JP2018076387A - Resin composition, and image display device and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can reduce the stress generated between different kinds of members.SOLUTION: A resin composition contains a compound having a polymerizable functional group (A), and oil gelator (B). In a cured product of the resin composition, the ratio of a storage elastic modulus at 25°C to a storage elastic modulus at 80°C is 9 or more.SELECTED DRAWING: None

Description

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

  Resin composition is adhesive; adhesive; filler; sealant; optical waveguide, solar cell member, light emitting diode (LED), phototransistor, photodiode, die bond material, dyattachi material, underfill material, anisotropic conductivity Widely used as various materials such as adhesive materials, sealing resins, printed wiring board adhesive materials, photoresist materials, semiconductor elements, optical semiconductor elements, image display devices, lighting devices, and dental materials.

  For example, an information input device of an image display device (for example, a liquid crystal panel such as a touch panel) is attached to a rear substrate including a thin film transistor, a pixel electrode, an alignment film, and a front substrate including a color filter, an electrode, an alignment film, and the like. As described above, the liquid crystal is sealed between the two substrates facing each other. A sealing agent is used for the purpose of bonding the two substrates.

  As the sealant between the constituent members of the information input device, an epoxy-based thermosetting resin may be used. This requires about 30 minutes or more to complete the curing. A lateral displacement may occur in the members of the sheet. Moreover, in the liquid crystal dropping method (ODF method) which is a manufacturing method of a liquid crystal panel, there is a problem that the component of the sealing agent being cured is dissolved in the liquid crystal during heating, and the voltage holding ratio of the obtained liquid crystal panel is lowered. There is. Therefore, recently, there is an increasing demand for a sealant using a photo-curing resin that can be cured quickly and used for a liquid crystal dropping method.

  As the photocurable resin, there are a cationic curable type and a radical curable type. The cationic curable type is not practical because it uses a photocationic initiator that generates ions when irradiated with light, so that ions may be easily dissolved in the liquid crystal.

  On the other hand, the radical curable type has a problem that since the curing shrinkage at the time of photocuring is large, internal stress is generated and the adhesiveness is poor. On the other hand, in order to improve adhesiveness, for example, it has been attempted to use a photopolymerizable monomer having a phosphate group in the molecule (see, for example, Patent Document 1 below).

  In addition, a thermoplastic composition having a softening point temperature of 50 to 120 ° C. obtained by copolymerizing a (meth) acrylate monomer and a monomer copolymerizable therewith in a resin composition that can be cured by light and heat. A liquid crystal sealing resin composition is also known (for example, see Patent Document 2 below). In Patent Document 2, when substantially spherical particles having a core-shell structure in which a non-cross-linked shell layer is provided around a cross-linked core layer having a micro-crosslinked structure as a thermoplastic polymer, liquid crystal sealing is used. It is described that it acts as a stress relaxation agent in a resin composition.

  In addition, for example, the transparent protective plate or the information input device (for example, touch panel) in the image display device is bonded to the display surface of the image display unit, or the transparent protective plate is bonded to the information input device. When bonding members having different expansion coefficients, by replacing the gap between the members with a sealing agent (transparent material or the like) having adhesiveness to the display surface of the transparent protective plate, the information input device and the image display unit, A method has been proposed in which the internal distortion resulting from the difference in linear expansion coefficient between members is reduced, the transparency is improved by suppressing the reflection, and the brightness and contrast of the image display device are suppressed. And as this sealing agent, using the adhesive agent hardened | cured by an ultraviolet-ray or visible light is proposed (for example, refer patent document 3 below). A schematic example of a liquid crystal display device is shown in FIG. 1 as an example of such an image display device. A liquid crystal display device 10 with a built-in touch panel includes a transparent protective plate (glass substrate or plastic substrate) 1, a touch panel 2, a polarizing plate 3, and a liquid crystal display cell 4. A case in which an adhesive layer 5 is provided between the transparent protective plate 1 and the touch panel 2 and an adhesive layer 6 is further provided between the touch panel 2 and the polarizing plate 3 in order to reduce impact and improve visibility. There is also.

  As the sealing agent between the constituent members of the image display device, liquid or film-like ones are known. For example, in Patent Document 4 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 5 listed below discloses a transparent pressure-sensitive adhesive sheet comprising a stress relaxation resin composition containing a copolymer of monomer components containing a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 18 carbon atoms. Is disclosed.

JP 2004-233858 A JP 2004-126211 A JP 2008-83491 A JP 2009-1654 A JP 2011-74308 A

  However, even if any of the above conventional techniques is used, it is difficult to suppress stress strain generated between different types of members. For example, in the technique described in Patent Document 1, although the adhesion at the member interface is slightly improved, the problem of internal stress generated due to curing shrinkage cannot be solved. is there.

  Moreover, since the composition of the said patent document 2 is a mixed type of acrylate-type photocurable resin and epoxy-type thermosetting resin substantially, a thermosetting process is essential. In this case, due to the difference in coefficient of linear expansion between different types of members, stress is generated when a stimulus such as heat is applied, causing peeling.

  An object of the present invention is to solve the above problems and provide a resin composition capable of relieving stress generated between different types of members, an image display device using the resin composition, and a method for manufacturing the same.

