KR102305152B1 - A photocurable resin composition, an image display apparatus, and its manufacturing method - Google Patents

Abstract

A radical polymerizable group-containing compound, a cationically polymerizable group-containing compound, an optical radical initiator, and a photo acid generator are included, wherein the content of the radical polymerizable group-containing compound is higher than the content of the cationically polymerizable group-containing compound, and the light The radical initiator is at least any one of an α-hydroxyalkylphenone-based photoradical initiator and a benzylmethylketal-based photoradical initiator, and the mass ratio of the photoradical initiator and the photoacid generator (radical photoinitiator/photoacid generator) 2) is a photocurable resin composition of 0.5-30.

Description

A photocurable resin composition, an image display apparatus, and its manufacturing method

The present invention relates to a photocurable resin composition, an image display device, and a manufacturing method thereof.

In recent years, in image display devices that are various electronic devices such as televisions, notebook PCs, tablet PCs, car navigation systems, electronic calculators, mobile phones, smartphones, electronic notebooks, and personal digital assistants (PDA), for example, liquid crystal displays (LCDs) ), an organic EL display (OLED), an electroluminescent display (ELD), a field emission display (FED), and a display element such as a plasma display (PDP) are used.

The said image display apparatus WHEREIN: In order to protect the said display element, bonding light-transmitting cover members, such as plate glass, to the said display element is performed, and a photocurable resin composition is used for bonding.

Here, as a general photocurable resin composition, the composition containing a radically polymerizable component and an optical radical initiator is known (for example, refer patent documents 1-2). Moreover, the composition containing a radically polymerizable component, a cationically polymerizable component, an optical radical initiator, and a photoacid generator is also proposed (for example, refer patent document 3).

Incidentally, a light-shielding layer is provided on the periphery of the surface of the light-transmitting cover member on the side of the image display section to improve the brightness, contrast, designability, and the like of the displayed image. Since light does not directly hit the photocurable resin composition sandwiched between such a light-shielding layer and an image display member at the time of hardening, hardening does not advance fully. Therefore, the problem that the component which is not hardened|cured enough seeps out (bleed-out) arises.

Therefore, a thermal polymerization initiator is blended with the photocurable resin composition to obtain a heat and photocurable resin composition, the heat and photocurable resin composition is applied to the surface of the light-transmissive cover member on which the light-shielding layer is formed, and the coated surface is displayed as an image After overlapping a member and photocuring by irradiating an ultraviolet-ray, it is proposed to thermoset the heat and photocurable resin composition pinched|interposed between a light shielding layer and an image display member by heating the whole (for example, refer patent document 4).

However, in this proposed technique, since it contains a thermal polymerization initiator, there exists a problem that the equipment for a thermal polymerization process is required, and storage stability falls.

Therefore, providing a photocurable resin composition that does not require a thermal polymerization process and can prevent bleed-out of the cured product by improving the curability of the region that is sandwiched between the light-shielding layer and the image display member and does not directly hit with light What is required is the present situation.

Japanese Patent Laid-Open No. 2015-34240 Japanese Patent Laid-Open No. 2000-67677 Japanese Patent Laid-Open No. 2000-336127 International Publication No. 2008/126860 pamphlet

An object of the present invention is to solve the above-mentioned various problems in the prior art and to achieve the following objects. That is, the present invention provides a photo-curable resin composition capable of preventing bleed-out of a cured product by improving curability in a region not directly exposed to light, an image display device using the photo-curable resin composition, and a photo-curable resin composition using the photo-curable resin composition An object of the present invention is to provide a method for manufacturing an image display device.

As a means for solving the said subject, it is as follows. in other words,

<1> A radical polymerizable group-containing compound, a cationically polymerizable group-containing compound, a radical photoinitiator, and a photoacid generator are contained;

Content of the said radically polymerizable group containing compound is more than content of the said cationically polymerizable group containing compound,

The optical radical initiator is at least any one of an α-hydroxyalkylphenone-based radical optical initiator and a benzylmethyl ketal-based radical optical initiator;

Mass ratio (optical radical initiator/photoacid generator) of the said radical photoinitiator and the said photoacid generator is 0.5-30, It is a photocurable resin composition characterized by the above-mentioned.

<2> The said cationically polymerizable group containing compound is the photocurable resin composition as described in said <1> which has a radically polymerizable group.

<3> The photocurable resin composition according to any one of <1> or <2>, wherein the cationically polymerizable group in the cationically polymerizable group-containing compound is at least any one of an alkoxysilyl group and an epoxy group.

<4> content of the said photo acid generator is 0.01 mass % or more,

It is the photocurable resin composition in any one of said <1>-<3> whose sum (optical radical initiator + photoacid generator) of content of the said radical photoinitiator and content of the said photoacid generator is 1.5 mass % or less. .

<5> It is the photocurable resin composition in any one of said <1>-<4> which further contains a plasticizer.

<6> It is an image display apparatus characterized by having the hardened|cured material of the photocurable resin composition in any one of said <1>-<5>.

<7> an image display member and a light-transmitting cover member;

The image display device according to <6>, wherein the image display member and the light transmissive cover member are adhered with the cured product therebetween.

<8> the light-transmitting cover member has a light-shielding layer on its periphery,

In the light-transmitting cover member, the image display device according to <7>, wherein the surface having the light-shielding layer faces the image display member.

<9> Application step of applying the photocurable resin composition according to any one of <1> to <5> above to the surface of the light-transmitting cover member having the light-shielding layer in the peripheral portion, on the side having the light-shielding layer, to obtain an application layer class,

a provisional curing step of irradiating the application layer with light from a side opposite to the light-transmitting cover member side, and temporarily curing the application layer to obtain a provisionally cured layer;

a bonding step of bonding the temporary cured layer and the image display member;

and a main curing step of irradiating light to the temporary curing layer from the light-transmitting cover member side to cause the temporary curing layer to be cured, and to obtain the main cured layer.

ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition which can solve the said various problems in the prior art, can achieve the said objective, improve curability in the area|region which light does not directly hit, and can prevent the bleed-out of hardened|cured material , the image display device using the said photocurable resin composition, and the manufacturing method of the image display device using the said photocurable resin composition can be provided.

Fig. 1(a) is a schematic cross-sectional view for explaining an example of a method for manufacturing an image display device of the present invention (first).
Fig. 1(b) is a schematic cross-sectional view for explaining an example of a method for manufacturing an image display device of the present invention (second).
Fig. 1C is a schematic cross-sectional view for explaining an example of a method for manufacturing an image display device of the present invention (third).
Fig. 1(d) is a schematic cross-sectional view for explaining an example of a method for manufacturing an image display device of the present invention (fourth).
Fig. 1(e) is a schematic cross-sectional view for explaining an example of a method for manufacturing an image display device of the present invention (fifth).
Fig. 2(a) is a schematic cross-sectional view for explaining a method for manufacturing a simulation panel in an Example (first).
Fig. 2(b) is a schematic cross-sectional view for explaining the manufacturing method of the simulation panel in the Example (second).
FIG.2(c) is a cross-sectional schematic diagram for demonstrating the manufacturing method of the simulation panel in an Example (3rd).
FIG.2(d) is a cross-sectional schematic diagram for demonstrating the manufacturing method of the simulation panel in an Example (fourth).
Fig. 2(e) is a schematic cross-sectional view for explaining the manufacturing method of the simulation panel in the Example (fifth).

(Photocurable resin composition)

The photocurable resin composition of this invention contains a radically polymerizable group containing compound, a cationically polymerizable group containing compound, an optical radical initiator, and a photoacid generator, and contains other components further as needed.

The optical radical initiator is at least any one of an α-hydroxyalkylphenone-based optical radical initiator and a benzylmethyl ketal-based optical radical initiator.

The said photocurable resin composition WHEREIN: There is more content of the said radically polymerizable group containing compound than content of the said cationically polymerizable group containing compound.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to provide the photocurable resin composition which can improve sclerosis|hardenability of the area|region which light does not directly hit, and can prevent the bleed-out of hardened|cured material. As a result, in the photo-curing system in which the cationic curing system is used in combination with the radical curing system, at least any one of an α-hydroxyalkylphenone-based optical radical initiator and a benzylmethyl ketal-based optical radical initiator is used as the optical radical initiator, By using a photoacid generator as a hardening|curing agent of a cationic curing system, sclerosis|hardenability of the area|region which light does not directly hit can be made favorable, and it discovered that the bleed-out of hardened|cured material could be prevented, and it led to the completion of this invention.

Here, the estimation mechanism in which the present inventor thinks that the effect of this invention is acquired is demonstrated using the following scheme 1. The following examples are examples in which an α-hydroxyalkylphenone-based optical radical initiator is used as the radical photoinitiator, and an onium salt is used as the photoacid generator.

When light is irradiated to the photocurable resin composition, the α-hydroxyalkylphenone-based photoradical initiator preferentially absorbs light, and the carbon-carbon bond between the carbonyl group and the hydroxyl group causes cleavage (α cleavage), thereby generating a radical. A part of the generated radicals (A) transfer electrons to the photoacid generator, and the radicals (A) become cations (B). The cation (B) translocates to the nonionic structure (C), which is a more stable structure. At this time, protons (H +) are generated.

The generation of protons has a time lag from light irradiation. In addition, protons are stable compared to radicals, and protons can diffuse in the system. Therefore, hardening continues even after light irradiation of a photocurable resin composition, and also enables hardening in the area|region which light does not directly reach. In addition, as for hardening after light irradiation, it is thought that cationic hardening is dominant.

Moreover, the benzylmethyl ketal-type radical photo-radical initiator is common in that the α-carbon adjacent to the carbonyl group does not have a hydroxyl group, but the bond adjacent to the carbonyl group undergoes α-cleavage. Therefore, when a benzyl methyl ketal-type radical photoinitiator is used, although the point of α cleavage is the same, it is thought that protons are generated by a mechanism different from that of Scheme 1 after electrons are transferred to the photoacid generator. .

<Radically polymerizable group-containing compound>

There is no restriction|limiting in particular as said radically polymerizable group containing compound (radical polymerization component), if it is a compound which has a radically polymerizable group, According to the objective, it can select suitably.

As said radically polymerizable group, a (meth)acryloyloxy group is mentioned, for example.

Here, the (meth)acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.

The number of radically polymerizable groups which the said radically polymerizable group containing compound has may be one, and two or more may be sufficient as it.

Examples of the radical polymerizable group-containing compound include an ester compound obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, an epoxy (meth)acrylate obtained by reacting (meth)acrylic acid with an epoxy compound, and a hydroxyl group in isocyanate The urethane (meth)acrylate etc. which are obtained by making the (meth)acrylic acid derivative which have been reacted are mentioned.

Here, (meth)acryl means acryl or methacryl, and (meth)acrylate means an acrylate or methacrylate.

As said radically polymerizable group containing compound which has one radically polymerizable group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, for example , 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylic Rate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene Glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate , 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl ( Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylic rate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropylphthalate, 2-(meth)acrylo yloxyethyl phosphate etc. are mentioned.

Examples of the radical polymerizable group-containing compound having two radical polymerizable groups include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanedioldi( Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) ) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylic rate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide Addition bisphenol F di (meth) acrylate, dimethyloldicyclopentadienyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified isocyanuric acid di (meth) acrylate, 2-hydr Roxy-3-(meth)acryloyloxypropyl (meth)acrylate, carbonatediol di(meth)acrylate, polyetherdiol di(meth)acrylate, polyesterdiol di(meth)acrylate, poly Caprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc. are mentioned.

As said radically polymerizable group containing compound which has 3 or more radically polymerizable groups, For example, pentaerythritol tri(meth)acrylate, trimethylol propane tri(meth)acrylate, propylene oxide addition trimethylol propane tri(meth) Acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tri(meth)acrylate, dipentaerythritol penta (meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide addition Glycerin tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, etc. are mentioned.

