27 mass%.

When the content of the component (B) is 1% by mass or more, the resin composition can be made into a resin composition having an appropriate viscosity, so that not only the workability at the time of coating can be improved but also the curing shrinkage rate can be lowered. In addition, not only the curing property of the obtained resin composition in the light shielding portion can be improved, but also the transparency of the cured product can be improved. On the other hand, if it is 40 mass% or less, the increase in the hardening shrinkage ratio can be suppressed.

Component (B2): a low molecular weight monomer having one ethylenic unsaturated group in the molecule other than the compound represented by the above general formula (1)

The resin composition of the present invention may contain a low molecular weight monomer (B2) having one ethylenic unsaturated group in a molecule other than the compound represented by the above general formula (1).

Examples of such a low molecular weight monomer (B2) include an alkyl (meth) acrylate represented by the following general formula (3) and a compound having a (meth) acrylic group and a hydroxyl or ether bond in the molecule have.

[Chemical Formula 8]

In the general formula (3), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an alkyl group having ⁴ to 20 carbon atoms. R ¹² is preferably an alkyl group having 6 to 18 carbon atoms, more preferably an alkyl group having 8 to 16 carbon atoms, from the viewpoint of giving more flexibility.

Examples of the alkyl (meth) acrylate represented by the general formula (3) include n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl Stearyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (meth) acrylate. These compounds may be used alone or in combination of two or more.

Examples of the compound having a (meth) acryl group and a hydroxyl group or an ether bond in the molecule include 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2- Acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate such as hydroxybutyl (meth) acrylate and 1-hydroxybutyl (meth) acrylate; Hydroxyl group-containing (meth) acrylamides such as hydroxyethyl (meth) acrylamide; Polyethylene glycol mono (meth) acrylate such as diethylene glycol and triethylene glycol; Polypropylene glycol mono (meth) acrylates such as dipropylene glycol and tripropylene glycol; Polybutylene glycol mono (meth) acrylate such as dibutylene glycol and tributylene glycol; (Meth) acrylate containing a morpholine group such as acryloylmorpholine.

Among them, a hydroxyl group-containing (meth) acrylate and a morpholine group-containing (meth) acrylate are preferable from the viewpoints of anti-wet heat resistance and workability at the time of coating, and 4-hydroxybutyl acrylate, More preferred is i-morpholine.

These low molecular weight monomers (B2) may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of these low molecular weight monomers (B2) is preferably 3,000 or less, more preferably 100 to 2,800, and still more preferably 150 to 2,000.

The content of the low-molecular-weight monomer (B2) is preferably 0 to 30 parts by mass, more preferably 0 to 15 parts by mass, per 100 parts by mass of the component (B).

≪ Component (C): Thiol compound having a group represented by formula (II)

The resin composition of the present invention contains, as the component (C), a thiol compound having a group represented by the following formula (II). These compounds may be used alone or in combination of two or more.

[Chemical Formula 9]

R ³ and R ⁴ in the general formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; q represents an integer of 0 to 3; * Represents a bonding portion. R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. The alkyl group may be either linear or branched. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and pentyl. Q in the general formula (II) represents an integer of 0 to 3, preferably an integer of 1 to 2, more preferably 1.

Among the thiol compounds having a group represented by the general formula (II), the thiol compounds represented by the following general formula (2) are preferable from the viewpoint of the stability of the obtained resin composition.

[Chemical formula 10]

R ³ and R ⁴ in the general formula (2) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group desirable. The alkyl group may be either linear or branched.

P in the general formula (2) represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 2 to 4.

Q in the general formula (2) represents an integer of 0 to 3, preferably an integer of 1 to 2, and more preferably 1.

Among the compounds represented by the general formula (2), in view of the stability of the obtained resin composition, q is 1, R ³ is a methyl group, and R ⁴ is a hydrogen atom. Thiol compounds are preferred.

(11)

(In the formula (2a), p represents an integer of 1 to 6, and A represents an organic group of p.)

In the general formulas (2) and (2a), A represents an organic group having a valence of p, specifically 1 to 6 valent organic groups.

Examples of the monovalent organic group include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 6 to 24 carbon atoms, a carbonyl group (-CO-R (Wherein R is a hydrocarbon group (preferably an alkyl group having 1 to 6 carbon atoms)), an ester group (-CO-OR or -O-CO-R wherein R is a hydrocarbon group An alkyl group having 1 to 6 carbon atoms)), and a carbamoyl group.

Examples of the alkyl group having 1 to 12 carbon atoms include the groups exemplified as R ² in the general formula (1). Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2- adamantyl group, a 1-norbornyl group, Boronyl group and the like.

Examples of the aryl group having 6 to 24 carbon atoms include a phenyl group, a biphenylyl group, and a naphthyl group.

Examples of the aralkyl group having 6 to 24 carbon atoms include a benzyl group, a phenethyl group, and a phenylpropyl group.

