WO2018038212A1

WO2018038212A1 - Manufacturing method of image display device

Info

Publication number: WO2018038212A1
Application number: PCT/JP2017/030351
Authority: WO
Inventors: 祐樹宮本
Original assignee: 日立化成株式会社
Priority date: 2016-08-24
Filing date: 2017-08-24
Publication date: 2018-03-01
Also published as: WO2018037514A1; TW201815580A

Abstract

A manufacturing method is provided of an image display device which comprises an image display unit which has a liquid crystal panel and a cover member, a frame unit which is provided around and supports the image display unit, and a light blocking layer which is formed between the frame unit and the image display unit. This method involves, in order, a step for coating the image display unit or frame unit with a curable resin composition containing a colorant to form a frame-shaped curable resin layer, a step for promoting the curing reaction of the curable resin layer by irradiating the curable resin layer with active energy rays, and a step for bonding the image display unit and the frame unit while the curable resin layer is interposed therebetween.

Description

Manufacturing method of image display device

The present invention relates to a method for manufacturing an 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 around the image display surface and the light shielding layer 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.

The present invention provides a method capable of efficiently forming a light-shielding layer having a light-shielding property that suppresses light leakage from between an image display part and a frame part even in a narrow region when manufacturing an image display device. The purpose is to do.

One aspect of the present invention is 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 the image display portion provided around the image display portion. There is provided a method of manufacturing an image display device comprising: a frame portion that supports a frame; and a light shielding layer formed between the frame portion and the image display portion. This method includes a step of applying a curable resin composition containing a colorant to the image display member or the frame portion to form a frame-shaped curable resin layer, and the curable resin layer. By irradiating an active energy ray, a step of proceeding a curing reaction of the curable resin layer and a step of bonding the image display unit and the frame unit while interposing the curable resin layer in this order. Prepare. The light shielding layer is the curable resin layer that has undergone a curing reaction.

According to the above method, the light shielding layer that suppresses light leakage between the image display portion and the frame portion can be efficiently formed even in a narrow region.

In the above method, the curable resin layer when the image display portion and the frame portion are bonded to each other can 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 0.4 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 above method 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. Thereby, an image display part and a frame part can be pasted up by higher adhesive strength.

In the above method, the width of the light shielding layer in a direction perpendicular to the direction in which the light shielding layer extends may be 0.5 mm or less. Even in such a narrow region, according to the above method, it is possible to form the light shielding layer more efficiently than in the case where a pressure sensitive adhesive tape is used.

The curable resin composition may further contain a photo radical polymerization initiator and a monomer component containing a monofunctional monomer having one radical polymerizable group.

The monofunctional monomer may include a compound having a reactive group that crosslinks polymer chains generated by radical polymerization of the monomer component by ionic reaction. When the curable resin composition contains a compound having a reactive group that crosslinks polymer chains by ionic reaction, curing of the curable resin layer by ionic reaction is followed by curing reaction by generation of polymer chain by photoradical polymerization. The reaction can easily proceed further. From the same viewpoint, the monofunctional monomer may include a compound having a silanol group and / or an alkoxysilyl group. Alternatively, the monofunctional monomer may include a compound having a cyclic ether group. In this case, the curable resin composition may further contain a photoacid generator. The monofunctional monomer may include a compound having an isocyanate group. The curable resin composition may further contain a photobase generator. The photobase generator may also serve as the photoradical polymerization initiator.

The curable resin composition may further contain a polymer. When the curable resin composition contains a polymer, the curable resin layer after being irradiated with active energy rays particularly easily has pressure-sensitive adhesive properties for bonding the image display portion and the frame portion together. be able to.

According to an aspect of the present invention, in manufacturing an image display device, a light-shielding layer having a light-shielding property that suppresses light leakage from between an image display unit and a frame unit can be efficiently formed even in a narrow region. Can be formed. According to some aspects of the present invention, the image display unit can be fixed with higher adhesive force. The high adhesive force can suppress the peeling and floating of the image display unit due to the impact force due to dropping or the repulsive force of the flexible wiring board (FPC).

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 schematic diagram which shows the method of measuring the pressure-sensitive adhesive force of a curable resin layer. It is a schematic diagram which shows the method of measuring the aspect-ratio of a curable resin layer. 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.

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”.

FIG. 1 is a cross-sectional view showing an embodiment of an image display device. The image display device 100 shown in FIG. 1 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 is generally sometimes 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.

1 has four light shielding layers 3, which are provided between the liquid crystal panel 41 or the cover member 20 (the 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.

The members constituting the image display unit 1 and the frame unit 5 can be appropriately selected from those normally employed in the field of image display devices. 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 configuration of the image display device is not limited to the configuration shown in FIG. 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.

2 and 3 are perspective views showing an embodiment of a method for manufacturing an image display device. The method shown in FIGS. 2 and 3 applies a curable resin composition to a predetermined portion (periphery 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. 2) 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. 2B) And the step of attaching the image display unit 1 and the frame unit 5 (FIG. 3) in this order while interposing the curable resin layer 3A having undergone the curing reaction. The light shielding layer 3 is formed by the progress of the curing reaction in the curable resin layer 3A.