  The resin composition of the present invention is a resin composition containing a compound (A) having a polymerizable functional group and an oil gelling agent (B), and a storage elasticity at 80 ° C. in a cured product of the resin composition. The ratio of the storage elastic modulus at 25 ° C. to the modulus is 9 or more.

  According to the resin composition of the present invention, stress strain generated between different types of members can be suppressed and stress can be relaxed. In particular, according to the resin composition of the present invention, it is possible to relieve stress generated between members having different linear expansion coefficients.

  By the way, in the conventional resin composition, since the storage elastic modulus at room temperature and the storage elastic modulus when heated are not greatly changed, it is generated when the members having different linear expansion coefficients are heated in a bonded state. The stress strain that is generated cannot be relieved well, and there is a concern about the generation of bubbles and peeling of the member. In order to avoid the problem of bubbles and peeling, there is a method of lowering the elastic modulus of the resin at room temperature, but the force to bond the two members at a high temperature is weakened. On the other hand, according to the resin composition of the present invention, the stress can be relaxed without causing such a problem.

［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, fatty acid amide, n-lauroyl-L-glutamic acid-α, γ-dibutylamide, 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, 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), and 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 ( At least selected from the group consisting of a compound represented by 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) One kind may be sufficient.

[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 polymerizable functional group of the component (A) is at least selected from the group consisting of ethylenically unsaturated groups, cyclic ether groups, amino groups, hydrosilyl groups, vinylsilyl groups, hydroxyl groups, isocyanate groups, acid anhydride groups, and carboxyl groups. It may be a kind.

  The resin composition of the present invention preferably further contains a photopolymerization initiator. The resin composition of the present invention may further contain a compound that is liquid at 25 ° C. The resin composition of the present invention may further contain a solid compound at 25 ° C.

  An embodiment of the image display device of the present invention is an image display 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. It is an apparatus, Comprising: The said resin layer contains the stress relaxation resin composition of this invention, or its hardened | cured material.

  An embodiment of a manufacturing method of an image display device of the present invention is a manufacturing method of an image display device having a laminated structure including an image display unit having an image display unit and a transparent protective plate, and the stress relaxation of the present invention The stress relaxation resin composition is cured by irradiating active energy rays to the laminate in which the adhesive resin composition is interposed between the image display unit and the transparent protective plate.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can relieve the stress which arises between different types of members, the image display apparatus using this resin composition, and its manufacturing method 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 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. .

<Stress relaxation resin composition>
The resin composition of this embodiment is a stress relaxation resin composition containing a compound (A) having a polymerizable functional group and an oil gelling agent (B). In the stress relaxation resin composition of this embodiment, the ratio of the storage elastic modulus between 25 ° C. and 80 ° C. of the cured stress relaxation resin composition is 9 times or more, that is, the stress relaxation resin composition is cured. The ratio of the storage elastic modulus at 25 ° C. to the storage elastic modulus at 80 ° C. in the product (storage elastic modulus at 25 ° C./storage elastic modulus at 80 ° C.) is 9 or more.

  When the stress relaxation resin composition and the cured product thereof according to the present embodiment are arranged between members having different linear expansion coefficients, stress generated therebetween can be relaxed. The reason is estimated as follows. That is, the oil gelling agent (B) contained in the stress relaxation resin composition and the cured product thereof is a hydrogen bond, electrostatic bond, π-π interaction, van der Waals in the resin composition and the cured product. 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”). Thereby, in the stress relaxation resin composition containing the compound (A) having a polymerizable functional group and the cured product thereof, at least a part of the oil gelling agent (B) is self-assembled at room temperature (25 ° C.), As a result, pseudo-crosslinking between the oil gelling agents (B) occurs, and the storage elastic modulus of the cured product of the resin composition increases. On the other hand, when the temperature is increased to 80 ° C., the hydrogen bond is reduced and the amount of pseudo-crosslinking is reduced as compared with the room temperature (25 ° C.), and the storage elastic modulus of the cured product of the resin composition is the amount of change in hydrogen bond ( Decrease by the amount of decrease). As a result, according to the stress relaxation resin composition of the present embodiment and the cured product thereof, the stress relaxation resin composition is disposed between members having different linear expansion coefficients, and stress is generated due to a temperature change due to the difference in linear expansion coefficient. It is presumed that the storage elastic modulus decreases by the amount of change in hydrogen bonds, and the stress can be relaxed.

The ratio of the storage elastic modulus at 25 ° C. to the storage elastic modulus at 80 ° C. in the cured product of the stress relaxing resin composition is preferably 15 or more, more preferably 30 or more, and 75 or more from the viewpoint of further excellent stress relaxation properties. Further preferred. The upper limit of the ratio of the storage elastic modulus is 1000, for example. The storage elastic modulus at 25 ° C. can be measured using, for example, a cured product obtained by irradiating the resin composition with ultraviolet rays (25 ° C., 1000 mJ / cm ² ). The storage elastic modulus at 80 ° C. is, for example, an 80 ° C. cured product obtained by irradiating the resin composition with ultraviolet rays (25 ° C., 1000 mJ / cm ² ) and then raising the temperature from 25 ° C. to 10 ° C./min. Can be measured. The ratio of the storage elastic modulus tends to increase when the content of the oil gelling agent (B) is increased.

