JP2017052864A - Photosetting resin composition, image display device and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosetting resin composition hard to leak and easy to shape to a desired shape, an image display device using the photosetting resin composition and a manufacturing method therefor.SOLUTION: A photosetting resin composition contains (A) a compound having a photopolymerizable functional group, (B) an oil gelling agent and (C) a photosetting agent, where (C) the photosetting agent contains phenyl glyoxylic acid methyl ester. An image display device comprises an image display unit having an image display part, a transparent protective sheet, and a laminated structure having a resin layer existing between the image display unit and the transparent protective sheet, where the resin layer is a cured article of the photosetting resin composition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photocurable resin composition, an image display device using the photocurable resin composition, and a method for producing the same.

The photo-curable resin composition is an optical component such as an adhesive, an adhesive, a filler, an optical waveguide, a solar cell member, a light emitting diode (LED), a phototransistor, a photodiode, an optical semiconductor element, an image display device, and an illumination device. Widely used as members, dental materials and the like.
For example, a gap between a transparent protective plate or an information input device (such as a touch panel) in the image display device and a display surface of the image display unit or a gap between the transparent protective plate and the information input device is compared with air. A method has been proposed in which the refractive index is replaced with a transparent material close to the display surface of the transparent protective plate, the information input device, and the image display unit, thereby improving the transparency and suppressing the decrease in luminance and contrast of the image display device. Yes. And as this transparent material, using the adhesive agent hardened | cured with an ultraviolet-ray or visible light is proposed (for example, patent document 1). A schematic example of a liquid crystal display device is shown in FIG. 4 as an example of this image display device. A liquid crystal display device with a built-in touch panel is composed of a transparent protective plate (glass or plastic substrate) 1, a touch panel 2, a polarizing plate 3, and a liquid crystal display cell 4. The liquid crystal display device is prevented from cracking and mitigating stress and impact. In addition, in order to improve visibility, the adhesive layer 5 may be provided between the transparent protective plate 1 and the touch panel 2, and the adhesive layer 6 may be further provided between the touch panel 2 and the polarizing plate 3.

  As said photocurable resin composition, a liquid thing and a film-form thing are known. For example, Patent Document 2 discloses a urethane (meth) acrylate (A) having two or more functional groups having an unsaturated double bond, a monomer (B) having one functional group having an unsaturated double bond, and light. A photocurable transparent adhesive composition containing a polymerization initiator (C) and a polythiol compound (D) having two or more thiol groups is disclosed. Patent Document 3 discloses a transparent pressure-sensitive adhesive sheet made of a photocurable resin composition containing a copolymer of monomer components containing (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms in the alkyl group. It is disclosed. Furthermore, Patent Document 4 discloses a photocurable resin composition containing an amine compound or an amine compound and a thiol compound as additive components in order to suppress bleed-out after curing.

  By the way, as a technique for gelling an oil agent, an oil gelling agent is added to the oil agent. The oil gelling agent is characterized by thickening by forming a network of molecules in oil. The oil agent can be gelled by dispersing the low molecular weight oil gelling agent in the oil agent under heating conditions and cooling to room temperature.

JP 2008-83491 A JP 2009-1654 A JP 2011-74308 A JP2013-185097A

When the photocurable resin composition is in a liquid state as in Patent Document 2 or the like, there is a problem that it easily leaks from the predetermined portion when formed at the predetermined portion.
On the other hand, if the photocurable resin composition is in the form of a sheet (solid) as in Patent Document 3, there is no problem of leakage, but it does not sufficiently deform in accordance with the shape of the predetermined portion, and the predetermined portion is not deformed. There is a problem that voids or the like are easily generated.

  Further, as in Patent Document 4, when a liquid photocurable resin composition is used in an image display device, a method of irradiating light from an end face and curing (side cure) is known in order to cure the light shielding part. Yes. However, in the side cure, there is a problem that the light does not reach the deep part and becomes uncured and bleeds out at a high temperature in the subsequent reliability evaluation. Therefore, before the transparent protective plate or the information input device and the display surface of the image display unit in the image display device or the transparent protective plate and the information input device are bonded together, the surface to which the liquid photocurable resin composition is applied is exposed to the atmosphere. The curability of the light-shielding part is ensured by a method of photocuring in the film and then bonding. However, in that case, there is a problem that oxygen inhibition occurs due to photocuring in the air, and the photocurable resin composition on the extreme surface layer on the air side is not cured and the adhesive strength is reduced.

  The present invention provides a photocurable resin composition that solves the above-described problems, is difficult to leak out, is easy to be molded into a desired shape, has a flat coating surface, and can be photocured in the atmosphere, and the photocurable resin composition An object of the present invention is to provide an image display device using the above and a manufacturing method thereof.

The present invention provides the following [1] to [10].
[1] comprising (A) a compound having a photopolymerizable functional group, (B) an oil gelling agent, and (C) a photocuring agent,
(C) The photocurable resin composition in which the photocuring agent contains phenylglyoxylic acid methyl ester.
[2] The oil gelling agent (B) is a hydroxy fatty acid, hydrogenated castor oil containing hydroxy fatty acid as a main component, n-lauroyl-L-glutamic acid-α, β-dibutylamide, di-p-methylbenzylidene sorbitol gluchi Tol, 1,3: 2,4-bis-0-benzylidene-D-glucitol, 1,3: 2,4-bis-0- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato ) The photocurable resin composition according to [1] above, which is at least one of hydroxyaluminum and compounds represented by the following general formulas (1) to (13).

（一般式（１）中、ｍは３〜１０の整数、ｎは２〜６の整数、Ｒ_１は炭素数１〜２０の飽和炭化水素基、Ｘは硫黄又は酸素である。
一般式（２）中、Ｒ_２は炭素数１〜２０の飽和炭化水素基、Ｙ_１は結合手又はベンゼン環である。
一般式（３）中、Ｒ_３は炭素数１〜２０の飽和炭化水素基、Ｙ_２は結合手又はベンゼン環である。
一般式（４）中、Ｒ_４は炭素数１〜２０の飽和炭化水素基である。
一般式（６）中、Ｒ_５及びＲ_６は、それぞれ独立に、炭素数１〜２０の飽和炭化水素基である。
一般式（７）中、Ｒ_７は、炭素数１〜２０の飽和炭化水素基である。
一般式（８）中、Ｒ_８は、炭素数１〜２０の飽和炭化水素基である。
一般式（１０）中、Ｒ_９及びＲ_１０は、それぞれ独立に、炭素数１〜２０の飽和炭化水素基である。
一般式（１３）中、Ｒ_１１は、炭素数１〜１０の飽和炭化水素基である。Ｒ_１２及びＲ_１３は、それぞれ独立に、炭素数１〜２０の飽和炭化水素基か、もしくは分子骨格中に少なくとも１つ以上の水酸基を有する炭素数１〜２０の飽和炭化水素基である。）
［３］前記（Ａ）光重合性官能基を有する化合物が、エチレン性不飽和基を有する化合物を含む、前記［１］〜［２］に記載の光硬化性樹脂組成物。
［４］前記（Ｃ）光硬化剤が、フェニルグリオキシリックアシッドメチルエステルと該フェニルグリオキシリックアシッドメチルエステルとは別の光重合開始剤とを含む、前記［１］〜［３］のいずれかに記載の光硬化性樹脂組成物。
［５］更に（Ｄ）２５℃で液状の化合物を含む、前記［１］〜［４］のいずれかに記載の光硬化性樹脂組成物。
［６］更に（Ｅ）２５℃で固状の化合物を含む、前記［１］〜［５］のいずれかに記載の光硬化性樹脂組成物。
［７］画像表示部を有する画像表示ユニットと、透明保護板と、前記画像表示ユニットと前記透明保護板との間に存在する樹脂層とを含む積層構造を有する画像表示装置であって、前記樹脂層は、前記［１］〜［６］のいずれかに記載の光硬化性樹脂組成物の硬化物である画像表示装置。
［８］画像表示部を有する画像表示ユニットと、タッチパネルと、透明保護板と、タッチパネルと前記透明保護板との間に存在する樹脂層とを含む積層構造を有する画像表示装置であって、前記樹脂層は、前記［１］〜［６］のいずれかに記載の光硬化性樹脂組成物の硬化物である画像表示装置。
［９］前記透明保護板が段差部を有する前記［７］又は［８］に記載の画像表示装置。
［１０］前記［７］〜［９］のいずれかに記載の画像表示装置の製造方法であって、画像表示部を有する画像表示ユニット又はタッチパネルと、透明保護板との間隙に前記光硬化性樹脂組成物を介在させ、少なくとも前記透明保護板側から光照射を行って硬化させる画像表示装置の製造方法。