What is called an oligomer may be sufficient as the said radically polymerizable group containing compound.

As said oligomer, a (meth)acrylate oligomer is mentioned, for example.

As said (meth)acrylate oligomer, a polyurethane (meth)acrylate oligomer, polyisoprene (meth)acrylate oligomer, polybutadiene (meth)acrylate oligomer, polyether (meth)acrylate oligomer etc. are mentioned, for example. can Moreover, what provided the radically polymerizable group to the following acrylic polymers may be sufficient.

Acrylic polymer: a copolymer of butyl acrylate, 2-hexyl acrylate and acrylic acid, or a copolymer of cyclohexyl acrylate and methacrylic acid

The polyurethane (meth)acrylate oligomer is a polyurethane-based (meth)acrylate oligomer having a polyurethane skeleton in the main chain. As specific examples, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, UV-3700B, UV-6640B, UV-8630B manufactured by Nippon Kosei Chemical Co., Ltd. UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7630B, UV-7640B, UV- 7650B, UT-5449, UT-5454, etc. are mentioned.

The polyisoprene (meth)acrylate oligomer is a polyisoprene-based (meth)acrylate oligomer having a polyisoprene skeleton in the main chain. As a specific example, the ester product of the addition product of maleic anhydride of a polyisoprene polymer and 2-hydroxyethyl methacrylate [UC102 (polystyrene conversion molecular weight 17000), Kuraray Co., Ltd.; UC203 (polystyrene conversion molecular weight 35000), Kuraray Co., Ltd.] etc. are mentioned.

The polybutadiene (meth)acrylate oligomer is a polybutadiene-based (meth)acrylate oligomer having a polybutadiene skeleton or a hydrogenated polybutadiene skeleton in the main chain. As a specific example, the ester of a polybutadiene polymer and 2-hydroxyethyl methacrylate [EMA-3000 (molecular weight 3700), Nippon Soda Co., Ltd.] etc. are mentioned.

The said polyether (meth)acrylate oligomer is a polyether type (meth)acrylate oligomer which has polyether skeletons, such as polyethyleneglycol and polypropylene glycol, in a main chain. Specific examples include terminal acrylic modified polyether [UN-6202 (molecular weight 6500), Negami Kogyo Co., Ltd.; EBECRYL 230 (molecular weight 5000), Daicel Allnex Co., Ltd.] etc. are mentioned.

There is no restriction|limiting in particular as a weight average molecular weight of the said oligomer, Although it can select suitably according to the objective, 1,000-100,000 are preferable, 2,000-80,000 are more preferable, 5,000-50,000 are especially preferable. The said weight average molecular weight is measured by GPC (gel permeation chromatography), for example.

There is no restriction|limiting in particular as content of the said radically polymerizable group containing compound in the said photocurable resin composition, Although it can select suitably according to the objective, 20 mass % - 80 mass % are preferable, 30 mass % - 70 mass % More preferably, 40 mass % - 60 mass % are especially preferable. In addition, when the said photocurable resin composition contains a volatile matter (for example, organic solvent), content in this specification is content with respect to the non-volatile matter of the said photocurable resin composition.

The numerical range shown using "to" in this specification represents the range which includes the numerical value described before and after "to" as a minimum value and a maximum value, respectively. That is, 20 mass % - 80 mass % means 20 mass % or more and 80 mass % or less.

The said radically polymerizable group containing compound may use together the said oligomer and the monomer of lower molecular weight than the said oligomer. As molecular weight of the said monomer, less than 1,000 is preferable and 500 or less are more preferable, for example.

When the said radically polymerizable group containing compound contains the said oligomer and the said monomer, there is no restriction|limiting in particular as content of the said oligomer in the said photocurable resin composition, Although it can select suitably according to the objective, 20 mass % - 70 mass % is preferable, and 30 mass % - 60 mass % are more preferable.

When the said radically polymerizable group containing compound contains the said oligomer and the said monomer, there is no restriction|limiting in particular as content of the said monomer in the said photocurable resin composition, Although it can select suitably according to the objective, 1 mass % - 20 mass % is preferable, and 3 mass % - 15 mass % are more preferable.

<Cationically polymerizable group-containing compound>

The cationically polymerizable group-containing compound (cationically polymerizable component) is not particularly limited as long as it has a functional group (cationically polymerizable group) that reacts with protons or carbocations derived from Bronsted acid or generated by the action of Lewis acid (cationically polymerizable group). can be appropriately selected according to

Examples of the cationically polymerizable group include an alkoxysilyl group, an epoxy group, a vinyl ether group, and an oxetanyl group. Among these, an alkoxysilyl group and an epoxy group are preferable.

There is no restriction|limiting in particular as said alkoxysilyl group, Although it can select suitably according to the objective, Group represented by the following general formula (1) is preferable.

However, in general formula (1), R<^1> represents any of a C1-C3 alkyl group and a C1-C3 alkoxy group. R ² and R ³ each independently represent an alkyl group having 1 to 3 carbon atoms.

As said alkoxysilyl group, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group, and a diethoxymethylsilyl group are preferable at the point excellent in cationic polymerizability.

An alicyclic epoxy group may be sufficient as the said epoxy group, and a non-alicyclic epoxy group may be sufficient as it. Examples of the epoxy group include groups represented by the following general formula (2) and the following general formula (3).

However, in general formula (2), R<^4> represents any of a hydrogen atom and a methyl group.

The cationically polymerizable group-containing compound preferably further has a radical polymerizable group from the viewpoint of improving the compatibility of the raw materials in the photocurable resin composition and preventing phase separation of the cured product of the photocurable resin composition. do.

In addition, in this invention, the said cationically polymerizable group containing compound which has a radically polymerizable group shall not belong to the said radically polymerizable group containing compound, but shall belong to the said cationically polymerizable group containing compound.

