JP2018030898A - Photocurable resin composition, and an image display device, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition that resists leakage and is easy to be molded into a desired shape.SOLUTION: A photocurable resin composition has a compound (A) having a photopolymerizable functional group, and an oil gelator (B), the photocurable resin composition having a viscosity at a shear rate 1.0 sat 25°C of 30-1000 Pa s.SELECTED DRAWING: None

Description

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

  The photocurable resin composition is widely used as an adhesive; an adhesive; a filler; an image display device and the like.

  For example, the air gap between the transparent protective plate or the information input device (for example, touch panel) in the image display device and the display surface of the image display unit or the air 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, the following 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 10 with a built-in touch panel includes a transparent protective plate (glass or plastic substrate) 1, a touch panel 2, a polarizing plate 3 and a liquid crystal display cell 4, and prevents the liquid crystal display device from cracking, stress and impact. In order to relax and improve visibility, an adhesive layer 5 may be provided between the transparent protective plate 1 and the touch panel 2, and an 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, in Patent Document 2 below, urethane (meth) acrylate having two or more functional groups having an unsaturated double bond, a monomer having one functional group having an unsaturated double bond, a photopolymerization initiator, and A photocurable transparent adhesive composition containing a polythiol compound having two or more thiol groups is disclosed. Patent Document 3 below discloses a transparent adhesive sheet comprising 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. Is disclosed.

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

  When the photocurable resin composition is in a liquid state as in Patent Document 2 or the like, there is a problem that it is likely to leak from the predetermined location when formed at the predetermined location. 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 deform sufficiently following the shape of the predetermined location, and the predetermined location is not affected. There is a problem that voids or the like are easily generated.

  The present invention has been made to solve the above problems, and is a photocurable resin composition that is difficult to leak and can be easily molded into a desired shape, and an image display device using the photocurable resin composition And it aims at providing the manufacturing method.

The photocurable resin composition according to the present invention is a photocurable resin composition containing a compound (A) having a photopolymerizable functional group and an oil gelling agent (B), and a shear rate at 25 ° C. The viscosity at 1.0 s ⁻¹ is 30 to 1000 Pa · s.

  The photocurable resin composition according to the present invention is difficult to leak and is easily molded into a desired shape. By using such a photocurable resin composition, an image display device or the like can be suitably obtained.

  It is preferable that content of the said (B) component is 0.2-20 mass% with respect to the whole quantity of the said photocurable resin composition.

［一般式（１）中、ｎ１は３〜１０の整数、ｎ２は２〜６の整数、Ｒ^１は炭素数１〜２０の飽和炭化水素基、Ｘ^１は硫黄原子又は酸素原子である。］

［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り、Ｒ^１２及びＲ^１３は、それぞれ独立に炭素数１〜２０の飽和炭化水素基である。］ The component (B) is hydroxy fatty acid, hydrogenated castor oil, 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, represented by the following general formula (1) A compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following formula (5) , A compound represented by the following general formula (6), a compound represented by the following general formula (7), a compound represented by the following general formula (8), a compound represented by the following formula (9), the following general formula Represented by equation (10) And at least one selected from the group consisting of a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following general formula (13): Also good.

[In General Formula (1), n1 is an integer of 3 to 10, n2 is an integer of 2 to 6, R ¹ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X ¹ is a sulfur atom or an oxygen atom. ]

In 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 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 General formula (7), ^{R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

In 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, and R ¹² and R ¹³ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

  The component (A) preferably contains a compound having an ethylenically unsaturated group. In this case, excellent curability and transparency can be obtained.

  The photocurable resin composition of the present invention preferably further contains a photopolymerization initiator. In this case, leakage can be further suppressed.

  The photocurable resin composition of the present invention may further contain a compound that is liquid at 25 ° C., and may further contain a solid compound at 25 ° C.

  An image display device of the present invention is 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 resin layer contains the photocurable resin composition or a cured product thereof.

  In the image display device of the present invention, the transparent protective plate may have a step portion.

  The method for producing an image display device of the present invention is a method for producing an image display device having a laminated structure including an image display unit having an image display unit and a transparent protective plate, wherein the photocurable resin composition is The laminated body interposed between the image display unit and the transparent protective plate is irradiated with active energy rays to cure the photocurable resin composition.

  In the image display device manufacturing method of the present invention, the transparent protective plate may have a stepped portion.

  According to the present invention, it is possible to provide a photocurable resin composition that is difficult to leak 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.

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 one Embodiment of the liquid crystal display device carrying a touch panel.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  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. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .

<Photocurable resin composition>
The photocurable resin composition of the present embodiment is a photocurable resin composition containing a compound (A) having a photopolymerizable functional group and an oil gelling agent (B). In the photocurable resin composition of the present embodiment, the viscosity at a shear rate of 1.0 s ^{−1 at} 25 ° C. is 30 to 1000 Pa · s.

The photocurable resin composition of this embodiment is difficult to leak out and is easy to mold 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 photocurable resin composition includes hydrogen bonds, electrostatic bonds, π-π interactions, van der Waals forces, 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”) at room temperature (25 ° C., the same applies hereinafter), and as a result, It is presumed that it is difficult to leak out compared to a liquid and that it can be easily formed into a desired shape compared to a solid.

  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 having an ethylenically unsaturated group curable with a photopolymerization initiator that generates radicals, such as an allyl group; a cyclic ether group curable with a photoacid generator that generates an acid, such as an epoxy group However, from the viewpoint of obtaining excellent curability and transparency, a compound having an ethylenically unsaturated group is preferable, and a compound having a (meth) acryloyl group is more preferable. As the compound having 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 preferable. Next, these compounds and polymers will be described in this order.