4 and 5 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.

Curable Resin Composition Hereinafter, some forms of the curable resin composition that can be used for forming the light shielding layer in the above method will be described. A curable resin composition according to an embodiment includes a monomer including a photo radical polymerization initiator (hereinafter also referred to as “component (A)”) and a monofunctional monomer having one radical polymerizable group. A component (hereinafter also referred to as “component (B)”) and a colorant (hereinafter also referred to as “component (C)”) may be contained.

(A) Component: Photoradical Polymerization Initiator The photoradical polymerization initiator is a component that generates a free radical 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 photo radical polymerization 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 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 and benzyldimethyl ketal Benzyl compounds such as β- (acridin-9-yl) (meth) acrylic acid, etc .; 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-Diff 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 -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-di Examples thereof include phosphine oxide compounds such as phenylphosphine oxide. A radical photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type. From the viewpoint of curability, reactivity, and surface curability, a radical photopolymerization initiator may be selected from aromatic ketone compounds, α-hydroxyalkylphenone compounds, and phenylglyoxylic acid methyl esters.

The photo radical polymerization initiator may be a compound that generates both a free radical and a base (for example, a secondary amino group or a tertiary amino group) by irradiation with active energy rays. In other words, the radical photopolymerization initiator may also serve as the photobase generator. Specific examples of the photo radical polymerization initiator that generates a base include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (“Irgacure 369”, manufactured by BASF Japan Ltd.), 4- (methylthiobenzoyl)- 1-methyl-1-morpholinoethane (“Irgacure 907”, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl ] Α-Aminoacetophenone compounds such as -1-butanone (“Irgacure 379”, manufactured by BASF Japan Ltd.); -1919 "," NCI-831 "(above, manufactured by Adeka), etc. Compounds. Among these, an α-aminoacetophenone compound may be selected.

The content of the radical photopolymerization initiator in the curable resin composition is the total amount of the curable resin composition from the viewpoint of pressure-sensitive adhesiveness, reliability, and curability, and from the viewpoint of efficiently promoting the curing reaction. On the other hand, 2 mass% or more, 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 The monomer component (B) contains one or more 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. The monomer component may be a compound having a (meth) acryloyl group.

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 alkyl such as 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, etc. (Meth) acrylates; (meth) acrylamides such as dimethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide; hydroxyl-containing (meth) acrylamides such as hydroxyethyl (meth) acrylamide; diethylene glycol, triethylene Polyethylene glycol mono (meth) acrylate such as glycol; dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate Polypropylene glycol mono (meth) acrylates such as dibutylene glycol mono (meth) acrylate and tributylene glycol mono (meth) acrylate; morpholine group-containing (meth) acrylates such as acryloylmorpholine; Examples include cyclopentanyl (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 dye solubility, adhesive strength, heat-and-moisture resistance reliability, and pressure-sensitive adhesiveness after curing, monofunctional monomers are dicyclopentanyl (meth) acrylate and dicyclopentenyl (meth) acrylate. And a compound selected from isobornyl (meth) acrylate, or a compound selected from dicyclopentenyl (meth) acrylate and isobornyl (meth) acrylate.

The content of the monofunctional monomer is curable resin 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 composition, and 80 mass% or less, 70 mass% or less, or 60 mass% or less may be sufficient. When the content of the monofunctional monomer is 10% by mass or more, it is easy to obtain a curable resin composition having an appropriate viscosity that contributes to good coating properties, and the solubility of the colorant tends to be improved. is there. When the content of the monofunctional monomer 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 may contain, as a monofunctional monomer, a compound having a reactive group that crosslinks polymer chains generated by radical polymerization of a monofunctional monomer by an ionic reaction. Examples of these compounds include a compound having a silanol group and / or an alkoxysilyl group, a compound having a cyclic ether group, and a compound having an isocyanate group.

Silanol groups and alkoxysilyl groups can advance the curing reaction by ionic reaction involving water (hydrolysis reaction). This reaction can be facilitated, for example, by a base generated from a photobase generator. Specific examples of the compound having a silanol group and / or alkoxysilyl group that can be contained in the monofunctional monomer include 3-acryloxypropyltrimethoxysilane (trade name: KBM5103, Shin-Etsu Chemical Co., Ltd.), 3-methacrylic acid. Compounds having (meth) acryloyl group and trialkoxysilyl group such as loxypropyltrimethoxysilane (trade name: KBM503, Shin-Etsu Chemical Co., Ltd.), methacryloxyoctyltrimethoxysilane (trade name: KBM5803, Shin-Etsu Chemical Co., Ltd.) Is mentioned. The compound having a silanol group and / or an alkoxysilyl group may be a compound having a (meth) acryloyl group and a dialkoxysilyl group, such as methacryloxypropylmethyldiethoxysilane.

