KR102241678B1 - Composition - Google Patents

Abstract

Provides a composition excellent in deep curing properties.
A composition containing the following (P), (C) to (F).
(P) Polymerizable vinyl monomer, (C) photoinitiator, (D) antioxidant, (E) thiol, (F) dicarboxylic acid diester.

Description

Composition {Composition}

The present invention relates to a composition.

As a touch panel mounted on a display such as an LCD (liquid crystal display), there are a resistive film type, a capacitive type, an electromagnetic induction type, and an optical type. On the surface of these touch panels, a decorative plate for imparting the design of the external appearance or an icon sheet for designating a touch position may be attached to the surface of the touch panel. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate and a transparent plate is bonded thereon.

Conventionally, bonding of a decorative plate and a touch panel, bonding of an icon sheet and a touch panel, and bonding of a transparent substrate and a transparent plate are performed using an adhesive.

Such an icon sheet or touch panel hides only the display area by concealing the IC for driving the display, the wiring or the edge sealant of the LCD, and in order to improve the design, the shading edge is sometimes covered with printing or the like. If there is such a light-shielding edge, the photocurable adhesive composition under the light-shielding edge is not cured because the light is obscured by the light-shielding edge and the light does not shine, so adhesion is insufficient.

In order to solve the insufficient adhesion problem due to uncuring, a method of adjusting the irradiation angle of light such as irradiating light from an angle or from the side, or adding a thermosetting catalyst to the photocurable adhesive composition to impart thermosetting properties in addition to photocuring properties and A method of curing by heat or the like is being used.

However, in the method of adjusting the irradiation angle of the light beam, since the width of the shading edge becomes wide, it becomes difficult to sufficiently cure the entire photocurable adhesive composition under the shading edge, and there is a problem that the uncured portion is liable to remain. The method of imparting thermosetting to the photocurable adhesive composition and curing it with light and heat requires heating display panels such as LCD, EL display, and LED display at 60 to 80°C for 30 to 60 minutes, thus reducing quality and product life. There are challenges such as shortening.

Patent Document 1 describes (A) polyisoprene, polybutadiene, or a (meth)acrylate oligomer having a polyurethane as a skeleton, (B) a softening component, and (C1) phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol ( Meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, nonylphenol EO adduct (meth)acrylate, methoxytriethylene glycol (meth)acrylate And a (meth)acrylate monomer selected from tetrahydrofurfuryl (meth)acrylate is disclosed.

Recently, the glass of display bodies such as LCDs has become thinner. When the glass thickness becomes thinner, it becomes easier to deform the LCD due to external stress. When a display body such as an LCD using thin glass and an optical functional material such as an acrylic plate or a polycarbonate plate are bonded together, the difference in linear expansion such as glass and acrylic, or when forming a plastic molding material such as an acrylic plate or polycarbonate Due to the deformation, in the heat-resistance test and the moisture-resistance test, the molding deformation is relieved and moisture absorption/drying occurs, and the surface accuracy such as dimensional change or warping occurs. Patent Document 2 discloses a cured resin containing urethane-based (meth)acrylate, polybutadiene-based (meth)acrylate, and isoprene-based (meth)acrylate as components.

In applications such as bonding a decorative plate and a touch panel, bonding an icon sheet and a touch panel, bonding a transparent substrate and a transparent plate, etc., the deformation of the adherend in a warm atmosphere that assumes the usage environment is beneficial. It is desirable to have as much flexibility as possible.

On the other hand, it has also been found that there are problems such as coloration and discoloration after a heat resistance test, and a decrease in strength after a moisture resistance test when the adherend has a degree of flexibility that can be harvested for the deformation of the adherend in a warm atmosphere assuming the use environment. As a solution to the above problems, Patent Document 4 discloses at least one oligomer and hindered amine selected from the group consisting of polyisoprene (meth)acrylate oligomer, polybutadiene (meth)acrylate oligomer, and polyurethane (meth)acrylate oligomer. A photocurable adhesive composition containing is disclosed.

Patent Document 5 includes (A) a specific sulfur-containing (meth)acrylate compound or a radical reactive composition containing the same, (B) an ultraviolet absorber, (C) an antioxidant, and (D) a polymerization initiator. The composition is disclosed.

