JP2017218477A - Photocurable resin composition for curved surface coating, image display device and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition for curved surface coating which hardly leaks and is easily molded into a desired shape, and to provide an image display device using the photocurable resin composition for curved surface coating.SOLUTION: A photocurable resin composition for curved surface coating contains a compound (A) having a photopolymerizable functional group and an oil gelling agent (B). An image display device has such a laminated structure as to include an image display unit having an image display portion, a transparent protective plate and a resin layer existing between the image display unit and the transparent protective plate, where the resin layer is a cured product of the photocurable resin composition for curved surface coating.SELECTED DRAWING: Figure 2

Description

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

The photocurable resin composition includes an adhesive; an adhesive; a filler; an optical waveguide, a member for a solar cell, a light emitting diode (LED), a phototransistor, a photodiode, an optical semiconductor element, an image display device, an illumination device, and other optical components. Member: Widely used as a dental material.
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. 1 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.

By the way, in recent years, for example, an image display that suppresses the load on the eyes by giving a curved surface to the image display device to reduce the difference between the distance from the center to the eye and the distance from the edge to the eye. An apparatus has been developed (Non-patent Document 1).
In addition, for example, an image display device has been developed that has a curved surface in the image display device used in a vehicle so that the display can be easily seen by the driver, and is excellent in design (Non-patent Document 2).

  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

Asahi Shimbun Digital September 18, 2015 Website http://www.asahi.com/and_M/interest/bcnnews/Cbcn2015091713.html September 29, 2015, Lecture sponsored by the Technical Information Association, 3D curved surface shaping of automotive touch panels, materials, and bonding technology

When the photocurable resin composition is in a liquid state as in Patent Document 2 or the like, particularly in an image display device having a curved surface that has been developed in recent years, there is a problem that it is likely to leak from the predetermined portion when formed at the predetermined portion. Becomes apparent.
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.
The present invention solves the above problems, and provides a photocurable resin composition that is difficult to leak out and that can be easily molded into a desired shape, an image display device using the photocurable resin composition, and a method for manufacturing the same. Objective.

The present invention provides the following [1] to [8].
[1] A photocurable resin composition for curved surface coating comprising a compound (A) having a photopolymerizable functional group and an oil gelling agent (B).
[2] The oil gelling agent (B) is a hydroxy fatty acid, hydrogenated castor oil containing hydroxy fatty acid as a main component, hydroxy fatty acid amide, n-lauroyl-L-glutamic acid-α, β-dibutyramide, di-p-methyl. Benzylidenesorbitol glucitol, 1,3: 2,4-bis-0-benzylidene-D-glucitol, 1,3: 2,4-bis-0- (4-methylbenzylidene) -D-sorbitol, bis (2 -Ethylhexanoato) A photocurable resin composition for curved surface application according to the above [1], 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、Ｒ₁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、Ｒ₂は炭素数１〜２０の飽和炭化水素基、Ｙ₁は結合手又はベンゼン環である。
一般式（３）中、Ｒ₃は炭素数１〜２０の飽和炭化水素基、Ｙ₂は結合手又はベンゼン環である。
一般式（４）中、Ｒ₄は炭素数１〜２０の飽和炭化水素基である。
一般式（６）中、Ｒ₅及びＲ₆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、Ｒ₇は、炭素数１〜２０の飽和炭化水素基である。
一般式（８）中、Ｒ₈は、炭素数１〜２０の飽和炭化水素基である。
一般式（９）中、Ｐｈは、フェニル基を示す。
一般式（１０）中、Ｒ₉及びＲ₁₀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、Ｒ₁₁は、炭素数１〜１０の飽和炭化水素基である。Ｒ₁₂及びＲ₁₃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。）