A compound having a cyclic ether group can advance a curing reaction by a cationic polymerization reaction of the cyclic ether group. This reaction can be facilitated, for example, by an acid generated from a photoacid generator. Examples of the compound having a cyclic ether group that can be contained in the monofunctional monomer include compounds having an epoxy group and / or an oxetane group. Specific examples of these compounds include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, propylene oxide (PO) modified bisphenol A diglycidyl ether diester. Acrylate, novolac partial epoxy acrylate, acrylic acid adduct of bisphenol A diglycidyl ether, 3-oxetanylmethyl (meth) acrylate, 3-methyl-3-oxetanylmethyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) ) Acrylate, 3-butyl-3-oxetanylmethyl (meth) acrylate, and 3-hexyl-3-oxetanylmethyl (meth) acrylate. The compound having a cyclic ether group may be allyl glycidyl ether.

The compound having an isocyanate group can advance a curing reaction by a reaction of an isocyanate group involving moisture. Specific examples of the compound having an isocyanate group that can be contained in the monofunctional monomer include isocyanatomethyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate.

The content of the compound having a reactive group is the total amount of the curable resin composition from the viewpoint of reactivity, the viewpoint of improving the adhesive force, and the stability when the curable resin composition is a solution. On the other hand, 0.1 mass% or more, 1 mass% or more, or 3 mass% or more may be sufficient, and 15 mass% or less, 10 mass% or less, or 5 mass% or less may be sufficient.

The monomer component (B) contains a monofunctional monomer having one radical polymerizable group as a main component, but in addition to this, a polyfunctional monomer having two or more radical polymerizable groups. It may contain a mer. 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 and / or a pigment. From the viewpoint of obtaining a uniform curable resin composition, a colorant that dissolves in the monomer component may be selected.

It can be confirmed by the following method that the colorant is dissolved in the monomer component. 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 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 and 0.1 part by mass of the colorant with a spectrocolorimeter (for example, manufactured by Konica Minolta, Inc.). “CM-3700A”) can be measured every 1 nm in the range of 400 to 700 nm, an average value of the obtained measurement values can be obtained, and the average transmittance can be obtained. 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 20% or more, 30% or more higher. 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 (active energy ray) irradiated to advance the curing reaction of the colorant solution consisting of 100 parts by mass of the solvent in which the colorant is dissolved and 0.1 part by mass of the colorant. The light transmittance of the colorant at the peak wavelength of) can be determined by a method of measuring the decomposition wavelength under the condition of 1 nm. As the measuring apparatus, 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 may further contain other components as necessary in addition to the components (A), (B) and (C) described above. The curable resin composition contains, for example, a compound having no radical polymerizable group selected from a compound having a silanol group and / or an alkoxysilyl group, a compound having a cyclic ether group, and a compound having an isocyanate group. May be. These compounds can also advance the curing reaction by ionic reaction.

Examples of the compound having a silanol group and / or alkoxysilyl group that can be included in the curable resin composition (excluding a compound having a photoradical polymerizable group; hereinafter also referred to as “compound (X)”) include, for example: A compound having a carboxylic anhydride group and a trimethoxysilyl group (for example, “X-12-967C” manufactured by Shin-Etsu Chemical Co., Ltd.), a compound having an isocyanurate group and a trimethoxysilyl group (for example, “KBM9659”) , Manufactured by Shin-Etsu Chemical Co., Ltd.), a compound having an epoxy group and a trimethoxysilyl group (for example, “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.), a compound having a mercapto group and a trimethoxysilyl group (for example, “ KBM803 ", manufactured by Shin-Etsu Chemical Co., Ltd.) and other compounds having a trialkoxysilyl group; dimethyldimethoxysilane, 3-glyci Propyl dimethoxysilane, 3-compound having a dialkoxy silyl group such as mercaptopropyl methyldimethoxysilane; tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc. tetraalkoxysilane or their oligomers such tetrabutoxy silane. A compound having a silanol group and / or an alkoxysilyl group may be used alone or in combination of two or more. Among these, from the viewpoint of increasing reactivity, a compound having a trialkoxysilyl group, tetraalkoxysilane, or an oligomer thereof may be selected. From the viewpoint of enhancing the stability when the curable resin composition is a solution, a compound having a trialkoxysilyl group, tetraalkoxysilane or an oligomer thereof, and a compound having a dialkoxysilyl group may be combined.

Other examples of the compound (X) include a compound having a trialkoxysilyl group, a compound having a dialkoxysilyl group, and a partial hydrolyzate of at least one compound selected from tetraalkoxysilane and oligomers thereof (for example, A partial hydrolyzate of tetramethoxysilane oligomer, a partial hydrolyzate of tetraethoxysilane and dimethyldimethoxysilane); a compound having trialkoxysilyl group, a compound having dialkoxysilyl group, and tetraalkoxysilane and oligomer thereof A reaction product of at least one selected from tetraalkoxytitanium and / or tetraalkoxyzirconium (for example, a reaction product of tetramethoxysilane oligomer and tetrabutoxytitanium, tetraethoxysilane and tetrabutoxytitanium Applied Physics, reaction products of tetraethoxysilane and tetraethoxysilane zirconium), and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, from the viewpoint of increasing reactivity, a compound having a trialkoxysilyl group, a compound having a dialkoxysilyl group, and a partial hydrolyzate of at least one compound selected from tetraalkoxysilane and oligomers thereof are selected. But you can.