Examples of the divalent organic group include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, an allylene group having 6 to 24 carbon atoms such as a phenylene group and a biphenylene group, a polyether group, A carbonyl group, an ester group, an amide group, and a urethane group.

Examples of the alkylene group having 1 to 12 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, pentylene, hexylene, A 2-ethylhexylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group.

Examples of the cycloalkylene group having 3 to 12 carbon atoms include a cyclopentylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a 1,3-adamantyl group, .

Examples of the arylene group include a phenylene group such as a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group, a biphenylene group, and a naphthylene group.

Examples of the polyether group include a polyethylene oxide group and a polypropylene oxide group.

Examples of the polysiloxane group include polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, and the like.

Examples of the organic group having 3 to 6 carbon atoms include an aliphatic hydrocarbon group having 3 to 6 carbon atoms and an aliphatic hydrocarbon chain having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms and an alicyclic structure, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, And a 3- to 6-membered heterocyclic group having a heterocyclic structure containing a hetero atom such as an oxygen atom, a nitrogen atom, and a sulfur atom, and the like.

These organic group A may further have a substituent.

Examples of the substituent that the organic group A may have include a substituent group which may have a substituent such as a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a carbonyl group, a formyl group, an ester group, an amide group, An aryl group, an amino group, a silyl group, and a silyloxy group.

Among the organic groups represented by A represented by A, preferred is a group represented by the following formula (C-1) or (C-2), or an alkylene group having 1 to 12 carbon atoms.

[Chemical Formula 12]

In the above-mentioned (C-1) or (C-2), * represents a bonding moiety and X ^{1 to} X ⁷ each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms, . Examples of the substituent include the same substituent as the above-mentioned organic group A may have. X ^{1 to} X ⁷ are preferably a single bond or an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and still more preferably a methylene group or an ethylene group.

The alkylene group having 1 to 12 carbon atoms is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 2 to 4 carbon atoms.

Specific examples of the compound of the component (C) include 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) , 5-triazine-2,4,6 (1H, 3H, 5H) -thione and pentaerythritol tetrakis (3-mercaptobutyrate).

These compounds may be used alone or in combination of two or more.

These compounds are available from Showa Denko KK as car lenses MT series ("car lens MT BD1", "car lens MT NR1", "car lens MT PE1", etc.).

The content of the component (C) in the resin composition of the present invention is preferably in the range of from 0.01 to 10 parts by weight, more preferably from 1 to 20 parts by weight, Is preferably from 1 to 30 mass%, more preferably from 2 to 20 mass%, and still more preferably from 3 to 12 mass%.

≪ Component (D): photopolymerization initiator >

Examples of the photopolymerization initiator (D) used in the present invention include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, , 4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone,? -Hydroxyisobutylphenone, 2-ethyl anthraquinone, tert-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-crown-2-methyl anthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, Phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2- Methyl-1-phenylpropan-1-one and the like; Benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether and benzoin phenyl ether; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2- hydroxyethoxy) -phenyl] -2- 2-methyl-1-propan-1-one and the like; Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl- Acylphosphine oxide-based compounds such as phenylphosphine oxide; Oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone); ester compounds of? - (acridin-9-yl) acrylic acid; Acridine compounds such as 9-phenylacridine, 9-pyridylacridine, and 1,7-diacridinoheptane; A dimer of 2- (o-chlorophenyl) -4,5-diphenylimidazole, a dimer of 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole, (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- methoxyphenyl) Diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5- 2,4,5-triarylimidazole dimer such as diphenylimidazole dimer and 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer; Benzyl, 2,2-diethoxyacetophenone, benzyldimethylketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methylthio) phenyl] -2-porphono-1-propane.

These photoinitiator (D) may be used alone or in combination of two or more.

Among them, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2- Hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Acylphosphine oxide-based compounds such as pin oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and a combination thereof.

From the viewpoint of obtaining a resin composition suitable for the production of a thick film, that is, a thick film sheet, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and other acylphosphine oxide compounds are preferable.

The content of the photopolymerization initiator (D) used in the present invention is preferably from 0.05 to 10 parts by mass, more preferably from 0.08 to 10 parts by mass based on 100 parts by mass of the total amount of the components (A) to (C) More preferably 0.1 to 4 parts by mass, and most preferably 0.2 to 2 parts by mass.

<Other additives>

The photo-curable resin composition of the present invention may further contain other additives insofar as the effect of the present invention is not impaired. Examples of other additives include stabilizers, plasticizers, and the like.

The stabilizer is added for the purpose of improving the stability of the photocurable resin composition, and examples thereof include triphenyl phosphite and the like.

The plasticizer is added for the purpose of adjusting the viscosity of the photo-curable resin composition, and examples thereof include a polyester plasticizer with a dibasic acid and a polyhydric alcohol; A liquid acrylic plasticizer comprising the acrylic acid alkyl ester monomer unit and / or the methacrylic acid alkyl ester monomer unit as the molecular chain; Polyether-based plasticizers such as polypropylene glycol and derivatives thereof; Urethane based plasticizers; And polystyrene-based plasticizers such as poly-alpha-methylstyrene and polystyrene.

