JP2019137710A - Curable resin composition, image display device and method for manufacturing image display device - Google Patents

Abstract

To provide a curable resin composition having light-shielding property for suppressing leakage of light through between an image display part and a frame part and allowing efficient formation of a light-shielding layer even in a narrow region in the process of manufacturing an image display device, and showing an effect in an adhesive force in a shearing direction at high temperature, and to provide an image display device using the composition and a method for manufacturing an image display device.SOLUTION: The curable resin composition comprises a photo-initiator, a monomer component and a colorant, in which the photo-initiator contains a photo-radial polymerization initiator, or a photo-radical polymerization initiator and a base generator, the monomer component contains a monomer having one radically polymerizable group and a silanol group or an alkoxysilyl group, and the radically polymerizable group is a methacryloyl group.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a curable resin composition, an image display device, and a method for manufacturing the image display device.

  An image display device used in an information terminal such as a smart phone has an image display unit (including a liquid crystal panel, a cover glass, etc.) having an image display surface and a frame unit that supports the image display unit. The image display unit and the frame unit are manufactured by bonding and fixing with a pressure-sensitive adhesive tape. As this pressure-sensitive adhesive tape, a black pressure-sensitive adhesive tape having a light shielding property is generally used in order to prevent deterioration of image quality due to light leakage from between the image display portion and the frame portion (for example, patents). Reference 1).

Japanese Patent No. 5658072

In recent years, in an image display device, the decoration part and the light-shielding part around the image display surface have been narrowed, and the frame part of the image display part that supports them has also been narrowed. Therefore, the adhesion area between the image display unit and the frame unit tends to be narrowed. Since it is difficult to finely process the pressure-sensitive adhesive tape to cope with the narrowed adhesive area and to bond the pressure-sensitive adhesive tape to the narrowed adhesive site, there is a concern about a decrease in productivity.
In addition, the manufacturing process of the image display device may include an aging process at a high temperature. For this reason, an image display device and a frame part that can be fixed by bonding even under high temperatures are required.

  In manufacturing an image display device, the present invention has a light-shielding property that suppresses light leakage from between an image display unit and a frame unit, can efficiently form a light-shielding layer even in a narrow region, and has a high temperature. An object of the present invention is to provide a curable resin composition having an effect on the adhesive force in the shear direction, and to provide an image display device using the same and a method for manufacturing the image display device.

  One aspect of the present invention contains a photoinitiator, a monomer component, and a colorant, and the photoinitiator comprises a photoradical polymerization initiator, or a photoradical polymerization initiator and a base generator. A curable resin composition, wherein the monomer component includes a monomer having one radical polymerizable group and a silanol group or an alkoxysilyl group, and the radical polymerizable group is a methacryloyl group. provide.

  Another aspect of the present invention contains a photoinitiator, a monomer component, a colorant, and a compound having a silanol group or an alkoxysilyl group, and the photoinitiator is a photoradical polymerization initiator, Or a photo radical polymerization initiator and a photo base generator, the monomer component contains a monomer having one radical polymerizable group, and the radical polymerizable group is a methacryloyl group A functional resin composition is provided.

  According to the curable resin composition of the present invention, the composition is applied to the image display portion or the frame portion of the image display device to form a frame-like curable resin layer, and active against this curable resin layer. After irradiating the energy beam, a simple method of bonding the image display unit and the frame unit has a light shielding property that suppresses light leakage from between the image display unit and the frame unit, and is a narrow area. However, the light-shielding layer can be efficiently formed, which is effective in the adhesive force in the shear direction at high temperatures, and the image display portion and the frame portion can be bonded and fixed even at high temperatures.

The present inventors consider the reason why the above effect is achieved as follows. Since the curable resin composition according to the present invention has the above-described configuration, it can be promoted by a base following the generation of a polymer chain by radically polymerizable photoradical polymerization, or a silanol group or alkoxysilyl by moisture (moisture). The curing reaction of the curable resin layer by the ionic reaction (hydrolysis reaction) of the group can be advanced. The ionic reaction proceeds at a relatively slower reaction rate than the radical polymerization reaction. By such delayed curing, the light-shielding curable resin layer can achieve both an elastic modulus suitable for bonding by irradiation with active energy rays and a sufficient curing rate after bonding. Thereby, even if it is a fine adhesive surface, it is possible to suppress dropping and peeling due to a drop impact and a repulsive force of a member constituting the image display device (for example, a flexible wiring board (FPC)), and it is also effective at high temperatures. The present inventors consider that a light-shielding layer having a certain adhesive strength, excellent light leakage prevention property and excellent high-temperature adhesive strength could be formed.
Moreover, by containing the methacryloyl group which is a radically polymerizable group, a steric hindrance is larger than other polymerizable groups, and a polymerization reaction is slow. For this reason, the present inventors consider that the elastic modulus in bonding of substrates is moderately low, the aspect ratio can be increased, and as a result, the adhesive force in the shear direction at high temperature is effective.

  The curable resin composition may further contain a polymer. When the curable resin composition contains a polymer, it is easy for the curable resin layer after being irradiated with active energy rays to have pressure-sensitive adhesiveness that facilitates bonding with the image display unit. it can.

  The curable composition can exhibit pressure-sensitive adhesiveness when irradiated with active energy rays.

It is preferable that the curable resin composition is held without dropping in a high temperature load resistance test required by the following method.
By applying a curable resin composition onto a PET film to form a cured resin layer having a thickness of 50 [mu] m, so that the light with the peak wavelength of 365nm to the curable resin layer to ^{3000mW / cm 2, 5000mJ / cm} 2 Irradiate ultraviolet rays. Next, within 1 minute from light irradiation, a load of 5 kgf is applied so that a polycarbonate plate having a width of 25 mm, a length of 100 mm, and a thickness of 1 mm is overlapped with a curable resin layer at a width of 25 mm and a width of 25 mm. Bonding while applying (49N). Next, a weight of 400 g is attached to the other end of the polycarbonate plate, and the polycarbonate plate is left in an environment of 25 ° C. and 50% RH for 24 hours while applying a shearing force to the curable resin layer in the vertical direction. Next, while keeping the polycarbonate plate in the vertical direction and applying a shearing force to the curable resin layer, it is observed whether a weight of 400 g is held or dropped when left in a constant temperature bath at a temperature of 70 ° C. for 24 hours. .

The curable resin composition may have an aspect ratio of 0.6 or more determined by the following method.
A curable resin composition is applied on a glass substrate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm, and a curable resin layer having a width of 0.6 mm, a length of 25 mm, and a thickness of 50 μm is formed as the length of the curable resin layer. It provided such that the direction is orthogonal to the long side of the glass substrate, the cured resin layer, the total dose at the irradiation intensity of 3000 mW / cm ² is irradiated with light having a wavelength of 365nm to be 5000 mJ / cm ^2, irradiation A polycarbonate plate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm is placed on the curable resin layer within 1 minute from 1 to 5 mm so that the long side of the glass substrate and the long side of the polycarbonate plate are aligned when viewed from the vertical direction. A measurement sample is obtained by laminating a 1 N load for 10 seconds. When the width of the curable resin layer in contact with the polycarbonate plate in the measurement sample is B (unit: mm), B / 0.6 is the aspect ratio.

  The curable resin composition according to the present invention can be used for forming a light shielding layer. In other words, the present invention contains a photoinitiator, a monomer component, and a colorant, and the photoinitiator is a photoradical polymerization initiator, or a photoradical polymerization initiator and a photobase generator. A light-blocking curable resin composition comprising a monomer component having one radical polymerizable group and a silanol group or an alkoxysilyl group, wherein the radical polymerizable group is a methacryloyl group. It relates to an application for forming a layer. The present invention also includes a photoinitiator, a monomer component, a colorant, and a compound having a silanol group or an alkoxysilyl group, and the photoinitiator is a photoradical polymerization initiator or a photon A curable resin composition comprising a radical polymerization initiator and a photobase generator, wherein the monomer component comprises a monomer having one radical polymerizable group, and the radical polymerizable group is a methacryloyl group. The present invention relates to an application for forming a light shielding layer.