Still another example of the compound (X) includes, for example, an oligomer having a silanol group and / or an alkoxysilyl group.

When the curable resin composition contains a compound having a silanol group and / or alkoxysilyl group as the component (B) and contains the compound (X), the content of the compound (X) From the viewpoint of stability, from the viewpoint of improving the adhesive strength, and from the viewpoint of stability when the curable resin composition is a solution, 0.1% by mass or more and 1% by mass with respect to the total amount of the curable resin composition It may be 3% by mass or more, 15% by mass or less, 10% by mass or less, or 5% by mass or less.

When the curable resin composition does not contain a compound having a silanol group and / or an alkoxysilyl group as the component (B) and contains the compound (X), the content of the compound (X) From the viewpoint of stability, from the viewpoint of improving the adhesive force, and from the viewpoint of stability when the curable resin composition is a solution, 1% by mass or more, 5% by mass or more with respect to the total amount of the curable resin composition, Or 10 mass% or more may be sufficient, and 70 mass% or less, 50 mass% or less, or 30 mass% or less may be sufficient.

Examples of the compound having a cyclic ether group that can be contained in the curable resin composition (however, excluding a compound having a radical photopolymerizable group; hereinafter also referred to as “compound (Y)”) include, for example, an epoxy group, and / or Or the compound which has an oxetane group is mentioned. Specific examples of these compounds include glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxy polyethylene glycol glycidyl ether, phenol polyethylene glycol glycidyl ether, phenyl glycidyl ether, p-methylphenyl Monofunctional epoxy compounds such as glycidyl ether, p-ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether; bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether , Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F Polyglycidyl ethers of bisphenols such as glycidyl ether and hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, Polyglycidyl ethers of polyhydric alcohols such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Aliphatic polyglycidyl ether of the resulting polyether polyol; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxy Chlohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4 -Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclo Pentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclo Polyfunctional epoxy compounds such as compounds having a 3,4-epoxycyclohexyl group such as hexanecarboxylate; 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2- Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (dodecyloxymethyl) oxetane, 3-ethyl-3- (octadecyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl Monofunctional oxetane compounds such as -3-hydroxymethyloxetane; xylylenebisoxetane, 1-butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane, 3-ethyl-3 {[[ (3-Ethyloxetane-3-yl) methoxy] methyl} oxy Tan, 1,1,1-tris [(3-ethyloxetan-3-yl) methoxymethyl] polyfunctional oxetane compounds such as propane.

Other examples of the compound (Y) include an oligomer having a cyclic ether group.

In the case where the curable resin composition contains a compound having a cyclic ether group as the component (B) and contains the compound (Y), the content of the compound (Y) From the viewpoint of improving the force, and from the viewpoint of stability when the curable resin composition is a solution, it is 0.1% by mass or more, 1% by mass or more, and 3% by mass with respect to the total amount of the curable resin composition. The above may be sufficient, and 15 mass% or less, 10 mass% or less, and 5 mass% or less may be sufficient.

When the curable resin composition does not contain a compound having a cyclic ether group as the component (B) and contains the compound (Y), the content of the compound (Y) is determined in terms of reactivity, adhesion. From the viewpoint of improving the force, and from the viewpoint of stability when the curable resin composition is a solution, it is 1% by mass or more, 5% by mass or more, or 10% by mass or more with respect to the total amount of the curable resin composition. 70 mass% or less, 50 mass% or less, or 30 mass% or less may be sufficient.

Compounds having an isocyanate group that can be included in the curable resin composition (however, excluding compounds having a radically polymerizable group; hereinafter, also referred to as “compound (Z)”) include monofunctional isocyanates and polyfunctional isocyanates. Can be mentioned. Specific examples of the monofunctional isocyanate include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl isocyanate, p-nitro. Phenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methylbenzyl isocyanate, (S )-(−)-Α-methylbenzyl isocyanate, (R)-( -)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p-toluenesulfonyl isocyanate. Specific examples of the polyfunctional isocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (also known as 4,4′-MDI), 2 , 4-Tolylene diisocyanate (also known as 2,4-TDI), 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate Aromatic polyisocyanates such as benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate; trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene dii Aliphatic acids such as cyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Polyisocyanate; ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethyl Aromatic aliphatic polyisocyanates such as xylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate; 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1, -Cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1, Examples thereof include alicyclic polyisocyanates such as 4-bis (isocyanatomethyl) cyclohexane, etc. Among these, polyfunctional isocyanates may be selected from the viewpoint of crosslinkability.