The photo-curable resin composition of the present invention is preferably substantially free of an organic solvent (solvent) from the viewpoint of suppressing moisture resistance and bubbling in the cured product.

The term &quot; substantially free of organic solvent &quot; means that the organic solvent is not intentionally added. If the photocurable resin composition of the present invention does not significantly lower the properties after photocuring, a small amount of organic solvent May be present.

Concretely, the content of the organic solvent should be 1000 ppm or less, preferably 500 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably, an organic solvent (0 ppm) at all.

Means an organic compound which does not have an ethylenic unsaturated group in its molecule and is liquid at 25 占 폚 and has a boiling point at atmospheric pressure of 250 占 폚 or less.

[Physical Properties of Photocurable Resin Composition]

The viscosity of the photocurable resin composition of the present invention at 25 占 폚 is preferably 500 to 5000 mPa 占 퐏, more preferably 1,000 to 5,000 mPa 占 퐏 in view of suppression of bleed out and workability, More preferably from 2,000 to 4,000 mPa 占 퐏, and most preferably from 2,500 to 3,800 mPa 占 퐏.

The viscosity at 25 ° C is a value measured at 0.5 min ^-1 by a 3 ° cone rotor using an E-type viscometer, and is specifically a value according to the measuring method described in Examples .

[Physical Properties of Cured Product of Photocurable Resin Composition]

The light transmittance of the cured product of the photo-curable resin composition of the present invention at a wavelength of 440 nm at 175 nm is preferably 98% or more, more preferably 99% or more.

The refractive index of the cured product of the photocurable resin composition of the present invention is preferably from 1.45 to 1.55, more preferably from 1.47 to 1.53.

The dielectric constant of the cured product of the photo-curable resin composition of the present invention at a frequency of 1 MHz is preferably 2.5 to 3.0, more preferably 2.7 to 2.9. When the dielectric constant is 2.5 or more, when the resin composition of the present invention is applied to a touch panel application, the response performance of the touch panel is improved. On the other hand, when the dielectric constant is 3.0 or less, it is possible to suppress the occurrence of malfunction due to an excessively high response when applied to a touch panel application.

These physical property values are values obtained by the measurement method described in the embodiment.

[Image display device]

An image display apparatus of the present invention is an image display apparatus having a laminated structure including an image display unit having an image display unit, a protection panel having a light shielding portion along an outer peripheral edge, and a resin layer interposed between the image display unit and the protection panel Wherein the resin layer is a cured product of the liquid photo-curable resin composition.

According to the present invention, there is also provided an image display apparatus comprising an image display unit having an image display unit, a touch panel, a protection panel having a light shielding portion along an outer peripheral edge, and a resin layer interposed between the touch panel and the protection panel The image display apparatus according to claim 1,

The resin layer is a cured product of the liquid photocurable resin composition.

Next, a liquid crystal display device which is an example of an image display device will be described.

Hereinafter, a liquid crystal display device which is an example of an image display device that can be manufactured by using the photo-curing resin composition of the present embodiment will be described.

&Lt; Liquid crystal display device &

1 is a cross-sectional view schematically showing an embodiment of a liquid crystal display device which is an example of an image display device of the present invention.

1 includes an image display unit 1 in which a backlight system 50, a polarizing plate 22, a liquid crystal display cell 10 and a polarizing plate 20 are stacked in this order, A resin layer 32 provided on the upper surface of the polarizing plate 20 serving as a viewing side (viewing side) of the liquid crystal display device, and a protection panel 40 provided on the surface thereof. The resin layer 32 is composed of a cured product of the photo-curable resin composition of the present embodiment. The protective panel 40 has a light shielding portion 41 along the outer peripheral edge of the protective panel.

2 is a cross-sectional view schematically showing a liquid crystal display device equipped with a touch panel, which is an embodiment of a liquid crystal display device which is an example of the image display device of the present invention. 2 includes an image display unit 1 in which a backlight system 50, a polarizing plate 22, a liquid crystal display cell 10 and a polarizing plate 20 are laminated in this order, A resin layer 32 provided on the upper surface of the polarizing plate 20 serving as the viewing side of the liquid crystal display device, a touch panel 30 provided on the upper surface of the resin layer 32, A ground layer 31, and a protective panel 40 provided on the surface thereof. The protective panel 40 has a light shielding portion 41 along the outer peripheral edge of the protective panel.

2, the resin layer is disposed between the image display unit 1 and the touch panel 30 and between the touch panel 30 and the protection panel 40 , And the resin layer may be provided on at least one of them. When the touch panel is an on-cell, the touch panel and the liquid crystal display cell are integrated. As a specific example thereof, the liquid crystal display cell 10 of the liquid crystal display device shown in Fig. 1 is replaced with an on-cell.