  Another aspect of the present invention supports a liquid crystal panel having an image display surface, an image display portion having a cover member having a light transmission portion facing the image display surface, and an image display portion provided around the image display portion. And a light shielding layer formed between the frame portion and the image display unit, wherein the light shielding layer is made of the curable resin composition according to the present invention. Provided is an image display device which is a cured product of a layer.

  Another aspect of the present invention supports a liquid crystal panel having an image display surface, an image display portion having a cover member having a light transmission portion facing the image display surface, and an image display portion provided around the image display portion. And a light shielding layer formed between the frame portion and the image display portion, wherein the image display portion or the frame portion includes the curable resin according to the present invention. Applying the composition to form a frame-shaped curable resin layer, irradiating the curable resin layer with an active energy ray to advance the curing reaction of the curable resin layer, and curing And a step of bonding the image display unit and the frame unit in this order while interposing the curable resin layer, and providing a method for manufacturing an image display device in which the light shielding layer is the curable resin layer in which the curing reaction has proceeded. .

  According to the method for manufacturing an image display device of the present invention, even in a narrow region, the light-shielding layer that can sufficiently suppress light leakage between the image display unit and the frame unit is provided, and at a high temperature. An image display device having a high adhesive force in the shear direction can be efficiently manufactured.

  In the above method, the curable resin layer when the image display unit and the frame unit are bonded together may have pressure-sensitive adhesiveness.

In the above method, the image display unit and the frame unit may be bonded so that an aspect ratio represented by the following formula is 0.6 or more.
Aspect ratio = B '/ A'
[In the formula, A ′ represents a width at a predetermined portion of the frame-shaped curable resin layer applied to one of the image display unit and the frame unit, and B ′ represents the image display unit and the image display unit. The width | variety which is in contact with the other of the said image display part and the said frame part in the said predetermined part of the said curable resin layer after the said frame part is bonded together is shown. ]

  The method for manufacturing the image display device may further include a step of further proceeding a curing reaction of the curable resin layer after the step of bonding the image display unit and the frame unit. As a result, the image display unit and the frame unit can be bonded with a high adhesive force even when the light-shielding layer is at a higher temperature, and an image display device having a light-shielding layer excellent in light leakage prevention can be obtained.

  According to the present invention, when manufacturing an image display device, it has a light shielding property to suppress light leakage between the image display unit and the frame unit, and a light shielding layer can be efficiently formed even in a narrow region. In addition, it is possible to provide a curable resin composition that is effective in the adhesive force in the shearing direction at high temperatures and an image display device using the same and a method for manufacturing the image display device.

It is a figure for demonstrating the method to measure the pressure-sensitive adhesive force of a curable resin layer. It is a figure for demonstrating the method to measure the aspect-ratio in bonding of the curable resin layer. It is sectional drawing which shows one Embodiment of an image display apparatus. It is a perspective view which shows one Embodiment of the method of manufacturing an image display apparatus. It is a perspective view which shows one Embodiment of the method of manufacturing an image display apparatus. It is a perspective view which shows one Embodiment of the method of manufacturing an image display apparatus. It is a perspective view which shows one Embodiment of the method of manufacturing an image display apparatus. It is a perspective view which shows the method of measuring adhesive force. It is a perspective view which shows the method of measuring adhesive force. It is a perspective view which shows the method of evaluating light-shielding property. It is a perspective view which shows the method of evaluating high temperature load resistance.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description may be omitted. The positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. The dimensional ratios in the drawings are not limited to the illustrated ratios.

  In this specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” and corresponding “methacryloyl”.

  The first curable resin composition of the present embodiment includes a photoinitiator (hereinafter also referred to as “(A) component”), a monomer component (hereinafter also referred to as “(B) component”), and coloring. And a monomer component having one radical polymerizable group and a silanol group or an alkoxysilyl group (hereinafter referred to as “( B1) component ”) and the radical polymerizable group may be a methacryloyl group.

  The second curable resin composition of the present embodiment includes a photoinitiator, a monomer component, a colorant, and a compound having a silanol group or an alkoxysilyl group (hereinafter also referred to as “(D) component”). And the monomer component includes a monomer having one radical polymerizable group (hereinafter also referred to as “component (B2)”), and the radical polymerizable group is a methacryloyl group. be able to.

(A) Component: Photoinitiator The photoinitiator can contain a photoradical polymerization initiator (hereinafter also referred to as “component (A1)”), or a photoradical polymerization initiator and a photobase generator.

  The radical photopolymerization initiator as component (A1) is a component that generates free radicals by irradiation with active energy rays and accelerates a curing reaction (polymerization reaction) by radical polymerization of the monomer component. Here, the active energy rays can be selected from ultraviolet rays, electron rays, α rays, β rays and the like.

Specific examples of the radical photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy- 4,4′-dimethylaminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, tert-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2- Methyl anthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane 1-on, 2 Aromatic ketone compounds such as 1,2-diethoxyacetophenone; 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; benzyl, benzyldimethyl Benzyl compounds such as ketals; ester compounds such as β- (acridin-9-yl) (meth) acrylic acid; acridine compounds such as 9-phenylacridine, 9-pyridylacridine, 1,7-diacridinoheptane; (O-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4 , 5-Di Phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di ( p-methoxyphenyl) 5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole 2,4,5-triarylimidazole dimer such as dimer; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- ( Alkylphenone compounds such as methylthio) phenyl] -2-morpholino-1-propane; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy Ci-2-methyl-1-phenyl-propan-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-propan-1-one, oligo {2-hydroxy-2-methyl-1- [4 Α-hydroxyalkylphenone compounds such as — (1-methylvinyl) phenyl] propanone}; phenylglyoxylic acid methyl ester; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl- Phosphine oxide-based compounds such as triphenylphosphine oxide.
From the viewpoint of curability, reactivity, and surface curability, a radical photopolymerization initiator may be selected from an aromatic ketone compound, an α-hydroxyalkylphenone compound, and phenylglyoxylic acid methyl ester.

  The radical photopolymerization initiator may be a compound that generates a base. Examples of the photo radical polymerization initiator that generates a base include compounds that generate both a free radical and a base (for example, a secondary amino group or a tertiary amino group) by irradiation with active energy rays. Specific examples of such a photo radical polymerization initiator include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (“Irgacure 369”, manufactured by BASF Japan Ltd.), 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one ("Irgacure 907", manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- Α-aminoacetophenone compounds such as (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379”, manufactured by BASF Japan Ltd.); “CGI-325”, “Irgacure OXE01”, “Irgacure OXE02” (above, BASF Japan ), "N-1919", "NCI-831" (above, manufactured by Adeka) etc. Muesuteru compounds. Among these, an α-aminoacetophenone compound may be selected. As the radical photopolymerization initiator for generating a base, one kind may be used alone, or two or more kinds may be used in combination.

  A radical photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the component (A1) in the curable resin composition is relative to the total amount of the curable resin composition from the viewpoints of pressure-sensitive adhesiveness, reliability, and curability, and efficiently promoting the curing reaction. 2 mass% or more, 4 mass% or more, or 6 mass% or more, 14 mass% or less, 12 mass% or less, or 10 mass% or less may be sufficient.

  As the photobase generator as component (A1), one or more types capable of functioning as a curing catalyst for ion reaction by silanol group or alkoxysilyl group due to change in molecular structure or cleavage of molecule upon irradiation with active energy rays The compound which produces | generates this basic substance is mentioned. Examples of such a photobase generator include a Co-amine complex photobase generator; a carbamate ester photobase generator; a quaternary ammonium salt photobase generator; an acyloxyimino group, and an N-formylated aromatic amino group. A compound having a group, an N-acylated aromatic amino group, a nitrobenzyl carbamate group, an alkoxybenzyl carbamate group, or the like can also be selected. Specific examples of the photobase generator include 9-antilmethyl N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, guanidinium 2- (3-benzoyl) Phenyl) propionate, 1- (anthraquinone-2-yl) ethyl imidazole carboxylate, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1- (anthraquinone-2-yl) -ethyl N, N-dicyclohexyl Carbamate, dicyclohexylammonium 2- (3-benzoylphenyl) propionate, cyclohexylammonium 2- (3-benzoylphenyl) propionate, 9-anthrylmethyl N, N-dicyclohexylcarbamate, 1,2-di Isopropyl-3- [bis (dimethylamino) methylene] guanidinium 2- (3-benzoylphenyl) propionate, 2-nitrobenzylcyclohexylcarbamate, O-carbamoylhydroxylamide, O-carbamoyloxime, {[(2,6-dinitrobenzyl ) Oxy] carbonyl} cyclohexylamine, bis {[(2-nitrobenzyl) oxy] carbonyl} hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4 -(2 ', 4'-dinitrophenyl) -1,4-dihydropyridine. A photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the photobase generator as the component (A1) in the curable resin composition is 2% by mass or more based on the total amount of the curable resin composition, from the viewpoint of efficiently accelerating the curing reaction by ionic reaction. 4 mass% or more, or 6 mass% or more may be sufficient, and 14 mass% or less, 12 mass% or less, or 10 mass% or less may be sufficient.