  Next, each component of the stress relaxation resin composition will be described.

(Compound having a polymerizable functional group (A))
The compound (A) having a polymerizable functional group (hereinafter sometimes referred to as “component (A)”) is not particularly limited as long as it is curable. Polymerizable functional groups include, for example, ethylenically unsaturated groups ((meth) acryloyl groups, vinyl groups, allyl groups, etc.), cyclic ether groups (epoxy groups, oxetane groups, etc.), amino groups, hydrosilyl groups, vinylsilyl groups, hydroxyl groups. It is at least one selected from the group consisting of an isocyanate group (including a phenolic hydroxyl group), an acid anhydride group, and a carboxyl group (carboxylic acid group). As the component (A), a compound having an ethylenically unsaturated group ((meth) acryloyl group, vinyl group, allyl group, etc.) that can be cured by a photopolymerization initiator that generates radicals; photoacid generation that generates an acid A compound having a cyclic ether group (epoxy group, oxetane group, etc.) curable with an agent; an epoxy group and a compound having an acid anhydride group, phenolic hydroxyl group, amino group, etc. capable of curing reaction with the epoxy group; Compound having an amino group and a carboxyl group or an acid anhydride group capable of curing reaction with amino group; Compound having a hydrosilyl group and vinylsilyl group capable of curing reaction with hydrosilyl group; Isocyanate group and isocyanate group A compound having a hydroxyl group capable of undergoing a curing reaction is preferred, but a compound having an ethylenically unsaturated group is preferred from the viewpoint of easy curing. And still more preferably compounds having a (meth) acryloyl groups.

[Compound having an ethylenically unsaturated group]
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 suitable. Next, these compounds and polymers will be described.

{(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 (for example, propoxylated trimethylolpropane triacrylate), tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Alkenyl groups such as polyfunctional (meth) acrylates having three or more (meth) acryloyl groups in the molecule; glycidyl (meth) acrylate; 3-butenyl (meth) acrylate C2-C18 alkenyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl (meth) acrylate and other aromatic (meth) acrylates; methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (Meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxyheptapropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxy Alkoxypolyalkylene glycols such as ethylene glycol (meth) acrylate and butoxydiethylene glycol (meth) acrylate (Meth) acrylate; (meth) acrylate having an alicyclic group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like (meth) acrylate having a hydroxyl group; tetrahydrofurfuryl (meth) acrylate; N, N-dimethyl Aminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N (Meth) acrylamide derivatives such as hydroxyethyl (meth) acrylamide; (meth) acrylates having an isocyanate group such as 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate; tetraethylene Glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) Polyalkylene glycol mono (meth) acrylate such as acrylate; polyalkylene glycol di (meth) acrylate; Ethyl of bisphenol A Di (meth) acrylate of oxide (EO) adduct; di (meth) acrylate of propylene oxide (PO) adduct of bisphenol A; (meth) acrylate having isocyanuric ring skeleton; (meth) acrylate having siloxane skeleton, etc. Is mentioned. FA-512AS (manufactured by Hitachi Chemical Co., Ltd.) can be used as the (meth) acrylate having an alicyclic group. FA-BZA (manufactured by Hitachi Chemical Co., Ltd.) can be used as the (meth) acrylate having an aromatic ring. A (meth) acrylate compound may be used individually by 1 type, and may use 2 or more types together.

  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 (meth) acrylate, and alkenyl (meth) acrylate having an alkenyl group having 2 to 18 carbon atoms may be collectively referred to as “aliphatic (meth) acrylate”. FA-112A (manufactured by Hitachi Chemical Co., Ltd.) can be used as the 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 “ It may be collectively referred to as “heteroatom (meth) acrylate”.

{Polymer having (meth) acryloyl group}
Examples of the polymer having a (meth) acryloyl group include polybutadiene (meth) acrylate, polyisoprene (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and an acrylic resin having a (meth) acryloyl group in the side chain. And modified products thereof. As a polymer having a (meth) acryloyl group, for example, UC-102 (manufactured by Kuraray Co., Ltd., number average molecular weight 17000) can be used. The polymer having a (meth) acryloyl group may be used alone or in combination of two or more.

{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 vinyl silicone, styrene, divinylbenzene, vinyl pyrrolidone, triallyl isocyanurate, and 1,2-polybutadiene. Each of the compound having a vinyl group and the compound having an allyl group may be used alone or in combination of two or more.

[Compound having a cyclic ether group]
Examples of the compound having a cyclic ether group (epoxy group, oxetane group, etc.) include 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, ε-caprolactone modified 3 ′, 4′-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, epoxidized polybutadiene, 3,4-epoxycyclohexylmethyl meta Examples thereof include acrylate, epoxidized styrene-butadiene block copolymer, hydrogenated bisphenol A diglycidyl ether, and the like. As the compound having a cyclic ether group, one type may be used alone, or two or more types may be used in combination.