[(Meth) acrylate compound]
Examples of (meth) acrylate compounds include (meth) acrylic acid; (meth) acrylic amide; (meth) acryloylmorpholine; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 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, isodecyl (Meth) acrylate, dodecyl (meth) acrylate (n-lauryl (meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate, etc., alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group Rate; alkanediol di (meth) acrylate having 1 to 18 carbon atoms such as ethylene glycol di (meth) acrylate, butanediol (meth) acrylate, nonanediol di (meth) acrylate; trimethylolpropane tri (meth) ) Acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. (meth) acryloyl group in the molecule Polyfunctional (meth) acrylate having 3 or more; 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 Alkoxypoly, such as glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxyheptapropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate Alkylene glycol (meth) acrylate; cyclohexyl (meth) acrylate, isovol (Meth) acrylates having an alicyclic group such as nyl (meth) acrylate and dicyclopentanyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylates such as (meth) acrylates; hydroxyl-containing (meth) acrylates; tetrahydrofurfuryl (meth) acrylates; N, N-dimethylaminoethyl (meth) acrylates, N, N-dimethylaminopropyl (meth) acrylamides, N, N -(Meth) acrylamide derivatives such as dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; 2- (2-methacryloyloxyethyloxy) D (Meth) acrylate having an isocyanate group, such as diisocyanate, 2- (meth) acryloyloxyethyl isocyanate; tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate , Dialkylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate such as octapropylene glycol mono (meth) acrylate; polyalkylene glycol di (meth) acrylate; isocyanuric ring skeleton (Meth) acrylate having siloxane; (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 heterogeneous. Sometimes referred to generically as atomic (meth) acrylate.

{Aliphatic (meth) acrylate}
As the aliphatic (meth) acrylate, specifically, compounds represented by the following formulas (14) to (24) are preferable.

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

  The compound represented by the formula (15) is commercially available as, for example, Light Ester L (trade name, lauryl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.), and FA-112M (Hitachi Chemical Co., Ltd.). (Commercially available as product name).

  The compound represented by the formula (16) is 2-ethylhexyl acrylate (EHA), which is commercially available from, for example, Wako Pure Chemical Industries, Ltd., and also from Nippon Shokubai Co., Ltd. Commercially available as 2-ethylhexyl.

  The compound represented by the formula (17) is commercially available, for example, as Light Acrylate IM-A (manufactured by Kyoeisha Chemical Co., Ltd., trade name, isomyristyl acrylate (C14 isomer mixture)).

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

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

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

  The compound represented by the formula (22) is commercially available, for example, as light acrylate TMP-A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

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

  The compound represented by the formula (24) is commercially available, for example, as light ester G (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) (sometimes referred to as GMA).

{(Meth) acrylate having an aromatic ring}
As the (meth) acrylate having an aromatic ring, one or more of the compounds represented by the following general formulas (a) to (c) and benzyl (meth) acrylate are preferably exemplified. The

［一般式（ａ）中、Ｒ^２１は水素原子又はメチル基を示し、Ｒ^２２は水素原子、炭素数１〜１２のアルキル基又はフェニル基を示し、ｎ３は１〜２０の整数を示す。］

[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 n3 represents an integer of 1 to 20. ]

［一般式（ｂ）中、Ｒ^２３は水素原子又はメチル基を示し、Ｒ^２４は水素原子又はメチル基を示し、ｎ４及びｎ５はそれぞれ独立に１〜２０の整数を示す。複数存在するＲ^２３はそれぞれ同一でも異なっていてもよく、複数存在するＲ^２４はそれぞれ同一でも異なっていてもよい。］

[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 n4 and n5 each independently represents an integer of 1 to 20. A plurality of R ²³ may be the same or different, and a plurality of R ²⁴ may be the same or different. ]

［一般式（ｃ）中、Ｒ^２５は水素原子又はメチル基を示し、ｎ６及びｎ７はそれぞれ独立に１〜２０の整数を示す。複数存在するＲ^２５はそれぞれ同一でも異なっていてもよい。］

[In General Formula (c), R ²⁵ represents a hydrogen atom or a methyl group, and n6 and n7 each independently represents an integer of 1 to 20. A plurality of R ²⁵ may be the same or different. ]

  As the (meth) acrylate having an aromatic ring, specifically, compounds represented by the following formulas (25) to (37) are preferable.

［一般式（２５）中、ｎ８の平均値は４である。］

[In the general formula (25), the average value of n8 is 4. ]

  The compound represented by the general formula (25) is commercially available, for example, as FA-314A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

［一般式（２６）中、ｎ９の平均値は８である。］

[In the general formula (26), the average value of n9 is 8. ]

  The compound represented by the general formula (26) is commercially available, for example, as FA-318A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The compound represented by the formula (27) is commercially available, for example, as FA-BZM (trade name, manufactured by Hitachi Chemical Co., Ltd.).

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

［一般式（２９）中、ｎ１０＋ｎ１１の平均値は１０である。］

[In the general formula (29), the average value of n10 + n11 is 10. ]

  The compound represented by the general formula (29) is commercially available as, for example, FA-321A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

［一般式（３０）中、ｎ１２＋ｎ１３の平均値は１８である。］

[In the general formula (30), the average value of n12 + n13 is 18. ]

  The compound represented by the general formula (30) is commercially available, for example, as FA-3218M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

［一般式（３１）中、ｎ１４＋ｎ１５の平均値は１０である。］

[In General Formula (31), the average value of n14 + n15 is 10. ]

  The compound represented by the general formula (31) is commercially available, for example, as FA-321M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

［一般式（３２）中、ｎ１６＋ｎ１７の平均値は３０である。］

[In General Formula (32), the average value of n16 + n17 is 30. ]

  The compound represented by the general formula (32) is commercially available, for example, as FA-323M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

  The compound represented by the formula (33) is commercially available, for example, as light acrylate PO-A (trade name, phenoxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.).