(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 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, 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, and 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 general formula (8), R < ₈ > is a C1-C20 saturated hydrocarbon group.
In general formula (9), Ph represents a phenyl group.
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 for curved surface coating according to the above [1] or [2], wherein the compound (A) having the photopolymerizable functional group contains a compound having an ethylenically unsaturated group.
[4] The photocurable resin composition for curved surface application according to any one of [1] to [3], further including a photopolymerization initiator (C).
[5] The photocurable resin composition for curved surface application according to any one of [1] to [4], further comprising a compound (D) that is liquid at 25 ° C.
[6] The photocurable resin composition for curved surface application according to any one of [1] to [5], further comprising a solid compound (E) 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 for curved surface application 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 for curved surface application 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] Image display in which the photocurable resin composition for curved surface application is cured by interposing the photocurable resin composition for curved surface application in the gap between the image display unit or touch panel having the image display unit and the transparent protective plate. A method for manufacturing an apparatus, wherein the photocurable resin composition for curved surface application according to any one of [1] to [6] is interposed in the gap, and light irradiation is performed at least from the transparent protective plate side. A method of manufacturing an image display device to be cured.
[11] The method for manufacturing an image display device according to [10], wherein the transparent protective plate has a stepped portion.

  According to the present invention, a photocurable resin composition for curved surface coating that is difficult to leak out even in a curved image display device and can be easily shaped into a desired shape, and an image display having a curved surface using the photocurable resin composition for curved surface coating An apparatus and a manufacturing method thereof can be provided.

It is the schematic which shows the cross-section of an example of an image display apparatus. 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.

[Photocurable resin composition for curved surface application]
The photocurable resin composition for curved surface coating of the present invention contains a compound (A) having a photopolymerizable functional group and an oil gelling agent (B).
The photocurable resin composition for curved surface application of the present invention is not easily leaked even on a curved surface and is easily shaped into a desired shape. Although the details of the reason are unknown, it is presumed as follows.
In the compound (A) having a photopolymerizable functional group, the oil gelling agent (B) contained in the photocuring resin composition for curved surface coating is a hydrogen bond, electrostatic bond, π-π interaction, van der Waals. Non-covalent molecular interactions such as force are expressed and linked to each other to form a fibrous bond (hereinafter sometimes referred to as “self-assembly”). As a result, at least a part of the photocurable resin composition for curved surface application becomes a physical gel-like substance (hereinafter sometimes referred to as gelation or gel) at room temperature of 25 ° C., and as a result, it leaks out compared to liquid. It is difficult to shape, and it is presumed that it becomes easier to shape into a desired shape than solid.
Next, each component of the photocurable resin composition for curved surface application 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; a cyclic ether group that can be cured by a photoacid generator that generates acid, such as an epoxy group Although a compound etc. are preferable, from the point of sclerosis | hardenability and transparency, the compound containing an ethylenically unsaturated group is preferable and the 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” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” and corresponding “methacryloyl”.

((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).

  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 (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 (a) to (c) and benzyl (meth) acrylate are preferably exemplified.

(In general formula (a), 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 (b), 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 general formula (c), 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 the aromatic ring, specifically, those represented by the following general formulas (25) to (37) are preferable.

(In general formula (25), the average value of n is 4.)
The general formula (25) is commercially available, for example, as FA-314A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (26), the average value of n is 8.)
The general formula (26) is commercially available, for example, as FA-318A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As General formula (27), it is commercially available as FA-BZM (Hitachi Chemical Co., Ltd. make, brand name), for example.

  The general formula (28) is commercially available, for example, as FA-BZA (manufactured by Hitachi Chemical Co., Ltd., trade name).

(In general formula (29), the average value of m + n is 10.)
The general formula (29) is commercially available, for example, as FA-321A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (30), the average value of m + n is 18.)
The general formula (30) is commercially available, for example, as FA-3218M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (31), the average value of m + n is 10.)
The general formula (31) is commercially available, for example, as FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (32), the average value of m + n is 30.)
The general formula (32) is commercially available, for example, as FA-323M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As general formula (33), it is commercially available as light acrylate PO-A (trade name, phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.).

(In general formula (34), the average value of m + n is 4.)
The general formula (34) is commercially available, for example, as FA-324M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (35), the average value of m + n is 4.)
The general formula (35) is commercially available, for example, as FA-324A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (36) is commercially available, for example, as FA-302A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (37) is commercially available, for example, as A-BPFE (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

[(Meth) acrylates having alicyclic groups]
As the (meth) acrylate having the alicyclic group, specifically, those represented by the following general formulas (38) to (44) are preferable.