[Content of Compound (A) Having Polymerizable Functional Group]
The content of the component (A) is preferably 0.5 to 99.5% by mass based on the total amount of the stress relaxation resin composition. When the content of the component (A) is 0.5% by mass or more, it can be sufficiently cured. When the content of the component (A) is 99.5% by mass or less, the content of the oil gelling agent (B) is relatively increased and the gelation can be sufficiently facilitated. From these viewpoints, the content of the component (A) is more preferably 1 to 95% by mass, and further preferably 2 to 90% by mass.

(Oil gelling agent (B))
The stress relaxation 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.

  As the component (B), 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), fatty acid amide (for example, 12-hydroxy Stearic acid amide), n-lauroyl-L-glutamic acid-α, γ-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, a compound represented by the following general formula (1), the following general formula (2 ), A compound represented by the following general formula (3), a compound represented by the following general formula (4), the following formula The compound represented by (5), the compound represented by the following general formula (6), the compound represented by the following general formula (7), the compound represented by the following general formula (8), the following formula (9) (Ph in the formula (9) represents a phenyl group), a compound represented by the following general formula (10), a compound represented by the following formula (11), represented by the following formula (12) And at least one selected from the group consisting of compounds represented by the following general formula (13). (B) A component may be used individually by 1 type and may use 2 or more types together.

［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。Ｒ^１２及びＲ^１３の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 of R ¹² and R ¹³ may be a C 1-20 saturated hydrocarbon group having at least one hydroxyl group in the molecular skeleton. ]

  Content of (B) component is 100 mass parts of (A) component (when (D) component and / or (E) component mentioned later are contained, (A) component and (D) component and / or ( E) 0.1 to 20 parts by mass is preferable with respect to 100 parts by mass in total with the component. When the content of component (B) is 0.1 parts by mass or more, the elastic modulus of the composition can be sufficiently increased. When the content of the component (B) is 20 parts by mass or less, the content of the component (A) is relatively increased, and the characteristics of the composition can be easily utilized. From these viewpoints, the content of the component (B) is more preferably 0.2 to 15 parts by mass, and still more preferably 0.3 to 10 parts by mass.

(Photopolymerization initiator (C))
The stress relaxation resin composition of the present embodiment preferably contains a photopolymerization initiator (C) (hereinafter sometimes referred to as “(C) component”). Thereby, after forming the physical gel-like substance containing the component (A) and the component (B) into a predetermined shape, the component (A) can be three-dimensionally cross-linked and the stability to heat can be improved. Such an effect can be obtained particularly remarkably when the component (A) has an ethylenically unsaturated group.

  (C) A component advances hardening reaction by irradiation of an active energy ray. Here, examples of the active energy rays include ultraviolet rays, electron beams, α rays, β rays, and γ rays.

  (C) There is no restriction | limiting in particular as a component, 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.

  Specific examples of the photopolymerization initiator include benzophenone, 4-methylbenzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diamino. Benzophenone, 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-Dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Aromatic ketone compounds such as hydroxy-2-methyl-1-propan-1-one, 2,2-diethoxyacetophenone and phenylglyoxylic acid methyl ester; benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin; Benzoin ether compounds such as 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-phenyl Acridine , 9-pyridylacridine, acridine compounds such as 1,7-diacridinoheptane; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (M-methoxyphenyl) 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, 2,4,5-triary such as 5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer Ruimidazole dimer; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 Α-aminoalkylphenone compounds such as propanone; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine Acylphosphine oxide compounds such as oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), etc. Is mentioned.

  Particularly, polymerization initiators that do not color the stress relaxation 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 Propanone) and a combination thereof are preferred.

  The content of the component (C) is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and 0.3 to 2% by mass based on the total amount of the stress relaxation resin composition. 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 stress relaxation property is further improved, and the hue of the obtained cured product is easily suppressed from being yellowish.

(Liquid compound (D) at 25 ° C.)
The stress relaxation 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 (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 Examples include tetrakis (3-mercaptobutyrate), liquid paraffin, and organic solvents.

  As other component (D), acrylic resin, liquid polybutadiene mainly composed of 1,4-structural units, liquid polybutadiene mainly composed of 1,2-structural units, hydrogenated polybutadiene, hydrogenated polyisoprene, water Examples thereof include liquid polymers such as additive polyisobutene, and these are used for other purposes such as low curing shrinkage and low dielectric constant.

  The acrylic resin is preferably an acrylic resin having a structural unit derived from an alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl group. An acrylic resin having 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 (manufactured by Nippon Zeon Co., Ltd.) is commercially available. G-1000 and G-3000 (manufactured by Nippon Soda Co., Ltd.) are commercially available as liquid polybutadienes mainly composed of 1,2-structural units. As the hydrogenated polyisobutene that is liquid at 25 ° C., for example, Pearl Ream (manufactured by NOF Corporation, trade name) 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 based on the total amount of the stress relaxation resin composition from the viewpoint of adjusting the stress relaxation property and the elastic modulus. -98 mass% is more preferable.