Other examples of the compound (Z) include, for example, an oligomer having an isocyanate group (for example, a urethane resin having an isocyanate group at both ends).

In the case where the curable resin composition contains a compound having an isocyanate group as the component (B) and contains the compound (Z), the content of the compound (Z) is determined in terms of reactivity and adhesive strength. From the viewpoint of improving the stability and the stability when the curable resin composition is a solution, 0.1% by mass or more, 1% by mass or more, 3% by mass or more with respect to the total amount of the curable resin composition It may be 15 mass% or less, 10 mass% or less, and 5 mass% or less.

When the curable resin composition does not contain a compound having an isocyanate group as the component (B) and contains the compound (Z), the content of the compound (Z) is determined in terms of reactivity, adhesive strength. 1% by mass or more, 5% by mass or more, or 10% by mass or more with respect to the total amount of the curable resin composition from the viewpoint of improving the stability and the stability when the curable resin composition is a solution. It may be 70 mass% or less, 50 mass% or less, or 30 mass% or less.

The curable resin composition according to this embodiment may further contain a photobase generator as the component (D). In the present specification, the term “photobase generator” refers to the generation of one or more basic substances that can function as a curing catalyst for ionic reaction by changing the molecular structure or cleaving the molecule upon irradiation with active energy rays. Means a compound. As the photobase generator, the aforementioned radical photopolymerization initiator that generates a base may be used.

Photobase generators include Co-amine complex photobase generators; carbamate ester photobase generators; quaternary ammonium salt photobase generators; acyloxyimino groups, N-formylated aromatic amino groups, N- It can also be selected from compounds having an acylated aromatic amino group, a nitrobenzyl carbamate group, an alkoxybenzyl carbamate group, and the like. 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, -Diisopropyl-3- [bis (dimethylamino) methylene] guanidinium 2- (3-benzoylphenyl) propionate, 2-nitrobenzylcyclohexylcarbamate, O-carbamoylhydroxylamide, O-carbamoyloxime, {[(2,6-dinitro Benzyl) 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- And 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 in the curable resin composition is 2% by mass or more, 4% by mass or more with respect to the total amount of the curable resin composition, from the viewpoint of efficiently accelerating the curing reaction by ionic reaction. 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. Here, when the photobase generator also serves as a radical photopolymerization initiator, the content thereof is regarded as a content as a radical photopolymerization initiator.

The curable resin composition according to the present embodiment may further contain a photoacid generator as the component (E). In this specification, the “photoacid generator” means a compound that generates one or more acidic substances that can function as a curing catalyst for ionic reaction by changing the molecular structure or cleaving the molecule upon irradiation with active energy rays. Means. The photoacid generator can particularly function as a curing catalyst for an ionic reaction of a compound having a cyclic ether group.

Examples of the photoacid generator include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, nitrobenzyl compounds, Organic halides and disulfone can be mentioned. Examples of commercially available photoacid generators include trade names “Syracure UVI-6970”, “Syracure UVI-6974”, “Syracure UVI-6990”, “Syracure UVI-950” (above, Union Carbide, USA) "Irgacure 250", "Irgacure 261", "Irgacure 264", "Irgacure 270", "Irgacure 290" (manufactured by BASF), "CG-24-61" (Ciba Geigy), "Adekaoptomer" “SP-150”, “Adekaoptomer SP-151”, “Adekaoptomer SP-170”, “Adekaoptomer SP-171” (manufactured by ADEKA Corporation), “DAICAT II” (Daicel Corporation) ), "UVAC1590", "UVAC1591" (above, Daicel-Cite) (CI Co., Ltd.), “CI-2064”, “CI-2539”, “CI-2624”, “CI-2481”, “CI-2734”, “CI-2855”, “CI-2823”, “ “CI-2758”, “CIT-1682” (manufactured by Nippon Soda Co., Ltd.), “PI-2074” (manufactured by Rhodia, tetrakis (pentafluorophenyl) borate toluylcumyliodonium salt), “FFC509” (3M Manufactured by the same company), “BBI-102”, “BBI-101”, “BBI-103”, “MPI-103”, “BDS-105”, “TPS-103”, “MDS-103”, “MDS-105” ”,“ MDS-203 ”,“ MDS-205 ”,“ DTS-102 ”,“ DTS-103 ”,“ NAT-103 ”,“ NDS-103 ”,“ BMS-105 ” “TMS-105” (above, manufactured by Midori Chemical Co., Ltd.), “CD-1010”, “CD-1011”, “CD-1012” (above, manufactured by Sartomer, USA), “CPI-100P”, “ "CPI-101A", "CPI-110P", "CPI-110A", "CPI-210S" (San Apro Co., Ltd.), "UVI-6922", "UVI-6976" (above, Dow Chemical Company) Manufactured).

The curable resin composition according to this embodiment may further contain a polymer as the component (F). 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 the present specification, the “polymer” as the component (F) includes the above-described components (A) to (C), a compound having a silanol group and / or an alkoxysilyl group, a compound having a cyclic ether group, and an isocyanate group. It is a component except the compound which does not have the radically polymerizable group chosen from the compound which has this.