There is no restriction|limiting in particular as said cationically polymerizable group containing compound which has the said radically polymerizable group, According to the objective, it can select suitably, For example, the compound etc. which are represented by the following general formula (2) are mentioned.

However, in the general formula (4), R represents either a hydrogen atom or a methyl group, X represents a cationically polymerizable group, and Y represents a divalent linking group.

As said X, group represented by the said General formula (1), group represented by the said General formula (2), group represented by the said General formula (3), etc. are mentioned, for example.

As said Y, an alkylene group, an alkylene oxyalkylene group, etc. are mentioned, for example. Examples of the alkylene group include a C _{1 to 6} alkylene group. Examples of the alkyleneoxy alkyl group, for example, and the like _1~ C ₆ alkyleneoxy C _{1 ~ 6} alkyl group. Here, C _1~6 shows a carbon number of 1 to 6.

There is no restriction|limiting in particular as content of the said cationically polymerizable containing compound in the said photocurable resin composition, Although it can select suitably according to the objective, 0.5 mass % - 30 mass % are preferable, 1 mass % - 20 mass % More preferably, 2 mass % - 15 mass % are especially preferable.

<Photoradical Initiator>

The optical radical initiator is at least any one of an α-hydroxyalkylphenone-based optical radical initiator and a benzylmethyl ketal-based optical radical initiator.

Examples of the α-hydroxyalkylphenone-based photoradical initiator include 1-hydroxycyclohexylphenylketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1- One, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-( 2-hydroxy-2-methyl propionyl)-benzyl]phenyl}-2-methyl-1-one, oligo[2-hydroxy-2-methyl-[1-(methylvinyl)phenyl]propanone], etc. can be heard

As said (alpha)-hydroxyalkylphenone type|system|group optical radical initiator, what was synthesize|combined suitably may be used and a commercial item may be used. As said commercial item, Irgacure 184 (1-hydroxycyclohexylphenyl ketone, BASF company make), Irgacure 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one, BASF company make), Irgacure Gacure 2959 (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, manufactured by BASF), Irgacure 127 (2-hydroxyl) Roxy-1-{4-[4-(2-hydroxy-2-methyl propionyl)-benzyl]phenyl}-2-methyl-1-one manufactured by BASF), Esacureone (oligo[2-hydroxy-2) -methyl-[1-(methylvinyl)phenyl]propanone], the Lamberti company make) etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.

As said benzylmethyl ketal type radical photo-radical initiator, 2,2-dimethoxy-1,2-diphenylethan-1-one etc. are mentioned, for example.

As said benzyl methyl ketal-type radical photo-radical initiator, what was synthesize|combined suitably may be used and a commercial item may be used. Irgacure 651 (2,2-dimethoxy-1,2-diphenylethan-1-one, BASF Corporation make) etc. are mentioned as said commercial item, for example.

There is no restriction|limiting in particular as content of the said radical photoinitiator in the said photocurable resin composition, Although it can select suitably according to the objective, 0.1 mass % or more is preferable, 0.1 mass % - 2.0 mass % are more preferable, 0.2 Mass % - 1.0 mass % are especially preferable.

<Light acid generator>

There is no restriction|limiting in particular as long as it is a compound which absorbs light and generate|occur|produces an acid as said photoacid generator, Although it can select suitably according to the objective, Onium salt is preferable.

As said onium salt, a diazonium salt, an iodonium salt, a sulfonium salt etc. are mentioned, for example. These may be used individually by 1 type, and may use 2 or more types together. Among these, an iodonium salt and a sulfonium salt are preferable from a stability viewpoint.

Examples of the diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

Examples of the iodonium salt include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4- Nonylphenyl)iodonium hexafluorophosphate, di(4-t-butylphenyl)iodonium hexafluorophosphate, di(4-t-butylphenyl)iodonium hexafluoroantimonate, trilcumylio Donium tetrakis(pentafluorophenyl)borate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, etc. are mentioned.

Examples of the sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and diphenyl[4-(phenylthio). )phenyl]sulfonium hexafluoroantimonate, 4,4'-bis[diphenylsulfonio]diphenylsulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy) )phenylsulfonio]diphenylsulfide bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluorophosphate, 7 -[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone Tetrakis(pentafluorophenyl)borate, 4-phenyl carbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'- Diphenylsulfonio-diphenylsulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)sulfonio-diphenylsulfidetetrakis (pentafluorophenyl) borate, the phosphate of diphenyl [4- (phenylthio) phenyl] sulfonium, etc. are mentioned.

As said photoacid generator, what was synthesize|combined suitably may be used and a commercial item may be used. As said commercial item, For example, CPI-100P, 101A, 200K, 210S (triaryl sulfonium salt, San-Apro Co., Ltd. make), Kayarad (trademark) PCI-220, PCI-620 (Nippon Kayaku Co., Ltd.) ), UVI-6990, UVI-6992 (manufactured by Union Carbide), ADEKA OPTOMER SP-150, SP-170 (made by ADEKA Corporation), CI-5102 (made by Nippon Soda Corporation), CIT- 1370, 1682, (manufactured by Nippon Soda Co., Ltd.), CIP-1866S, 2048S, 2064S, (manufactured by Nippon Soda Co., Ltd.), DPI-101, 102, 103, 105 (manufactured by Midori Chemical Co., Ltd.), MPI -103, 105 (Midori Chemical Co., Ltd.), BBI-101, 102, 103, 105, 109, 201 (Midori Chemical Co., Ltd.), TPS-101, 102, 103, 105 (Midori Chemical) Co., Ltd.), MDS-103, 105 (Midori Chemical Co., Ltd.), DTS-102, 103, 2000 (Midori Chemical Co., Ltd.), PI-2074 (Rodia Japan Co., Ltd.), WPI-113, 116 (manufactured by Wako Pure Chemical Industries, Ltd.), Irgacure 250 (manufactured by BASF), and the like.