(In General Formula (1), m is an integer of 3 to 10, n is an integer of 2 to 6, R ₁ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X is sulfur or oxygen.
In the general formula (2), R ₂ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ₁ is a bond or a benzene ring.
In the general formula (3), _{R 3} is a saturated hydrocarbon group having 1 to 20 carbon atoms, _{Y 2} is a bond or a benzene ring.
In the general formula _{(4), R} 4 is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (6), R ₅ and R ₆ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In the general formula (7), _{R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In the general formula (8), _{R 8} is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (10), R ₉ and R ₁₀ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (13), R ₁₁ is a saturated hydrocarbon group having 1 to 10 carbon atoms. R ₁₂ and R ₁₃ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or a saturated hydrocarbon group having 1 to 20 carbon atoms having at least one hydroxyl group in the molecular skeleton. )
[3] The photocurable resin composition according to the above [1] to [2], wherein the compound (A) having a photopolymerizable functional group includes a compound having an ethylenically unsaturated group.
[4] Any of the above [1] to [3], wherein the (C) photocuring agent comprises phenylglyoxylic acid methyl ester and a photopolymerization initiator different from the phenylglyoxylic acid methyl ester. A photocurable resin composition according to claim 1.
[5] The photocurable resin composition according to any one of [1] to [4], further including (D) a compound that is liquid at 25 ° C.
[6] The photocurable resin composition according to any one of [1] to [5], further including (E) a solid compound at 25 ° C.
[7] An image display device having a laminated structure including an image display unit having an image display unit, a transparent protective plate, and a resin layer existing between the image display unit and the transparent protective plate, The image display device, wherein the resin layer is a cured product of the photocurable resin composition according to any one of [1] to [6].
[8] An image display device having a laminated structure including an image display unit having an image display unit, a touch panel, a transparent protective plate, and a resin layer existing between the touch panel and the transparent protective plate, The image display device, wherein the resin layer is a cured product of the photocurable resin composition according to any one of [1] to [6].
[9] The image display device according to [7] or [8], wherein the transparent protective plate has a stepped portion.
[10] The method for manufacturing an image display device according to any one of [7] to [9], wherein the photocurable resin is provided in a gap between an image display unit or a touch panel having an image display unit and a transparent protective plate. A method for producing an image display device, wherein a resin composition is interposed, and light is irradiated and cured at least from the transparent protective plate side.

  ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition which is hard to leak out and is easy to shape in a desired shape, the image display apparatus using this photocurable resin composition, and its manufacturing method can be provided.

It is side surface sectional drawing which shows typically one Embodiment of a liquid crystal display device. It is side surface sectional drawing which shows typically embodiment of the liquid crystal display device carrying a touch panel. It is a figure which shows typically embodiment of a shear strength measurement sample. It is the schematic which shows the cross-section of an example of the conventional image display apparatus.

[Photocurable resin composition]
The photocurable resin composition of the present invention comprises (A) a compound having a photopolymerizable functional group, (B) an oil gelling agent, and (C) a photoinitiator, and the (C) photocuring agent is phenyl. It is a photocurable resin composition containing glyoxylic acid methyl ester.
The photocurable resin composition of the present invention is difficult to leak out and can be easily shaped into a desired shape, has excellent surface flatness, and can be photocured in the air. Although the details of the reason are unknown, it is presumed as follows.
The (B) oil gelling agent contained in the photocurable resin composition includes (A) a compound having a photopolymerizable functional group, such as hydrogen bond, electrostatic bond, π-π interaction, van der Waals force, etc. Non-covalent intermolecular interactions are expressed and linked to each other to form a fibrous bond (hereinafter sometimes referred to as “self-assembly”). Thereby, at least a part of the photocurable resin composition becomes a physical gel-like substance (hereinafter sometimes referred to as gelation or gel-like) at a room temperature of 25 ° C., and as a result, it is difficult to leak out compared to a liquid. It is presumed that it will be easier to shape into a desired shape than solid. Furthermore, it is presumed that by using phenylglyoxylic acid methyl ester as a photoinitiator, a photocurable resin composition having a large number of radical generation routes and less susceptible to oxygen inhibition can be obtained.
Next, each component of the photocurable resin composition will be described.

<Compound (A) having a photopolymerizable functional group>
The compound (A) having a photopolymerizable functional group (hereinafter sometimes referred to as “component (A)”) is not particularly limited as long as it is photocurable, and includes a (meth) acryloyl group, a vinyl group. A compound containing an ethylenically unsaturated group that can be cured by a photopolymerization initiator that generates radicals, such as an allyl group, or a cyclic ether group that can be cured by a photoacid generator that generates acid, such as an epoxy group. A compound containing an ethylenically unsaturated group is preferable from the viewpoint of curability and transparency, and a compound containing a (meth) acryloyl group is more preferable. As the compound containing an ethylenically unsaturated group, a (meth) acrylate compound, a polymer having a (meth) acryloyl group, a compound having a vinyl group, a compound having an allyl group, and the like are suitable. Next, these compounds and polymers will be described in this order.
In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” or “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” or “methacryloyl” corresponding thereto.

((Meth) acrylate compound)
Examples of the (meth) acrylate compound include (meth) acrylic acid; (meth) acrylic amide; (meth) acryloylmorpholine; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Alkyl having 1 to 18 carbon atoms in the alkyl group such as isodecyl (meth) acrylate, dodecyl (meth) acrylate (n-lauryl (meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate, etc. Acrylate; alkanediol di (meth) acrylate having 1 to 18 carbon atoms such as ethylene glycol di (meth) acrylate, butanediol (meth) acrylate, nonanediol di (meth) acrylate, etc .; trimethylolpropane tri (meth) Three (meth) acryloyl groups such as acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate in the molecule Multifunctional (meth) acrylate having glycidyl methacrylate; alkenyl (meth) acrylate having 2 to 18 carbon atoms of alkenyl group such as 3-butenyl (meth) acrylate; benzyl (meth) (Meth) acrylates with aromatic rings such as acrylate and phenoxyethyl (meth) acrylate; methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynonaethylene glycol Alkoxypolyalkylenes such as (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxyheptapropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate Glycol (meth) acrylate; cyclohexyl (meth) acrylate, isoborni (Meth) acrylates having an alicyclic group such as di (meth) acrylate and dicyclopentanyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate having a hydroxyl group such as (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide derivatives such as (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; 2- (2-methacryloyloxyethyloxy) ethyl ester (Meth) acrylates having isocyanate groups such as cyanate and 2- (meth) acryloyloxyethyl isocyanate; tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, di Polyalkylene glycol mono (meth) acrylates such as propylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate and octapropylene glycol mono (meth) acrylate; polyalkylene glycol di (meth) acrylate; having an isocyanuric ring skeleton (Meth) acrylate; (Meth) acrylate having a siloxane skeleton and the like. These may be used alone or in combination of two or more.
In addition, polyfunctionality having 3 or more alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group, alkanediol di (meth) acrylate having 1 to 18 carbon atoms in the alkane, and (meth) acryloyl groups in the molecule ( The meth) acrylate, glycidyl methacrylate, and alkenyl (meth) acrylate having 2 to 18 carbon atoms in the alkenyl group may be collectively referred to as aliphatic (meth) acrylate. In addition, alkoxy polyalkylene glycol (meth) acrylate, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol di (meth) acrylate, (meth) acrylate having an isocyanuric ring skeleton, and (meth) acrylate having a siloxane skeleton are heteroatoms. Sometimes referred to as system (meth) acrylate.