  The general formula (38) is commercially available as light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., Ltd., trade name, dimethylol-tricyclodecane diacrylate).

  The general formula (39) is commercially available, for example, as FA-512M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (40) is commercially available, for example, as FA-512AS (manufactured by Hitachi Chemical Co., Ltd., trade name).

  The general formula (41) is commercially available, for example, as FA-513M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (42) is commercially available, for example, as FA-513AS (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  As general formula (43), it is commercially available as light acrylate IB-XA (Kyoeisha Chemical Co., Ltd., a brand name, isobonyl acrylate).

  The general formula (44) 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 (meth) acrylate, polyalkylene glycol di (meth) acrylate represented by the following formula (d), alkoxy polyalkylene glycol (meth) acrylate represented by the following formula (e), 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 (d), 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 (e), 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.)

  Specifically, as the heteroatom-based (meth) acrylate, those represented by the following general formulas (45) to (50) are preferable.

  The general formula (45) is commercially available, for example, as FA-731A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In general formula (46), the average value of n is 7.)
The general formula (46) is commercially available, for example, as FA-P240A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The general formula (47) is commercially available, for example, as FA-731AT (trade name, manufactured by Hitachi Chemical Co., Ltd.).

(In the general formula (48), the average value of n is 9)
As the general formula (48), for example, light acrylate 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) is commercially available.

  The general formula (49) is commercially available, for example, as X-22-164AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

  As general formula (50), 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) As a polymer having (meth) acryloyl group, for example, polybutadiene (meth) acrylate, polyisoprene (meth) acrylate, urethane acrylate, epoxy acrylate, (meth) acryloyl group in the side chain And acrylic resins having a modified form, and modified products thereof. 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 (51) to (53) are suitable.

  As the general formula (51), for example, 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) are used. It can be obtained by reacting (hereinafter sometimes referred to as PB-MOI).

  The general formula (52) is commercially available, for example, as TEAI-1000 (trade name, manufactured by Nippon Soda Co., Ltd.).

  As the general formula (53), 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 (54) to (56) are preferable.

  General formula (54) is STC (styrene), and is commercially available from Wako Pure Chemical Industries, Ltd., for example.

  As general formula (55), it is commercially available as RICON 130 and RICON 131 (both manufactured by CRAY VALLEY, trade name, polybutadiene mainly composed of 1,2-structural units).

  The general formula (56) is commercially available, for example, as TAIC (trade name, manufactured by Nippon Kasei Co., Ltd.).

Among the above compounds, all compounds are more preferable from the viewpoints of transparency, gelation (self-organization), and step embedding.
From the viewpoint of low curing shrinkage, the compound of general formula (55) is preferred.
From the viewpoint of a low dielectric constant, compounds of general formulas (55) and (56) are preferred.

(Content of Compound (A) Having Photopolymerizable Functional Group)
It is preferable that content of the compound (A) which has a photopolymerizable functional group is 0.5-99 mass% with respect to the 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.

<Oil gelling agent (B)>
Examples of the oil gelling agent (B) (hereinafter also referred to as “component (B)”) include hydroxystearic acid, particularly hydroxy fatty acids such as 12-hydroxystearic acid, and hydrogenated castor oil mainly composed of hydroxy fatty acids. Hydroxy fatty acid amide, n-lauroyl-L-glutamic acid-α, β-dibutyramide, di-p-methylbenzylidene sorbitol glucitol, 1,3: 2,4-bis-O-benzylidene-D-glucitol, 1 , 3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato) hydroxyaluminum, compounds represented by the following general formulas (1) to (12), and the like. It is done. 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 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, 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, and 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 general formula (8), R < ₈ > is a C1-C20 saturated hydrocarbon group.
In general formula (9), Ph represents a phenyl group.
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 content of the oil gelling agent (B) is preferably 0.1 to 20% by mass with respect to the total amount of the photocurable resin composition. 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.

<Photopolymerization initiator (C)>
The photocurable resin composition of the present invention preferably contains a photopolymerization initiator (C) (hereinafter sometimes referred to as “component (C)”). 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.
This photopolymerization initiator (C) undergoes a curing reaction upon 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.