［一般式（３４）中、ｎ１８＋ｎ１９の平均値は４である。］

[In the general formula (34), the average value of n18 + n19 is 4. ]

  The compound represented by the general formula (34) is commercially available, for example, as FA-324M (trade name, manufactured by Hitachi Chemical Co., Ltd.).

［一般式（３５）中、ｎ２０＋ｎ２１の平均値は４である。］

[In the general formula (35), the average value of n20 + n21 is 4. ]

  The compound represented by the general formula (35) is commercially available, for example, as FA-324A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

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

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

{(Meth) acrylate having alicyclic group}
As the (meth) acrylate having the alicyclic group, specifically, compounds represented by the following formulas (38) to (44) are preferable.

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

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

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

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

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

  The compound represented by the formula (43) is commercially available, for example, as light acrylate IB-XA (trade name, isobornyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.).

  The compound represented by formula (44) is commercially available, for example, as FA-511AS (trade name, manufactured by Hitachi Chemical Co., Ltd.).

{Heteroatom (meth) acrylate}
“Heteroatom-based (meth) acrylate” is classified as having no heterocycle and containing many heteroatoms. As the heteroatom-based (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 polyalkylene glycol mono One or more of (meth) acrylate, (meth) acrylate having an isocyanuric ring skeleton, and (meth) acrylate having a siloxane skeleton are preferably exemplified.

［一般式（ｄ）中、Ｒ^２６は水素原子又はメチル基を示し、Ｘ^２はエチレン基、プロピレン基又はイソプロピレン基を示し、ｓ１は２〜２０の整数を示す。複数存在するＲ^２６はそれぞれ同一でも異なっていてもよい。］

[In General Formula (d), R ²⁶ represents a hydrogen atom or a methyl group, X ² represents an ethylene group, a propylene group or an isopropylene group, and s1 represents an integer of 2 to 20. A plurality of R ²⁶ may be the same or different. ]

［一般式（ｅ）中、Ｒ^２７は炭素数１〜５のアルキル基を示し、Ｒ^２８は水素原子又はメチル基を示し、Ｘ^３はエチレン基、プロピレン基又はイソプロピレン基を示し、ｓ２は２〜２０の整数を示す。］

[In General Formula (e), R ²⁷ represents an alkyl group having 1 to 5 carbon atoms, R ²⁸ represents a hydrogen atom or a methyl group, X ³ represents an ethylene group, a propylene group or an isopropylene group, and s2 represents An integer of 2 to 20 is shown. ]

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

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

［一般式（４６）中、ｎ２２の平均値は７である。］

[In the general formula (46), the average value of n22 is 7. ]

  The compound represented by the general formula (46) is commercially available, for example, as FA-P240A (trade name, manufactured by Hitachi Chemical Co., Ltd.).

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

［一般式（４８）中、ｎ２３の平均値は９である。］

[In the general formula (48), the average value of n23 is 9. ]

  The compound represented by the general formula (48) is commercially available as, for example, Light Acrylate 130A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

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

  The compound represented by the general formula (50) is commercially available, for example, as Silaplane TM-0701 (manufactured by JNC Corporation, trade name) (compound name: 3-tris (trimethylsiloxy) silylpropyl methacrylate). (Also referred to as “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, compounds represented by the following formulas (51) to (53) are preferable.

  The compound represented by the formula (51) is, for example, G-3000 (Nippon Soda Co., Ltd. trade name, α, ω-polybutadiene glycol), Karenz MOI (Showa Denko Co., Ltd. trade name; 2-isocyanato Ethyl methacrylate) can be obtained by reaction (also referred to as “PB-MOI”).

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

［式（５３）中、ｎ２７は５０〜１０００の数を示し、ｎ２８は１〜５の数を示す。］

[In Formula (53), n27 shows the number of 50-1000, n28 shows the number of 1-5. ]

  The compound represented by the formula (53) has, for example, a structure shown in UC-102 (manufactured by Kuraray Co., Ltd., n28 = 2, number average molecular weight 17000), and UC-203 (manufactured by Kuraray Co., Ltd., n28 = 3). , Number average molecular weight 35000).

[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, compounds represented by the following formulas (54) to (56) are preferable.

  The compound represented by the formula (54) is STC (styrene), and is commercially available from, for example, Wako Pure Chemical Industries, Ltd.

  The compound represented by the general formula (55) is commercially available, for example, as RICON 130 or RICON 131 (both manufactured by CRAY VALLEY, trade name, polybutadiene mainly composed of 1,2-structural units).

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

  Among the above compounds, all compounds are preferable from the viewpoint of further excellent transparency, gelation (self-organization), and step embedding property. From the viewpoint of low curing shrinkage, the compound represented by the general formula (55) is preferable. From the viewpoint of a low dielectric constant, a compound represented by the general formula (55) and a compound represented by the formula (56) are preferable.

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

(Oil gelling agent (B))
The photocurable resin composition of the present embodiment contains an oil gelling agent (B) (hereinafter sometimes referred to as “component (B)”). By adding an oil gelling agent to the oil agent, the oil agent can be gelled. The oil gelling agent is characterized by thickening by forming a network of molecules in oil. The oil agent can be gelled by dispersing an oil gelling agent (for example, a low molecular weight oil gelling agent) in the oil under heating conditions and cooling to room temperature.