(B) Component: Monomer component In the first curable resin composition of the present embodiment, the monomer component is a monomer having one radical polymerizable group and a silanol group or an alkoxysilyl group. Can be included. The silanol group and the alkoxysilyl group can cause the curing reaction to proceed by an ionic reaction involving water (hydrolysis reaction). This reaction can be promoted, for example, by a base generated from a photobase generator or a photoradical polymerization initiator that generates a base.

Examples of the radical polymerizable group possessed by the component (B1) include a (meth) acryloyl group, a vinyl group, an ethynyl group, an isopropenyl group, a vinyl ether group, and a vinyl thioether group, and a methacryloyl group is selected.
Examples of the component (B1) include 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, Shin-Etsu Chemical Co., Ltd.) and methacryloxyoctyltrimethoxysilane (trade name: KBM5803, Shin-Etsu Chemical Co., Ltd.) ) A compound having an acryloyl group and a trialkoxysilyl group. Further, the component (B1) may be a compound having a (meth) acryloyl group and a dialkoxysilyl group, such as methacryloxypropylmethyldiethoxysilane.

  (B1) A component can be used individually by 1 type or in combination of 2 or more types.

  The content of the component (B1) is from the viewpoint of reactivity, from the viewpoint of improving the adhesive force, and from the viewpoint of stability when the curable resin composition is a solution, with respect to the total amount of the curable resin composition, It may be 0.1 mass% or more, 1 mass% or more, or 3 mass% or more, or 15 mass% or less, 10 mass% or less, or 5 mass% or less.

  Examples of the component (B2) include monofunctional monomers having one radical polymerizable group. Examples of the radical polymerizable group possessed by the monomer component include a (meth) acryloyl group, a vinyl group, an ethynyl group, an isopropenyl group, a vinyl ether group, and a vinyl thioether group, and a methacryloyl group is selected.

  The monofunctional monomer having a (meth) acryloyl group may be an alkyl (meth) acrylate, and the carbon number of the alkyl group in that case is 4 from the viewpoint of imparting flexibility to the curable resin composition. As described above, it may be 6 or more, or 8 or more, and may be 20 or less, 18 or less, or 16 or less. The alkyl group of the alkyl (meth) acrylate may have a substituent such as a hydroxyl group.

  Specific examples of the monofunctional monomer having a (meth) acryloyl group include n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n- Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) Alkyl (meth) acrylates such as acrylate; 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate Hydroxyl-containing alkyls such as 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate ( (Meth) acrylate; (meth) acrylamide such as dimethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide; hydroxyl-containing (meth) acrylamide such as hydroxyethyl (meth) acrylamide; diethylene glycol mono (meth) Polyethylene glycol mono (meth) acrylates such as acrylate and triethylene glycol mono (meth) acrylate; dipropylene glycol mono (meth) acrylate, Polypropylene glycol mono (meth) acrylates such as propylene glycol mono (meth) acrylate; polybutylene glycol mono (meth) acrylates such as dibutylene glycol mono (meth) acrylate and tributylene glycol mono (meth) acrylate; morpholines such as acryloylmorpholine Group-containing (meth) acrylates: dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl methacrylate, and isobornyl (meth) acrylate. These compounds may be used alone or in combination of two or more. From the viewpoints of pigment dispersibility or dye solubility, adhesive strength, moisture and heat resistance reliability, and pressure-sensitive adhesiveness after curing, monofunctional monomers are dicyclopentanyl (meth) acrylate, dicyclopentenyl (meta ) Acrylate and a compound selected from isobornyl (meth) acrylate, or a compound selected from dicyclopentenyl (meth) acrylate and isobornyl (meth) acrylate.

  As the component (B2), one type may be used alone, or two or more types may be used in combination.

  In the first curable resin composition of the present embodiment, the component (B) can contain one or more components (B2) in addition to the component (B1). In the first curable resin composition of the present embodiment, the component (B2) is a compound other than the component (B1).

  The content of the component (B2) is from the viewpoint of obtaining a curable resin composition having an appropriate viscosity, from the viewpoint of adjusting the curing shrinkage and the elastic modulus of the cured product, and from the viewpoint of solubility of the colorant. 10 mass% or more, 15 mass% or more, or 20 mass% or more may be sufficient with respect to the total amount of a thing, and 80 mass% or less, 70 mass% or less, or 60 mass% or less may be sufficient. When the content of the component (B2) is 10% by mass or more, a curable resin composition having an appropriate viscosity that contributes to good coatability is easily obtained, and the solubility of the colorant tends to be improved. . When the content of the component (B2) is 80% by mass or less, the curing shrinkage rate tends to be low. When the curing shrinkage rate is low, it is possible to suppress a decrease in adhesive force due to stress.

  The monomer component (B) may further contain a polyfunctional monomer having two or more radical polymerizable groups. In that case, content of a polyfunctional monomer may be 5 mass% or less with respect to the total amount of a monomer component ((B) component).

(C) Component: Colorant The colorant is a component that colors the curable resin composition and the light-shielding layer and imparts appropriate light-shielding properties to the formed light-shielding layer, and there is no particular limitation on the hue of the colorant. Although colorants with various hues can be used, the colorants typically exhibit a black color. The colorant can include, for example, a dye or a pigment. From the viewpoint of obtaining a uniform curable resin composition, a colorant that dissolves in the monomer component may be selected.

  The dissolution or dispersion of the colorant in the monomer component can be confirmed by the following method. To a 50 mL beaker, 10 mL of monomer component (temperature 25 ° C.) and 10 mg of colorant (solid mass) are added and stirred for 1 minute using a glass rod. Thereafter, when the solid matter of the colorant cannot be visually confirmed, it is determined that the colorant is dissolved or dispersed in the monomer component.

  From the viewpoint of light shielding properties, the average visible light transmittance of the colorant may be 50% or less, 45% or less, or 40% or less. Here, the average transmittance of visible light refers to the average transmittance of light having a wavelength of 400 to 700 nm. The average visible light transmittance is obtained by measuring the light transmittance of a colorant solution composed of 100 parts by mass of a solvent in which the colorant is dissolved or dispersed and 0.1 part by mass of the colorant with a spectrocolorimeter (for example, Konica Corporation). Using “CM-3700A”) manufactured by Minolta, it can be measured by a method of measuring every 1 nm in a range of 400 to 700 nm, obtaining an average value of each obtained measurement value, and obtaining an average transmittance. The dissolution of the colorant in the solvent can be confirmed by the same method as that described above for “the colorant dissolves in the monomer component”.

  The light transmittance (hereinafter also referred to as “irradiation transmittance”) of the colorant at the peak wavelength of the light (active energy ray) irradiated to advance the curing reaction is 10% of the average visible light transmittance. As mentioned above, it may be higher by 20% or more and 30% or more. The irradiation light transmittance may be 60% or more, 65% or more, or 70% or more. By using a colorant having a high irradiation light transmittance, a curing reaction by radical photopolymerization can be efficiently advanced while ensuring a sufficient light shielding property. The irradiation light transmittance of the colorant is determined by the light irradiated to promote the curing reaction of the colorant solution composed of 100 parts by mass of the solvent in which the colorant is dissolved or dispersed and 0.1 part by mass of the colorant (activity) The light transmittance of the colorant at the peak wavelength of the energy beam can be determined by a method of measuring the decomposition wavelength under the condition of 1 nm. As the measuring device, a visible ultraviolet spectrophotometer (for example, “UV-2400PC” manufactured by Shimadzu Corporation) can be used. The measurement range is set to 300 to 780 nm, for example.