Patent Document 6 includes an acrylic polymer (E), a urethane (meth)acrylate containing two or more functional groups having an unsaturated double bond (A), a monomer containing one functional group containing an unsaturated double bond (B), and photopolymerization In a composition containing an initiator (C) and a polythiol compound (D) containing two or more thiol groups, the weight ratio of the urethane (meth)acrylate (A) in the composition is 2% to 30% by weight A chemical conversion transparent adhesive composition is described.

In Patent Document 7, in the allyl ester oligomer having an allyl group at the terminal, 10 to 80 mol% of the constituents are aliphatic dicarboxylic acids containing organic residues derived from itaconic acid, and the remainder contains unsaturated groups other than itaconic acid. It is disclosed to use an arylester oligomer comprising an organic moiety derived from an aliphatic and/or saturated aliphatic and/or aromatic aliphatic dicarboxylic dicarboxylic acid and an organic moiety derived from a polyol as a thermosetting resin composition.

Patent Document 1: International Publication No. 2010/027041 Patent Document 2: Japanese Laid-Open Patent No. 2004-77887 Patent Document 3: Japanese Laid-Open Patent Publication No. 64-85209 Patent Document 4: Japanese Laid-Open Patent 2012-46658 Patent Document 5: Japanese Laid-Open Patent No. 2002-097224 Patent Document 6: Japanese Laid-Open Patent No. 2009-001655 Patent Document 7: Japanese Laid-Open Patent Publication No. Hei 7-324123

However, the existing technology described in the above document has room for improvement in the following points.

In the method of Patent Document 2, when deformation such as a change in surface precision is suppressed, the adhesive surface is peeled off, the LCD is broken, or the LCD display is uneven.

As a solution to the problem of patent document 2, the UV-curable resin of patent document 3 is mentioned. However, in Patent Document 3, since a highly elastic resin based on a rigid skeletal monomer such as isovolyl (meth)acrylate is used, it cannot withstand the expansion and contraction of the adherend in the high temperature reliability test (moist heat resistance test), and peeling occurs.

In addition, in the description of any literature, for example, when bonding a decorative plate or icon sheet used for a display body such as a touch panel, when bonding between a transparent substrate and a transparent substrate, and bonding a printed portion, etc. In this case, when the part that is not exposed to visible or ultraviolet rays from the front side of the shading edge due to printing on the front side of the adherend is cured with visible light or ultraviolet rays from the side, the curable resin composition under the shading edge causes curing failure. There was an assignment.

The present invention has been made in view of the above circumstances, for example, when a decorative plate or icon sheet used for a display body such as a touch panel is bonded, when a transparent substrate and a transparent substrate are bonded, and a display body and an optical function It is an object of the present invention to provide a composition that can be preferably used in the case of bonding materials.

That is, according to the present invention, a composition containing the following (P), (C) to (F) is provided.

(P) polymerizable vinyl monomer

(C) photopolymerization initiator

(D) antioxidant

(E) thiol

(F) dicarboxylic acid diester

It is preferable that it is a composition in which said (F) is a dicarboxylic acid diester represented by Formula (1).

(R ₁ , R ₂ is an alkyl group having 1 to 18 carbon atoms, R ₃ is an alkylene group having 1 to 10 carbon atoms, and may be the same as or different from _{R 1} and R _{2 .)}

It is preferable that the (E) thiol is polythiol.

It is preferable that the (P) polymerizable monomer is the composition containing (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate.

In addition, it is preferable that the (A) polyfunctional (meth)acrylate is the composition of urethane (meth)acrylate.

It is preferable that the (B) monofunctional (meth)acrylate is the composition comprising at least one selected from the group consisting of hydroxyalkyl (meth)acrylate and alkyl (meth)acrylate.

The content of the (F) dicarboxylic acid diester is preferably 5 to 50 parts by mass when the total of (P) the polymerizable vinyl monomer and (F) dicarboxylic acid diester is 100 parts by mass.

In addition, according to the present invention, a curable resin composition comprising the composition is provided.

In addition, according to the present invention, there is provided an adhesive composition comprising the composition.

Further, according to the present invention, a cured product of the adhesive composition is provided.

Further, according to the present invention, a composite is provided in which an adherend is coated or bonded by the cured body.

It is preferable that the adherend is a composite containing one or more of triacetyl cellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, metal, and the like.

Further, according to the present invention, a touch panel laminate is provided in which an adherend made of the adhesive composition is bonded to each other.