[Aliphatic (meth) acrylate]
Specifically, the aliphatic (meth) acrylate is preferably represented by the following general formulas (14) to (24).

  The general formula (14) is commercially available, for example, as FA-129AS (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As the general formula (15), for example, light ester L (trade name, lauryl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) is commercially available, and as FA-112M (trade name, manufactured by Hitachi Chemical Co., Ltd.). It is commercially available.

  General formula (16) is 2-ethylhexyl acrylate (EHA), which is commercially available from, for example, Wako Pure Chemical Industries, Ltd., and also commercially available from Nippon Shokubai Co., Ltd. as 2-ethylhexyl acrylate. is there.

  The general formula (17) is commercially available, for example, as light acrylate IM-A (trade name, isomyristyl acrylate (mixture of isomers of C14) manufactured by Kyoeisha Chemical Co., Ltd.).

  The general formula (18) is commercially available, for example, as FA-121M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (19) is commercially available, for example, as FA-112A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (20) is commercially available, for example, as FA-126AS (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As General formula (21), it can obtain as VBMA (the Hitachi Chemical Co., Ltd. make, prototype name), for example.

  As General formula (22), it is commercially available as light acrylate TMP-A (Kyoeisha Chemical Co., Ltd. make, brand name), for example.

  The general formula (23) is commercially available, for example, as FA-125M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As General formula (24), it is commercially available as light ester G (Kyoeisha Chemical Co., Ltd. make, brand name), for example (it may be called GMA).

[(Meth) acrylate having an aromatic ring]
As the (meth) acrylate having an aromatic ring, one or more of compounds represented by the following formulas (25) to (27) and benzyl (meth) acrylate are preferably exemplified.

(In the general formula (25), R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a phenyl group, and n represents an integer of 1 to 20)

(In General Formula (26), R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents a hydrogen atom or a methyl group, and m and n each independently represents an integer of 1 to 20.)

(In the general formula (27), R ²⁵ represents a hydrogen atom or a methyl group, and m and n each independently represents an integer of 1 to 20.)

  As the (meth) acrylate having an aromatic ring, those specifically represented by the following general formulas (28) to (40) are preferable.

(In general formula (28), the average value of n is 4.)
The general formula (28) is commercially available, for example, as FA-314A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (29), the average value of n is 8.)
The general formula (29) is commercially available, for example, as FA-318A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (30) is commercially available, for example, as FA-BZM (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (31) is commercially available, for example, as FA-BZA (manufactured by Hitachi Chemical Co., Ltd., trade name).

(In general formula (32), the average value of m + n is 10.)
The general formula (32) is commercially available, for example, as FA-321A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (33), the average value of m + n is 18.)
The general formula (33) is commercially available, for example, as FA-3218M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In the general formula (34), the average value of m + n is 10.)
The general formula (34) is commercially available, for example, as FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (35), the average value of m + n is 30.)
The general formula (35) is commercially available, for example, as FA-323M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As general formula (36), it is commercially available as light acrylate PO-A (trade name, phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.).

(In general formula (37), the average value of m + n is 4.)
The general formula (37) is commercially available, for example, as FA-324M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In the general formula (38), the average value of m + n is 4.)
The general formula (38) is commercially available, for example, as FA-324A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (39) is commercially available, for example, as FA-302A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (40) is commercially available, for example, as A-BPFE (trade name, manufactured by Shin-Nakamura Kogyo Co., Ltd.).

[(Meth) acrylates having alicyclic groups]
As the (meth) acrylate having the alicyclic group, those specifically represented by the following general formulas (41) to (47) are preferable.

  The general formula (41) is commercially available as light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., trade name, dimethylol-tricyclodecane diacrylate).

  The general formula (42) is commercially available, for example, as FA-512M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (43) is commercially available, for example, as FA-512AS (manufactured by Hitachi Chemical Co., Ltd., trade name).

  The general formula (44) is commercially available, for example, as FA-513M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As general formula (45), it is commercially available as FA-513AS (Hitachi Chemical Co., Ltd. make, brand name), for example.

  As general formula (46), it is commercially available as light acrylate IB-XA (trade name, isobonyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.).

  The general formula (47) is commercially available, for example, as FA-511AS (trade name, manufactured by Hitachi Chemical Co., Ltd.).

[Heteroatom (meth) acrylate]
In the present invention, the heteroatom-based (meth) acrylate is classified as not containing an aromatic ring and containing many heteroatoms.
As the heteroatom-based (meth) acrylate, a polyalkylene glycol di (meth) acrylate represented by the following formula (48), an alkoxy polyalkylene glycol (meth) acrylate represented by the following formula (49), and One or more of polyalkylene glycol mono (meth) acrylate, (meth) acrylate having an isocyanuric ring skeleton, and (meth) acrylate having a siloxane skeleton are preferably exemplified.

(In General Formula (48), R ²⁶ represents a hydrogen atom or a methyl group, X ₁ represents an ethylene group, a propylene group or an isopropylene group, and s represents an integer of 2 to 20).

(In the general formula (49), R represents an alkyl group having 1 to 5 carbon atoms, R ²⁷ represents a hydrogen atom or a methyl group, X ₁ represents an ethylene group, a propylene group or an isopropylene group, and s represents 2 Represents an integer of ~ 20.)

  Specific examples of the heteroatom-based (meth) acrylate are those represented by the following general formulas (50) to (55).

  The general formula (50) is commercially available, for example, as FA-731A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (51), the average value of n is 7.)
As General formula (51), it is commercially available as FA-P240A (Hitachi Chemical Co., Ltd. make, brand name), for example.

  The general formula (52) is commercially available, for example, as FA-731AT (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In the general formula (53), the average value of n is 9)
The general formula (53) is commercially available, for example, as light acrylate 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

  The general formula (54) is commercially available, for example, as X-22-164AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  As general formula (55), for example, Silaplane TM-0701 (manufactured by JNC Corporation, trade name) (compound name: 3-tris (trimethylsiloxy) silylpropyl methacrylate) is commercially available (hereinafter, Sometimes called TRIS).

(Polymer having (meth) acryloyl group)
Examples of the polymer having a (meth) acryloyl group include polybutadiene (meth) acrylate, polyisoprene (meth) acrylate, urethane acrylate, epoxy acrylate, an acrylic resin having a (meth) acryloyl group in the side chain, and modified products thereof. Is mentioned. These may be used alone or in combination of two or more.
As the polymer having a (meth) acryloyl group, specifically, those represented by the following general formulas (56) to (58) are preferable.

  Examples of the general formula (56) include G-3000 (trade name, α, ω-polybutadiene glycol manufactured by Nippon Soda Co., Ltd.) and Karenz MOI (trade name, 2-isocyanatoethyl methacrylate manufactured by Showa Denko KK). It can be obtained by reacting (hereinafter sometimes referred to as PB-MOI).