  Examples of the component (B) include hydroxy fatty acids (for example, hydroxystearic acid such as 12-hydroxystearic acid), hydrogenated castor oil (for example, hydrogenated castor oil mainly composed of hydroxy fatty acid), n-lauroyl-L- Glutamic acid-α, β-dibutyramide, di-p-methylbenzylidenesorbitol glucitol, 1,3: 2,4-bis-O-benzylidene-D-glucitol, 1,3: 2,4-bis-O— (4-Methylbenzylidene) -D-sorbitol, bis (2-ethylhexanoato) hydroxyaluminum, a compound represented by the following general formula (1), a compound represented by the following general formula (2), the following general formula ( 3), a compound represented by the following general formula (4), a compound represented by the following formula (5), a compound represented by the following general formula (6) Compound, compound represented by the following general formula (7), compound represented by the following general formula (8), compound represented by the following formula (9), compound represented by the following general formula (10), Examples include at least one selected from the group consisting of a compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following general formula (13). These may be used alone or in combination of two or more. In addition, Ph in Formula (9) shows a phenyl group.

［一般式（１）中、ｎ１は３〜１０の整数、ｎ２は２〜６の整数、Ｒ^１は炭素数１〜２０の飽和炭化水素基、Ｘ^１は硫黄原子又は酸素原子である。］

[In General Formula (1), n1 is an integer of 3 to 10, n2 is an integer of 2 to 6, R ¹ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X ¹ is a sulfur atom or an oxygen atom. ]

［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（単結合）又はベンゼン環（置換基を有していてもよいフェニレン基）である。］

[In General Formula (2), R ² is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ¹ is a bond (single bond) or a benzene ring (a phenylene group which may have a substituent). ]

［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（単結合）又はベンゼン環（置換基を有していてもよいフェニレン基）である。］

[In General Formula (3), R ³ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and Y ² is a bond (single bond) or a benzene ring (a phenylene group which may have a substituent). ]

［一般式（４）中、Ｒ^４は炭素数１〜２０の飽和炭化水素基である。］

[In the general formula ^{(4), R} 4 is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［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。］

[In General Formula (6), R ⁵ and R ⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（７）中、Ｒ^７は、炭素数１〜２０の飽和炭化水素基である。］

In General formula (7), ^{R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（８）中、Ｒ^８は、炭素数１〜２０の飽和炭化水素基である。］

In General formula (8), ^{R 8} is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［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。］

[In General Formula (10), R ⁹ and R ¹⁰ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

［一般式（１３）中、Ｒ^１１は、炭素数１〜１０の飽和炭化水素基であり、Ｒ^１２及びＲ^１３は、それぞれ独立に炭素数１〜２０の飽和炭化水素基である。前記飽和炭化水素基は、分子骨格中に少なくとも１つの水酸基を有する炭素数１〜２０の飽和炭化水素基であってもよい。］

[In General Formula (13), R ¹¹ is a saturated hydrocarbon group having 1 to 10 carbon atoms, and R ¹² and R ¹³ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. The saturated hydrocarbon group may be a C 1-20 saturated hydrocarbon group having at least one hydroxyl group in the molecular skeleton. ]

  It is preferable that content of (B) component is 0.2 mass% or more with respect to the whole quantity of a photocurable resin composition. When the content of the component (B) is 0.2% by mass or more, it is easily gelled. It is preferable that content of (B) component is 20 mass% or less. When the content of the component (B) is 20% by mass or less, the content of the component (A) is relatively increased, and the photocuring is sufficiently easy. In light of sufficient gelation and photocuring, the content of the component (B) is more preferably 0.2 to 15% by mass, and still more preferably 0.3 to 10% by mass.

(Photopolymerization initiator (C))
The photocurable resin composition of the present embodiment 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. The photopolymerization initiator is not particularly limited, and known materials such as benzophenone-based, anthraquinone-based, benzoyl-based, sulfonium salt, diazonium salt, onium salt and the like can be used.

  Specifically, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4,4′- Dimethylaminobenzophenone, 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-diphenyl D Aromatic ketone compounds such as N-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,2-diethoxyacetophenone; benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Benzoin ether compounds such as methyl ether, 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- Acridine compounds such as phenylacridine, 9-pyridylacridine, 1,7-diacridinoheptane; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5 -Di (m-met Ciphenyl) 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-a, such as 4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone Minoalkylphenone compounds; acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; oligo (2-hydroxy-2-methyl-1- (4- (1-methyl) Vinyl) 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) 0.1-5 mass% is preferable with respect to the whole quantity of a photocurable resin composition, as for content of a component, 0.2-3 mass% is more preferable, 0.3-2 mass% is Further preferred. Photopolymerization can be favorably started when the content of the component (C) is 0.1% by mass or more. When the content of the component (C) is 5% by mass or less, the step embedding property and the self-organizing property are easily excellent, and the hue of the obtained cured product is easily suppressed from being yellowish.

(Liquid compound (D) at 25 ° C.)
The photocurable resin composition of the present embodiment may further contain a compound (D) that is liquid at 25 ° C. (hereinafter sometimes referred to as “component (D)”). (D) A component should just be added according to the objective in the range which does not impair self-organization property. (D) As a component, the compound corresponding to (A) component, (B) component, or (C) component is remove | excluded.

  As the component (D), di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (the following 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.

  Pentaerythritol tetrakis (3-mercaptobutyrate) is commercially available, for example, as Karenz MT PE1 (Showa Denko KK, formula (58) below).

  These are used for the purpose of adjusting the degree of gelation by reducing the viscosity of the photocurable resin composition.

  Other components (D) include liquid polymers such as acrylic resins, liquid polybutadiene mainly composed of 1,4-structural units, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated polyisobutene, and the like. 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.

  As the liquid polybutadiene mainly composed of 1,4-structural units, for example, polyoil (Nippon Zeon Co., Ltd.) is commercially available. As the hydrogenated polyisobutene which is liquid at 25 ° C., for example, Pearl Ream (trade name, manufactured by NOF 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 component (D) is used, the content of the component (D) is preferably 1 to 99% by mass with respect to the total amount of the photocurable resin composition from the viewpoints of self-organization and transparency. From the same viewpoint, the content of the compound (D) is more preferably 2 to 98% by mass.