  The colorant may include, for example, at least one selected from the group consisting of phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, aniline black, perylene black, and fluoran.

  The content of the colorant is 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more with respect to the total amount of the curable resin composition from the viewpoint of obtaining an effect of shielding visible light. It may be 10 mass% or less, 7.5 mass% or less, or 5 mass% or less.

The curable resin composition according to this embodiment may further contain a polymer (hereinafter also referred to as “component (E)”). The polymer contained in the curable resin composition may be an oligomer. In the present specification, the “oligomer” means a polymer having a weight average molecular weight of 1 × 10 ⁴ or more. When the curable resin composition contains a polymer (particularly an oligomer), the curable resin layer after light irradiation tends to have appropriate pressure-sensitive adhesiveness. In this specification, a weight average molecular weight means the value of standard polystyrene conversion measured by gel permeation chromatography. In this specification, the “polymer” as the component (E) is a component excluding the components (A) to (C) described above.

  Specific examples of the polymer (oligomer) include butadiene rubber, isoprene rubber, silicon rubber, styrene butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, urethane rubber, acrylic rubber, chlorosulfonated polyethylene rubber, fluorine rubber, Liquid or solid materials of various rubbers such as hydrogenated nitrile rubber and epichlorohydrin rubber; poly α-olefins such as polybutene; hydrogenated α-olefin oligomers such as hydrogenated polybutene; polyvinyl oligomers such as atactic polypropylene; biphenyl and tri Aromatic oligomers such as phenyl; Hydrogenated polyene oligomers such as hydrogenated liquid polybutadiene; Paraffinic oligomers such as paraffin oil and chlorinated paraffin oil; Cycloparaffinic oligomers such as naphthene oil; Polyester oligomer that can be produced by transesterification of a compound having a hydroxyl group at the end and a compound having an ester group or a carboxy group at both ends, or a polycondensation reaction; a polyether, polycarbonate, or having a hydroxyl group at both ends Polyurethane oligomers that can be produced by a polymerization reaction of polyester and polyisocyanate; (meth) acrylic acid polymers can be mentioned. Among these, a (meth) acrylic acid polymer is preferable from the viewpoint of pressure-sensitive adhesiveness.

  The (meth) acrylic acid polymer is a polymer containing one or more monomer units derived from a monomer having one (meth) acryloyl group. The (meth) acrylic acid-based polymer is a compound having two or more (meth) acryloyl groups, a polymerizable compound not having a (meth) acryloyl group (for example, acrylonitrile, As a comonomer, a compound having one polymerizable unsaturated bond such as styrene, vinyl acetate, ethylene or propylene, or a compound having two or more polymerizable unsaturated bonds such as divinylbenzene in the molecule) May be included.

Specific examples of the monomer constituting the (meth) acrylic acid polymer include (meth) acrylic acid; (meth) acrylic acid amide; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) Alkyl (meth) acrylates such as acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, stearyl (meth) acrylate ; (Meth) acrylate having an aromatic ring such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate; butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethyleneglycol (Meth) acrylates having an alkoxy group such as ru (meth) acrylate; alicyclic groups such as cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate (Meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; tetraethylene glycol monomethyl ether (meta ) Acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol methyl ether (meth) Polyethylene glycol monomethyl ether (meth) acrylate such as acrylate; Polypropylene glycol monomethyl ether (meth) acrylate such as heptapropylene glycol monomethyl ether (meth) acrylate; Polyethylene glycol ethyl ether (meth) such as tetraethylene glycol ethyl ether (meth) acrylate Acrylate; tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polyester oligomer having (meth) acryloyl group, urethane polymer having (meth) acryloyl group, Polyethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate Examples thereof include rate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, butadiene polymer having (meth) acryloyl group, and isoprene polymer having (meth) acryloyl group.
The (meth) acrylic acid polymer may be a homopolymer or copolymer containing these monomers as monomer units. The (meth) acrylic acid polymer may be a homopolymer or a copolymer containing a monofunctional monomer having one (meth) acryloyl group as a monomer unit. The (meth) acrylic acid polymer may contain a (meth) acrylate having an alkyl group as a monomer unit, and a (meth) acrylate having a C 4-18 alkyl group as a monomer unit. May be included.

  The proportion of the (meth) acrylate having an alkyl group contained as a monomer unit per molecule of the (meth) acrylic acid polymer is 5% by mass or more based on the mass of the (meth) acrylic acid polymer. 10 mass% or more may be sufficient, and 95 mass% or less and 90 mass% or less may be sufficient. When the proportion of the alkyl group-containing (meth) acrylate is within the above range, the adhesion of the cured curable resin layer (light-shielding layer) to an adherend such as glass, plastic, polarizing plate or polycarbonate is improved. Tend.

  The (meth) acrylic acid polymer has a polar group such as a hydroxyl group, a morpholino group, an amino group, a carboxyl group, a cyano group, a carbonyl group, or a nitro group from the viewpoint of improving the pressure-sensitive adhesiveness with a base material such as plastic. It may be a copolymer containing the (meth) acrylate as a monomer unit.

The weight average molecular weight of the (meth) acrylic acid polymer (oligomer) may be 1 × 10 ⁴ to 1 × 10 ⁷ . When the weight average molecular weight is within the above range, it is particularly easy to provide a pressure-sensitive adhesive force that does not cause peeling on a substrate or the like in a high temperature (eg, 80 ° C. or higher) and high humidity (eg, 90% or higher) environment. Can be obtained. Moreover, it is easy to obtain a curable resin composition having a viscosity suitable for coating and good workability.

  The (meth) acrylic acid polymer can be prepared using a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

  As a polymerization initiator in these polymerization methods, a compound that generates a radical by heat may be used. Specific examples thereof include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, Organic peroxides such as tert-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide, didodecyl peroxide 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2.2′-azobis ( 2,4-dimethylvaleronitrile), 2,2′-azobis (2 , 4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis ( Azo compounds such as 2-hydroxymethylpropionitrile) and 2,2′-azobis [2- (imidazolin-2-yl) propane].

  (E) Content of a component may be 1 mass% or more, 5 mass% or more, 10 mass% or more with respect to the total amount of curable resin composition, 90 mass% or less, 80 mass% or less, It may be 70% by mass or less. When the content of the polymer is within the above range, a curable resin composition having a viscosity suitable for coating and good workability is easily obtained. In addition, the pressure-sensitive adhesiveness to the adherend such as glass, plastic, polarizing plate and polycarbonate of the curable resin layer after light irradiation tends to be particularly good.

  The curable resin composition may contain a gelling agent such as 1,2-hydroxystearic acid or a thixotropic agent instead of or together with the polymer.

  The curable resin composition may further contain other additives as necessary. Examples of other additives include adhesion improving agents such as silane coupling agents, thermal polymerization initiators, antioxidants, chain transfer agents, stabilizers, and photosensitizers.

The curable resin composition may not substantially contain an organic solvent from the viewpoint of moisture and heat resistance reliability and from the viewpoint of suppressing the generation of bubbles in the cured product. In the present specification, the “organic solvent” means an organic compound that does not have a radical polymerizable group, is liquid at 25 ° C., and has a boiling point of 250 ° C. or less at atmospheric pressure. In the present specification, “substantially free of an organic solvent” means that it does not contain an intentionally added organic solvent, and an embodiment in which a trace amount of an organic solvent is present in the curable resin composition. Do not exclude. Specifically, the content of the organic solvent in the curable resin composition is 1.0 × 10 ³ ppm or less, 5.0 × 10 ² ppm or less, or 1 with respect to the total amount of the curable resin composition. It may be 0.0 × 10 ² ppm or less. The curable resin composition may not contain any organic solvent.