  The general formula (57) is commercially available, for example, as TEAI-1000 (trade name, manufactured by Nippon Soda Co., Ltd.).

  As general formula (58), for example, it has a structure shown in UC-102 (manufactured by Kuraray Co., Ltd., n = 2, number average molecular weight 17,000), and UC-203 (manufactured by Kuraray Co., Ltd., n = 3, Number average molecular weight 35,000).

(Compounds having a vinyl group and compounds having an allyl group)
Examples of the compound having a vinyl group and the compound having an allyl group include styrene, divinylbenzene, vinylpyrrolidone, triallyl isocyanurate, and 1,2-polybutadiene. These may be used alone or in combination of two or more.
As the compound having a vinyl group and the compound having an allyl group, specifically, those represented by the following general formulas (59) to (61) are preferable.

  General formula (59) is STC (styrene), and is commercially available from Wako Pure Chemical Industries, Ltd., for example.

  As the general formula (60), RICON 130 and RICON 131 (both manufactured by CRAY VALLEY, trade name, polybutadiene mainly composed of 1,2-structural units) are commercially available.

  General formula (61) is commercially available, for example, as TAIC (trade name, manufactured by Nippon Kasei Co., Ltd.).

Among the above compounds, all compounds can be used from the viewpoints of transparency, gelation (self-organization), and step embedding.
From the viewpoint of low curing shrinkage, the compound of general formula (60) is preferred.
From the viewpoint of a low dielectric constant, compounds of general formulas (60) and (61) are preferred.

((A) Content of compound having photopolymerizable functional group)
(A) It is preferable that content of the compound which has a photopolymerizable functional group is 0.5-99 mass% with respect to photocurable resin composition whole quantity. When it is 0.5% by mass or more, it can be sufficiently photocured, and when it is 99% by mass or less, the content of the oil gelling agent is relatively increased, and it can be sufficiently gelled. In this respect, the content is more preferably 1 to 90% by mass, and further preferably 2 to 85% by mass.

<(B) Oil gelling agent>
Examples of the (B) oil gelling agent (hereinafter sometimes referred to as “component (B)”) include hydroxystearic acid, particularly hydroxy fatty acids such as 12-hydroxystearic acid, hydrogenated castor oil mainly composed of hydroxy fatty acids, n-lauroyl-L-glutamic acid-α, β-dibutylamide, di-p-methylbenzylidene sorbitol glucitol, 1,3: 2,4-bis-O-benzylidene-D-glucitol, 1,3: 2, Examples thereof include 4-bis-O- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato) hydroxyaluminum, and compounds represented by the following general formulas (1) to (13). These may be used alone or in combination of two or more.

In general formula (1), m is an integer of 3 to 10, n is an integer of 2 to 6, R ₁ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X is sulfur or oxygen.
In the general formula (2), R ₂ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ₁ is a bond or a benzene ring.
In the general formula (3), _{R 3} is a saturated hydrocarbon group having 1 to 20 carbon atoms, _{Y 2} is a bond or a benzene ring.
In the general formula _{(4), R} 4 is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (6), R ₅ and R ₆ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In the general formula (7), _{R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In the general formula (8), _{R 8} is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (10), R ₉ and R ₁₀ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (13), R ₁₁ is a saturated hydrocarbon group having 1 to 10 carbon atoms. R ₁₂ and R ₁₃ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or a saturated hydrocarbon group having 1 to 20 carbon atoms having at least one hydroxyl group in the molecular skeleton. )

  (B) It is preferable that content of an oil gelling agent is 0.1-20 mass% with respect to the photocurable resin composition whole quantity. When it is 0.1% by mass or more, it can be sufficiently gelled, and when it is 20% by mass or less, the content of the compound (A) having a photopolymerizable functional group is relatively large, It can be photocured. In this respect, the content is more preferably 0.2 to 15% by mass, and further preferably 0.3 to 10% by mass.

<(C) Photopolymerization initiator>
The photocurable resin composition of the present invention preferably contains (C) a photopolymerization initiator (hereinafter sometimes referred to as “(C) component”). Thereby, after forming the physical gel-like substance containing the component (A) and the component (B) into a predetermined shape, the component (A) can be three-dimensionally crosslinked, and leakage can be further suppressed. Furthermore, (C) By including phenylglyoxylic acid methyl ester as a photoinitiator in particular, it is possible to obtain a photocurable resin composition that has many radical generation routes and is less susceptible to oxygen inhibition.
This (C) photopolymerization initiator has a curing reaction that proceeds by irradiation with active energy rays. Here, active energy rays refer to ultraviolet rays, electron beams, α rays, β rays, γ rays and the like.
There is no restriction | limiting in particular in a photoinitiator, It is possible to use well-known materials, such as a benzophenone series, anthraquinone series, a benzoyl series, a sulfonium salt, a diazonium salt, and an onium salt.

  Specifically, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4,4′-dimethyl Aminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,2 -Benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane − Aromatic ketone compounds such as 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,2-diethoxyacetophenone; Benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Benzoin methyl ether Benzoin ether compounds such as benzoin ethyl ether, benzoin isobutyl ether and benzoin phenyl ether; benzyl compounds such as benzyl and benzyldimethyl ketal; ester compounds of β- (acridin-9-yl) (meth) acrylic acid, 9-phenylacridine , 9-pyridylacridine, acridine compounds such as 1,7-diacridinoheptane; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (M-methoxy Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole 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, 2,4,5-triarylimidazole dimer such as 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer; 2-benzyl-2-dimethylamino-1- ( Α-aminoa such as 4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone Ruylphenone compounds; acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl)) Phenyl) propanone) and the like.

  In particular, polymerization initiators that do not color the photocurable resin composition include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- ( Α-hydroxyalkylphenone compounds such as 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Acylphosphine oxide compounds such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; Hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) Ropanon) and a combination thereof are preferred.

  (C) It is preferable that content of a photoinitiator is 0.1-5 mass% with respect to the whole quantity of a photocurable resin composition, 0.2-3 mass% is more preferable, and 0.2. 3-2 mass% is still more preferable. When it is 0.1% by mass or more, photopolymerization can be favorably started. When it is 5% by mass or less, the step embedding property and the self-organizing property are excellent, and the hue of the obtained cured product does not have a yellowish color.

<(D) Compound liquid at 25 ° C.>
Moreover, the photocurable resin composition of the present invention may further contain (D) a compound that is liquid at 25 ° C. (hereinafter sometimes referred to as “component (D)”). (D) A compound that is liquid at 25 ° C. may be added according to the purpose within a range in which the self-organizing property is not impaired.
This (D) liquid compound at 25 ° C. includes di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (the following general formula ( 62), DUP), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4 Examples include 6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), liquid paraffin, and organic solvents.

  Pentaerythritol tetrakis (3-mercaptobutyrate) is commercially available, for example, as Karenz MT PE1 (manufactured by Showa Denko KK, general formula (63) below).

These components (D) are used for the purpose of adjusting the degree of gelation by reducing the viscosity of the photocurable resin composition.
Other (D) liquid compounds at 25 ° C. include liquid polymers such as acrylic resins, liquid polybutadiene mainly composed of 1,4-structural units, hydrogenated polybutadiene, hydrogenated polyisoprene, and hydrogenated polyisobutene. They are used for other purposes such as low cure shrinkage and low dielectric constant.
As the acrylic resin which is liquid at 25 ° C., an acrylic resin containing a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is preferable. Further, an acrylic resin containing a structural unit derived from an alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl group and a structural unit derived from styrene or benzyl (meth) acrylate is more preferable.
Moreover, as a hydrogenated polyisobutene that is liquid at 25 ° C., for example, Pearl Ream (trade name, manufactured by NOF Corporation) is commercially available.
In addition, as a liquid polybutadiene mainly composed of 1,4-structural units, for example, polyoil (Nippon Zeon Corporation) is commercially available.
The number average molecular weight (Mn) of the liquid polymer is preferably 500 to 5000, more preferably 800 to 4000, and particularly preferably 1000 to 3000.