(Compound (E) solid at 25 ° C.)
The photocurable resin composition of the present embodiment may further contain a solid (solid) compound (E) (hereinafter sometimes referred to as “component (E)”) at 25 ° C. (E) A component should just be added according to the objective in the range which does not impair self-organization property. (E) As a component, the compound corresponding to (A) component, (B) component, or (C) component is remove | excluded.

  Examples of the component (E) include terpene-based hydrogenated resins and the like, which are used for the purpose of improving the adhesiveness of the photocurable resin composition and adjusting the degree of gelation. The terpene hydrogenated resin is commercially available, for example, as Clearon P series (Yasuhara Chemical Co., Ltd., trade name).

  When the component (E) is used, the content of the component (E) is 0.1 to 20 with respect to the total amount of the photocurable resin composition from the viewpoint of further excellent self-organization, transparency, and leakage resistance. Mass% is preferred. From the same viewpoint, the content of the component (E) is more preferably 1 to 10% by mass.

(Other additives)
The photocurable resin composition of this embodiment may contain various additives separately from the components (A) to (E) as necessary. Examples of various additives that can be included include polymerization inhibitors, antioxidants, light stabilizers, silane coupling agents, surfactants, leveling agents, inorganic fillers, and the like.

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 a cured product obtained by curing a photocurable resin composition with light, and are phosphorus-based such as triphenyl phosphite; phenol-based; thiol-based antioxidant. Agents and the like.
The light stabilizer is added for the purpose of increasing resistance to active energy rays 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, and methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino Examples include propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane.
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 a plurality of additives may be used in combination. 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.

  The photocurable resin composition of the present embodiment may contain an inorganic filler, such as crushed silica, fused silica, mica, clay mineral, short glass fiber or fine powder, and hollow glass, calcium carbonate, quartz. Examples thereof include powders and metal hydrates. The content of the inorganic filler is preferably 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass with respect to 100 parts by mass of the photocurable resin composition, based on the total solid content. -30 mass parts is still more preferable. When the content of the inorganic filler is 0.01 to 100 parts by mass, sufficient low shrinkability, improvement in mechanical strength, low thermal expansion coefficient, and the like can 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, or a nanomizer to improve the dispersibility of the inorganic filler.

[Physical properties]
As the viscosity of the photocurable resin composition of the present embodiment, the viscosity at a shear rate (shear rate) of 1.0 s ^{−1 at} 25 ° C. is 30 to 1000 Pa · s from the viewpoint of excellent shape retention. When the viscosity 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. The viscosity is preferably 50 to 800 Pa · s, more preferably 70 to 750 Pa · s, and still more preferably 80 to 700 Pa · s. The viscosity of the photocurable resin composition can be measured using, for example, an E-type viscometer (such as TPE-100H manufactured by Toki Sangyo Co., Ltd.).

  The curing shrinkage rate when the photocurable resin composition of the present embodiment is cured is preferably less than 10% from the viewpoint of further suppressing the warpage of a substrate such as a transparent protective plate and an image display unit, and is preferably 5%. Less than, more preferably less than 2%, still more preferably less than 1%. 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 device 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 embodiment is preferably 7 or less, more preferably 5 or less, still more preferably 4 or less, and more preferably 3 or less. Particularly preferred. The lower limit of the dielectric constant is preferably 2 or more from a practical viewpoint.

<Method for producing photocurable resin composition>
There is no restriction | limiting in particular in the manufacturing method of the photocurable resin composition of this embodiment, The said (A) component and (B) component, and (C)-(E) component and said additive as needed. It can be produced by mixing and stirring.
In addition, when any of the components is in a solid state, it is preferable that the solid component is heated and dissolved at least at 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. When the heating temperature 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 embodiment will be described.
The photocurable resin composition of the present embodiment 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 embodiment 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. Multi-layered products obtained from the above; transparent protective plates made of glass, acrylic resin, alicyclic polyolefin, polycarbonate, etc .; multi-layered products obtained by forming or laminating functional layers having various functions on these transparent protective plates. Moreover, the photocurable resin composition of the present embodiment 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 embodiment 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 resin or a silicone 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 obtained by making it melt | dissolve in resin, and forming or laminating | stacking 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, an acrylic resin such as urethane acrylate or epoxy acrylate; an epoxy resin or the like formed or laminated on a base film such as a polyethylene film can be used. Similarly, in order to increase the surface hardness, a transparent protective plate made of glass, acrylic resin, alicyclic polyolefin, polycarbonate, or the like with a hard coat layer formed or laminated may be used.

The photocurable resin composition of the present embodiment 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 further 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, or a single wafer bonding machine.

  The image display device has, for example, a laminated structure including an image display unit having an image display unit, a transparent protective plate, and a resin layer containing a photocurable resin composition or a cured product thereof. The resin layer containing the photocurable resin composition or the cured product thereof is 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, and is appropriate on the viewing side. It is preferable to arrange in a position. Specifically, it is preferably applied between the image display unit and the transparent protective plate.

  Moreover, the image display apparatus which combined the touch panel with the image display unit is, for example, an image display unit having an image display unit, a transparent protective plate, a touch panel, and a resin layer containing a photocurable resin composition or a cured product thereof. And a laminated structure including. The touch panel is disposed, for example, between the image display unit and the transparent protective plate. The resin layer is preferably applied between the image display unit and the touch panel, and at least one between the transparent protective plate (protective panel) and the touch panel. However, the photocurable resin of the present embodiment is used in view of the configuration of the image display device. As long as the composition is applicable, it is not limited to the positions described above.