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; A polyester-based oligomer that can be produced by transesterification of a compound having a hydroxyl group at a terminal and a compound having an ester group or a carboxy group at both terminals, or a polycondensation reaction; a polyether, a polycarbonate having a hydroxyl group at both terminals, or 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, etc. ; (Meth) acrylates having aromatic rings such as benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylates having an alkoxy group such as acryl (meth) acrylate; cycloaliphatic such as cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate (Meth) acrylate having a group; (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; tetraethylene glycol monomethyl ether ( (Meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol methyl ether (meta) 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 relate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, butadiene polymer having a (meth) acryloyl group, isoprene polymer having a (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 is a homopolymer or copolymer containing a monofunctional monomer having one (meth) acryloyl group contained in the monomer component (B) as a monomer unit. May be. The (meth) acrylic acid polymer may contain a (meth) acrylate having an alkyl group as a monomer unit, or a (meth) acrylate having an alkyl group having 4 to 18 carbon atoms 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 obtain a pressure-sensitive adhesive force that does not cause peeling on a substrate or the like under a high temperature (for example, 80 ° C. or higher) and high humidity (for example, 90% or higher) environment. be able to. Moreover, it is easy to obtain a curable resin composition having a viscosity suitable for coating and good workability.

(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-butylperoxyneodecanoate, t-butylperoxypivalate, (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 Examples include azo compounds such as (2-hydroxymethylpropionitrile) and 2,2′-azobis [2- (imidazolin-2-yl) propane].

The content of the polymer may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 90% by mass or less, 80% by mass or less, 70% by mass with respect to the total amount of the curable resin composition. It may be the following. 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. Moreover, the pressure-sensitive adhesiveness to the adherend such as glass, plastic, polarizing plate and polycarbonate of the cured 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 at least a part of the range of 25 ° C. to 70 ° C. is 10 mPa · s or more, 4.0 × 10 ² mPa · s or more, 5.0 × It may be 10 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 It may be the following. The viscosity at 25 ° C. is a value measured based on JIS Z 8803, and specifically, a value measured using a B-type viscometer (for example, BL2 manufactured by Toki Sangyo Co., Ltd.). Calibration of the B-type viscometer can be performed based on JIS Z 8809-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. For example, the pressure-sensitive adhesive force of the curable resin composition after irradiation with active energy rays may be 10 N / cm ² or more, 20 N / cm ² or more, or 40 N / cm ² or more, and 400 N / cm. ^It may be ² or less. The measurement of pressure-sensitive adhesive force here is performed 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 second glass substrate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm on the curable resin layer within 1 minute from the light irradiation, the long side of the first glass substrate and the second glass substrate It arrange | positions so that it may align with the long side of a material seeing from a perpendicular direction, and a 1N load is bonded over 10 second, and a measurement sample is obtained (FIG. 6). Within one hour after bonding, the test force when the first glass substrate and the second glass substrate of the measurement sample are peeled in the opposite long side directions is measured, and this test force is set to be curable. The value divided by the contact area between the resin layer and the second glass substrate is defined as the pressure-sensitive adhesive force. In FIG. 6, 101 shows a 1st glass base material, 102 shows a 2nd glass base material, 3A shows a curable resin layer, D shows the direction to peel off.

From the viewpoint of wettability of the curable resin layer, the curable resin composition preferably has a resin characteristic such that the aspect ratio after bonding of the curable resin layer to be formed is high. Specifically, the aspect ratio after bonding of the curable resin layer may be 0.4 or more, 0.6 or more, or 0.8 or more. When the aspect ratio is 0.4 or more, wettability is easily secured, and adhesion to the member is easily obtained. The upper limit of the aspect ratio is usually 1.0. The aspect ratio value is measured by the following method and conditions.

(Aspect ratio measurement method)
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 second glass substrate having a width of 25 mm, a length of 75 mm, and a thickness of 1 mm on the curable resin layer within 1 minute from the light irradiation, the long side of the first glass substrate and the second glass substrate It arrange | positions so that it may align with the long side of a material seeing from a perpendicular direction, and a 1N load is bonded together over 10 second, and a measurement sample is obtained ((a) and (b) of FIG. 7). When the width of the curable resin layer in contact with the second glass substrate in the measurement sample is B (unit: mm), B / 0.6 is the aspect ratio. In FIG. 7, 104 indicates a first glass substrate, 106 indicates a second glass substrate, 105 indicates a curable resin layer, and A indicates a curable resin in contact with the first glass substrate. The width of the layer (here 0.6 mm) is indicated.

Hereinafter, an embodiment of a method for manufacturing the image display device 100 of FIG. 1 will be described in more detail by taking the method of FIGS. 2 and 3 as an example.