(Compound (E) solid at 25 ° C.)
The stress relaxation resin composition of the present embodiment may further contain a compound (E) that is solid at 25 ° C. (hereinafter sometimes referred to as “component (E)”). The component (E) may be added according to the purpose as long as the stress relaxation property is not impaired. (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 adjusting the adhesiveness by improving the tackiness of the stress relaxation resin composition. The terpene-based hydrogenated resin is commercially available, for example, as Clearon P series (trade name, manufactured by Yasuhara Chemical Co., Ltd.).

  In the case of using the component (E), the content of the component (E) is 0.1 to 0.1 on the basis of the total amount of the stress relaxation resin composition from the viewpoint that the stress relaxation property, transparency, and elastic modulus can be easily adjusted. 80 mass% is preferable. From the same viewpoint, the content of the component (E) is more preferably 1 to 70% by mass.

(Other additives)
The stress relaxation resin composition of the present embodiment may contain various additives separately from the components (A) to (E) as necessary. Examples of various additives that can be included include a chain transfer agent, a polymerization inhibitor, an antioxidant, a light stabilizer, a silane coupling agent, a surfactant, a leveling agent, a curing accelerator, and a catalyst.

The polymerization inhibitor is added for the purpose of enhancing the storage stability of the stress relaxation 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 stress relaxation resin composition with heat or light. Phosphorus-based such as triphenyl phosphite; phenol-based; thiol-based An antioxidant etc. are mentioned.
The light stabilizer is added for the purpose of increasing resistance to light such as ultraviolet rays, and examples thereof include HALS (Hindered Amine Light Stabilizer).
The silane coupling agent is added to improve adhesion to glass or the like, 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 flatness to the stress relaxation resin composition, and examples thereof include silicon-based and fluorine-based compounds that lower the surface tension.

  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 about 0.01 to the total amount of the stress relaxation resin composition. About 5% by mass.

[Physical properties]
The curing shrinkage rate when the stress relaxation resin composition of the present embodiment is cured is preferably less than 10%, preferably 5% from the viewpoint of further highly suppressing the warpage of the substrate such as the transparent protective plate and the image display unit. 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 the dielectric constant at 100 kHz of the cured product of the stress relaxation resin composition of the present embodiment is used between the touch panel and the transparent protective plate, it is preferably 15 or less, more preferably 13 or less, still more preferably 12 or less, 10 or less is particularly preferable. The lower limit of the dielectric constant is preferably 2 or more from a practical viewpoint.

<Method for producing stress relaxation resin composition>
There is no restriction | limiting in particular in the manufacturing method of the stress relaxation resin composition of this embodiment, For example, said (A) component and (B) component, (C)-(E) component and said additive as needed Can be mixed and stirred.
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 stress relaxation resin composition is obtained by cooling after that.
Although there is no restriction | limiting in particular in this heating temperature, When using 12-hydroxy stearic acid as (B) component, it is preferable to heat at 60-150 degreeC. When the heating temperature is 60 ° C. or higher, 12-hydroxystearic acid can be sufficiently dissolved. When the heating temperature is 150 ° C. or less, high transparency can be maintained.
The stirring time is not particularly limited, but is preferably 10 to 600 seconds, and more preferably 20 to 300 seconds.

<Image display device>
Next, an image display device using the stress relaxation resin composition of the present embodiment will be described.
The stress relaxation 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 stress relaxation resin composition of this 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 stress relaxation resin composition of this embodiment can also be used as an optical filter in combination with such a multilayer product by photocuring to obtain a cured product. In this case, it is preferable that the stress relaxation resin composition of this 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 stress relaxation resin composition of this 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 and the like can be further laminated on the viewing surface side of the stress relaxation resin composition. When it is used between the layers, a functional layer can be laminated on the viewing surface side of the polarizing plate.
When setting it as such a laminated body, a stress relaxation 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 the stress relaxation resin composition according to the present embodiment or a cured product thereof. . The resin layer containing the stress relaxation 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.

  An image display device in which a touch panel is combined with an image display unit includes, for example, an image display unit having an image display unit, a transparent protective plate, a touch panel, and a stress relaxation resin composition according to the present embodiment or a cured product thereof. And a resin layer containing a laminated structure. 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 stress relaxation resin of the present embodiment is used because 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 stress relaxation resin composition of the present embodiment or a cured product thereof. The thickness of the stepped portion 130a varies depending on the size of the liquid crystal display device and the like, but when the thickness is 30 to 100 μm, it is particularly useful to use the stress relaxation resin composition of the present embodiment or a cured product thereof. is there.

(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 stress relaxation 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 stepped portion 130a 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 stress relaxation 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 stress relaxation resin composition of the present embodiment or a cured product thereof is provided as the transparent resin layers 120 and 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. However, from the viewpoint of excellent step embedding property and workability, 0.1 mm to 1 mm is preferable, and 0.15 mm (150 μm). ˜0.5 mm (500 μm) is more preferable. In particular, in the stress relaxation 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 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)
The liquid crystal display device of FIG. 2 described above is a laminate in which the stress relaxation resin composition of the present embodiment is interposed between the image display unit 110 and a transparent protective plate (protective panel) 130 having a stepped portion 130a. On the other hand, it can manufacture with a manufacturing method provided with the process of irradiating an active energy ray and hardening a stress relaxation resin composition.