There is no restriction|limiting in particular as content of the said photo acid generator in the said photocurable resin composition, Although it can select suitably according to the objective, 0.01 mass % or more is preferable, 0.01 mass % - 2.0 mass % are more preferable, 0.01 mass % - 1.0 mass % are especially preferable.

The mass ratio (optical radical initiator/photoacid generator) of the said radical photoinitiator and the said photoacid generator is 0.5-30, and 1.0-20 are preferable. If the said mass ratio is less than 0.5, bleed will generate|occur|produce, and even if it exceeds 30, bleed will generate|occur|produce.

There is no restriction|limiting in particular as a sum (optical radical initiator + photoacid generator) of content of the said radical photoinitiator, and content of the said photoacid generator, Although it can select suitably according to the objective, The said radical photoinitiator and the said photoacid generator When there is too much content of a generator, since there exists a possibility that the discoloration of hardened|cured material may arise, 4.0 mass % or less is preferable, 2.5 mass % or less is more preferable, and 1.5 mass % or less is especially preferable.

<Other ingredients>

There is no restriction|limiting in particular as said other component unless the effect of this invention is impaired, According to the objective, it can select suitably, For example, other radical photoinitiators, a plasticizer, a tackifier, a sensitizer, etc. are mentioned. have.

<<Other radical photoinitiators>>

As said other radical optical initiator, an acylphosphine oxide-type radical optical polymerization initiator, an oxime ester-type radical optical polymerization initiator, etc. are mentioned, for example.

Examples of the acylphosphine oxide-based radical photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: lucirin TPO, lucirin is a registered trademark of BASF), bis(2,4, 6-trimethylbenzoyl)-phenylphosphine oxide (trade name: Irgacure 819), etc. are mentioned.

As said oxime ester type radical photopolymerization initiator, (2E)-2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (brand name Irgacure OXE-01), for example ) and the like.

There is no restriction|limiting in particular as content of the said other radical photoinitiator in the said photocurable resin composition, Although it can select suitably according to the objective, 0.1 mass % or more is preferable, 0.1 mass % - 2.0 mass % are more preferable, , 0.2 mass % - 1.0 mass % are especially preferable.

<<Plasticizer>>

There is no restriction|limiting in particular as said plasticizer, According to the objective, it can select suitably, For example, as a plasticizer component, it does not have a radically polymerizable group and a cationically polymerizable group in a molecule|numerator, and is irradiated with ultraviolet rays and does not radically polymerize and cationic polymerization is known. plasticizers may be used. For example, phthalate ester plasticizer, phosphate ester plasticizer, adipic acid ester plasticizer, trimellitic acid ester plasticizer, polyester plasticizer, epoxy plasticizer, sebacate ester plasticizer, azelaic acid ester plasticizer, citric acid and ester plasticizers, glycolic acid plasticizers, ricinoleic acid plasticizers, maleic acid ester plasticizers, fumaric acid ester plasticizers, pyromellitic acid ester plasticizers, itaconic acid ester plasticizers, and cyclohexanedicarboxylate plasticizers. .

The said plasticizer provides flexibility to the hardened|cured material after hardening, and reduces the cure shrinkage rate.

There is no restriction|limiting in particular as content of the said plasticizer in the said photocurable resin composition, Although it can select suitably according to the objective, 10 mass % - 50 mass % are preferable, and 20 mass % - 40 mass % are more preferable.

<<Tackifier>>

There is no restriction|limiting in particular as said tackifier, According to the objective, it can select suitably, For example, a terpene type resin (For example, a terpene resin, a terpene phenol resin, hydrogenated terpene resin, etc.), a rosin resin (for example, , natural rosin, polymerized rosin, rosin ester, hydrogenated rosin, etc.), and petroleum resins (eg, polybutadiene, polyisoprene, etc.).

Moreover, the material which polymerized the photo-radically polymerizable (meth)acrylate beforehand may be sufficient as the said tackifier. Examples of the polymerized material include a copolymer of butyl acrylate, 2-hexyl acrylate, and acrylic acid, a copolymer of cyclohexyl acrylate and methacrylic acid, and the like.

The said tackifier provides adhesiveness to hardened|cured material, and raises adhesive strength.

There is no restriction|limiting in particular as content of the said tackifier in the said photocurable resin composition, Although it can select suitably according to the objective, 10 mass % - 50 mass % are preferable, and 20 mass % - 40 mass % are more preferable. do.

<<sensitizer>>

There is no restriction|limiting in particular as said sensitizer, According to the objective, it can select suitably, The sensitizer which sensitizes the said radical photoinitiator may be sufficient, and the sensitizer which sensitizes the said photoacid generator may be sufficient.

As said sensitizer, a benzophenone type sensitizer, an anthracene type sensitizer, a thioxanthone type sensitizer, a carbazole type sensitizer etc. are mentioned, for example.

(image display device)

The image display apparatus of this invention has at least the hardened|cured material of the said photocurable resin composition of this invention, Preferably it has an image display member and a light transmissive cover member, and further has another member as needed.

The image display member and the light transmissive cover member are adhered with the cured product of the photocurable resin composition interposed therebetween.

<No image display>

Examples of the image display member include a liquid crystal display (LCD) panel, an organic EL display (OLED) panel, an electroluminescence display (ELD) panel, a field emission display (FED) panel, and a plasma display (PDP) panel. have.

<Light-transmitting cover member>

The light-transmitting cover member should just have light transmittance which makes the image formed on the image display member visible, and as the material, glass, acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, etc. can be heard

As a shape of the said light transmissive cover member, plate shape etc. are mentioned, for example.

The light-transmitting cover member may be subjected to a single or double-sided hard coating treatment, an antireflection treatment, or the like.

Physical properties such as average thickness and elasticity of the light-transmitting cover member may be appropriately determined according to the purpose of use.

The light-transmitting cover member has a light-shielding layer on its periphery. The light-shielding layer is provided, for example, to improve luminance, contrast, designability, and the like of a display image. In this case, in the light-transmitting cover member, the surface having the light-shielding layer faces the image display member.