1 and 2, the cured product of the photo-curing resin composition of the present invention is provided as the resin layer 31 or 32, whereby it is possible to provide a liquid crystal display device which is excellent in impact resistance, has no image overlapping, An image can be obtained.

As the liquid crystal display cell 10, a liquid crystal material known in the art can be used. In addition, it can be classified into TN (Twisted Nematic), STN (super-twisted nematic), VA (Virtical Alignment), IPS (In-Place-Switching) In the invention, a liquid crystal display cell using any control method may be used.

As the polarizers 20 and 22, polarizers common in the art can be used. The surface of these polarizing plates may be subjected to treatment such as reflection prevention, dirt prevention, hard coat and the like. Such a surface treatment may be performed on one surface of the polarizing plate or on both surfaces thereof.

As the touch panel 30, those generally used in the art can be used.

The resin layer 31 or 32 can be formed to have a thickness of 0.02 mm to 3 mm, for example. In particular, the photo-curing resin composition of the present embodiment is effective for formation of a thick film, and is preferable in the case of forming a resin layer 31 or 32 of 0.1 mm or more.

As the protective panel 40, a general optical transparent substrate can be used.

Examples of the optical transparent substrate include inorganic substrates such as a glass plate and a quartz plate, resin substrates such as an acrylic plate and a polycarbonate plate, and resin sheets such as a thick polyester sheet. When a high surface hardness is required, a plate of glass, acrylic or the like is preferable, and a glass plate is more preferable.

The surface of these optical transparent substrates may be subjected to treatment such as reflection prevention, contamination prevention, hard coat, and the like. Such a surface treatment may be performed on one side or both sides of the substrate. Further, a plurality of the substrates may be used in combination.

In addition, for the purpose of improving the contrast of a display image and the like, the protective panel 40 made of these substrates is provided with a frame-shaped shielding portion 41 with a predetermined width along the outer peripheral edge of the protective panel. The light-shielding portion 41 has a function of intercepting unnecessary light in the periphery of the image display panel and preventing deterioration of display quality due to light leakage.

The configuration of the backlight system 50 is not limited, but generally includes a reflecting means such as a reflection plate and a lighting means such as a lamp. As the reflecting means and the illuminating means, well-known means used in a normal image display apparatus can be applied.

[Manufacturing Method of Image Display Device]

A method of manufacturing an image display apparatus according to the present invention is a method of manufacturing an image display apparatus comprising a liquid crystal display device in which an image display unit or a touch panel having an image display portion and a protective panel having a light shielding portion along an outer peripheral edge are arranged to face each other, And curing the liquid photocurable resin composition by curing the liquid photocurable resin composition of the present invention and irradiating at least light from the protective panel side.

For example, in the liquid crystal display device 1A of Fig. 1, the image display unit 1 and the protection panel 40 having the light shielding portion 41 along the outer peripheral edge are arranged opposite to each other, Can be produced by interposing the photo-curing resin composition of the present invention and irradiating light from at least the protective panel side to cure the photo-curable resin composition to form the resin layer (32).

2 includes a protective panel 40 having an image display unit 1, a touch panel 30, and a light shielding portion 41 along the outer peripheral edge thereof. The liquid crystal display device 1B includes the image display unit 1, the touch panel 30, And at least the light-curable resin composition of the present invention is interposed between the touch panel 30 and the protective panel and light is irradiated from at least the protective panel side to cure the photo-curable resin composition to form the resin layer ( 31). The resin composition is cured between the image display unit 1 and the touch panel 30 with the photo-curing resin composition of the present invention interposed therebetween in the same manner as described above to form the resin layer 32 It is possible.

Here, when a conventional liquid crystal display device is manufactured by using the photo-curing resin composition, for example, the light scattered in the space of the back side portion of the light shielding portion 41 corresponding to the portion P in Figs. 1 and 2 Sufficient light does not reach the curable resin composition and curing is interfered with so that the curing of the photocurable resin composition in the vicinity of the light shielding portion does not progress sufficiently and the quality of the image display device is greatly lowered and the reliability is lowered.

By the way, in the method for producing an image display device of the present invention, since the photo-curable resin composition of the present invention having excellent curability is used, when the ultraviolet ray is irradiated, only the light transmitting portion corresponding to the Q portion in Figs. (Part of P) of the light-shielding portion 41, which is not in direct ultraviolet radiation, in the vicinity of the light-transmitting portion (portion of Q). Thus, according to the method for manufacturing an image display apparatus of the present invention, an image display apparatus having excellent quality can be manufactured with good productivity.

As a method of interposing the photo-curable resin composition, a photo-curable resin composition is coated on an image display unit, a touch panel, or a protective panel using a dispenser, and then vacuum (reduced pressure) , Or a method of injecting a photo-curing resin composition into a mold in a space portion arranged at regular intervals. When molding the photo-curable resin composition, a dam may be formed around the image display unit and the protective panel.