Process (I) (Coating process)
As shown in FIG. 2, a curable resin composition is applied to the peripheral edge of the main surface of the image display unit 1 to form a frame-shaped curable resin layer 3A. 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 case where the curable resin layer 3A contains (A) a photo radical polymerization initiator and (B) a monomer component including a monofunctional monomer having one radical polymerizable group, Immediately after the irradiation, a curing reaction mainly proceeds by radical polymerization reaction. Due to the progress of the curing reaction, appropriate pressure-sensitive adhesiveness can be imparted to the curable resin layer 3A. When the curable resin layer 3A contains a photobase generator or a photoacid generator, these usually generate a base or an acid by the action of active energy rays, but the ionic reaction catalyzed by the base or acid is a radical. It proceeds at a relatively slower reaction rate than the 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. 3A, the image display unit 1 and the frame unit 5 are bonded to each other while an active energy ray is irradiated and a curable resin layer 3A having pressure-sensitive adhesiveness is interposed. 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 balance between 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 500,000 Pa, 30000. It may be ˜250,000 Pa, or 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 0.4 or more. The following aspect ratio may be 0.6 or more, or 0.8 or more. The upper limit of the aspect ratio is usually 1.0.
Aspect ratio = B '/ A'
In the formula, A ′ indicates the width of a predetermined part of the frame-shaped curable resin layer 3A applied to the image display unit 1, and B ′ is after 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 | prescribed site | part of 3 A of curable resin layers 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 ′. When the curable resin layer 3A is formed on the frame part 5, the line width where the curable resin layer 3A before bonding and the frame part 5 are in contact with each other on the cut surface is A ′, and curing after bonding. The line width where the conductive 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. 3B, the curing reaction of the curable resin layer 3 </ b> A may be further cured in the state of a laminated body 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 is allowed to proceed for 12 hours or more in an environment where the temperature is 10 ° C or higher, 15 ° C or higher, or 20 ° C or higher, and the humidity is 30% or higher, 40% or higher, or 50% or higher. Can do. 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 and / or a step of inspecting the image display device may be performed.

The delayed curing may be radical polymerization, but more typically is a curing reaction by an ionic reaction having a reaction rate slower than that of radical polymerization. When the curable resin layer 3A contains a compound having a reactive group having ionic reactivity, delayed curing proceeds by an ionic reaction of the reactive group of the compound. This ionic reaction can be promoted by a base generated from the photobase generator or an acid generated from the photoacid generator. 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 for curable resin composition (A) Photoradical polymerization initiator / photobase generator Photoradical polymerization initiator:
・ IRG-651 (manufactured by BASF Japan, IRGACURE-651,2,2-dimethoxy-1,2-diphenylethane-1-one)
Photoradical polymerization initiator / photobase generator:
IRG-907 (manufactured by BASF Japan, IRGACURE-907, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one)
(B) Monomer component (monofunctional monomer)
(B1) Monofunctional monomer silanol group having a reactive group and / or compound having an alkoxysilyl group:
・ KBM-5103 (Shin-Etsu Chemical Co., Ltd., KBM-5103, 3-acryloxypropyltrimethoxysilane)
Compound having cyclic ether group:
・ 4HBAGE (Nippon Kasei Co., Ltd., 4HBAGE, 4-hydroxybutyl acrylate glycidyl ether)
Compound having an isocyanate group:
・ AOI (Showa Denko KK, Karenz AOI, 2-isocyanatoethyl acrylate)
(B2) Other monofunctional monomers:
・ NOAA (manufactured by Osaka Organic Chemical Industry Co., Ltd., NOAA, n-octyl acrylate)
・ IBXA (Kyoeisha Chemical Co., Ltd., light acrylate IB-XA, isobornyl acrylate)
・ HPA (Osaka Organic Chemical Co., Ltd., HPA, hydroxypropyl acrylate)
(C) Colorant / elexa Black850 (Orient Chemical Co., Ltd., black dye)
(E) Photoacid generator CPI-210S (manufactured by Sun Apro Co., Ltd., CPI-210S)

(F) Oligomer An oligomer (a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate) was synthesized by the following procedure.
Charge 2-ethylhexyl acrylate (90.0 g), 2-hydroxyethyl acrylate (10.0 g), methyl ethyl ketone (30.0 g), and ethyl acetate (170.0 g) into a container and purge with nitrogen at a flow rate of 100 mL / min. While heating, from normal temperature (25 ° C.) to 65 ° C. After reaching 65 ° C., azobisisobutyronitrile (0.3 g) was added, and kept at this temperature for 8 hours.
Subsequently, isostearyl acrylate (100.0 g) was added, and the solvent methyl ethyl ketone and ethyl acetate were distilled off, whereby a copolymer of 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate (weight average molecular weight 600,000) was obtained. An isostearyl acrylate solution (heating residue 50%) was obtained.