Further, according to the present invention, there is provided a liquid crystal panel laminate in which the adherend made of the adhesive composition is bonded.

In addition, according to the present invention, a display using the touch panel laminate is provided.

Further, according to the present invention, a display using the liquid crystal panel laminate is provided.

ADVANTAGE OF THE INVENTION According to this invention, the composition excellent in deep hardenability can be provided.

Hereinafter, embodiments of the present invention will be described in detail. The composition of the present invention contains the following (P), (C) to (F).

(P) polymerizable vinyl monomer

(C) photopolymerization initiator

(D) antioxidant

(E) thiol

(F) dicarboxylic acid diester

According to the above composition, when adhering a decorative plate or icon sheet used for a display such as a touch panel, when adhering between a transparent substrate and a transparent substrate, and when adhering a printed part, from the front of the adherend It is possible to provide a curable resin composition in which a portion not irradiated with visible light or ultraviolet rays from the front side due to a light-shielding edge such as printing is cured through visible light or ultraviolet rays from the side surface.

Further, according to the above composition, since a composition having excellent deep curing properties can be provided, the curable resin composition under the light-shielding edge can be cured, and the curing failure of the adhesive can be suppressed.

The composition of one embodiment of the present invention contains (P), (C) to (F) as described above, so even if a rigid skeleton monomer such as isovolyl (meth)acrylate is not used, it can be tested for reliability. I can bear it.

<(P) Polymerizable vinyl monomer>

(P) It is preferable to use (meth)acrylate as a polymerizable vinyl monomer, and it is more preferable to contain (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate.

<(A) polyfunctional (meth)acrylate>

(A) Polyfunctional (meth)acrylate refers to a (meth)acrylate having two or more (meth)acryloyl groups. Examples of polyfunctional (meth)acrylates include oligomers/polymers of polyfunctional (meth)acrylates formed by two or more (meth)acryloyl groups at the end or side chain of the oligomer/polymer.

For example, as an oligomer/polymer of polyfunctional (meth)acrylate, 1,2-polybutadiene-terminated urethane (meth)acrylate (for example, "TEA-1000" manufactured by Nippon Soda Corporation), 1,2-poly Hydrogenated product of butadiene-terminated urethane (meth)acrylate (e.g., urethane having (meth)acryloyloxy groups at both ends of hydrogenated polybutadiene in which hydrogen is added to a carbon-carbon bond in a 1,2-polybutadiene skeleton Refers to (meth)acrylate, for example, "TEAI-1000" manufactured by Nippon Soda Corporation, "KRM-8776" manufactured by DAICEL-ALLNEX LTD., "KRM-8792"), 1 ,4-polybutadiene-terminated urethane (meth)acrylate (for example, "BAC-45" manufactured by Osaka Organic Chemical Co., Ltd.), polyisoprene-terminated (meth)acrylate, polyester-based urethane (meth)acrylate (e.g. For example, "UV-2000B", "UV-3000B", "UV-7000B" manufactured by Nippon Gooseisha, "KHP-11", "KHP-17" manufactured by Negami Kogyo Corporation), polyether urethane (meth)acrylic Rate (for example, "UV-3700B" and "UV-6100B" manufactured by Nippon Corporation), bisphenol A type epoxy (meth)acrylate, and the like.

In addition, in the polybutadiene terminal (meth)urethane acrylate, the terminal of the molecular structure is (meth)acrylate.

Urethane (meth)acrylate is preferred from the viewpoint of having a large effect among the oligomers/polymers of the polyfunctional (meth)acrylate described above.

In addition, among urethane (meth)acrylates, hydrogenated products of polybutadiene-based urethane (meth)acrylate, polybutadiene-terminated urethane (meth)acrylate, polyester-based urethane (meth)acrylate, and polyether-based urethane (meth)acrylate At least one selected from the group consisting of is preferable, and the hydrogenated product of polybutadiene-based urethane (meth)acrylate and/or polybutadiene-terminated urethane (meth)acrylate is more desirable, and polybutadiene-terminated urethane (meth) Hydrogenated acrylates are most preferred.

In addition, among the hydrogenated products of polybutadiene-terminated urethane (meth)acrylate, a hydrogenated product of 1,2-polybutadiene-terminated urethane (meth)acrylate is preferable. Among the polybutadiene-based urethane (meth)acrylates, 1,4-polybutadiene-terminated urethane (meth)acrylate is preferable.