The light irradiation is carried out by irradiating ultraviolet rays from the side of the protective panel so as to be substantially perpendicular to the charged photo-curing resin composition, for example, by using an ultraviolet ray irradiation apparatus.

As the amount of exposure in this case is preferably ^{500 mJ / cm 2 ~5000 mJ /} cm 2. The exposure amount refers to a value obtained by multiplying the illuminance, which can be measured with an ultraviolet light illuminometer (product name: UV-M02 (receiving unit: UV-36), manufactured by Orc), with the irradiation time (second). Examples of the ultraviolet light source include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LED lamps. Of these, high-pressure mercury lamps and metal halide lamps are preferable.

At the time of light irradiation, irradiation from the side surface may be used simultaneously with irradiation from the protective panel surface side. The curing may be promoted by a method such as heating the laminate including the photo-curing resin composition at the same time of light irradiation.

As described above, the liquid crystal display device which is one of the image display devices which can be manufactured by using the photo-curable resin composition of the present invention has been described. However, the liquid crystal display device which can be manufactured by using the photo- Is not limited to the liquid crystal display device. For example, a plasma display (PDP), a cathode ray tube (CRT), a field emission display (FED), an organic EL display, a 3D display, an electronic paper and the like.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

First, examples of synthesis of a photo-curing resin composition usable in an image display apparatus to which the present invention is applied will be described below.

In the following synthesis examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured based on the following methods.

[Weight average molecular weight (Mw), number average molecular weight (Mn)] [

Was carried out using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and determined using polystyrene as a standard substance. The GPC conditions are shown below.

Measuring instrument: HLC-8320GPC (product name, manufactured by Tosoh Corporation)

· Analytical column: TSKgel SuperMultipore HZ-H (3 connections) (product name, TOSOH CORPORATION)

· Guard column: TSKguardcolumn SuperMP (HZ) -H (product name, TOSOH Corporation)

Eluent: THF

· Measuring temperature: 25 ℃

[Synthesis Example 1]

(Synthesis of polybutadiene methacrylate)

(Manufactured by Nippon Soda Co., Ltd., trade name: &quot; polybutadiene glycol G-3000 &quot;, &quot; 1,2 &quot;, polybutadiene glycol 978.2 parts by mass of the structural unit / 1,4-structural unit content = 90/10 and the hydroxyl value = 27 mgKOH / g), 0.5 part by mass of p-methoxyphenol as a polymerization inhibitor, , And 0.05 parts by mass of dibutyltin dilaurate (trade name &quot; L101 &quot;, manufactured by Tokyo Fine Chemicals Co., Ltd.). After raising the temperature to 70 캜 while flowing air into the reaction vessel, 2-isocyanate ethyl methacrylate (trade name: CALENSE MOI, manufactured by Showa Denko K.K.) was added thereto while stirring at 70 to 75 캜, 20.3 parts by mass were uniformly added dropwise over 1 hour to carry out the reaction.

After completion of the dropwise addition, when the reaction was carried out for 5 hours, IR (infrared absorption analysis) measurement was carried out. As a result, it was confirmed that the isocyanate had disappeared and the reaction was terminated. Polybutadiene methacrylate having a methacryloyl group at the terminal 7,700). The average value (average functional group number) of the methacryloyl groups per one molecule of the polybutadiene methacrylate was 0.5 (calculated value from input amount).

[Comparative Synthesis Example 1]

(Synthesis of hydrogenated polybutadiene methacrylate)

(Polybutadiene glycol GI-3000, manufactured by Nippon Soda Co., Ltd.), hydroxyl value = 29 mg KOH / g (manufactured by Nippon Soda Co., Ltd.) was placed in a reaction vessel equipped with a stirrer, a thermometer, a stirrer, a dropping funnel and an air- ), 0.5 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 0.05 parts by mass of dibutyltin dilaurate (trade name: "L101", manufactured by Tokyo Fine Chemicals Co., Ltd.) Respectively. Thereafter, 20.3 parts by mass of 2-isocyanate ethyl methacrylate (trade name: "CALENSE MOI", trade name, manufactured by Showa Denko K.K.) was added while stirring the mixture at 70 to 75 ° C, The mixture was uniformly added dropwise over 1 hour, and the reaction was carried out.

After completion of the dropwise addition, when reaction was carried out for 5 hours, IR (infrared absorption analysis) measurement was carried out. As a result, it was confirmed that the isocyanate had disappeared and the reaction was terminated. Hydrogenated polybutadiene methacrylate having a methacryloyl group at the terminal Molecular weight 7,700). The average value (average functional group number) of the methacryloyl groups per molecule of the hydrogenated polybutadiene methacrylate was 0.5 (calculated value from the amount of injection).