  The content of the photopolymerization initiator (C) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, based on the total amount of the photocurable resin composition. 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.

<Liquid compound (D) at 25 ° C.>
The photocurable resin composition of the present invention may further contain a compound (D) that is liquid at 25 ° C. (hereinafter sometimes referred to as “component (D)”). The compound (D) which is liquid at 25 ° C. may be added according to the purpose within a range where the self-organizing property is not impaired.
Examples of the liquid compound (D) at 25 ° C. include di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and diundecyl phthalate (general formula (57) ), DUP), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), liquid paraffin, organic solvent and the like can be mentioned.

Pentaerythritol tetrakis (3-mercaptobutyrate) is commercially available, for example, as Karenz MT PE1 (manufactured by Showa Denko KK, general formula (58)).
These are used for the purpose of adjusting the degree of gelation by reducing the viscosity of the photocurable resin composition.
Other examples of the compound (D) that is liquid at 25 ° C. include liquid polymers such as acrylic resin, 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 still more preferably 1000 to 3000.

  When the liquid compound (D) is used at 25 ° C., the content is 1 to 99% by mass with respect to the total amount of the photocurable resin composition for curved surface application. To preferred. In this respect, the content of the compound (D) is more preferably 2 to 98% by mass.

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

[Other additives]
In addition to the above components (A) to (E), various additives may be included in the photocurable resin composition for curved surface coating of the present invention, if necessary. In the present invention, examples of various additives that can be included include polymerization inhibitors, antioxidants, light stabilizers, silane coupling agents, surfactants, and leveling agents.

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 enhancing 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 components (A) to (E), and is generally 0 with respect to the total amount of the photocurable resin composition for curved surface coating. About 0.01 to 5% by mass.

(Inorganic filler)
In the photocurable resin composition for curved surface coating 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, hollow glass, calcium carbonate , Quartz powder, metal hydrate and the like. 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.

The photocuring resin composition for curved surface coating, which can be produced by mixing and stirring the components (A), (B), and (C) to (E) and the additives as necessary, The viscosity at a shear rate of 1.0 s ⁻¹ at 25 ° C. is preferably 30 to 10,000 Pa · s from the viewpoint of shape retention. Further, the viscosity at 25 ° C. and the shear rate of 1.0 s ⁻¹ is more preferably 50 to 9000 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 10000 Pa · s, the applicability is lowered during film formation.

<Method for producing photocurable resin composition for curved surface application>
There is no restriction | limiting in particular in the manufacturing method of the photocurable resin composition for curved surface coating, Said (A) component, (B) component, (C)-(E) component, and said additive are mixed as needed. It can be produced by stirring.
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 the photocurable resin composition for curved surface coating 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 apparatus using the photocurable resin composition for curved surface application of the present invention will be described.
The photocurable resin composition for curved surface application 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 for curved surface coating 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 for curved surface application of the present invention is applied to a multilayer product and then cured, and then cured.

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 layer obtained by forming 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 for curved surface coating of the present invention can be used by being laminated on a polarizing plate. In this case, it can also be laminated on the viewing surface side of the polarizing plate, or can be laminated 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 photo-curing resin composition for applying a curved surface is disposed between an image display unit of an image display device having a curved surface and a transparent protective plate (protective panel) on the foremost side of the viewing side, at an appropriate position on the viewing side. It is preferable. Specifically, it is preferably applied between the image display unit and the transparent protective plate.
Further, in the image display device having a curved surface in which the touch panel is combined with the image display unit, it 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 for curved surface application of this invention is applicable on the structure of an image display apparatus, it will not be restricted 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. 2>
FIG. 2 is a cross-sectional view schematically showing one 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. 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 for curved surface application of the present embodiment. The thickness of the stepped portion 60 varies depending on the size of the liquid crystal display device, etc., but when the thickness is 30 μm to 100 μm, it is particularly useful to use the photocurable resin composition for curved surface application of the present embodiment. .