From the viewpoint of workability, the viscosity of the curable resin composition at a temperature in the range of at least a part of 25 to 70 ° C. is 10 mPa · s or more, 4.0 × 10 ² mPa · s or more, 5.0 × 10. ^It may be ² mPa · s or more, 1.0 × 10 ³ mPa · s or more, 2.0 × 10 ³ mPa · s or more, or 3.0 × 10 ³ mPa · s or more, 5.0 × 10 ⁴ mPa · s or less, 2.0 × 10 ⁴ mPa · s or less, 1.5 × 10 ⁴ mPa · s or less, 1.25 × 10 ⁴ mPa · s or less, or 1.0 × 10 ⁴ mPa · s or less It may be. The viscosity at 25 ° C. is a value measured based on JIS Z 8803 (liquid viscosity measurement method), and specifically measured using a B-type viscometer (for example, BL2 manufactured by Toki Sangyo Co., Ltd.). It is the value. Calibration of the B-type viscometer can be performed based on JIS Z 8809 (viscosity standard solution for calibration) -JS14000. The viscosity at a temperature exceeding 25 ° C. can be measured according to the method for measuring the viscosity at 25 ° C.

  The curable resin composition can exhibit pressure-sensitive adhesiveness when irradiated with active energy rays.

The curable resin composition preferably has a pressure-sensitive adhesive strength of 10 N / cm ² or more, more preferably 100 N / cm ² or more, and further preferably 200 N / cm ² or more. The pressure-sensitive adhesive force is measured by the following method and conditions.

(Measurement method of pressure-sensitive adhesive force)
A curable resin composition is applied onto a first glass substrate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm, and a curable resin layer having a width of 0.6 mm, a length of 25 mm, and a film thickness of 50 μm is applied to the curable resin layer. length direction arranged so as to be perpendicular to the long side of the first glass substrate, the curable resin layer, irradiation intensity 3000 mW / total dose in cm ² of wavelength 365nm to be 5000 mJ / cm ² light The polycarbonate plate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm is observed on the curable resin layer within 1 minute from the light irradiation, and the long side of the polycarbonate substrate and the long side of the glass substrate are viewed from the vertical direction. They are arranged so that they are aligned, and a 1N load is applied for 10 seconds to obtain a measurement sample (FIG. 1). Within one hour after bonding, the test force when the glass substrate of the measurement sample and the polycarbonate plate are peeled in the opposite long side direction is measured, and this test force is measured between the curable resin layer and the polycarbonate plate. The value divided by the contact area is taken as the pressure sensitive adhesive force. In FIG. 1, 101 indicates a glass substrate, 102 indicates a polycarbonate plate, 103 indicates a curable resin layer, and D indicates a peeling direction.

  Moreover, it is preferable from a viewpoint of the wettability of resin that a curable resin composition has a resin characteristic that the aspect ratio after bonding of the curable resin layer formed becomes high. The specific aspect ratio value is preferably 0.6 or more, and more preferably 0.8 or more. The aspect ratio value is measured by the following method and conditions.

(Aspect ratio measurement method)
A curable resin composition is applied on a glass substrate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm, and a curable resin layer having a width of 0.6 mm, a length of 25 mm, and a thickness of 50 μm is formed as the length of the curable resin layer. It provided such that the direction is orthogonal to the long side of the glass substrate, the cured resin layer, the total dose at the irradiation intensity of 3000 mW / cm ² is irradiated with light having a wavelength of 365nm to be 5000 mJ / cm ^2, irradiation A polycarbonate plate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm is placed on the curable resin layer within 1 minute from 1 to 5 mm so that the long side of the glass substrate and the long side of the polycarbonate plate are aligned when viewed from the vertical direction. A measurement sample is obtained by laminating a 1 N load over 10 seconds ((a) and (b) of FIG. 2). When the width of the curable resin layer in contact with the polycarbonate plate in the measurement sample is B (unit: mm), B / 0.6 is the aspect ratio. 2, 104 indicates a glass substrate, 106 indicates a polycarbonate plate, 105 indicates a curable resin layer, and A indicates 0.6 (width of the curable resin layer).

  The curable resin composition of the present embodiment has a light shielding property that suppresses light leakage from between the image display unit and the frame unit and is efficient even in a narrow region in manufacturing an image display device. The image display device and the frame portion can be bonded and fixed even under high temperature and can be used to form a light shielding layer.

  Next, an image display device including a light shielding layer formed from a curable resin composition and a method for manufacturing the image display device will be described.

  FIG. 3 is a cross-sectional view showing an embodiment of the image display device. The image display apparatus 100 shown in FIG. 3 supplies light to the liquid crystal panel 41 and the image display unit 1 including the liquid crystal panel 41 having the image display surface 41S, the cover member 20, and the light-transmitting pressure-sensitive adhesive layer 42. A backlight unit 43, a frame unit 5 that supports the image display unit 1 and accommodates the liquid crystal panel 41 and the backlight unit 43, and a light shielding layer 3 formed between the frame unit 5 and the image display unit 1. Prepare. The cover member 20 includes a cover glass 21 having a light transmission portion 25 facing the image display surface 41S, and a frame portion 22 provided on the peripheral portion of the main surface of the cover glass 21 on the image display surface 41S side. The light transmissive pressure sensitive adhesive layer 42 is bonded between the liquid crystal panel 41 and the cover member 20 while being interposed. The light transmissive pressure-sensitive adhesive layer 42 may be generally referred to as OCA (Optical clear adhesive). The backlight unit 43 includes a light source 45 and an optical sheet unit 46 for supplying light from the light source 45 to the liquid crystal panel 41.

  The frame unit 5 includes a resin frame 51 provided around the liquid crystal panel 41 and the backlight unit 43, a backlight frame 52 that houses the backlight unit 43 outside the resin frame 51, and a backlight frame 52. And a housing frame 53. The resin frame 51 supports the image display unit 1 by adhering to the peripheral portion of the liquid crystal panel 41 and the frame portion 22 of the cover member 20 with the light shielding layer 3 interposed therebetween. The backlight frame 52 supports the image display unit 1 by adhering to the frame unit 22 with the light shielding layer 3 interposed therebetween. The housing frame 53 supports the image display unit 1 by adhering to the frame unit 22 with the light shielding layer 3 interposed.

  The image display device 100 of FIG. 3 has four light shielding layers 3, which are provided between the liquid crystal panel 41 or the cover member 20 (frame portion 22) and the frame portion 5, respectively. The light shielding layer 3 can have such a light transmittance that light leakage from the backlight unit 43 is substantially invisible. Specifically, the average light transmittance at 400 to 700 nm of the light shielding layer 3 may be less than 10%. This average light transmittance may be, for example, a value measured under the condition of irradiating light in the thickness direction of the light shielding layer 3.

  The light-shielding layer 3 may form a closed frame-like body that completely surrounds the periphery of the backlight unit 43, and surrounds a part of the periphery of the backlight unit 43 as long as light leakage can be sufficiently suppressed. An open frame-like body may be formed. As will be described later, the light shielding layer 3 between at least one selected from the resin frame 51, the backlight frame 52, and the housing frame 53 and the image display unit 1 is coated with a curable resin composition and active energy rays. It can be formed by a method including irradiation. A part of the light shielding layer of the image display device may be formed of a pressure sensitive adhesive tape.

  The width W of each light shielding layer 3 in a direction perpendicular to the direction in which the light shielding layer 3 extends may be 0.5 mm or less. When the width W is narrow, an image display device having a narrower frame portion and excellent design can be obtained. The lower limit of the width W is not particularly limited, but may be about 0.2 mm.

  Each member which comprises the image display part 1 and the frame part 5 can be suitably selected from what is normally employ | adopted in the field | area of an image display apparatus. The optical sheet unit 46 of the backlight unit 43 generally includes a lens sheet, a diffusion sheet, a light guide plate, a reflection sheet, and the like. The configurations of the optical sheets and the image display device are not limited to the configurations in FIG. 3, and the number and shape of the frames, the portion where the light shielding layer is provided, and the like can be changed as appropriate. For example, the frame portion 22 may not be provided, and the peripheral portion of the cover glass 21 and the frame portion 5 may be bonded with the light shielding layer 3 interposed.