[Comparative Synthesis Example 2]

(Synthesis of hydrogenated isoprene methacrylate)

(Product name: "Epol", hydroxyl value = 51 mgKOH / g), which is a hydroxyl end-terminated hydrogen isoprene (manufactured by Idemitsu Kosan Co., Ltd.), was added to a reaction vessel equipped with a stirrer, a condenser, a dropping funnel and an air- 0.5 part by mass of p-methoxyphenol and 0.05 part by mass of dibutyltin dilaurate (trade name: &quot; L101 &quot;, manufactured by Tokyo Fine Chemical Co., Ltd.) as a polymerization inhibitor were added. Thereafter, 20.3 parts by mass of 2-isocyanate ethyl methacrylate (trade name: "CALENSE MOI", trade name, manufactured by Showa Denko K.K.) was added while stirring the mixture at 70 to 75 ° C, The mixture was uniformly added dropwise over 1 hour, and the reaction was carried out.

After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and IR (infrared absorption analysis) measurement was carried out. As a result, it was confirmed that the isocyanate had disappeared and the reaction was terminated. Hydrogenated isoprene methacrylate having a terminal methacryloyl group 7,700). The average value (average number of functional groups) of the methacryloyl group per molecule of the hydrogenated isoprene methacrylate was 0.5 (calculated value from input amount).

[Comparative Synthesis Example 3]

(Synthesis of propylene glycol acrylate [PPGUA]

155 parts by mass of polypropylene glycol (molecular weight: 2,000) and 17.9 parts by mass of 2-hydroxyethyl acrylate were placed in a reaction container equipped with a stirrer, a condenser, a dropping funnel and an air inlet tube, 0.5 part by mass of p-methoxyphenol, and 0.05 part by mass of dibutyltin dilaurate as a catalyst. Then, the mixture was heated to 70 DEG C while flowing air into the reaction vessel, and then 32.4 parts by mass of 2,2,4-trimethylhexamethylene diisocyanate was uniformly added dropwise over 2 hours while stirring at 70 to 75 DEG C, Respectively.

After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours, and IR (infrared absorption analysis) measurement was carried out. As a result, it was confirmed that the isocyanate had disappeared and the reaction was terminated, and polypropylene glycol and trimethylhexamethylene diisocyanate Propylene glycol acrylate [PPGUA] (weight average molecular weight: 7,000) having an ethylenic unsaturated bond was obtained. The average value of the number of ethylenically unsaturated bonds per one molecule of this propylene glycol acrylate was 2.0 (calculated value from the amount of injection).

[Examples 1 to 8 and Comparative Examples 1 to 9]

The components (A) to (D) were blended at the blending ratios shown in Tables 1 and 2, and the mixture was stirred and mixed to prepare the photocurable resin compositions of Examples 1 to 8 and Comparative Examples 1 to 9. In Tables 1 and 2, the unit of numerical values for the components (A) to (D) is the mass part (solid content ratio).

The compounds used as the components in Tables 1 and 2 are as follows.

(A1) Component

&Quot; Synthesis Example 1 &quot;: Polybutadiene methacrylate obtained in Synthesis Example 1.

(A1) &lt; / RTI &gt;

Comparative Synthesis Example 1: Hydrogenated polybutadiene methacrylate obtained in Comparative Synthesis Example 1.

&Quot; UC-102 &quot; manufactured by KURARAY CO., LTD. (N = 2 in the following formula (a), number average molecular weight: 17,000) represented by the following formula (a) and having a methacryloyl group and a constituent unit derived from polyisoprene.

Comparative Synthesis Example 2: Hydrogenated isoprene methacrylate obtained in Comparative Synthesis Example 2.

Comparative Synthesis Example 3: Propylene glycol acrylate obtained in Comparative Synthesis Example 3.

[Chemical Formula 13]

(A2) Component

&Quot; RICON 156 &quot;: trade name, manufactured by CRAY VALLEY CO., LTD. Polybutadiene homopolymer (number average molecular weight 1400).

Component (B)

&Quot; FA-314 A &quot;: trade name, manufactured by Hitachi Chemical Co., Ltd. (Mw: 452) wherein R ¹ is a hydrogen atom, R ² is a nonyl group, and an average value of n is 4 in the above general formula (1).

(B) &lt; / RTI &gt;

&Quot; FA-512 AS &quot;: trade name, manufactured by Hitachi Chemical Co., Ltd. Dicyclopentenyloxyethyl acrylate.

&Quot; FA-318 A &quot;: trade name, manufactured by Hitachi Chemical Co., Ltd. In the above general formula (1), R ¹ is a hydrogen atom, R ² is a nonyl group, and the average value of n is 8.

· "ACMO": acryloylmorpholine.

&Quot; EHA &quot;: 2-ethylhexyl acrylate.

&Quot; LA &quot;: lauryl acrylate.