The light-shielding layer can be produced, for example, by applying black ink to a predetermined area on the light-transmitting cover member and drying it.

Examples of the image display device include a television, a notebook PC, a tablet personal computer, a car navigation system, an electronic calculator, a mobile phone, a smart phone, an electronic notebook, and a PDA (Personal Digital Assistant).

(Manufacturing method of image display device)

The manufacturing method of the image display apparatus of this invention contains at least an application|coating process, a provisional hardening process, a bonding process, and a main hardening process, Furthermore, other processes are included as needed.

<Applying process>

The application step is not particularly limited as long as it is an application step of applying the light-curable resin composition of the present invention to the surface of the light-transmitting cover member having the light-shielding layer on the periphery and obtaining the coating layer on the side having the light-shielding layer. , can be appropriately selected according to the purpose.

The said photocurable resin composition used for the said application|coating process is liquid, for example.

As said light transmissive cover member, the said light transmissive cover member etc. which were illustrated in description of the said image display device of this invention are mentioned, for example.

The said application|coating process WHEREIN: It is preferable that the said photocurable resin composition is apply|coated also on the said light-shielding layer. In this case, it may apply|coat to the whole surface of the surface of the said light shielding layer, and you may apply|coat to a part.

In the application step, it is preferable to apply the photocurable resin composition so that the level difference formed on the light-shielding layer formation side surface of the light-shielding layer and the light-transmitting cover member is canceled out.

There is no restriction|limiting in particular as an average thickness of the said application layer, Although it can select suitably according to the objective, It is preferable that it is thicker than the average thickness of the said light-shielding layer.

The average thickness of the coating layer is preferably 2.5 to 40 times the average thickness of the light blocking layer, and 2.5 times the average thickness of the light blocking layer in order to offset the step formed on the light blocking layer formation side surface of the light blocking layer and the light transmissive cover member -10 times are more preferable, and 2.5 times - 4.0 times are especially preferable.

There is no restriction|limiting in particular as a coating method in the said application|coating process, According to the objective, it can select suitably.

In addition, you may perform application|coating of the said photocurable resin composition multiple times so that a required thickness may be obtained.

<Temporary hardening process>

The provisional curing step is not particularly limited as long as it is a step of irradiating the coating layer with light from the side opposite to the light-transmitting cover member side and temporarily curing the coating layer to obtain a provisional curing layer, and may be appropriately selected according to the purpose. can

According to the said temporary hardening process, let the photocurable resin composition be in the state which does not flow from a liquid phase, for example. By doing so, handleability improves. Moreover, the thickness uniformity of the main hardening layer obtained by a main hardening process improves.

The temporary cured layer may be cured to such a degree that it does not flow, and the curing rate (gel fraction) is preferably 90% or more, and more preferably 95% or more.

There is no restriction|limiting in particular as light irradiated to the said application layer in the said provisional hardening process, Although it can select suitably according to the objective, An ultraviolet-ray is preferable and near-ultraviolet rays are more preferable.

There is no restriction|limiting in particular as irradiation time, According to the objective, it can select suitably.

As an apparatus which irradiates the said near-ultraviolet-ray, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a fluorescent chemical lamp, a fluorescent blue lamp, an LED lamp etc. are mentioned, for example. Moreover, as a wavelength range of a near-ultraviolet ray, it is preferable that they are 300 nm or more and 500 nm or less.

The irradiation amount of the light irradiated to the said coating layer in the said provisional hardening process is less than the irradiation amount of the light irradiated to the said provisional hardening layer in the said main hardening process, for example.

<Joining process>

The bonding step is not particularly limited as long as it is a step of bonding the temporary cured layer and the image display member, and can be appropriately selected according to the purpose. can be done by

As said image display member, the said light transmissive cover member etc. which were illustrated in description of the said image display member of this invention are mentioned, for example.

<Main curing process>

The main curing step is not particularly limited, and may be appropriately selected depending on the purpose, as long as it is a step of irradiating light to the temporary curing layer from the light-transmitting cover member side, curing the temporary curing layer, and obtaining the main curing layer. .

There is no restriction|limiting in particular as light irradiated to the said temporary hardening layer in the said main hardening process, Although it can select suitably according to the objective, An ultraviolet-ray is preferable and near-ultraviolet rays are more preferable.

There is no restriction|limiting in particular as irradiation time, According to the objective, it can select suitably.

As an apparatus which irradiates the said near-ultraviolet-ray, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a fluorescent chemical lamp, a fluorescent blue lamp, an LED lamp etc. are mentioned, for example. Moreover, as a wavelength range of a near-ultraviolet ray, it is preferable that they are 300 nm or more and 500 nm or less.

The light source used in the said provisional hardening process and the light source used in the said main hardening process may be same or different.

As light transmittance of the said main cured layer obtained, what is necessary is just the light transmittance by which the image formed in the said image display member can be visually recognized.

Here, an example of the manufacturing method of the image display apparatus of this invention is demonstrated using drawings.

1(a) to 1(e) are schematic cross-sectional views for explaining an example of a method for manufacturing an image display device of the present invention.

First, the light-transmitting cover member 1 having the light-shielding layer 1A formed on the periphery of one side is prepared (Fig. 1(a)).

Next, a liquid photo-curable resin composition is applied to the surface of the light-transmitting cover member 1 to block the light so that the step formed on the light-shielding layer-forming surface of the light-shielding layer 1A and the light-transmissive cover member 1 is canceled out. The coating layer 2A is formed by coating to be thicker than the thickness of the layer 1A (FIG. 1(b)).

Next, the provisional hardening layer 2B is formed by irradiating ultraviolet-ray using the light source 100 with respect to the formed coating layer 2A, and temporarily hardening (FIG. 1(c)).

Next, the light-transmitting cover member 1 is bonded to the image display member 3 from the side of the temporary cured layer 2B (FIG. 1(d)).