  4 and 5 are perspective views showing an embodiment of a method for manufacturing an image display device. The method shown in FIGS. 4 and 5 applies a curable resin composition to a predetermined portion (periphery portion of the main surface on the back side) of the image display unit 1 (for example, a cover member) to form a frame-like curable property. A step of forming the resin layer 3A (FIG. 4) and a step of proceeding the curing reaction of the curable resin layer 3A by irradiating the curable resin layer 3A with the active energy ray hν (FIG. 4B). ) And a step of attaching the image display unit 1 and the frame unit 5 (FIG. 5) in this order with the curable resin layer 3A having undergone a curing reaction interposed therebetween. The light shielding layer 3 is formed by the progress of the curing reaction in the curable resin layer 3A.

  6 and 7 are also perspective views showing an embodiment of a method for manufacturing an image display device. In the case of this method, the frame-shaped curable resin layer 3A is formed by applying the curable resin composition to the frame portion 5. The other points are the same as the method of FIGS.

  Hereinafter, an embodiment of a method for manufacturing the image display device 100 of FIG. 3 will be described in more detail with the method of FIGS. 4 and 5 as an example.

Process (I) (Coating process)
As shown in FIG. 4, the curable resin composition of this embodiment mentioned above is apply | coated to the peripheral part of the main surface of the image display part 1, and 3A of frame-shaped curable resin layers are formed. By adjusting the application means, a curable resin layer can be efficiently formed in a narrow region. For example, the curable resin composition can be applied efficiently and with high accuracy by a method of discharging a liquid curable resin composition from the opening.

Process (II) (active energy ray irradiation process)
Thereafter, the active energy ray hν is irradiated to the curable resin layer 3A to advance the curing reaction of the curable resin layer 3A. In the curable resin layer 3 </ b> A, a curing reaction mainly by a radical polymerization reaction proceeds immediately after irradiation with active energy rays. Due to the progress of the curing reaction, appropriate pressure-sensitive adhesiveness can be imparted to the curable resin layer 3A. The silanol group or alkoxysilyl group contained in the curable resin layer 3A advances a curing reaction by an ionic reaction (hydrolysis reaction) involving moisture (moisture), and this reaction generates photobase by the action of active energy rays. Although it can be catalyzed by a base generated from a photoradical polymerization initiator that generates an agent or a base, this ionic reaction proceeds at a slower reaction rate than the radical polymerization reaction. Therefore, it can be said that the curable resin layer 3A is semi-cured by radical polymerization reaction at the stage of irradiation with active energy rays.

Process (III) (bonding process)
As shown in FIG. 5 (a), the image display unit 1 and the frame unit 5 are bonded together with the curable resin layer 3A that is irradiated with active energy rays and has pressure-sensitive adhesiveness interposed therebetween. If necessary, the image display unit 1 and the frame unit 5 may be bonded together while heating the curable resin layer 3A.

  From the viewpoint of balancing step absorbability, pressure-sensitive adhesive strength (adhesive strength), and wettability for developing adhesive strength, the storage elastic modulus at 25 ° C. of the curable resin layer at the time of bonding is 10,000 to 500. It is preferably 30,000 Pa, more preferably 30,000 to 250,000 Pa, and even more preferably 50,000 to 200,000 Pa.

In the bonding process, it is preferable to bond the image display unit 1 and the frame unit 5 so that the aspect ratio represented by the following formula is 0.6 or more. The following aspect ratio is more preferably 0.8 or more.
Aspect ratio = B '/ A'
[In the formula, A ′ indicates the width of a predetermined portion of the frame-shaped curable resin layer 3A applied to the image display unit 1, and B ′ indicates that the image display unit 1 and the frame unit 5 are bonded together. The width | variety which is contacting the flame | frame part 5 in the predetermined site | part of 3 A of curable resin layers after is shown. Here, A ′ and B ′ indicate widths at the same positions as A and B shown in FIG. ]

  The widths of A ′ and B ′ are, for example, that the predetermined part is a direction in which the curable resin layer 3A extends from the curable resin layer 3A before and after the image display unit 1 and the frame unit 5 are bonded to each other. When it is a cut surface when cut on the same vertical surface, the line width where the curable resin layer 3A before bonding and the image display unit 1 are in contact is A ′, the curable resin layer 3A after bonding, and The line width in contact with the frame portion 5 is B ′. In addition, when forming curable resin layer 3A on the frame part 5, the line width which the curable resin layer 3A before bonding in the said cut surface and the frame part 5 contact | connect is A ', and after bonding The line width where the curable resin layer 3A and the image display unit 1 are in contact is B ′.

  When the aspect ratio (B ′ / A ′) is within the above range, wettability is easily secured, and adhesion to the image display unit 1 or the frame unit 5 is easily obtained.

Process (IV) (Curing process)
As shown in FIG. 5B, the curing reaction of the curable resin layer 3 </ b> A may be further cured in the state of a laminate having the image display unit 1 and the frame unit 5 and bonded together. In this specification, the curing reaction that proceeds after the bonding may be referred to as “delayed curing”. The delayed curing can be allowed to proceed over 12 hours in an environment of 10 ° C. or higher, 15 ° C. or higher, or 20 ° C. or higher, and a humidity of 30% or higher, 40% or higher, or 50% or higher. . The environment for allowing delayed curing to proceed may be a temperature of 80 ° C. or lower and a humidity of 95% or lower. While the delayed curing is proceeding, other necessary steps such as a step of further processing the image display device or a step of inspecting the image display device may be performed.

  Although delayed curing may be radical polymerization, it is more typically a curing reaction by ionic reaction (hydrolysis reaction) having a reaction rate slower than that of radical polymerization. Delayed curing proceeds by an ionic reaction (hydrolysis reaction) of the silanol group or alkoxysilyl group having the component (B1) contained in the curable resin layer 3A. This ionic reaction (hydrolysis reaction) can be promoted by a base generated from a photobase generator or a photoradical polymerization initiator that generates a base. The curable resin layer 3A (that is, the light shielding layer 3) after delayed curing can bond the cover member and the image display unit with higher adhesive force.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these.

Raw material of curable resin composition (A) Photoinitiator (A1) Photoradical polymerization initiator and photoradical polymerization initiator that generates a base:
IRG-907 (manufactured by BASF Japan, IRGACURE-907, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one)
(B) Monomer component (B1) Monomer having one radical polymerizable group and a silanol group or an alkoxysilyl group. KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503, 3-methacrylic) Roxypropyltrimethoxysilane)
・ KBM-502 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-502, 3-methacryloxypropylmethyldimethoxysilane)
・ KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5803, methacryloxyoctyltrimethoxysilane)
・ KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103, 3-acryloxypropyltrimethoxysilane)
(B2) Monofunctional monomer / IBOA having one radical polymerizable group (Isobornyl acrylate, manufactured by Nippon Shokubai Co., Ltd.)
・ HPA (Osaka Organic Chemical Co., Ltd., HPA, hydroxypropyl acrylate)
(C) Colorant / AF BLACK AG 4003 (manufactured by Sanyo Color Co., Ltd., black pigment dispersion)

(E) Polymer (oligomer)
The oligomer (2-ethylhexyl acrylate and 2-hydroxyethyl acrylate copolymer) was synthesized by the following procedure.
In a reaction vessel equipped with a condenser, a thermometer, a stirrer, a dropping funnel and a nitrogen injection tube, 84.0 g of 2-ethylhexyl acrylate and 36.0 g of 2-hydroxyethyl acrylate were used as initial monomers, and methyl isobutyl ketone as a solvent. 225 g was taken to prepare Solution 1. The solution 1 was heated from room temperature to 70 ° C. over 15 minutes while maintaining the temperature at 70 ° C. while replacing nitrogen with an air flow of 100 ml / min for 15 minutes. As an additional monomer, 21.0 g of 2-ethylhexyl acrylate and 9.0 g of 2-hydroxyethyl acrylate were taken, and a solution 2 in which 0.6 g of lauryl peroxide was dissolved was prepared. Next, this solution 2 was dripped over 60 minutes to the solution 1 maintained at 70 degreeC. After completion of dropping, the reaction was further continued for 2 hours. Subsequently, methyl isobutyl ketone was distilled off to obtain a 2-ethylhexyl acrylate solution (heat residue 19% by mass) of a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight 200,000).