Among them, urethane (meth)acrylate reacts with a polyol compound (hereinafter referred to as X) and an organic polyisocyanate compound (hereinafter referred to as Y) and hydroxy (meth)acrylate (hereinafter referred to as Z). For example, it refers to a urethane (meth)acrylate having a urethane bond in a molecule obtained by polycondensation reaction).

As polyol compound (X), ethylene glycol, diethylene glycol triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, polybutylene glycol, 1 ,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl1,5-pentanediol , 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypenta Polyether polyol, which is a polyhydric alcohol such as erythritol, sorbitol, mannitol, glycerin, polyglycerin, and polytetramethylene glycol, or has at least one structure of block or random copolymerization of polyethylene oxide, polypropylene oxide, ethylene oxide/propylene oxide, Polyester polyol, which is a condensation product of polybasic acids such as polyhydric alcohol or polyether polyol, maleic anhydride, maleic acid, fumaric acid, itacomic anhydride, itaconic acid, adipic acid, isophthalic acid, caprolactone-modified polytetramethylene polyol, etc. Polydiene-based polyols such as caprolactone-modified polyol, polyolefin-based polyol, polycarbonate-based polyol, polybutadiene polyol, polyisoprene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, and silicone polyols such as polydimethylsiloxane polyol.

Among these, as the polyol compound (X), it is preferable to contain at least one of polybutadiene polyol, hydrogenated polybutadiene polyol, polyether polyol and polyester polyol, and hydrogenated polybutadiene polyol is more preferable. Among hydrogenated polybutadiene polyols, the compound represented by formula (3) (n is an integer) is preferred.

Here, as for the polybutadiene-based urethane (meth)acrylate, for example, the polyol compound (X) is a polybutadiene polyol. In addition, as for the polyester-based urethane (meth)acrylate, for example, the polyol compound (X) is a polyester polyol. In addition, as for the polyether urethane (meth)acrylate, for example, the polyol compound (X) is a polyether polyol.

The organic polyisocyanate compound (Y) is not particularly limited, but polyisocyanates such as aromatic, aliphatic, cyclic aliphatic, and alicyclic can be used.

Among the polyisocyanates, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (Modified MDI), hydrogenated xylene diisocyanate (H-XDI), xylene diisocyanate (XDI), hexadiisocyanate (HMDI), trimethylhexadiisocyanate (TMXDI), tetramethylxylene diisocyanate (m-TMXDI), Polyisocyanates such as isopolone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), trimer compounds of these polyisocyanates, and these The reaction product of polyisocyanate and polyol, etc. are preferably used.

Among the above substances, hydrogenated xylene diisocyanate (H-XDI) and/or isopolone diisocyanate (IPDI) are preferable as the organic polyisocyanate compound (Y), and isopolone diisocyanate (IPDI) is more preferable.

As hydroxy (meth) acrylate (Z), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (Meth)acryloylphosphate, 4-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalate, glycerindi(meth)acrylate, 2-hydroxy- 3-(meth)acryloyloxypropylacrylate, caprolactone-modified 2-hydroxyethyl(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone Modified 2-hydroxyethyl (meth)acrylate and the like.

Among them, as the hydroxy (meth) acrylate (Z), hydroxyalkyl (meth) acrylate is preferred. At least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate among hydroxyalkyl (meth)acrylates It is preferable to include.

The weight average molecular weight of the polyfunctional (meth)acrylate is not particularly limited, but is preferably 1000 to 60000, and more preferably 1500 to 40000. The weight average molecular weight was determined by using tetrahydrofuran as a solvent under the following conditions, using a GPC system (SC-8010 manufactured by Tosoh Corporation), etc., and preparing an analysis curve from commercially available standard polystyrene.

Flow rate: 1.0ml/min

Set temperature: 40℃

Column configuration: Tososha's "TSK guardcolumn MP(×L)" 6.0mmID×4.0cm 1 pc. and Tosohsha's "TSK-GELMULTIPOREHXL-M" 7.8mmID×30.0cm (theoretical level 16,000) 2 pcs., total 3 pcs. (32,000 total theoretical stages)

Sample injection volume: 100μl (sample solution concentration 1mg/ml)

Liquid feed pressure: 39kg / cm ²

Detector: RI detector

<(B) monofunctional (meth)acrylate>

(B) Monofunctional (meth)acrylate refers to a (meth)acrylate having one (meth)acryloyl group. (B) Among monofunctional (meth)acrylates, at least one selected from the group consisting of hydroxy (meth)acrylate and alkyl (meth)acrylate is preferred, and hydroxyalkyl (meth)acrylate and alkyl (meth)acrylate ) It is more preferable to use an acrylate together.