Next, the temporary curing layer 2B sandwiched between the image display member 3 and the light-transmitting cover member 1 is irradiated with ultraviolet rays using the light source 200 to make the main curing layer 2C. to form

Thereby, the image display member 3 and the light transmissive cover member 1 are laminated|stacked with the light transmissive main hardened layer 2C interposed, and the image display apparatus is obtained.

Example

Hereinafter, although the Example of this invention is described, this invention is not limited to these Example at all.

(Examples 1 to 27, and Comparative Examples 1 to 10)

The photocurable resin composition of the composition and content shown in following Table 1-1 - Table 1-7 was manufactured. After mixing a radically polymerizable group containing compound, a cationically polymerizable group containing compound, an optical radical initiator, a photoacid generator, a sensitizer, and a plasticizer specifically, it stirred until solid content melt|dissolved.

In addition, the unit of content in Table 1-1 - Table 1-7 is a mass part.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

[Table 1-5]

[Table 1-6]

[Table 1-7]

Various materials in Tables 1-1 to 1-7 are as follows.

<<Radically polymerizable group-containing compound>>

・UV-3700B: Nippon Kosei Chemical Co., Ltd.

Urethane acrylate

・LA (light acrylate): Kyoeisha Chemical Co., Ltd.

Lauryl Acrylate

・4HBA: Nippon Kasei Co., Ltd.

4-hydroxybutyl acrylate

<<Cationically polymerizable group-containing compound>>

・KBM-5103: Shin-Etsu Chemical High School Co., Ltd.

3-Acryloxypropyltrimethoxysilane

・KBM-502: Shin-Etsu Chemical High School Co., Ltd.

3-methacryloxypropylmethyldimethoxysilane

・KBM-503: Shin-Etsu Chemical High School Co., Ltd.

3-Methacryloxypropyltrimethoxysilane

・KBE-502: Shin-Etsu Chemical High School Co., Ltd.

3-Methacryloxypropylmethyldiethoxysilane

・KBE-503: Shin-Etsu Chemical High School Co., Ltd.

3-Methacryloxypropyltriethoxysilane

・4HBAGE: Nihon Kasei Co., Ltd.

4-hydroxybutyl acrylate glycidyl ether

・M-100: Daicel Corporation

3,4-Epoxycyclohexylmethylmethacrylate

<<Photoradical Initiator>>

·Irgacure 184: BASF

1-Hydroxycyclohexylphenylketone

·Irgacure 1173: BASF

2-hydroxy-2-methyl-1-phenylpropan-1-one

·Irgacure 651: BASF

2,2-dimethoxy-1,2-diphenylethan-1-one

·Irgacure 2959: BASF

1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one

·Irgacure 127: BASF

2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-1-one

·esacureone: Lamberti

Oligo[2-hydroxy-2-methyl-[1-(methylvinyl)phenyl]propanone

·Speed Cure TPO: Lamberti

2,4,6-trimethylbenzoyl-diphenylphosphine oxide

·OXE-01: BASF

1.2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)]

・DETX-S: Nihon Gayaku Co., Ltd.

2,4-diethylthioxanthone

· Benzophenone: Tokyo Kasei High School Co., Ltd.

<<Light acid generator>>

・PI-2074: Rhodia Japan Co., Ltd.

・BBI-105: Midori Chemical Co., Ltd.

・BBI-109: Midori Chemical Co., Ltd.

・BBI-201: Midori Chemical Co., Ltd.

・DTS-2000: Midori Chemical Co., Ltd.

<<sensitizer>>

・benzophenone

·esacureTZT: Lamberti

A mixture of 4-methylbenzophenone and 2,4,6-trimethylbenzophenone

<<Plasticizer>

·Hexamoll DINCH: BASF

Diisononylcyclohexane-1,2-dicarboxylate

(evaluation)

The photocurable resin composition was used for the following evaluation.

<Compatibility>

It visually observed whether the photocurable resin composition had cloudiness, and the following evaluation criteria evaluated it. A result is shown to Table 2-1 - Table 2-7.

〔Evaluation standard〕

(circle): There was no cloudiness.

x: There was cloudiness.

<Post-curing>

About the obtained photocurable resin composition, using the UV rheometer (MARS, the HAKKE company make), the following measurement conditions and evaluation criteria evaluated the presence or absence of post-curing. A result is shown to Table 2-1 - Table 2-7.

-Measuring conditions-

Light source: LED 365nm

UV illuminance at a wavelength of 365 nm: 200 mW/cm 2

Irradiation Time: 60 seconds

Temperature: 25℃

〔Evaluation standard〕

○: G' value after 360 seconds from the end of irradiation / G' value immediately after the end of irradiation is 1.10 seconds

x: G' value after 360 seconds from the end of irradiation / G' value immediately after the end of irradiation is 1.10 or less

In addition, G' means a storage elastic modulus.

[Table 2-1]

[Table 2-2]

[Table 2-3]

[Table 2-4]

[Table 2-5]

[Table 2-6]

[Table 2-7]

About the photocurable resin composition (Example 18 and Example 19) containing a sensitizer, also when changing the wavelength to irradiate from 365 nm to 385 nm on the longer wavelength side, similarly to the case where the wavelength to irradiate is 365 nm later curing was confirmed.

<Bleed Test>

-Print and Exposure-

Printing and exposure were performed using any of the substrates [a glass plate or a PMMA (polymethyl methacrylate) plate] shown in Table 3 below and a light source, and a simulation panel was produced. A manufacturing procedure is demonstrated using FIGS. 2(a) to 2(e).

A 5 cm square substrate 11 having a light shielding portion 11A having a width of 3 mm and a thickness of 20 μm centered at a point 1 cm from the outer periphery was used (FIG. 2(a)).

4 cm square from the center of the board|substrate 11, the photocurable resin composition was printed so that an average thickness might be set to 100 micrometers, and the application layer 12A was obtained (FIG.2(b)).