Preparation of curable resin composition Each raw material was mixed with the content shown in Table 1, and stirred for 30 minutes while heating to prepare a curable resin composition. Content of each component shown by Table 1 is content (unit: mass%) on the basis of the total mass of curable resin composition.

Evaluation method 1. High temperature load resistance test (24-hour delayed curing product)
As shown in FIGS. 11A to 11G ′, a frame using a tape as a spacer is formed around the PET film (a), and a curable resin composition is applied on the PET film in the frame. Then, a curable resin layer was formed so as to have a thickness of 50 μm (b). The curable resin layer, an ultraviolet irradiation apparatus (manufactured by Panasonic Corporation, UV40 curing system) by irradiating ultraviolet rays so that the light with the peak wavelength of 365nm at the ^{3000mW / cm 2, 5000mJ / cm} 2, curing The curing reaction of the resin layer was allowed to proceed (c). Irradiation output was measured with an illuminometer (“UIT-250” manufactured by USHIO INC.). Thereafter, the tape was peeled off (d) and divided as indicated by broken lines (e).

  Within 1 minute after light irradiation, a polycarbonate plate (PC, thickness 1.0 mm) having a width of 25 mm and a length of 100 mm was applied, and a load of 5 kgf (49 N) was applied so that 25 mm from the tip of the plate overlapped the curable resin layer. (F). Then, a weight of 400 g is attached to the other end of the polycarbonate plate, the polycarbonate plate is set in the vertical direction, a shearing force (400 gf (3.9 N)) is applied to the curable resin layer, and the environment is kept at 25 ° C. and 50% RH for 24 hours. Leave (g) (g ′). After that, when placed in a constant temperature bath at a temperature of 70 ° C., the weight of a load of 400 g is held or dropped when the polycarbonate plate is placed in the vertical direction and a shearing force (400 gf (3.9 N)) is applied to the curable resin layer and left standing. Observe after 24 hours (g) (g ′).

  As described above, when a shearing force (400 gf (3.9 N)) with a weight of 400 g is applied and left in a constant temperature bath at a temperature of 70 ° C. for 24 hours, a weight of 400 g is held when “○” is indicated. When the weight dropped, the high temperature load resistance was evaluated as “x”. The results are shown in Table 1 as a “high temperature load resistance test (24h cured product)”.

2. Adhesive strength (168 hours delayed curing product)
(2.1 Adhesive strength by peeling tensile test)
8 and 9 are schematic views showing a method for measuring the adhesive force. As shown in FIG. 8, a curable resin composition is applied to both ends at the center of a strip-shaped glass base (glass substrate) 60 of 25 cm × 75 cm × 0.1 cm, and two pieces facing each other on the glass base 60. The curable resin layer 3A (height 0.05 mm, width 0.4 to 0.6 mm, length 30 mm to 40 mm) was formed. Against the formed cured resin layer 3A, an ultraviolet irradiation apparatus (manufactured by Panasonic Corporation, UV40 curing system) ultraviolet so that the light with the peak wavelength of 365nm to ^{3000mW / cm 2, 5000mJ / cm} 2 was irradiated with Thus, the curing reaction of the curable resin layer 3A was partially advanced. Irradiation output was measured with an illuminometer (“UIT-250” manufactured by USHIO INC.).

  Next, as shown in FIG. 9, the glass base 60 and the strip-shaped polycarbonate plate 61 (25 cm × 75 cm × 0.1 cm) are placed on the short side of the glass base 60 while interposing the curable resin layer 3 </ b> A after ultraviolet irradiation. Bonding was performed while applying a load of 5 kgf (49 N) in a direction in which the side and the long side of the polycarbonate plate 61 were parallel to obtain a joined body of glass and polycarbonate plate (glass joined body).

  Next, this glass joined body was delayed-cured by standing in a room at 25 ° C. and 50% RH for 168 hours, and then the adhesion in the peeling direction was measured by the following method.

As shown in FIG. 9, both end portions 61 </ b> E of the polycarbonate plate 61 of the glass joined body are fixed in a state where the glass base 60 is horizontal with respect to the ground and the glass base 60 is positioned below the polycarbonate plate 61. In that state, a load was applied vertically downward (in the direction of arrow F) to the glass base 60, and the load was increased until the glass base 60 was peeled off. A test force (load) at the time when the glass base 60 peels from the polycarbonate plate is measured, and a value obtained by dividing this test force by the adhesion area between the curable resin layer 3A (or the light shielding layer 3) and the polycarbonate plate 61, Recorded as adhesion. This result is shown in Table 1 as “adhesive strength (N / cm ² ) (168h cured product) by peeling tensile test”.

(2.2 Adhesive strength by shear tensile test)
The glass-polycarbonate plate joined body (glass joined body) produced by the above-described 2.2 peel-off tensile test was used. In the same manner as described above, this glass bonded body was delayed cured by standing in a room at 25 ° C. and 50% RH for 168 hours, and then the adhesive strength in the shear direction was measured by the following method.

As shown in FIG. 9, the glass base 60 of the glass joined body is fixed, the polycarbonate plate 61 is pulled in the long side direction (the direction of the arrow F ′ in FIG. 9), and a load in the shear direction is applied. The test force (load) at the time of peeling from the plate was measured, and a value obtained by dividing the test force by the adhesion area between the curable resin layer 3A (or the light shielding layer 3) and the polycarbonate plate 61 was defined as the adhesive force. The results are shown in Table 1 as “Adhesive strength by shear tensile test (N / cm ² ) (168 h cured product)”.

3. Aspect ratio (A / B ratio)
A curable resin composition is applied on a glass substrate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm, and a width of about 0.6 mm (measured value Amm, corresponding to A in FIG. 2), a length of 25 mm, and a film thickness of 50 μm. provided the curable resin layer so that the length direction of the curable resin layer is orthogonal to the long side of the glass substrate, the cured resin layer, the total dose at the irradiation intensity of 3000 mW / cm ² is the 5000 mJ / cm ² Irradiate light with a wavelength of 365 nm so that a polycarbonate plate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm is formed on the curable resin layer within 1 minute from the light irradiation, and the long side of the glass substrate and the long side of the polycarbonate plate Are aligned so as to be seen from the vertical direction, and a 1N load is applied for 10 seconds to obtain a measurement sample. When the width of the curable resin layer in contact with the polycarbonate plate in the measurement sample is B (unit: mm), B / A is the aspect ratio. The case where the aspect ratio is 0.8 or more is indicated by “◯”, the case where the aspect ratio is 0.4 to less than 0.8 is indicated by “Δ”, and the case where the aspect ratio is less than 0.4 is indicated by “X”. The results are shown in Table 1 as “Aspect ratio (A / B ratio)”.

4). Light-shielding plate-like soda glass 62 (float glass, “MICRO SLIDE GLASSS 9213” manufactured by Matsunami Glass Industrial Co., Ltd., size 76 × 52 mm, thickness 1.2 to 1.5 mm, irradiation light transmittance 90%), acetone It was wiped well with a non-woven fabric soaked ("Bencot" manufactured by Asahi Kasei Fibers Co., Ltd.) and used as a glass substrate for testing. As shown in FIG. 10, a tape (“No. 402 cloth tape” manufactured by Okamoto Co., Ltd., width 5.00 mm) is attached along four sides of one main surface of the soda glass 62 to form a frame-shaped guide 65. did.

Next, a curable resin composition (1 mL) was dropped on the surface 62S of the soda glass 62 inside the guide 65 and stretched with a glass rod to form a curable resin layer. Respect formed cured resin layer, an ultraviolet irradiation apparatus (manufactured by Panasonic Corporation, UV40 curing system) by irradiating ultraviolet rays so that the light with the peak wavelength of 365nm at the ^{3000mW / cm 2, 5000mJ / cm} 2 The curing reaction of the curable resin layer 3A was partially advanced. Irradiation output was measured with an illuminometer (“UIT-250” manufactured by USHIO INC.). The thickness of the curable resin layer after light irradiation was 150 μm.