  (D) When using a liquid compound at 25 degreeC, it is preferable from a viewpoint of self-organization property and transparency that it is 1-99 mass% with respect to the photocurable resin composition whole quantity. In this respect, the content of the component (D) is more preferably 2 to 98% by mass.

<(E) Compound Solid at 25 ° C.>
The photocurable resin composition of the present invention may further contain (E) a compound that is solid at 25 ° C. (hereinafter sometimes referred to as “component (E)”). (E) The compound that is solid at 25 ° C. may be added according to the purpose within a range in which the self-organization property is not impaired.
Examples of the (E) compound that is solid at 25 ° C. include terpene-based hydrogenated resins and the like, and these are for the purpose of improving the adhesiveness of the photocurable resin composition and adjusting the degree of gelation. used. The terpene-based hydrogenated resin is commercially available, for example, as Clearon P series (Yasuhara Chemical Co., Ltd., trade name).
(E) The content of the solid compound at 25 ° C. is 0.1 to 20% by mass with respect to the total amount of the photocurable resin composition, which is self-organizing, transparent and leak-proof. It is preferable from the viewpoint. In this respect, the content of the component (E) is more preferably 1 to 10% by mass.

[Other additives]
In addition to the above components (A) to (E), the photocurable resin composition of the present invention may contain various additives as necessary. In the present invention, examples of various additives that can be included include a polymerization inhibitor, an antioxidant, a light stabilizer, a silane coupling agent, a surfactant, and a leveling agent.

The polymerization inhibitor is added for the purpose of enhancing the storage stability of the photocurable resin composition, and examples thereof include paramethoxyphenol.
Antioxidants are added for the purpose of enhancing the heat-resistant colorability of cured products obtained by curing a photocurable resin composition with light. Phosphorus-based such as triphenyl phosphite; phenol-based; thiol-based antioxidants Agents.
The light stabilizer is added for the purpose of increasing resistance to light such as ultraviolet rays, and examples thereof include HALS (Hindered Amine Light Stabilizer).
The silane coupling agent is added to improve adhesion to glass or the like. For example, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane and the like.
The surfactant is added to control the peelability, and examples thereof include polydimethylsiloxane compounds and fluorine compounds.
The leveling agent is added to impart the flatness of the photocurable resin, and examples thereof include a compound that lowers the surface tension of silicon-based and fluorine-based resins.

  These additives may be used alone or in combination with a plurality of additives. In addition, content in the case of using these additives is usually small compared with the total content of the above components (A) to (E), and generally 0.01 to the total amount of the photocurable resin composition. About 5% by mass.

(Inorganic filler)
In the photocurable resin composition of the present invention, an inorganic filler may be blended, for example, crushed silica, fused silica, mica, clay mineral, short glass fiber or fine powder, and hollow glass, calcium carbonate, quartz powder. And metal hydrates. The blending amount is preferably 0.01 to 100 parts by weight, more preferably 0.05 to 50 parts by weight, and more preferably 0.1 to 100 parts by weight of the photocurable resin composition in terms of solid content. It is especially preferable to set it as -30 mass parts. If it is 0.01-100 mass parts, sufficient low contractility, the improvement of mechanical strength, a low thermal expansion coefficient, etc. will be obtained. The filler may be treated with a commercially available surface treatment agent such as a coupling agent, a three-roller, a bead mill, a nanomizer, or the like to improve the dispersibility of the inorganic filler.

Photocurable resin that can be produced by mixing and stirring the (A) component, the (B) component, the (C) component, and, if necessary, the (D) component, the (E) component, and the additive. The composition preferably has a viscosity at 25 ° C. and a shear rate of 1.0 s ⁻¹ of 30 to 1000 Pa · s from the viewpoint of shape retention. Further, the viscosity at a shear rate of 1.0 s ⁻¹ at 25 ° C. is more preferably 50 to 500 Pa · s. When it is less than 30 Pa · s, the shape retention of the coating film is insufficient, and when it is higher than 1000 Pa · s, the applicability is lowered during film formation.

  Photocurable resin that can be produced by mixing and stirring the (A) component, the (B) component, the (C) component, and, if necessary, the (D) component, the (E) component, and the additive. The composition preferably has a thixotropic ratio of 1.3 to 10.0 at 25 ° C. from the viewpoint of shape retention. Furthermore, at 25 ° C., the thixo ratio is more preferably 1.5 to 5.0. When it is less than 1.3, the shape retention of the coating film is insufficient, and when it is higher than 10.0, the coating property is deteriorated during film formation.

<Method for producing photocurable resin composition>
There is no restriction | limiting in particular in the manufacturing method of a photocurable resin composition, Said (A) component, (B) component and (C) component, (D) component and (E) component and said additive as needed Can be mixed and stirred.
In addition, when any of the components is solid, it is preferable that the solid component is heated and dissolved at at least one timing before mixing stirring, during mixing stirring, and after mixing stirring. Thereby, each component disperse | distributes favorably, and a photocurable resin composition is obtained by cooling after that.
Although there is no restriction | limiting in particular in this heating temperature, Although it is based also on melting | fusing point of the oil gelling agent to be used, if it is a hydrogenated castor oil type fatty acid amide, it is preferable to heat at 60-150 degreeC. If it is 60 ° C. or higher, the oil gelling agent can be sufficiently dissolved. High transparency can be maintained as it is 150 degrees C or less.
Although there is no restriction | limiting in particular in stirring time, Preferably it is 10 to 600 second, More preferably, it is 20 to 300 second.

<Image display device>
Next, an image display device using the photocurable resin composition of the present invention will be described.
The photocurable resin composition of the present invention can be applied to various image display devices. Examples of the image display device include a plasma display (PDP), a liquid crystal display (LCD), a cathode ray tube (CRT), a field emission display (FED), an organic EL display (OELD), a 3D display, and electronic paper (EP). .
The photocurable resin composition of the present invention can be suitably used for bonding various layers constituting the image display device. Examples of the various layers include functional layers having functionality such as an antireflection layer, an antifouling layer, a dye layer, and a hard coat layer; these functional layers are formed or laminated on a base film such as a polyethylene film or a polyester film. And a multilayer protective material formed by laminating or laminating functional layers having various functions on the transparent protective plate. Moreover, the photocurable resin composition of the present invention can be photocured to obtain a cured product, and can also be used as an optical filter in combination with such a multilayer product. In this case, it is preferable that the photocurable resin composition of the present invention is cured after being applied to, and filled in, a multilayer product.

The antireflection layer may be a layer having an antireflection property with a visible light reflectance of 5% or less, and is a layer treated by a known antireflection method on a transparent substrate such as a transparent plastic film. Can be used.
The antifouling layer is for preventing the surface from getting dirty, and a known layer composed of a fluorine-based resin or a silicone-based resin can be used to reduce the surface tension.