(C) Component

&Quot; PE1 &quot;: trade name, manufactured by Showa Denko K.K. Pentaerythritol tetrakis (3-mercaptobutyrate) represented by the following formula (c1).

[Chemical Formula 14]

&Quot; BD1 &quot;: trade name, manufactured by Showa Denko K.K. 1,4-bis (3-mercaptobutyryloxy) butane represented by the following formula (c2).

[Chemical Formula 15]

&Quot; NR1 &quot;: trade name, manufactured by Showa Denko K.K. (1H, 3H, 5H) -tri (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 On.

[Chemical Formula 16]

(D) Component

&Quot; TPO &quot;: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (maximum absorption wavelength: 380 nm) manufactured by BASF.

The following tests were performed on the resin compositions obtained in the respective Examples and Comparative Examples and the transparent sheets obtained by curing the resin compositions. The results are shown in Tables 1 and 2.

(Viscosity)

(Manufactured by Toki Kogyo Co., Ltd., product name: &quot; RE-80L &quot;) and a 3 ° cone rotor at 0.5 min -1, the resin composition obtained in each of the Examples and Comparative Examples (MPa &amp;bull; s) was measured.

(Compatibility)

The resin compositions obtained in the respective Examples and Comparative Examples were charged in a glass bottle and visually checked for compatibility and evaluated according to the following criteria.

A: The resin composition is transparent, and the compatibility is good.

F: The resin composition is cloudy, and the compatibility is poor.

(Light transmittance at a wavelength of 440 nm)

The resin composition obtained in each of the Examples and Comparative Examples was dropped onto a PET (polyethylene terephthalate) film (product name: "A4100", 86 mm × 56 mm × 100 μm) One other identical PET film was bonded to each other via a spacer of 175 mu m so that the film thickness after curing of the resin composition became 175 mu m. Then, the resin composition was cured by irradiating ultraviolet rays at 2,000 mJ / cm ² using an ultraviolet ray irradiating device (product name: "ELM-3000B-6N" Respectively.

The PET film was peeled from the obtained three-layer laminate (PET film / cured product / PET film) as a baseline of the transmittance, and the light transmittance of the remaining cured product at a wavelength of 440 nm was measured with a spectrophotometer ( Quot; UV-2400PC &quot; manufactured by Shimadzu Corporation).

Further, the measured value of the light transmittance at 400 nm was evaluated according to the following criteria.

A: The light transmittance at a wavelength of 440 nm is 98% or more, and the light transmittance is good.

F: The light transmittance at a wavelength of 440 nm is less than 98%, and the transmittance is poor.

(Refractive index)

The resin composition obtained in each of the Examples and Comparative Examples was dropped onto a PET (polyethylene terephthalate) film (product name: "A4100", 86 mm × 56 mm × 100 μm) One other identical PET film was bonded to each other via a spacer of 350 mu m so that the film thickness after curing of the resin composition became 350 mu m. Then, the resin composition was cured by irradiating ultraviolet rays at 2,000 mJ / cm ² using an ultraviolet ray irradiating device (product name: "ELM-3000B-6N" Respectively.

The PET film was peeled off from the obtained three-layer laminate (PET film / cured product / PET film), and the refractive index of the remaining cured product at 25 ° C and wavelength 589 nm was measured with an ABBE refractive index meter (product name: -M2 &quot;).

(Dielectric constant at a frequency of 1 MHz)

A circular frame of silicone rubber having a diameter of 50 mm and a film thickness of 2 mm was mounted on a release PET film and the resin composition obtained in each of the Examples and Comparative Examples was filled therein, A PET film was placed on the substrate, and ultraviolet rays were irradiated at 1 J / cm ² using an ultraviolet irradiator (product name: "ELM-3000B-6N", manufactured by Orc) to cure the resin composition to prepare a transparent film Respectively. The dielectric constant at a frequency of 1 MHz of the transparent film was measured using a dedicated electrode for dielectric measurement "HP16451B" and "HP4275A" (product name: Precision LCR meter manufactured by HEWLETT PACKARD).

(Light shielding hardening width)

The resin composition obtained in each of the Examples and Comparative Examples was dropped onto a glass substrate having a width of 16 cm and a length of 16 cm and a spacer having a thickness of 175 탆 and a spacer having a thickness of 175 탆 was interposed therebetween. The glass substrate was bonded. Then, the test piece (cured product) was cured by irradiating ultraviolet rays at 2,000 mJ / cm ² from one glass substrate side using an ultraviolet ray irradiation apparatus (product name: "ELM-3000B-6N" Respectively. At this time, on one side of the glass substrate on the ultraviolet ray irradiation side, a light shielding portion of 8 cm x 16 cm was formed of black ceramics having a light transmittance of 0% at a wavelength of 200 to 800 nm and provided on the surface of the resin composition side .

Thereafter, one glass of the test piece was peeled off, and the width of the completely shielded portion of the resin composition in the light shielding portion was measured by a nog- nizer, and this value was defined as the curing width of the light shielding portion. The larger the above value, the better the curing property in the light-shielding portion.