In addition, as an embodiment of the present invention, it is not necessary to use a rigid skeleton monomer such as isovolyl (meth)acrylate. Because one embodiment of the present invention can exhibit good results in the moisture resistance test without using isovolyl (meth) acrylate.

Among the hydroxyalkyl (meth)acrylates, (meth)acrylates represented by formula (2) are preferred.

(Z represents a (meth)acryloyl group, R ₁ represents an alkylene group, and p represents an integer of 1 to 10.)

Moreover, 1-8 are preferable and, as for the carbon number of the alkylene group of _{R 1} in Formula (2), 2-6 are more preferable.

As hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, diethylene glycol mono (meth)acrylic Rate and polypropylene glycol (meth)acrylate. Among these, 2-hydroxybutyl (meth)acrylate is preferable from the viewpoint of adhesiveness and moisture resistance.

Among the alkyl (meth) acrylates, (meth) acrylate alkyl esters are preferred. Among the alkyl esters, the alkyl group preferably has 1 to 16 carbon atoms, more preferably 2 to 14 carbon atoms, most preferably 4 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. The alkyl group is preferably a saturated aliphatic hydrocarbon group. In addition, it is preferable that the alkyl group is unsubstituted.

As alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, normal octyl (meth) Acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate And the like. Among these, octyl (meth)acrylate is preferable from the viewpoint of adhesiveness and moisture resistance, and normal octyl (meth)acrylate is more preferable.

(P) When the total amount of (P) and (F) is 100 parts by mass, the content of the (P) polymerizable vinyl monomer is preferably 50 to 95 parts by mass, more preferably 55 to 90 parts by mass, and most preferably 60 to 80 parts by mass. . (P) When the content of the polymerizable vinyl monomer is 50 parts by mass or more, more excellent curability can be obtained, and when the content is 95 parts by mass or less, a decrease in adhesiveness can be further suppressed. (P) The content of the polymerizable vinyl monomer is, for example, 50, 51, 54, 55, 56, 59, 60, 61, 65, 69, 70, 71, 75, 79, 80, 81, 85, 89, 90 , 91, 94, or 95 parts by mass may be sufficient, and any two of them may be in the range of values.

(P) When the polymerizable vinyl monomer contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, (A) polyfunctional (meth)acrylate and (B) short The content of the functional (meth)acrylate is in 100 parts by mass in total of (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, mass ratio (A): (B) = 30 to 95: 5 to 70 are preferred, 40 to 90: 10 to 60 are more preferred, and 50 to 70:30 to 50 are most preferred.

(B) When monofunctional (meth)acrylate is used in combination with hydroxyalkyl (meth)acrylate and alkyl (meth)acrylate, the content of hydroxyalkyl (meth)acrylate and alkyl (meth)acrylate is hydroxy Hydroxyalkyl (meth) acrylate: alkyl (meth) acrylate = 5 to 70: 30 to 95 are preferable in a mass ratio of 100 parts by mass of the total of oxyalkyl (meth) acrylate and alkyl (meth) acrylate, 10 to 50:50 to 90 are more preferable, and 20 to 40:60 to 80 are most preferable.

<(C) Photoinitiator>

(C) The photoinitiator is used to increase or decrease by active light of visible or ultraviolet light and to accelerate photocuring of the resin composition.

As a photoinitiator, benzophenone and its derivatives, benzyl and its derivatives, anthraquinone and its derivatives, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin derivatives such as benzoin isobutyl ether, benzyl Alkylphenol derivatives such as dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, diethoxyacetophenone, 4-t-butyltrichloroacetophenone Acetophenone derivatives such as, 2-dimethylaminoethylbenzoate, P-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and derivatives thereof, camphorquinone, 7,7-dimethyl-2,3-dioxobi Cyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 7, 7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methylester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane Camphorquinone derivatives such as -1-carboxylic acid chloride, 2-methyl-1[4-(methylthiol)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- Α-aminoalkylphenone derivatives such as (4-morpholinophenyl)-butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, Acylphos, such as 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide Pin oxide derivatives, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy] -Ethyl ester and the like. (C) The photoinitiator can be used 1 type or in combination of 2 or more types. From the viewpoint of the high effect of the above, (C) the photopolymerization initiator preferably contains at least one selected from the group consisting of alkylphenone derivatives and acylphosphine oxide derivatives, and alkylphenone derivatives and acylphosphine oxide derivatives are used in combination. It is more preferable to do it.