The dye layer is used to increase color purity, and is used to reduce unnecessary light when the color purity of light emitted from an image display unit such as a liquid crystal display unit is low. The pigment | dye which absorbs the light of an unnecessary part can be melt | dissolved in resin, and it can form and laminate | stack on base films, such as a polyethylene film and a polyester film.
The hard coat layer is used to increase the surface hardness. As the hard coat layer, it is possible to use an acrylic resin such as urethane acrylate or epoxy acrylate; a film obtained by laminating or laminating an epoxy resin or the like on a base film such as a polyethylene film. Similarly, in order to increase the surface hardness, a transparent protective plate made of glass, acrylic resin, alicyclic polyolefin, polycarbonate or the like and having a hard coat layer formed or laminated can be used.

The photocurable resin composition of the present invention can be used by being laminated on a polarizing plate. in this case,
It can also laminate | stack on the visual recognition surface side of a polarizing plate, and can also laminate | stack on the opposite side.
When used on the viewing surface side of the polarizing plate, an antireflection layer, an antifouling layer, a hard coat layer, etc. can be laminated on the viewing surface side of the photocurable resin composition. When used in between, a functional layer can be laminated on the viewing surface side of the polarizing plate.
When setting it as such a laminated body, a photocurable resin composition can be laminated | stacked using a roll laminator, a bonding machine, a vacuum bonding machine, a single wafer bonding machine, etc.

The photocurable resin composition is preferably disposed between the image display unit of the image display device and the transparent protective plate (protective panel) on the front side of the viewing side, at an appropriate position on the viewing side. Specifically, it is preferably applied between the image display unit and the transparent protective plate.
Further, in the image display device in which the touch panel is combined with the image display unit, the image display device is preferably applied between the touch panel and the image display unit and / or between the touch panel and the transparent protective plate (protective panel). If the photocurable resin composition of this invention is applicable on the structure of this, it will not restrict to the position described above.

Hereinafter, a liquid crystal display device which is one of image display devices will be described in detail with reference to FIGS.
<Liquid Crystal Display Device of FIG. 1>
FIG. 1 is a cross-sectional view schematically showing an embodiment of a liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 1 includes an image display unit 7 in which a backlight system 50, a polarizing plate 22, a liquid crystal display cell 10, and a polarizing plate 20 are laminated in this order, and a polarizing plate on the viewing side of the liquid crystal display device. The transparent resin layer 32 provided on the upper surface 20 and a transparent protective plate (protective panel) 40 provided on the surface thereof. The step portion 60 provided on the surface of the transparent protective plate 40 is embedded with the transparent resin layer 32. The transparent resin layer 32 basically corresponds to the photocurable resin composition of the present embodiment. Although the thickness of the stepped portion 60 varies depending on the size of the liquid crystal display device and the like, it is particularly useful to use the photocurable resin composition of the present embodiment when the thickness is 30 μm to 100 μm.

<Liquid Crystal Display Device of FIG. 2>
FIG. 2 is a cross-sectional view schematically showing a liquid crystal display device equipped with a touch panel, which is an embodiment of the liquid crystal display device of the present invention. The liquid crystal display device shown in FIG. 2 includes an image display unit 7 in which a backlight system 50, a polarizing plate 22, a liquid crystal display cell 10, and a polarizing plate 20 are laminated in this order, and a polarizing plate on the viewing side of the liquid crystal display device. 20, a transparent resin layer 32 provided on the top surface, a touch panel 30 provided on the top surface of the transparent resin layer 32, a transparent resin layer 31 provided on the top surface of the touch panel 30, and a transparent protective plate provided on the surface thereof 40.
The step portion 60 provided on the surface of the transparent protective plate 40 is embedded with the transparent resin layer 31. The transparent resin layer 31 and the transparent resin layer 32 basically correspond to the photocurable resin composition of the present embodiment.
The purpose of providing the stepped portion 60 is, for example, to make these wirings invisible or difficult to see from the transparent protective plate side when providing input / output wirings in the peripheral portions of the information input device and the image display unit. . From the viewpoint of making the wiring invisible or difficult to see, the stepped portion 60 is preferably a light shielding material. However, the step portion may be provided for other purposes such as decoration or may be transparent. The step portion 60 is provided on the lower surface (surface on the side in contact with the transparent resin layer 31) of the transparent protective plate 40, but may be provided on the upper surface (surface on the side far from the transparent resin layer 31). The stepped portion 60 is made of a material different from that of the transparent protective plate 40, but may be made of the same material or may be integrally formed. The step portion 60 has a frame shape along the outer peripheral edge of the lower surface of the transparent protective plate 40, but is not limited to this, and the plan view shape is partially or entirely of the transparent protective plate 40. Any shape such as a frame shape, a U shape, an L shape, a linear shape, a waveform, a dotted line shape, a lattice shape, or a curved shape that does not follow the outer peripheral edge of the lower surface can be used. The same applies to the stepped portion 60 of the liquid crystal display device of FIG.
In the liquid crystal display device of FIG. 2, the transparent resin layers 32 and 31 are interposed between the image display unit 7 and the touch panel 30 and between the touch panel 30 and the transparent protective plate 40. The resin layer may be interposed in at least one of these. When the touch panel is on-cell, the touch panel and the liquid crystal display cell are integrated. As a specific example, the liquid crystal display cell 10 of the liquid crystal display device of FIG. 1 may be replaced with an on-cell.
In recent years, development of a liquid crystal display cell incorporating a touch panel function, called an in-cell type touch panel, is in progress. The liquid crystal display device provided with such a liquid crystal display cell is composed of a transparent protective plate, a polarizing plate, and a liquid crystal display cell (liquid crystal display cell with a touch panel function), and the photocurable resin composition of the present invention includes: It can also be suitably used for a liquid crystal display device employing such an in-cell type touch panel.

As described above, since the liquid crystal display device shown in FIGS. 1 and 2 includes the photocurable resin composition of the present embodiment as the transparent resin layer 31 or 32, the liquid crystal display device has impact resistance and has no double image and is clear. A high contrast image can be obtained.
The liquid crystal display cell 10 can be made of a liquid crystal material well known in the art. Further, according to the control method of the liquid crystal material, it is classified into a TN (Twisted Nematic) method, a STN (Super-twisted nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, etc. Then, it may be a liquid crystal display cell using any control method.

As the polarizing plates 20 and 22, a polarizing plate common in this technical field can be used. The surfaces of these polarizing plates may be subjected to treatments such as antireflection, antifouling, and hard coat. Such surface treatment may be performed on one side of the polarizing plate or on both sides thereof.
As the touch panel 30, what is generally used in this technical field can be used.
The transparent resin layer 31 or 32 can be formed with a thickness of, for example, 0.02 mm to 3 mm, but is preferably 0.1 to 1 mm, and preferably 0.15 mm (150 μm) from the viewpoint of step embedding property and workability. 0.5 mm (500 μm) is more preferable. In particular, in the photocurable resin composition of the present embodiment, it is possible to exert a more excellent effect by forming a thick film, which is suitable when the transparent resin layer 31 or 32 of 0.1 mm or more is formed. Can be used.
The light transmittance of the transparent resin layer 31 or 32 with respect to light in the visible light region (wavelength: 380 to 780 nm) is preferably 80% or more, preferably 90% or more, and 95% or more. More preferably.

As the transparent protective plate 40, a general optical transparent substrate can be used. Specific examples thereof include inorganic plates such as glass and quartz, resin plates such as acrylic resin, alicyclic polyolefin, and polycarbonate, and resin sheets such as thick polyester sheets. When high surface hardness is required, a plate of glass, acrylic resin, alicyclic polyolefin or the like is preferable, and a glass plate is more preferable. When thinness and lightness are required, acrylic resin, alicyclic polyolefin, and polycarbonate are preferable. The surface of these transparent protective plates may be subjected to treatments such as antireflection, antifouling, and hard coat. Such surface treatment may be performed on one side of the transparent protective plate or on both sides. A plurality of transparent protective plates can be used in combination.
The backlight system 50 typically includes a reflecting unit such as a reflecting plate and an illuminating unit such as a lamp.
As the material of the stepped portion 60, for example, an acrylic resin composition containing a black pigment, a low melting point glass containing a metal oxide, or the like is used.