<Liquid Crystal Display Device of FIG. 3>
FIG. 3 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. 3 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 for curved surface application 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. 3, the transparent resin layer is interposed between the image display unit 7 and the touch panel 30 and between the touch panel 30 and the transparent protective plate 40. It suffices to intervene 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. 2 is 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. A liquid crystal display device having 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 for curved surface application of the present invention. The object can be suitably used for a liquid crystal display device employing such an in-cell type touch panel.

<Liquid Crystal Display Device in FIGS. 2 and 3>
According to the liquid crystal display device shown in FIGS. 2 and 3, since the photo-curing resin composition for curved surface application according to the present embodiment is provided as the transparent resin layer 31 or 32, it has impact resistance, is clear and has no double image. 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 for curved surface application of the present embodiment, a thicker film can exhibit a more excellent effect, and the transparent resin layer 31 or 32 of 0.1 mm or more is formed. It can be suitably used in some cases.
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. 2)
In the liquid crystal display device of FIG. 2 described above, the step of interposing the photocurable resin composition for curved surface application according to the present embodiment between the image display unit 7 and the transparent protective plate (protective panel) 40 having the stepped portion 60. It can manufacture with a manufacturing method provided with.

That is, the photocurable resin composition for curved surface application of the present invention is formed on the surface of the transparent protective plate (protective panel) 40 where the stepped portion 60 is formed. The said formation may be performed by apply | coating the photocurable resin composition for curved-surface application | coating of this invention on the transparent protective board (protection panel) 40. FIG. In addition, a gel-like photocurable resin composition for curved surface application is formed on a release sheet in advance, and the gel-like photocurable resin composition for curved surface application is brought into contact with a transparent protective plate (protective panel) 40. After pressing, the release sheet may be peeled off.
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-curing resin composition for curved surface application is cured by light irradiation to form the transparent resin layer 32, whereby the image display device of FIG. 2 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. 3)
3 is applied 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 according to the curved surface application of the present embodiment. It can manufacture with a manufacturing method provided with the process of interposing the photocurable resin composition for water.
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 is manufactured by the same method as the transparent resin layer 32 of FIG. 2 except that the photocurable resin composition for curved surface application is applied to the touch panel 30 instead of the transparent protective plate (protective panel) 40. Can do.
The curing shrinkage rate when the photocuring resin composition for curved surface coating of the present invention is cured is preferably less than 10% from the viewpoint of further suppressing the warpage of the substrate such as the transparent protective plate and the image display unit, Less than 9% is more preferable, less than 8% is still more preferable, and less than 7% 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.
The dielectric constant at 100 kHz of the cured product of the photocuring resin composition for curved surface application of the present invention is preferably 8 or less, more preferably 7 or less, when used between the touch panel and the transparent protective plate. More preferably, it is more preferably 5 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]
The photocurable resin composition for curved surface coating obtained in each example and comparative example was evaluated by the following test methods.

(1) Evaluation of transparency 2 g of a photocurable resin composition for curved surface application is added to a 2 ml screw tube, and an oil gelling agent is added in an oven at 100 ° C. (air blowing thermostat DN-400, manufactured by Yamato Scientific Co., Ltd.). Allowed to dissolve. Next, the solution was quickly homogenized with a self-revolving mixer ARE-250 (manufactured by Sinky Co., Ltd.) under the conditions of 2000 rpm and 20 seconds, and left at 25 ° C. for 30 minutes. The transparency of the contents of the screw tube was evaluated.
(Evaluation criteria)
A: Turbidity is not seen B: Turbidity

(2) Viscosity measurement Using an E-type viscometer (TPE-100H manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. (unit: Pa · s) of the resin composition obtained in each example and each comparative example. Was measured. Measurement conditions and methods are shown below.
Measurement conditions and rotor name: 3 ° × R9.7, rotor code 06
・ Shear speed: 1 (s ^-1 ) to 100 (s ^-1 )
Measuring method:
The sample heated to 80 ° C. was put in a measurement container and left at 25 ° C. for 30 minutes to start measurement.