  Hereinafter, a liquid crystal display device which is one of the 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 an embodiment of a liquid crystal display device. The liquid crystal display device 100 illustrated in FIG. 2 includes an image display unit 110 in which a backlight system 110a, a polarizing plate 110b, a liquid crystal display cell 110c, and a polarizing plate 110d are stacked in this order, and polarization on the viewing side of the liquid crystal display device. A transparent resin layer 120 provided on the upper surface of the plate 110d and a transparent protective plate (protective panel) 130 provided on the upper surface of the transparent resin layer 120 are configured. A step portion 130 a provided on the surface of the transparent protective plate 130 (the surface on the image display unit 110 side, the surface opposite to the viewing side) is embedded with the transparent resin layer 120. The transparent resin layer 120 basically corresponds to the photocurable resin composition of the present embodiment or a cured product thereof. Although the thickness of the stepped portion 130a varies depending on the size of the liquid crystal display device, etc., when the thickness is 30 to 100 μm, it is particularly useful to use the photocurable resin composition of the present embodiment or a cured product thereof. .

(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 another embodiment of the liquid crystal display device. The liquid crystal display device 200 shown in FIG. 3 includes an image display unit 110 in which a backlight system 110a, a polarizing plate 110b, a liquid crystal display cell 110c, and a polarizing plate 110d are stacked in this order, and polarization on the viewing side of the liquid crystal display device. The transparent resin layer 120 provided on the upper surface of the plate 110d, the touch panel 140 provided on the upper surface of the transparent resin layer 120, the transparent resin layer 150 provided on the upper surface of the touch panel 140, and the upper surface of the transparent resin layer 150 The transparent protective plate 130 is formed. A step portion 130 a provided on the surface of the transparent protective plate 130 (the surface on the image display unit 110 side, the surface opposite to the viewing side) is embedded with a transparent resin layer 150. The transparent resin layer 150 and the transparent resin layer 120 basically correspond to the photocurable resin composition of the present embodiment or a cured product thereof.

  The purpose of providing the stepped portion 130a is, for example, to make the wiring invisible or difficult to see from the transparent protective plate side when providing input / output wiring at the peripheral portion 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 130a is preferably formed of a light shielding material. However, the step portion may be provided for other purposes such as decoration or may be transparent. The stepped portion 130a is provided on the lower surface of the transparent protective plate 130 (surface on the side in contact with the transparent resin layer 150), but may be provided on the upper surface (surface on the side far from the transparent resin layer 150). The stepped portion 130a is made of a material different from that of the transparent protective plate 130, but may be made of the same material or may be integrally formed. The stepped portion 130 a has a frame shape along the outer peripheral edge of the lower surface of the transparent protective plate 130, but is not limited to this, and the plan view shape is partially or entirely part of the transparent protective plate 130. 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 130a of the liquid crystal display device of FIG.

  In the liquid crystal display device of FIG. 3, a transparent resin layer is interposed between the image display unit 110 and the touch panel 140 and between the touch panel 140 and the transparent protective plate 130. May be present in at least one of them. When the touch panel is on-cell, the touch panel and the liquid crystal display cell are integrated. As a specific example, a liquid crystal display device in which the liquid crystal display cell 110c of the liquid crystal display device of FIG.

  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 embodiment is It can also be suitably used for a liquid crystal display device employing such an in-cell type touch panel.

(Liquid crystal display device of FIGS. 2 and 3)
According to the liquid crystal display device shown in FIG.2 and FIG.3, since the photocurable resin composition of this embodiment or its cured product is provided as the transparent resin layers 120, 150, it has impact resistance and has a double image. A clear, high-contrast image can be obtained.

  As the liquid crystal display cell 110c, a liquid crystal material that is well known in the art can be used. Also, depending on the control method of the liquid crystal material, it is classified into TN (Twisted Nematic) method, STN (Super-twisted nematic) method, VA (Vertical Alignment) method, IPS (In-Place-Switching) method, etc. It may be a liquid crystal display cell using a control method.

As the polarizing plates 110b and 110d, 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 or both sides of the polarizing plate.
As the touch panel 140, what is generally used in this technical field can be used.
The transparent resin layers 120 and 150 can be formed with a thickness of, for example, 0.02 mm to 3 mm, but are preferably 0.1 mm to 1 mm, and preferably 0.15 mm (150 μm) from the viewpoint of further improving the step embedding property and workability. ) To 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 layers 120 and 150 of 0.1 mm or more are formed. Can be used.
Further, the light transmittance of the transparent resin layers 120 and 150 with respect to light rays in the visible light region (wavelength: 380 to 780 nm) is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.

As the transparent protective plate 130, 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 or both sides of the transparent protective plate. A plurality of transparent protective plates can be used in combination.
The backlight system 110a typically includes a reflecting means such as a reflecting plate and an illuminating means such as a lamp.
As the material of the stepped portion 130a, for example, an acrylic resin composition containing a 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 photocurable resin composition of the present embodiment is interposed between the image display unit 110 and the transparent protective plate (protective panel) 130 having the stepped portion 130a (gap). It can manufacture with the manufacturing method provided with the process of irradiating an active energy ray with respect to the laminated body, and hardening a photocurable resin composition.