That is, the stress relaxation resin composition of the present embodiment is formed on the surface 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 stress relaxation resin composition of this embodiment on the transparent protective board (protection panel) 130. FIG. In addition, a gel-like stress relaxation resin composition is formed in advance on a release sheet, and the gel-like stress relaxation resin composition is pressed against a transparent protective plate (protection 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 observed in the stress relaxation resin composition after lamination using a bonding machine or the like, it is preferable to use an autoclave or the like to remove bubbles while adjusting the degree of pressurization at a predetermined temperature. Moreover, it can also degas | foam by pressure reduction.
Then, when a photopolymerization initiator is added to the stress relaxation resin composition and photocuring is possible, the stress relaxation resin composition is cured by light irradiation to form a transparent resin layer 120. 2 image display devices can be manufactured. 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 liquid crystal display device of FIG. 3 described above includes the stress relaxation resin composition of the present embodiment between the image display unit 110 and the touch panel 140 and / or between the touch panel 140 and the transparent protective plate (protective panel) 130. 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 thing, and hardening a stress relaxation 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 stress relaxation resin composition is applied to the touch panel 140 instead of the transparent protective plate (protective panel) 130.

  The present invention will be described below with reference to examples. In addition, this invention is not restrict | limited to these Examples.

<Preparation of resin composition>
Example 1
In the screw tube, 63% by mass of hydrogenated bisphenol A diglycidyl ether (HBPAG, manufactured by Kyoeisha Chemical Co., Ltd., Epolite-4000) as a compound (A) having a polymerizable functional group, an acid anhydride curing agent (manufactured by Hitachi Chemical Co., Ltd.) , HN-5500) 37% by mass, 12-hydroxystearic acid (HSA, manufactured by Wako Pure Chemical Industries, Ltd.) 1% by mass as the oil gelling agent (B), and 2-phenylimidazole (accelerating curing acceleration as other additives) Oil gelling agent (B) is dissolved by applying sonic waves with an ultrasonic washing machine (Nihon Emerson Corporation 2510 type) that is adjusted to a water temperature of 60 ° C by adding 1% by mass of Shikoku Kasei Kogyo Co., Ltd., 2PZ) Thus, a stress relaxation resin composition (1) was obtained.

(Example 2)
In the screw tube, as a compound (A) having a polymerizable functional group, vinyl silicone (DMS-V31, manufactured by Gelest) 56 mass%, hydrosilicone (HMS-013, manufactured by Gelest) 44 mass%, an oil gelling agent (B ) 12-hydroxystearic acid (HSA, manufactured by Wako Pure Chemical Industries, Ltd.) 1% by mass, and as other additives, 1% by mass of Karstedt catalyst (KC, manufactured by Wako Pure Chemical Industries, Ltd.), which promotes acceleration of curing, The oil gelling agent (B) was dissolved by applying a sound wave with an ultrasonic cleaner adjusted to a water temperature of 60 ° C. (Model 2510 manufactured by Emerson Japan Ltd.) to obtain a stress relaxation resin composition (2).

(Example 3)
In the screw tube, 2% by mass of propoxylated trimethylolpropane triacrylate (SR492, manufactured by Sakai Kogyo Co., Ltd.) as the compound (A) having a polymerizable functional group, and 12-hydroxystearic acid (HSA, as an oil gelling agent (B)) 1% by mass of Wako Pure Chemical Industries, Ltd.), 1% by mass of 4-methylbenzophenone (BP, manufactured by Wako Pure Chemical Industries, Ltd.) as a photopolymerization initiator (C), and the following Production Example 1 as a liquid compound (D) The oil gelling agent (B) is dissolved by applying ultrasonic waves with an ultrasonic cleaning machine (2510 model manufactured by Nippon Emerson Co., Ltd.) in which 97% by mass of the compound (D1) shown in FIG. A stress relaxation resin composition (3) was obtained.

[Production Example 1]
A liquid compound (D1) at 25 ° C. was produced by the following operation.
In a screw tube, 7.5 g of ethylhexyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 2.0 g of vinyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.5 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), Parroyl L (day (Oil Co., Ltd.) 0.05 g and n-octyl mercaptan 0.01 g (Wako Pure Chemical Industries, Ltd.) were added, and after stirring, placed in a 60 ° C. water bath and heated for 4 hours. Next, after heating for 1 hour with a 100 ° C. blast constant temperature incubator (DN-400, manufactured by Yamato Scientific Co., Ltd.), the blast constant temperature incubator is taken out and left to reach room temperature (25 ° C.). ) To obtain a viscous liquid compound (D1).