(3) Sagging evaluation An air brush (manufactured by Anest Iwata Co., Ltd.) is filled with the photocurable resin composition for application to curved surfaces in Table 1, and the glass portion (curvature radius 13.) of the screw tube (No. 5, Marum Co., Ltd.). 5 mm), and a resin film was applied. Thereafter, the mouth portion of the screw tube was suspended and allowed to stand for 10 minutes to evaluate the sagging.
(Evaluation criteria)
A: The coated material on the screw tube does not sag.
B: The applied material of the screw tube hangs down.

[material]
In the following examples and comparative examples, the following raw materials were used.
(A component)
In addition, as for this component, the number average molecular weight (Mn) or the weight average molecular weight (Mw) of the compound used for the polymer synthesized in the following examples is a value measured based on the following method.
[Method for measuring number average molecular weight (Mn) or weight average molecular weight (Mw)]
The determination was carried out using gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and a calibration curve was prepared using polystyrene as a standard substance.
In preparing the calibration curve, 5 sample sets (PStQuickMP-H, PStQuickB [trade name, manufactured by Tosoh Corporation]) were used as standard polystyrene.
Apparatus: High-speed GPC apparatus HCL-8320GPC (detector: differential refractometer or UV) (trade name, manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran (THF)
Column: Column TSKGEL SuperMultipore HZ-H (manufactured by Tosoh Corporation, trade name)
Column size: Column length is 15 cm, column inner diameter is 4.6 mm
Measurement temperature: 40 ° C
Flow rate: 0.35 ml / min Sample concentration: 10 mg / THF 5 ml
Injection volume: 20 μl
・ "Polybutadiene methacrylate"
(Synthesis of polybutadiene methacrylate)
In a reaction vessel equipped with a cooling pipe, a thermometer, a stirrer, a dropping funnel and an air injection pipe, α, ω-polybutadiene glycol (trade name “polybutadiene glycol G-3000” manufactured by Nippon Soda Co., Ltd., [1,2- (Structural unit / 1,4-structural unit) content ratio = 90/10, hydroxyl value = 27 mgKOH / g) is 978.2 parts by mass, p-methoxyphenol is 0.5 parts by mass as a polymerization inhibitor, and catalyst As a result, 0.05 part by mass of dibutyltin dilaurate (trade name “L101” manufactured by Tokyo Fine Chemical Co., Ltd.) was added. Then, after raising the temperature to 70 ° C. while flowing air into the reaction vessel, stirring at 70 to 75 ° C., 20.3 parts by mass of 2-isocyanatoethyl methacrylate (made by Showa Denko KK, trade name “Karenz MOI”) Was added dropwise over 1 hour to carry out the reaction.
When the reaction was completed for 5 hours after completion of the dropwise addition, the reaction was terminated after confirming that the isocyanate had disappeared as a result of IR (infrared absorption analysis), and polybutadiene methacrylate having a methacryloyl group at the terminal (weight average molecular weight 7, 700). The average value (average number of functional groups) of methacryloyl groups per molecule of this polybutadiene methacrylate was 0.5 (calculated value from the charged amount).

・ "Polyacrylate; Compound (D) which is liquid at 25 ° C"
(Synthesis of polyacrylate)
Take 96 g of 2-ethylhexyl acrylate, 24 g of hydroxyethyl acrylate and 150 g of methyl ethyl ketone as initial monomers in a reaction vessel equipped with a condenser, thermometer, stirrer, dropping funnel and nitrogen inlet tube, and replace with nitrogen at an air volume of 100 ml / min. However, it heated from normal temperature (25 degreeC) to 80 degreeC in 15 minutes. Thereafter, while maintaining the temperature at 80 ° C., 24 g of 2-ethylhexyl acrylate monomer and 6 g of 2-hydroxyethyl acrylate were used as additional monomers, and 5 g of t-butylperoxy-2-ethylhexanoate was dissolved in the solution. And this solution was added dropwise over 120 minutes. After completion of dropping, the reaction was further continued for 2 hours.
Subsequently, methyl ethyl ketone was distilled off to obtain a copolymer of 2-ethylhexyl acrylate monomer and 2-hydroxyethyl acrylate (weight average molecular weight 3.0 × 10 ⁴ ).