That is, the photocurable resin composition of the present embodiment is formed on the side of the transparent protective plate (protective panel) 130 where the stepped portion 130a is formed. The said formation may be performed by apply | coating the photocurable resin composition of this embodiment on the transparent protective board (protection panel) 130. FIG. In addition, a gel-like photocurable resin composition is formed in advance on a release sheet, the gel-like photocurable resin composition is pressed against a transparent protective plate (protective panel) 130, and then peeled off. You may carry out by peeling a sheet | seat.
Then, it superimposes on the upper surface of the polarizing plate 110d, and these are laminated | stacked using the above-mentioned bonding machine.
When air bubbles are seen in the photocurable resin composition after lamination using a bonding machine or the like, it is preferable to use an autoclave or the like to defoam while adjusting the degree of pressurization at a predetermined temperature. Moreover, it can also degas | foam by pressure reduction.
Then, the image display apparatus of FIG. 2 can be suitably manufactured by hardening | curing a photocurable resin composition by light irradiation, and setting it as the transparent resin layer 120. FIG. As this light irradiation, it is preferable to irradiate active energy rays such as ultraviolet rays from the transparent protective plate 130 side, the image display unit 110 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 active energy rays such as ultraviolet rays at least from the image display unit 110 side (the image display unit 110 side having no stepped portion). The irradiation amount of the active energy rays such as ultraviolet rays is not particularly limited, but is preferably about 500 to 5000 mJ / cm ² .

(Manufacturing method of the liquid crystal display device of FIG. 3)
The above-described liquid crystal display device of FIG. 3 is the photo-curing property of the present embodiment between the image display unit 110 and the touch panel 140 or between the touch panel 140 and the transparent protective plate (protective panel) 130 (gap). It can manufacture with a manufacturing method provided with the process of irradiating an active energy ray with respect to the laminated body which interposed the resin composition, and hardening a photocurable resin composition.

  The transparent resin layer 150 can be manufactured by the same method as the transparent resin layer 120 in FIG. The transparent resin layer 150 can be manufactured by the same method as the transparent resin layer 120 in FIG. 2 except that the photocurable resin composition is applied to the touch panel 140 instead of the transparent protective plate (protective panel) 130.

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

<Preparation of photocurable resin composition>
(Example)
The components (A) to (E) were blended at the blending ratios shown in Tables 1 and 2, and heated and stirred at 90 ° C. for 30 minutes to prepare the liquid curable resin compositions of the examples. In Tables 1 and 2, the units of numerical values for the components (A) to (E) are parts by mass.

(Comparative example)
Components (A) to (C) were blended at the blending ratio shown in Table 3, and heated and stirred at 90 ° C. for 30 minutes to prepare a liquid curable resin composition of a comparative example. In Table 3, the unit of numerical values for the components (A) to (C) is part by mass.

[material]
In the examples and comparative examples, the following raw materials were used.
{A component}
UC-102: Compound of formula (53), manufactured by Kuraray Co., Ltd., n28 = 2, number average molecular weight 17000, trade name FA-512M: compound of formula (39), product of Hitachi Chemical Co., Ltd., trade name FA-512AS : Compound of formula (40), manufactured by Hitachi Chemical Co., Ltd., trade name {B component}
DISPARLON 308: manufactured by Enomoto Kasei Co., Ltd., hydrogenated castor oil, product name DISPARLON 6500: manufactured by Enomoto Kasei Co., Ltd., aliphatic amine system, product name DISPARLON 6650: manufactured by Enomoto Kasei Co., Ltd., aliphatic amine system, product Name {C component}
I-184: Irgacure 184, 1-hydroxy-cyclohexyl-phenyl-ketone {component D}
G-1000: Nippon Soda Co., Ltd., both end hydroxyl group polybutadiene, number average molecular weight 1100, trade name G-3000: Nippon Soda Co., Ltd., both end hydroxyl group polybutadiene, number average molecular weight 3200, trade name {E component}
P85 (Clearon P-85): Yasuhara Chemical Co., Ltd., terpene hydrogenated resin

<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 The photocurable resin composition sealed in a 5 ml syringe was applied to a glass substrate A of 58 mm × 86 mm × 0.7 mm (thickness) using a slit coater and 40 mm × 40 mm × A 0.15 mm resin film was obtained.
Next, a glass substrate B (step difference 60 μm) having a step portion whose outer peripheral portion is decorated so as to have a thickness of 60 μm on the other side where the glass substrate A of the photocurable resin composition (resin film) is not bonded. ) Was bonded using a bonding machine so as to sandwich the photocurable resin composition. In addition, the glass substrate B which has the level | step-difference part by which the outer peripheral part was decorated has the same outer dimension as the glass substrate A, and has an opening part with an internal dimension of 45 mm x 68 mm. The glass substrates A and B were used as a substitute for an information input device or an image display unit, and the embedding property was evaluated according to the following evaluation criteria.
{Evaluation criteria}
A: The photocurable resin composition is embedded in the stepped portion without gaps and without leakage. B: The photocurable resin composition flows out from between the glass substrates to the surroundings.

(2) Evaluation of self-organizing property A photocurable resin composition is added to a 2 ml screw tube, and an 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 until. Next, the solution was quickly homogenized with a self-revolving mixer ARE-250 (manufactured by THINKY) under the conditions of 2000 rpm for 20 seconds and left at 25 ° C. for 30 minutes. Thereafter, the screw tube was tilted at about 60 degrees and left for 3 minutes, and the self-organization property was evaluated according to the following evaluation criteria.
{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 has Liquid and fluid

(3) Evaluation of transparency 2 g of the 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. Next, the solution was quickly homogenized with a self-revolving mixer ARE-250 (manufactured by THINKY) under the conditions of 2000 rpm for 20 seconds and left at 25 ° C. for 30 minutes. The transparency of the contents of the screw tube was evaluated according to the following evaluation criteria.
{Evaluation criteria}
4: No turbidity is seen even if the screw tube is seen through the fluorescent lamp 3: It turns out that it is turbid when the screw tube is seen through the fluorescent lamp 2: When the object is seen through the screw tube, the turbidity is slightly seen 1: It is cloudy to the extent that objects cannot be clearly seen through the screw tube.