[Table 1]

[Table 2]

From Table 1, it can be seen that the photocurable resin compositions of Examples 1 to 8 have appropriate viscosity, good compatibility, a curing width of the light shielding portion of 40 mm or more, and excellent curing property at the light shielding portion. In addition, both of the light transmittance, the refractive index, and the dielectric constant of the cured product of the resin composition were satisfactory.

On the other hand, from Table 2, the photocurable resin compositions of Comparative Examples 1 to 4 and 6 to 9 could not sufficiently cure in the light shielding portion. In addition, the photo-curable resin compositions of Comparative Examples 5 to 9 had poor compatibility and also resulted in poor light transmittance of the cured product obtained from the resin composition.

[Industrial applicability]

The photo-curable resin composition of the present invention is excellent in curability in a light-shielding portion, has an appropriate viscosity, and is excellent in compatibility. Accordingly, the photo-curable resin composition of the present invention is preferably applied as a material for filling a space portion between a protective panel having a light shielding portion along an outer peripheral edge and an image display unit or the like in an image display apparatus .

1A, 1B: Device for liquid crystal display
1: image display unit
10: LCD display cell
20, 22: Polarizer
30: Touch panel
31, 32: resin layer
40: Protection panel
41:
50: Backlight system

Claims (14)

(A) a compound having a structural unit derived from polybutadiene;
(B) a compound represented by the following general formula (1);
(C) a thiol compound having a group represented by the following general formula (II); And
(D) a photopolymerization initiator
&Lt; / RTI &gt;
A photocurable resin composition comprising, as the component (A), a compound having (A1) a (meth) acryloyl group and a structural unit derived from polybutadiene:
[Chemical Formula 1]

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n represents a number of 1 to 7)
(2)

(R ³ and R ⁴ in the general formula (II) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, q represents an integer of 0 to 3, and * represents a bonding moiety). The method according to claim 1,
Wherein the component (C) is a thiol compound represented by the following general formula (2):
(3)

(Wherein R ³ and R ⁴ in the general formula (2) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 6, q represents an integer of 0 to 3 , And A represents an organic group of p). 3. The method according to claim 1 or 2,
In the general formula (1), R ² is an alkyl group having 4 to 12 carbon atoms. 4. The method according to any one of claims 1 to 3,
Wherein the photocurable resin composition contains substantially no organic solvent and has a viscosity at 25 DEG C of 500 to 5000 mPa.s. 5. The method according to any one of claims 1 to 4,
Wherein the content of the component (C) is 3 to 30 mass% with respect to the total amount of the components (A) to (C). 6. The method according to any one of claims 1 to 5,
Wherein the content of the component (A1) is 25 to 100 mass% with respect to the total amount of the component (A). 7. The method according to any one of claims 1 to 6,
The photocurable resin composition according to the above (1), further comprising as the component (A), a compound having a structural unit derived from polybutadiene and having no (A2) (meth) acryloyl group. 8. The method of claim 7,
Wherein the mass ratio [(A1) / (A2)] of the component (A1) and the component (A2) is 25/75 to 95/5. 9. The method according to any one of claims 2 to 8,
Wherein A in the general formula (2) is a group represented by the following formula (C-1) or the following formula (C-2) or an alkylene group having 1 to 12 carbon atoms:
[Chemical Formula 4]

(In the formula (C-1) or the formula (C-2), * represents a linking moiety and X ^{1 to} X ⁷ each independently represent a single bond or a group of 1 to 12 carbon atoms Alkylene group. 10. The method according to any one of claims 1 to 9,
Wherein the content of the component (B) is 1 to 40% by mass based on the total amount of the components (A) to (C). 11. The method according to any one of claims 1 to 10,
Wherein the content of the component (A) is 50 to 98 mass% with respect to the total amount of the components (A) to (C). An image display unit having an image display unit;
A protective panel having a light shielding portion along an outer peripheral edge; And
A protective layer provided between the image display unit and the protection panel,
And an image display device having a stacked structure including a plurality of pixels,
Wherein the resin layer is a cured product of the photo-curable resin composition according to any one of claims 1 to 11. An image display unit having an image display unit;
Touch panel;
A protective panel having a light shielding portion along an outer peripheral edge; And
A protective layer disposed between the touch panel and the protective panel,
And an image display device having a stacked structure including a plurality of pixels,
Wherein the resin layer is a cured product of the photo-curable resin composition according to any one of claims 1 to 11. An image display unit or a touch panel having an image display portion and a protective panel having a light shielding portion along the outer peripheral edge are arranged to face each other and a photo-curing resin composition is interposed between these portions to cure the photo- A method for manufacturing an image display apparatus,
11. A method for manufacturing an image display apparatus, comprising the steps of: (a) providing a photocurable resin composition according to any one of claims 1 to 11 on the gap;

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