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. Adhesive strength (initial, after delayed curing)
8 and 9 are schematic views showing a method for measuring the adhesive force. As shown in FIG. 8, two curable resins facing each other on the glass base 60 by applying a curable resin composition to both ends of the center of a strip-shaped glass base 60 of 25 cm × 75 cm × 0.1 cm. Layer 3A (height 0.05 mm, width 0.4 to 0.6 mm, length 30 to 40 mm) was formed. Irradiation to the formed curable resin layer 3A using an ultraviolet irradiation device (made by Eye Graphics Co., Ltd., US5-X0401, light source used: made by Eye Graphics Co., Ltd., metal halide lamp M04-L41) The curing reaction of the curable resin layer 3A was partially advanced by irradiating with ultraviolet rays so that the intensity was 400 mW / cm ² and the total irradiation amount was 2000 mJ / cm ² . The irradiation output was measured with an illuminance meter (“UIT-250” manufactured by USHIO INC.).
Next, as shown in FIG. 9, the glass base 60 and another strip-shaped glass base 61 (25 cm × 75 cm × 0.1 cm) are connected to the glass base 60 while interposing the curable resin layer 3 </ b> A after ultraviolet irradiation. In the direction in which the short side of the glass base 61 and the long side of the glass base 61 are parallel to each other, bonding was performed while applying a load of 5 kgf.
Both end portions 61E of the glass base 61 of the obtained glass joined body were fixed in a state where the glass base 61 was horizontal with respect to the ground and the glass base 60 was positioned below the glass base 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. The test force (load) at the time when the glass base 60 is peeled off is measured, and the 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 glass base 61 is defined as the adhesive force. Recorded.
By this method, the initial adhesive strength measured within 2 hours after obtaining the glass joined body, and the delayed post-cured adhesive strength measured after leaving the glass joined body in a room at 25 ° C. and 50% RH for 48 hours. And measured.

2. Light shielding property Plate-like soda glass 62 (float glass, Matsunami glass “MICRO SLIDE GLASSS 9213”, size 76 × 52 mm, thickness 1.2 to 1.5 mm, irradiation light transmittance 90%) was impregnated with acetone. It was wiped well with a non-woven fabric ("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 50 mm) was attached along four pieces of one main surface of the soda glass 62 to form a frame-shaped guide 65. .
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. Irradiation intensity with respect to the formed curable resin layer using an ultraviolet irradiation device (Igraphics Co., Ltd., US5-X0401, use light source: Eyegraphics Co., Ltd., metal halide lamp M04-L41) total dose at 400 mW / cm ² is irradiated such that the 2000 mJ / cm ^2, was allowed to proceed a curing reaction of the curable resin layer. The irradiation output was measured with an illuminance meter (“UIT-250” manufactured by USHIO INC.). The thickness of the curable resin layer after light irradiation was 150 μm.
The light transmittance of the curable resin layer after light irradiation at a wavelength of 400 to 700 nm 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.
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

Table 1 shows the evaluation results of the adhesive strength and the light shielding property regarding each curable tree composition. 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.

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, 41 ... Liquid crystal panel, 41S ... Image display surface, 42 DESCRIPTION OF SYMBOLS ... Light-transmitting pressure sensitive adhesive layer, 43 ... Backlight part, 45 ... Light source, 46 ... Optical sheet part, 51 ... Resin frame, 52 ... Backlight frame, 53 ... Housing frame, 60, 61 ... Glass base, 61E ... Both ends of the

glass base

61, 62 ... soda glass, 62S ... surface of the

soda glass

62, 65 ... guide, 100 ... image display device, W ... width of the light shielding layer.

Claims

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 a curable resin composition containing a colorant to the image display part or the frame part 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
Bonding the image display unit and the frame unit while interposing the curable resin layer;
In this order,
The light-shielding layer is the curable resin layer that has undergone a curing reaction.
Method.
The method according to claim 1, wherein the curable resin layer when the image display unit and the frame unit are bonded has pressure-sensitive adhesiveness.
The method according to claim 1 or 2, wherein the image display unit and the frame unit are bonded so that an aspect ratio represented by the following formula is 0.4 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 method according to any one of claims 1 to 3, 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.
The method according to any one of claims 1 to 4, wherein a width of the light shielding layer in a direction perpendicular to a direction in which the light shielding layer extends is 0.5 mm or less.
6. The curable resin composition according to claim 1, further comprising a photo radical polymerization initiator and a monomer component including a monofunctional monomer having one radical polymerizable group. The method according to one item.
The method according to claim 6, wherein the monofunctional monomer includes a compound having a reactive group that crosslinks polymer chains generated by radical polymerization of the monomer component by ionic reaction.
The method according to claim 6, wherein the monofunctional monomer contains a compound having a silanol group and / or an alkoxysilyl group.
The method according to claim 6, wherein the monofunctional monomer contains a compound having a cyclic ether group, and the curable resin composition further contains a photoacid generator.
The method according to claim 6, wherein the monofunctional monomer includes a compound having an isocyanate group.
The curable resin composition further contains a photobase generator, and the photobase generator may also serve as the photoradical polymerization initiator. Method.
The method according to any one of claims 5 to 11, wherein the curable resin composition further contains a polymer.