<Method for Manufacturing Image Display Device>
(Manufacturing method of the liquid crystal display device of FIG. 1)
The liquid crystal display device of FIG. 1 described above is a manufacturing method including the step of interposing the photocurable resin composition of the present embodiment between the image display unit 7 and a transparent protective plate (protective panel) 40 having a stepped portion 60. It can be manufactured by a method.

That is, the photocurable resin composition of the present invention is formed on the surface of the transparent protective plate (protective panel) 40 on which the step portion 60 is formed. The said formation may be performed by apply | coating the photocurable resin composition of this invention on the transparent protection board (protection panel) 40. FIG. In addition, a gel-like photocurable resin composition is previously formed on a release sheet, and the gel-like photocurable resin composition is pressed against a transparent protective plate (protective panel) 40 and then peeled off. You may carry out by peeling a sheet | seat.
Then, it superimposes on the upper surface of the polarizing plate 20, and these are laminated | stacked using the above-mentioned bonding machine.
When bubbles are observed in the photocurable resin composition after lamination using a laminating machine or the like, it is preferable to use an autoclave or the like to eliminate bubbles while adjusting the degree of pressurization at a predetermined temperature. Moreover, it can also degas | foam by pressure reduction.
Thereafter, the photo-curable resin composition is cured by light irradiation to form the transparent resin layer 32, whereby the image display device of FIG. 1 can be suitably manufactured. As this light irradiation, it is preferable to irradiate ultraviolet rays from the transparent protective plate 40 side, the image display unit 7 side, and the side of the image display device. Thereby, the reliability (reduction of bubbles and suppression of peeling) and adhesive strength under high temperature and high humidity can be further improved. From the viewpoint of further improving the reliability under high temperature and high humidity, it is preferable to irradiate ultraviolet rays from the image display unit 7 side having no stepped portion. Although there is no restriction | limiting in particular in the irradiation amount of the said ultraviolet-ray, It is preferable that it is about 500-5000mJ / cm < ² >.

(Manufacturing method of the liquid crystal display device of FIG. 2)
The liquid crystal display device of FIG. 2 described above is the photocuring of the present embodiment between the image display unit 7 and the touch panel 30 and / or between the touch panel 30 and the transparent protective plate (protective panel) 40. It can manufacture with a manufacturing method provided with the process of interposing a conductive resin composition.
The transparent resin layer 31 can be manufactured by the same method as the transparent resin layer 32 of FIG. The transparent resin layer 32 can be manufactured by the same method as the transparent resin layer 32 in FIG. 1 except that the photocurable resin composition is applied to the touch panel 30 instead of the transparent protective plate (protective panel) 40.
The curing shrinkage rate when the photocurable resin composition of the present invention is cured is preferably less than 10%, more preferably less than 5% from the viewpoint of further suppressing the warpage of the substrate such as the transparent protective plate and the image display unit. Is more preferable, less than 2% is more preferable, and less than 1% is particularly preferable. If the curing shrinkage rate is less than 10%, warpage that may occur in the image display unit can be sufficiently suppressed, and occurrence of problems such as color unevenness when used in an image display apparatus can be prevented.
When used between the touch panel and the transparent protective plate, the dielectric constant at 100 kHz of the cured product of the photocurable resin composition of the present invention is preferably 7 or less, more preferably 5 or less, and 4 or less. More preferably, it is particularly preferably 3 or less. The lower limit of the dielectric constant is preferably 2 or more from a practical viewpoint.

  Hereinafter, the present invention will be described by way of examples. In addition, this invention is not restrict | limited to these Examples.

[Evaluation]
About the photocurable resin composition obtained by each Example and the comparative example, it evaluated with the following test methods.

(1) Evaluation of step embedding property A resin film of 40 mm × 40 mm × 0.15 mm is formed on a 58 mm × 86 mm × 0.7 mm (thickness) glass substrate using a photocurable resin composition sealed in a 5 ml syringe using a slit coater. Was applied.
Next, a glass substrate (step difference 60 μm) having a step portion with an outer peripheral portion printed so as to have a thickness of 60 μm on the other side where the glass substrate of the photocurable resin composition is not bonded together is photocurable. It bonded together using the bonding machine so that a resin composition might be inserted | pinched. In addition, the glass substrate which has the level | step-difference part by which the outer peripheral part was printed has the same outer dimension as a glass substrate, and has an opening part with an internal dimension of 45 mm x 68 mm. The glass substrate was used as a substitute for an information input device or an image display unit, and the embedding property was evaluated.
(Evaluation criteria)
A: The photocurable resin composition can be embedded in the step portion without gaps and without leakage. B: The photocurable resin composition flows out from the glass substrate to the periphery.

(2) Evaluation of self-organizing property A photocurable resin composition is added to a 2 ml screw tube, and the oil gelling agent is dissolved in an oven at 100 ° C. (air blowing thermostat DN-400, manufactured by Yamato Scientific Co., Ltd.). Left until. Subsequently, the solution was quickly homogenized with a self-revolving mixer ARE-250 (manufactured by THINKY Co., Ltd.) at 2000 rpm for 20 seconds and left at 25 ° C. for 30 minutes. Thereafter, the screw tube was tilted about 60 degrees and left for 3 minutes to evaluate self-organization.
(Evaluation criteria)
3: The photocurable resin composition does not flow and maintains its shape 2: The entire photocurable resin composition maintains a gel state, but has fluidity 1: all of the photocurable resin composition Liquid and fluid

(3) Evaluation of transparency Until 2 g of the photocurable resin composition is added to a 2 ml screw tube, and until the oil gelling agent is dissolved in an oven at 100 ° C. (air blowing thermostat DN-400, manufactured by Yamato Scientific Co., Ltd.) I left it alone. Subsequently, the solution was quickly homogenized with a self-revolving mixer ARE-250 (manufactured by THINKY Co., Ltd.) at 2000 rpm for 20 seconds and left at 25 ° C. for 30 minutes. The transparency of the contents of the screw tube was evaluated.
(Evaluation criteria)
4: No turbidity is seen even after seeing through the fluorescent lamp 3: It turns out that it is turbid when seen through the fluorescent lamp 2: It is slightly turbid 1: It is cloudy enough that the opposite side is not clearly visible when viewed from the observation side Have

(4) Evaluation of foam entrainment at the time of bonding Using a slit coater, a photocurable resin composition sealed in a 5 ml syringe was placed on a glass substrate of 100 mm × 100 mm × 0.7 mm (thickness) 60 mm × 60 mm × A 0.15 mm resin film was applied. Irradiate 5000 mJ with a metal halide lamp 120 mW / cm ² , and then paste a cover glass substrate of 100 mm × 100 mm × 0.07 mm so as to become glass-resin surface-glass using a vacuum laminate, and visually check for the presence of bubbles Confirmed with.

(5) Shear strength measurement (glass-glass)
A resin film of 25 mm × 25 mm × 0.15 mm is formed on a glass substrate of 100 mm × 30 mm × 0.7 mm (thickness), irradiated with 5000 mJ with a metal halide lamp 120 mW / cm ² , and then 100 mm × 30 mm × 0.7 mm. The glass substrate of (thickness) is bonded as shown in FIG. 3, and after 24 hours, using Tensilon, the upper and lower glass non-bonded portions are grasped, the bottom is fixed, and the upward direction is 25 mm / The sample was pulled at a speed of min and the tensile strength was measured.