From the surface side on which the photocurable resin composition was printed, the 1st exposure was performed using the light source 100, and the provisional hardening layer 12B was obtained (FIG.2(c)).

Next, a 5 cm square polarizing plate 13 (manufactured by Sumitomo Chemical Co., Ltd.) is bonded to the temporary cured layer 12B (FIG. 2(d)), and from the substrate 1 side, the light source 200 is used for the second time. was exposed to obtain a main cured layer 12C (FIG. 2(e)).

As described above, a simulation panel was produced.

[Table 3]

-Assessment Methods-

The produced simulated panel was stored for 100 hours at 95°C under 0% RH (storage condition A), or stored at 60°C under 90% RH for 100 hours (storage condition B), and the presence or absence of bleed of the cured product of the photocurable resin composition was checked. It visually observed and evaluated by the following evaluation criteria. The results are shown in Tables 4-1 to 4-7.

〔Evaluation standard〕

(circle): There was no bleed.

x: There was bleed.

<yellowing>

The simulated panel produced was irradiated with light for 100 hours using an ultraviolet fade meter (U48, Suga Shikenki Co., Ltd.), and the presence or absence of yellowing after light irradiation was visually observed and evaluated according to the following evaluation criteria. . The results are shown in Tables 4-1 to 4-7.

〔Evaluation standard〕

○: There was no yellowing.

x: There was yellowing.

[Table 4-1]

[Table 4-2]

[Table 4-3]

[Table 4-4]

[Table 4-5]

[Table 4-6]

[Table 4-7]

About the process c and d, it performed about the photocurable resin composition of Examples 19 and 21 on behalf of the photocurable resin composition of Examples 1-27. As a result, no bleed was observed in any of the storage conditions A and B.

In the photocurable resin composition of the present invention, curing continues even after light irradiation, and curing proceeds even in a region not directly exposed to light, so that bleed due to insufficient curing in a region not directly exposed to light can be prevented. Moreover, yellowing did not arise even if it irradiated with ultraviolet-ray for a long time with respect to hardened|cured material.

On the other hand, in the following Comparative Examples 1 to 10, post-curing did not arise, and bleed|bleeding arose.

Comparative Example 1: Although the photo acid generator is contained, the photo radical initiator and the cationic polymerization component are not contained.

Comparative Example 2: Although it contains a photo acid generator and a cationic polymerization component, it does not contain a photo radical initiator.

Comparative Example 3: Although it contains a photo acid generator and a cationic polymerization component, the photo-radical initiator is not an α-hydroxyalkylphenone-based photo-radical initiator or a benzylmethylketal-based photo-radical initiator.

Comparative Example 4: Although the photo acid generator was contained, the cationic polymerization component was not contained.

Comparative Example 5: A photo acid generator and a cationic polymerization component were not contained.

Comparative Example 6: Although it contains a photo acid generator and a cationic polymerization component, the mass ratio (A/B) exceeds 30.

Comparative example 7: Although it contains a photo acid generator and a cationic polymerization component, mass ratio (A/B) is less than 0.5.

Comparative Examples 8 to 10: Although containing a photo acid generator and a cationic polymerization component, the photo radical initiator is not an α-hydroxyalkylphenone photo radical initiator or a benzylmethyl ketal photo radical initiator.

Since the photocurable resin composition of the present invention can prevent bleed-out of the cured product by improving curability in a region not directly hit by light, the light-transmitting cover member having a light-shielding layer on the periphery, and the image display member can be used well.

1: light transmissive cover member
1A: light blocking layer
2A: coating layer
2B: Temporarily hardened layer
2C: main cured layer
3: No image display
11: Substrate
11A: shading part
12A: coating layer
12B: temporary cured layer
12C: main cured layer
13: polarizer
100: light source
200: light source

Claims (9)

A radical polymerizable group-containing compound, a cationically polymerizable group-containing compound, a radical photoinitiator, and a photoacid generator are included;
Content of the said radically polymerizable group containing compound is more than content of the said cationically polymerizable group containing compound,
The photo-radical initiator is an α-hydroxyalkylphenone-based photoradical initiator, a benzylmethylketal-based photoradical initiator, or both;
A mass ratio of the radical photoinitiator and the photoacid generator (radical photoinitiator/photoacid generator) is 0.5 to 30;
The sum (optical radical initiator + photoacid generator) of content of the said radical photoinitiator and content of the said photoacid generator is 1.5 mass % or less, The photocurable resin composition characterized by the above-mentioned. The photocurable resin composition of Claim 1 in which the said cationically polymerizable group containing compound has a radically polymerizable group. The photocurable resin composition according to claim 1, wherein the cationically polymerizable group in the cationically polymerizable group-containing compound is an alkoxysilyl group, an epoxy group, or both. The photocurable resin composition of Claim 1 whose content of the said photo acid generator is 0.01 mass % or more. The photocurable resin composition according to claim 1, further comprising a plasticizer. It has hardened|cured material of the photocurable resin composition in any one of Claims 1-5, The image display apparatus characterized by the above-mentioned. 7. The method according to claim 6, comprising an image display member and a light-transmitting cover member;
The image display device in which the said image display member and the said light-transmitting cover member are adhere|attached with the said hardened|cured material interposed therebetween. The light-transmitting cover member according to claim 7, wherein the light-transmitting cover member has a light-shielding layer on its periphery;
In the light-transmitting cover member, the surface having the light-shielding layer faces the image display member. A coating step of applying the photocurable resin composition according to any one of claims 1 to 5 to the surface of the light-transmitting cover member having the light-shielding layer on the periphery of the light-shielding layer to obtain an application layer;
a provisional curing step of irradiating the application layer with light from a side opposite to the light-transmitting cover member side, and temporarily curing the application layer to obtain a provisionally cured layer;
a bonding step of bonding the temporary cured layer and the image display member;
and a main curing step of irradiating light to the provisionally cured layer from the light-transmitting cover member side to cause the provisional cured layer to be cured to obtain a main cured layer.

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