Example 4
In the screw tube, 9.6% by mass of FA-BZA (manufactured by Hitachi Chemical Co., Ltd.), 14.4% by mass of FA-112A (manufactured by Hitachi Chemical Co., Ltd.) and hydroxypropyl acrylate as the compound (A) having a polymerizable functional group (HPA, Kyoeisha Chemical Co., Ltd.) 6.0% by mass, 12-hydroxystearic acid (HSA, manufactured by Wako Pure Chemical Industries, Ltd.) 2% by mass and 12-hydroxystearic acid amide (HSAM, as oil gelling agent (B)) Wako Pure Chemical Industries, Ltd.) 1% by mass, i-184 (Irgacure 184, 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF) 0.5% by mass as a photopolymerization initiator (C), liquid at room temperature (25 ° C.) G-3000 (both end hydroxyl group polybutadiene, manufactured by Nippon Soda Co., Ltd., number average molecular weight 3200) as a compound (D) of 10 mass In addition, as a solid compound (E) at room temperature (25 ° C.), an ultrasonic washer (2510 manufactured by Nippon Emerson Co., Ltd.) containing 60% by mass of the compound (E1) shown in the following Production Example 2 and adjusted to a water temperature of 60 ° C. The oil gelling agent (B) was dissolved by applying ultrasonic waves in the mold) to obtain a stress relaxation resin composition (4).

[Production Example 2]
Compound (E1) solid at 25 ° C. was produced by the following operation.
In a screw tube, 3.0 g of styrene (manufactured by Wako Pure Chemical Industries, Ltd.), 7.0 g of FA-117A (manufactured by Hitachi Chemical Co., Ltd.), 0.05 g of Parroyl O (manufactured by NOF Corporation), and 0.005 g of n-octyl mercaptan. 01 g (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and after stirring, placed in an 80 ° C. water bath and heated for 5 hours. Next, after heating for 2 hours with a 110 ° C. air constant temperature incubator (DN-400, manufactured by Yamato Kagaku Co., Ltd.), the air is removed from the air constant temperature incubator and allowed to reach room temperature (25 ° C.). ) To obtain a solid compound (E1).

(Example 5)
In the screw tube, 20% by mass of UC-102 (manufactured by Kuraray Co., Ltd., number average molecular weight 17000) and FA-512AS (dicyclopentenyloxyethyl acrylate, manufactured by Hitachi Chemical Co., Ltd.) as the compound (A) having a polymerizable functional group 5.0% by mass, DISPARLON 308 (hydrogenated castor oil system, manufactured by Enomoto Kasei Co., Ltd.) 1.5% by mass as an oil gelling agent (B), and bis (2,4,6-trimethyl) as a photopolymerization initiator (C) 1% by mass of benzoyl) -phenylphosphine oxide (TPO, manufactured by BASF) and 3% by mass of phenylglyoxylic acid methyl ester (MBF, manufactured by BASF), G as liquid compound (E) at room temperature (25 ° C.) -1000 (both end hydroxyl group polybutadiene, manufactured by Nippon Soda Co., Ltd., number average molecular weight 1100) 75 quality The oil gelling agent (B) is dissolved by applying ultrasonic waves with an ultrasonic washer (2510 model manufactured by Nippon Emerson Co., Ltd.) adjusted to a water temperature of 60 ° C., and the stress relaxation resin composition ( 5) was obtained.

(Example 6)
In the screw tube, as a compound (A) having a polymerizable functional group, FA-328A (diacrylate of ethylene oxide (EO) adduct of bisphenol A, manufactured by Hitachi Chemical Co., Ltd.) 6.5% by mass, ethylhexyl acrylate (EHA, Wako Pure Chemical Industries, Ltd.) 39.3 mass%, acryloylmorpholine (ACMO, Tokyo Chemical Industry Co., Ltd.) 18.7 mass% and 4-hydroxybutyl acrylate (4HBA, Osaka Organic Chemical Industries, Ltd.) 4.2 2% by mass of 12-hydroxystearic acid (HSA, manufactured by Wako Pure Chemical Industries, Ltd.) as an oil gelling agent (B), 0.5% by mass of i-184 (manufactured by BASF) as a photopolymerization initiator (C) 30.8% by mass of the compound (D2) shown in the following Production Example 3 was added as a liquid compound (D) at room temperature (25 ° C.), 60 Of the by applying the ultrasonic modulating the ultrasonic cleaner to the water temperature (2510 type manufactured by Emerson Japan, Ltd.), was dissolved oil gelling agent (B), to obtain the stress relaxing resin composition (6).

[Production Example 3]
A liquid compound (D2) at 25 ° C. was produced by the following operation.
In a screw tube, 7.0 g of ethylhexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 3.0 g of hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.05 g of Parroyl L (manufactured by NOF Corporation) and n-octyl mercaptan 0.01 g (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and after stirring, placed in a 60 ° C. water bath and heated for 4 hours. Next, after heating for 1 hour with a 100 ° C. blast constant temperature incubator (DN-400, manufactured by Yamato Scientific Co., Ltd.), the blast constant temperature incubator is taken out and left to reach room temperature (25 ° C.). ) To obtain a liquid compound (D2).

(Comparative Examples 1-6)
As resin compositions of Comparative Examples 1 to 6, resin compositions having compositions obtained by removing the oil gelling agent (B) from the resin compositions of Examples 1 to 6 were prepared.