The light transmittance at a wavelength of 400 to 700 nm of the curable resin layer after light irradiation was measured using a visible ultraviolet spectrophotometer (“UV-2400PC” manufactured by Shimadzu Corporation). Based on the average light transmittance at 400 to 700 nm, the light shielding property was evaluated according to the following criteria. The results are shown in Table 1 as “light shielding properties”.
A: Average light transmittance at 400 to 700 nm is less than 10% F: Average light transmittance at 400 to 700 nm is 10% or more

* High temperature load resistance test ○: Holding ×: Dropping, Aspect ratio ○: 0.8 or more △: Less than 0.4 to 0.8

Table 1 shows the evaluation results of the high temperature load resistance, aspect ratio, adhesive strength, and light shielding properties for each curable resin composition. In Comparative Example 2 that does not contain a compound having a silanol group or alkoxysilyl group, and Comparative Example 1 in which the radical polymerizable group is not a methacryloyl group even if they are contained, the high temperature load resistance and adhesive strength are poor.
On the other hand, in the Example which has a silanol group or an alkoxy silyl group, and a radical polymerizable group contains a methacryloyl group, it is excellent in a high temperature load resistance, and an aspect ratio and adhesiveness become favorable.
In each Example, it was confirmed that a light shielding layer having sufficient light shielding properties can be easily formed in a narrow region by a method of applying a curable resin composition. Furthermore, the formed light shielding layer expressed high adhesive force in the shear direction.

  According to the present invention, in manufacturing an image display device, the light-shielding layer has a light-shielding property that suppresses light leakage from between the image display unit and the frame unit, and can be efficiently formed even in a narrow region. The curable resin composition which can be used in order to form can be provided. In addition, according to the present invention, even if it is a fine adhesive surface, the adhesive force that can suppress a drop impact and peeling due to a repulsive force of a member (for example, a flexible wiring board (FPC)) constituting the image display device can be suppressed. It is possible to provide a method for manufacturing an image display device that is obtained and has a light-shielding layer excellent in light leakage prevention properties and is effective in adhesive strength in the shearing direction even at high temperatures. These are useful for industrial manufacture of information terminals such as smart phones, touchpads, personal computers, and televisions.

  DESCRIPTION OF SYMBOLS 1 ... Image display part, 3 ... Light-shielding layer, 5 ... Frame part, 3A ... Curable resin layer, 20 ... Cover member, 21 ... Cover glass, 22 ... Frame part, 25 ... Light transmission part, 41 ... Liquid crystal panel, 41S DESCRIPTION OF SYMBOLS ... Image display surface 42 ... Light-transmissive pressure-sensitive adhesive layer 43 ... Backlight part 45 ... Light source 46 ... Optical sheet part 51 ... Resin frame 52 ... Backlight frame 53 ... Housing frame 60 ... Glass Base, 61 ... Polycarbonate plate, 61E ... Both ends of glass base 61, 62 ... Soda glass, 62S ... Surface of soda glass 62, 65 ... Guide, 100 ... Image display device, W ... Width of light shielding layer, 101 ... Glass base Material: 102 ... Polycarbonate substrate (plate), 103 ... Curable resin layer, 104 ... Glass substrate, 105 ... Curable resin layer, 106 ... Polycarbonate plate, A ... 0.6mm ( Width), D ... peeled off direction of the resistant resin layer.

Claims (12)

  A photoinitiator, a monomer component, and a colorant, and the photoinitiator includes a photoradical polymerization initiator, or a photoradical polymerization initiator and a base generator, and the monomer component A curable resin composition comprising a monomer having one radical polymerizable group and a silanol group or an alkoxysilyl group, wherein the radical polymerizable group is a methacryloyl group.   A photoinitiator, a monomer component, a colorant, and a compound having a silanol group or an alkoxysilyl group, wherein the photoinitiator is a photoradical polymerization initiator, or a photoradical polymerization initiator and A curable resin composition comprising a photobase generator, wherein the monomer component comprises a monomer having one radical polymerizable group, and the radical polymerizable group is a methacryloyl group.   The curable resin composition according to claim 1 or 2, further comprising a polymer.   The curable resin composition according to any one of claims 1 to 3, which is used for forming a light shielding layer.   The curable resin composition according to any one of claims 1 to 4, which exhibits pressure-sensitive adhesiveness when irradiated with active energy rays. The curable resin composition according to claim 5, wherein the curable resin composition is held without being dropped in a high temperature load bearing test in the following method.
By applying a curable resin composition onto a PET film to form a cured resin layer having a thickness of 50 [mu] m, so that the light with the peak wavelength of 365nm to the curable resin layer to ^{3000mW / cm 2, 5000mJ / cm} 2 Irradiate ultraviolet rays. Next, within 1 minute from the light irradiation, a polycarbonate plate having a width of 25 mm, a length of 100 mm, and a thickness of 1 mm is placed in an area of 25 mm long and 25 mm wide so that 25 mm from the front end of the plate overlaps the curable resin layer. Bonding while applying 5 kgf (49 N). Next, a weight of 400 g is attached to the other end of the polycarbonate plate, and the polycarbonate plate is left in an environment of 25 ° C. and 50% RH for 24 hours while applying a shearing force to the curable resin layer in the vertical direction. Next, observe whether the weight of the load of 400 g is held or dropped when left in a constant temperature bath at a temperature of 70 ° C. while applying a shearing force to the curable resin layer with the polycarbonate plate in the vertical direction. To do. The curable resin composition of Claim 5 or 6 whose aspect-ratio calculated | required with the following method is 0.6 or more.
A curable resin composition is applied on a glass substrate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm, and a curable resin layer having a width of 0.6 mm, a length of 25 mm, and a thickness of 50 μm is formed as the length of the curable resin layer. It provided such that the direction is orthogonal to the long side of the glass substrate, the cured resin layer, the total dose at the irradiation intensity of 3000 mW / cm ² is irradiated with light having a wavelength of 365nm to be 5000 mJ / cm ^2, irradiation A polycarbonate plate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm is placed on the curable resin layer within 1 minute from 1 to 5 mm so that the long side of the glass substrate and the long side of the polycarbonate plate are aligned when viewed from the vertical direction. A measurement sample is obtained by laminating a 1 N load for 10 seconds. When the width of the curable resin layer in contact with the polycarbonate plate in the measurement sample is B (unit: mm), B / 0.6 is the aspect ratio. A liquid crystal panel having an image display surface; an image display portion having a cover member having a light transmission portion facing the image display surface; a frame portion provided around the image display portion and supporting the image display portion; An image display device comprising a light shielding layer formed between the frame portion and the image display portion,
The image display apparatus whose said light shielding layer is a hardened | cured material of the curable resin layer which consists of a curable resin composition as described in any one of Claims 1-7. A liquid crystal panel having an image display surface; an image display portion having a cover member having a light transmission portion facing the image display surface; a frame portion provided around the image display portion and supporting the image display portion; A method of manufacturing an image display device comprising: a light shielding layer formed between the frame portion and the image display portion,
Applying the curable resin composition according to any one of claims 1 to 7 to the image display unit or the frame unit to form a frame-shaped curable resin layer;
Irradiating active energy rays to the curable resin layer to advance a curing reaction of the curable resin layer; and
A step of adhering the image display unit and the frame unit in this order while interposing the curable resin layer,
The manufacturing method of an image display apparatus whose said light shielding layer is the said curable resin layer in which hardening reaction advanced.   The method for manufacturing an image display device according to claim 9, wherein the curable resin layer when the image display unit and the frame unit are bonded has pressure-sensitive adhesiveness. The method for manufacturing an image display device according to claim 9 or 10, wherein the image display unit and the frame unit are bonded so that an aspect ratio represented by the following formula is 0.6 or more.
Aspect ratio = B '/ A'
[In the formula, A ′ represents a width at a predetermined portion of the frame-shaped curable resin layer applied to one of the image display unit and the frame unit, and B ′ represents the image display unit and The width | variety which has contacted the other of the said image display part and the said frame part in the said predetermined part of the said curable resin layer after the said frame part was bonded together is shown. ]   The image display device according to any one of claims 9 to 11, further comprising a step of further proceeding a curing reaction of the curable resin layer after the step of bonding the image display unit and the frame unit. Manufacturing method.