(6) Shear strength measurement (glass-polarizing plate)
A resin film of 25 mm × 25 mm × 0.15 mm is formed on a glass substrate of 100 mm × 30 mm × 0.7 mm (thickness), irradiated with 5000 mJ with a metal halide lamp 120 mW / cm ² , and then 100 mm × 30 mm × 0. A surface having a polarizing plate attached to a 7 mm (thickness) glass substrate is bonded to a sample having the same shape as that shown in FIG. 3 (differing from FIG. 3 in that the adhesive surface with the glass substrate becomes a polarizing plate). .) Was produced. After 24 hours from this sample, Tensilon was used to grasp the upper and lower portions of the glass that were not bonded together, the lower part was fixed, the upper part was pulled upward at a speed of 25 mm / min, and the tensile strength was measured.

[material]
In the following examples and comparative examples, the following raw materials were used.
(Component A)
FA-512M: compound of general formula (42), manufactured by Hitachi Chemical Co., Ltd., trade name FA-512AS: compound of general formula (43), manufactured by Hitachi Chemical Co., Ltd., trade name UC-102: of general formula (58) Compound, manufactured by Kuraray Co., Ltd., n = 2, number average molecular weight 17,000, trade name (component B)
DISPARLON 308: Made by Enomoto Kasei Co., Ltd., hydrogenated castor oil, product name (C component)
I-184: Irgacure 184, 1-hydroxy-cyclohexyl-phenyl-ketone D-MBF: Darocur MBF, phenyl glyoxylic acid methyl ester D-TPO: Darocur TPO, 2,4,6-trimethylbenzoyl-diphenyl-phos Fin oxide (component D)
G-1000: Nippon Soda Co., Ltd., both end hydroxyl group polybutadiene, number average molecular weight 1,100, trade name G-3000: Nippon Soda Co., Ltd., both end hydroxyl group polybutadiene, number average molecular weight 3,200, trade name (E component)
P85 (Clearon P-85): Yasuhara Chemical Co., Ltd., terpene hydrogenated resin

[Examples 1 to 60]
<Example>
The components (A) to (E) were blended at the blending ratio shown in Table 1, and the mixture was heated and stirred at 90 ° C. for 30 minutes to prepare liquid curable resin compositions of Examples 1 to 10. In addition, the unit of the numerical value about (A)-(E) component in Table 1 is a mass part.
<Comparative example>
The components (A) to (D) were blended at the blending ratio shown in Table 2, and heated and stirred at 90 ° C. for 30 minutes to prepare liquid curable resin compositions of Comparative Examples 1 to 5. In addition, the unit of the numerical value about (A)-(D) component in Table 2 is a mass part.

  As shown in Table 1, the photocurable resin compositions of Examples 1 to 10 are phenylglyoxylic acid methyl which is less susceptible to oxygen inhibition as a photocuring agent, together with an oil gelling agent having a function of forming a physical gel substance. Since it contains an ester, it has good characteristics with respect to step embedding, self-organization, transparency, entrainment of bubbles during bonding, and shear strength. On the other hand, the photocurable resin compositions of Comparative Examples 1 to 4 shown in Table 2 are good in step embedding property, self-organizing property, transparency, and entrainment of bubbles at the time of bonding, but in the examples. It can be seen that the share strength is low. Furthermore, in Comparative Example 5, since the component (B) was not included, there was no self-organization, edge fat was generated, foam was involved during bonding, and a sample for measuring the shear strength could not be produced. .

  As described above, according to the present invention, it is possible to obtain a photocurable resin composition that is difficult to leak and that can be easily shaped into a desired shape, has a flat coating film surface, and can be photocured in the atmosphere. Furthermore, in an image display device having a laminated structure including an image display unit or touch panel having an image display unit, a transparent protective plate, and a resin layer present between the image display unit or touch panel and the transparent protective plate, By forming the resin layer with the photocurable resin composition of the present invention, it is possible to provide an image display device that has excellent impact resistance, has no sharpness and has high contrast, and a method for manufacturing the same.

DESCRIPTION OF SYMBOLS 1 Transparent protective plate 2 Touch panel 3 Polarizing plate 4 Liquid crystal display cell 5 Adhesive layer 6 Adhesive layer 7 Image display unit 10 Liquid crystal display cell 20 Polarizing plate 22 Polarizing plate 30 Touch panel 31 Transparent resin layer 32 Transparent resin layer 40 Transparent protective plate (protective panel) )
50 Backlight system 60 Stepped portion 61 Glass 62 Transparent resin

Claims (10)

(A) a compound having a photopolymerizable functional group,
(B) an oil gelling agent, and (C) a photocuring agent,
(C) The photocurable resin composition in which the photocuring agent contains phenylglyoxylic acid methyl ester. (B) The oil gelling agent is a hydroxy fatty acid, hydrogenated castor oil containing hydroxy fatty acid as a main component, n-lauroyl-L-glutamic acid-α, β-dibutyramide, di-p-methylbenzylidene sorbitol glucitol, 1 , 3: 2,4-bis-0-benzylidene-D-glucitol, 1,3: 2,4-bis-0- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato) hydroxyaluminum And the photocurable resin composition of Claim 1 which is at least 1 sort (s) of the compound represented by following General formula (1)-(13).

(In General Formula (1), m is an integer of 3 to 10, n is an integer of 2 to 6, R ₁ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X is sulfur or oxygen.
In the general formula (2), R ₂ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ₁ is a bond or a benzene ring.
In the general formula (3), _{R 3} is a saturated hydrocarbon group having 1 to 20 carbon atoms, _{Y 2} is a bond or a benzene ring.
In the general formula _{(4), R} 4 is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (6), R ₅ and R ₆ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In the general formula (7), _{R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In the general formula (8), _{R 8} is a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (10), R ₉ and R ₁₀ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms.
In General Formula (13), R ₁₁ is a saturated hydrocarbon group having 1 to 10 carbon atoms. R ₁₂ and R ₁₃ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or a saturated hydrocarbon group having 1 to 20 carbon atoms having at least one hydroxyl group in the molecular skeleton. )   The photocurable resin composition according to claim 1 or 2, wherein the compound (A) having a photopolymerizable functional group includes a compound having an ethylenically unsaturated group.   The photocuring agent according to any one of claims 1 to 3, wherein the (C) photocuring agent comprises a phenylglyoxylic acid methyl ester and a photopolymerization initiator different from the phenylglyoxylic acid methyl ester. Resin composition.   Furthermore, (D) The photocurable resin composition in any one of Claims 1-4 containing a liquid compound at 25 degreeC.   Furthermore, (E) The photocurable resin composition in any one of Claims 1-5 containing a solid compound at 25 degreeC.   An image display device having a laminated structure including an image display unit having an image display unit, a transparent protective plate, and a resin layer present between the image display unit and the transparent protective plate, wherein the resin layer is The image display apparatus which is a hardened | cured material of the photocurable resin composition in any one of Claims 1-6.   An image display device having a laminated structure including an image display unit having an image display unit, a touch panel, a transparent protective plate, and a resin layer existing between the touch panel and the transparent protective plate, wherein the resin layer is The image display apparatus which is a hardened | cured material of the photocurable resin composition in any one of Claims 1-6.   The image display device according to claim 7 or 8, wherein the transparent protective plate has a stepped portion.   The method for manufacturing an image display device according to any one of claims 7 to 9, wherein the photocurable resin composition is interposed in a gap between an image display unit having an image display unit or a touch panel and a transparent protective plate. And a method for producing an image display device that is cured by irradiating light from at least the transparent protective plate side.

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