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

(Evaluation of ratio of storage modulus)
Using a rheometer (MCR301 manufactured by Anton Paar Co., Ltd.), the storage elastic modulus at 25 ° C. and 80 ° C. of the cured product obtained by curing the resin composition obtained in each example and each comparative example was measured. The ratio of storage elastic modulus was calculated from the following formula (1). The storage elastic modulus at 25 ° C. was measured by using a cured product obtained by irradiating the resin composition placed in the measurement part of the rheometer with ultraviolet rays (25 ° C., 1000 mJ / cm ² ). The storage elastic modulus at 80 ° C. is from 25 ° C. to 10 ° C./min after leaving the resin composition placed in the measurement part of the rheometer to be irradiated with ultraviolet rays (25 ° C., 1000 mJ / cm ² ) for 1 minute. It can be measured using an 80 ° C. cured product obtained by raising the temperature. Tables 1 and 2 show the storage elastic modulus at each temperature and the ratio of the storage elastic modulus.
Storage elastic modulus ratio = Storage elastic modulus at 25 ° C./Storage elastic modulus at 80 ° C. (1)

In addition, the measurement conditions of storage elastic modulus are shown below.
・ Strain, swing angle gamma = 5%
・ Frequency f = 1Hz
・ Thickness 150 μm, 20 ° C. jig PP12; [d = 0.15 mm]

(Stress evaluation (birefringence ratio))
A 10 cm square silicone spacer (thickness: 100 μm) with a 10 mm × 10 mm hole was placed on a 10 cm square glass to form a mold for producing a film. Next, the resin composition was poured into a 10 mm × 10 mm mold and covered with a polycycloolefin film (manufactured by Nippon Zeon Co., Ltd., thickness: 100 μm × 12 mm × 12 mm). After exposing (high power metal halide lamp, 10 mW / cm ² , 1000 mJ / cm ² ) and curing the composition, only the silicone spacer is removed, and the evaluation film in which the cured product is sandwiched between glass and an olefin film Obtained. Next, the evaluation sample was left at room temperature (25 ° C.), and birefringence (manufactured by Photonic Lattice Co., Ltd., birefringence evaluation apparatus) was measured from the film side. Next, the evaluation sample was heated to 80 ° C., and birefringence was measured again.

Here, the relationship between the birefringence generated in the resin and the stress is expressed by the following formula (2).
Δn = C × δ (2)
[Δn: birefringence, C: photoelastic coefficient, δ: stress]

And since a photoelastic coefficient is a numerical value intrinsic | native to resin, if the ratio of the birefringence in 25 degreeC and 80 degreeC is evaluated, the variation | change_quantity of stress can be estimated. Therefore, the stress ratio was calculated from the following formula (3) based on the birefringence ratio. The larger the ratio of the introduced stress, the greater the difference in stress between 25 ° C. and 80 ° C., and the smaller the stress ratio, the more relaxed the stress. The evaluation results are shown in Tables 1 and 2.
Stress ratio (birefringence ratio) = Δn at 80 ° C./Δn at 25 ° C. (3)

  As shown in Tables 1 and 2, in the examples, it is confirmed that the ratio of the storage elastic modulus is large and the stress is sufficiently relaxed, whereas in the comparative example, It is confirmed that the ratio of the storage elastic modulus is small and the stress is not sufficiently relaxed.

  Since the stress relaxation resin composition of the present invention can relieve stress generated between different materials by utilizing hydrogen bond breakage, an adhesive; an adhesive; a filler; a sealant; an optical waveguide; Solar cell components, light emitting diodes (LEDs), phototransistors, photodiodes, die bonding materials, diattach materials, underfill materials, anisotropic conductive materials, sealing resins, printed wiring board adhesive materials, photoresist materials, semiconductor elements, Various semiconductor elements such as optical semiconductor elements, image display devices, and illumination devices; can be widely used as dental materials.

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 (8)

A resin composition containing a compound (A) having a polymerizable functional group and an oil gelling agent (B),
The resin composition whose ratio of the storage elastic modulus of 25 degreeC with respect to the storage elastic modulus of 80 degreeC in the hardened | cured material of the said resin composition is 9 or more. The component (B) is hydroxy fatty acid, hydrogenated castor oil, fatty acid amide, n-lauroyl-L-glutamic acid-α, γ-dibutylamide, 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, 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), and 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 ( At least selected from the group consisting of a compound represented by 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 resin composition of Claim 1 which is 1 type.

[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 polymerizable functional group of the component (A) is at least selected from the group consisting of ethylenically unsaturated groups, cyclic ether groups, amino groups, hydrosilyl groups, vinylsilyl groups, hydroxyl groups, isocyanate groups, acid anhydride groups, and carboxyl groups. The resin composition according to claim 1 or 2, which is a kind.   The resin composition according to any one of claims 1 to 3, further comprising a photopolymerization initiator.   The resin composition according to any one of claims 1 to 4, further comprising a liquid compound at 25 ° C.   The resin composition as described in any one of Claims 1-5 which further contains a solid compound at 25 degreeC. An image display device having a laminated structure including an image display unit having an image display unit, a transparent protective plate, and a resin layer existing between the image display unit and the transparent protective plate,
The image display apparatus in which the said resin layer contains the stress relaxation resin composition as described in any one of Claims 1-6, or its hardened | cured material. 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 stress relaxation property is obtained by irradiating active energy rays to a laminate in which the stress relaxation resin composition according to any one of claims 1 to 6 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.

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