(4) Viscosity measurement Using an E-type viscometer (TPE-100H, manufactured by Toki Sangyo Co., Ltd.), the viscosity (unit: Pa · s) at 25 ° C. of the resin compositions obtained in each Example and each Comparative Example was measured. did. Measurement conditions and measurement methods are shown below.
{Measurement condition}
Rotor name: 3 ° × R9.7, Rotor code 06
Shear rate: 1.0 (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.

(5) Evaluation of the amount of dripping Using a slit coater, the photocurable resin composition sealed in a 5 ml syringe was applied to a glass substrate of 100 mm × 100 mm × 0.7 mm (thickness) and 60 mm × 60 mm × 0.00 mm. A 15 mm resin film was obtained.
Stand the glass substrate vertically using a jig so that the 100 mm x 0.7 mm surface of the coated glass substrate becomes the bottom surface, hold it at 25 ° C for 1 hour, and adjust the amount of sagging from the end surface during resin film production. Measured on a scale.

(6) Evaluation of seepage amount Using a slit coater, a photocurable resin composition sealed in a 5 ml syringe was applied to a 100 mm × 100 mm × 0.7 mm (thickness) glass substrate and 60 mm × 60 mm × 0. A resin film of 15 mm was obtained.
The coating was allowed to stand at 25 ° C. for 24 hours so that the film-forming surface of the glass substrate was the upper surface, and the amount of seepage from the end surface during resin film production was measured on a scale.

(7) Evaluation of glass bonding position displacement property Using a slit coater, the photocurable resin composition sealed in a 5 ml syringe was applied to a glass substrate of 100 mm × 100 mm × 0.7 mm (thickness) and 60 mm × A resin film of 60 mm × 0.15 mm was obtained. A 20 mm × 20 mm × 0.07 mm cover glass substrate is bonded to the center of the applied resin surface, and the glass substrate is attached using a jig so that the 0.7 mm surface of the coated glass substrate becomes the bottom surface. Standing vertically and holding at 25 ° C. for 10 minutes, the amount of displacement from the end face of the bonded cover glass was measured with a scale.

  The compounding component and evaluation result of the photocurable resin composition in an Example and a comparative example are shown to Tables 1-3.

  The photocurable resin composition of Examples 1-12 has a favorable characteristic about level | step difference embedding property, self-organization property, transparency, shape retention property, and glass bonding position shift property. With regard to the amount of seepage, a better result was obtained if the gelling agent was included and the viscosity was 50 Pa · s or more. About glass bonding position shift | offset | difference, if it had the gelatinizer and the viscosity was 90 Pa.s or more, it became a more favorable result. About the photocurable resin composition of Comparative Examples 1-8, although it is favorable about level | step difference embedding property and transparency, even if it is a viscosity equivalent to the photocurable resin composition of an Example, it is a shape compared with an Example. It can be seen that the retainability is low and the glass bonding position shift is large.

  DESCRIPTION OF SYMBOLS 1 ... Transparent protective plate, 2 ... Touch panel, 3 ... Polarizing plate, 4 ... Liquid crystal display cell, 5, 6 ... Adhesion layer, 10, 100, 200 ... Liquid crystal display device, 110 ... Image display unit, 110a ... Backlight system, 110b, 110d ... Polarizing plate, 110c ... Liquid crystal display cell, 120, 150 ... Transparent resin layer, 130 ... Transparent protective plate (protective panel), 130a ... Stepped portion, 140 ... Touch panel.

Claims (11)

A photocurable resin composition comprising a compound (A) having a photopolymerizable functional group and an oil gelling agent (B),
A photocurable resin composition having a viscosity of 30 to 1000 Pa · s at a shear rate of 1.0 s ^{−1 at} 25 ° C.   The photocurable resin composition of Claim 1 whose content of the said (B) component is 0.2-20 mass% with respect to the whole quantity of the said photocurable resin composition. The component (B) is hydroxy fatty acid, hydrogenated castor oil, 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, represented by the following general formula (1) A compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following formula (5) , A compound represented by the following general formula (6), a compound represented by the following general formula (7), a compound represented by the following general formula (8), a compound represented by the following formula (9), the following general formula Represented by equation (10) A compound represented by the following formula (11), a compound represented by the following formula (12), and a compound represented by the following general formula (13): The photocurable resin composition according to claim 1 or 2.

[In General Formula (1), n1 is an integer of 3 to 10, n2 is an integer of 2 to 6, R ¹ is a saturated hydrocarbon group having 1 to 20 carbon atoms, and X ¹ is a sulfur atom or an oxygen atom. ]

In 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 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 General formula (7), ^{R 7} is a saturated hydrocarbon group having 1 to 20 carbon atoms. ]

In 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, and R ¹² and R ¹³ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms. ]   The photocurable resin composition as described in any one of Claims 1-3 in which the said (A) component contains the compound which has an ethylenically unsaturated group.   The photocurable resin composition according to any one of claims 1 to 4, further comprising a photopolymerization initiator.   The photocurable resin composition as described in any one of Claims 1-5 which further contains a liquid compound at 25 degreeC.   The photocurable resin composition according to any one of claims 1 to 6, further comprising a solid compound at 25 ° C. 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 apparatus in which the said resin layer contains the photocurable resin composition as described in any one of Claims 1-7, or its hardened | cured material.   The image display device according to claim 8, wherein the transparent protective plate has a stepped portion. An image display unit having an image display unit, and a transparent protective plate, a manufacturing method of an image display device having a laminated structure,
The photocurable resin composition according to any one of claims 1 to 7 is irradiated with active energy rays to the laminate in which the photocurable resin composition is interposed between the image display unit and the transparent protective plate. A method for producing an image display device, wherein a resin composition is cured.   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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