UC-102: Compound of general formula (53), manufactured by Kuraray Co., Ltd., n = 2, number average molecular weight 17,000, trade name acryloylmorpholine, KJ Chemicals Corporation lauryl acrylate, Hitachi Chemical Co., Ltd. hydroxybutyl acrylate, Hitachi 2-ethylhexyl acrylate manufactured by Kasei Co., Ltd., hydroxyethyl acrylate manufactured by Hitachi Chemical Co., Ltd., manufactured by Kyoeisha Chemical Co., Ltd.

(B component)
12-hydroxystearic acid, Wako Pure Chemical Industries, Ltd.

(C component)
I-184: Irgacure 184, 1-hydroxy-cyclohexyl-phenyl-ketone, BASF Japan Ltd.

(D component)
B-1000: Nippon Soda Co., Ltd., both terminal hydroxyl group polybutadiene, number average molecular weight 1,100, trade name LBR-307: Kuraray Co., Ltd., polyisoprene, number average molecular weight 8,000, trade name

[Examples 1 to 4]
Each component was mix | blended with the compounding ratio shown in Table 1, and it heat-stirred and mixed for 30 minutes at 90 degreeC, and prepared the photocurable resin composition for curved surface coating of Examples 1-4. In Table 1, the unit of numerical values for each component is parts by mass.

[Comparative Examples 1-4]
(B) Except not mix | blending a component, it mix | blends each component by the compounding ratio shown in Table 1 similarly to an Example, and heat-stir-mixes for 30 minutes at 90 degreeC, The resin composition of Comparative Examples 1-4 is used. Prepared. In addition, the unit of the numerical value about each component in Table 1 is a mass part.

  Regarding the photo-curing resin composition for curved surface application of Example 1-4, excellent transparency was obtained, and the coated result on the curved surface did not sag and gave good results. With respect to the photocurable resin composition of Comparative Example 1-4, although the transparency was good, the applied material applied to the screw tube dripped.

1 Transparent protective plate (glass or plastic substrate)
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 part

Claims (11)

  A photocurable resin composition for curved coating, comprising a compound (A) having a photopolymerizable functional group and an oil gelling agent (B). The oil gelling agent (B) is hydroxy fatty acid, hydrogenated castor oil containing hydroxy fatty acid as a main component, hydroxy fatty acid amide, n-lauroyl-L-glutamic acid-α, β-dibutyramide, di-p-methylbenzylidene sorbitol glu Cytol, 1,3: 2,4-bis-0-benzylidene-D-glucitol, 1,3: 2,4-bis-0- (4-methylbenzylidene) -D-sorbitol, bis (2-ethylhexa) The photocurable resin composition for curved-surface application | coating of Claim 1 which is at least 1 sort (s) of the compound represented by Noato) hydroxyaluminum and the 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 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, 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, and 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 general formula (8), R < ₈ > is a C1-C20 saturated hydrocarbon group.
In general formula (9), Ph represents a phenyl group.
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 for curved-surface application | coating of Claim 1 or Claim 2 in which the compound (A) which has the said photopolymerizable functional group contains the compound which has an ethylenically unsaturated group.   Furthermore, the photocurable resin composition for curved-surface application | coating as described in any one of Claims 1-3 containing a photoinitiator (C).   Furthermore, the photocurable resin composition for curved-surface application | coating as described in any one of Claims 1-4 containing a liquid compound (D) at 25 degreeC.   Furthermore, the photocurable resin composition for curved-surface application | coating as described in any one of Claims 1-5 containing a solid compound (E) 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 for curved-surface application | coating as described 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 for curved-surface application | coating as described in any one of Claims 1-6.   The image display device according to claim 7, wherein the transparent protective plate has a stepped portion.   Manufacture of an image display device in which a photo-curing resin composition for curved surface coating is interposed in a gap between an image display unit or touch panel having an image display unit and a transparent protective plate to cure the photo-curable resin composition for curved surface coating An image display device comprising the curved photocurable resin composition according to any one of claims 1 to 6 interposed in the gap and cured by light irradiation from at least the transparent protective plate side. Production method.   The method for manufacturing an image display device according to claim 10, wherein the transparent protective plate has a stepped portion.

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