When the alkylphenone derivative and the acylphosphine oxide derivative are used in combination, the combination ratio is preferably 50 to 400 parts by mass, more preferably 100 to 300 parts by mass of the alkylphenone derivative based on 100 parts by mass of the acylphosphine oxide derivative, It is most preferably 150 to 250 parts by mass.

Among the alkyl phenone derivatives, it is preferable to contain at least one selected from the group consisting of benzyl dimethyl ketal and 1-hydroxycyclohexylphenyl ketone. In addition, among the acylphosphine oxide derivatives, at least one selected from the group consisting of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethyru benzoyl)-phenylphosphine oxide It is preferable to include.

(C) The photopolymerization initiator content is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 1 part by mass when the sum of (P) and (F) is 100 parts by mass. When the content of the photoinitiator is 0.01 parts by mass or more, better curing properties can be obtained, and when the content is 10 parts by mass or less, better deep curing properties can be obtained. (C) The photopolymerization initiator is, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.09, 1, 1.01, 1.5, 1.9, 2, 3, 4, 4.5, 4.9, 5, 6, 7, 8, 9 Alternatively, it may be 10 parts by mass, or within the range of any two values among them.

<(D) antioxidant>

(D) Antioxidants can improve storage safety.

Antioxidants are methylhydroquinone, hydroquinone, 2,2-methylenebis(4-methyl-6-tertiarybutylphenol), 6-tert-butyl-4-[3[(2,4,8,10-tetra-tert -Butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol, catechol, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2 ,5-diteributylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butylcate Chol, 2-butyl-4-hydroxyanisole and 2,6-tertiary butyl-p-cresol.

(D) When the total of (P) and (F) is 100 parts by mass, the content of the (D) antioxidant is preferably 0.001 to 0.5 parts by mass, more preferably 0.005 to 0.1 parts by mass. When the content of the antioxidant is 0.001 parts by mass or more, coloration or discoloration due to heat of the curable resin composition is less, and when it is 0.5 parts by mass or less, more excellent deep curing properties can be obtained. (D) Antioxidants are, for example, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.009, 0.010, 0.011, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.30, 0.40, 0.45, It may be 0.49 or 0.5 parts by mass, and may be in the range of any two values among them.

<(E) Thiol>

(E) Thiol is a compound having one or more thiol groups. Among thiols, polythiols are preferred from the viewpoint of deep curing properties. (E) Polythiol refers to a compound having two or more thiol groups. As polythiols, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetris Thiopropionate, pentaerythritol tetrakistiopropionate, dipentaerythritol hexakis (3-mercaptopropionate), tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate, 3-mercaptobutyrate derivatives, etc. are mentioned. One or more of the above polythiols can be used.

Among polythiols, 3-mercaptobutyrate derivatives are preferred. As a 3-mercaptobutyrate derivative, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazin- 2,4,6-(1H, 3H, 5H)-trione, pentaerythritol tetrakis (3-mercaptobutyrate), and the like. Among the polythiols, secondary polythiols are preferred.

The content of (E) thiol is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, when the total of (P) and (F) is 100 parts by mass. (E) If the content of thiol is 0.1 parts by mass or more with respect to the total 100 parts by mass of (P) and (F), better deep curing properties can be obtained, and if less than 10 parts by mass, the curable resin composition is colored or discolored by heat. Less than this. In addition, (E) thiol is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.9, 1.0, 2.0, 3.0, 4.0, 4.5, 4.9, 5.0, 6.0, 7.0, 8.0, 9.0, 9.9 or 10 parts by mass This may be sufficient, and it may be within the range of any two values among them.

<(F) Dicarboxylic acid diester>

(F) As dicarboxylic acid diester, diester of aliphatic dibasic acid is preferable. As a diester of an aliphatic dibasic acid, the compound represented by formula (1) is preferable.

[Formula 1]

Equation (1)

(R ₁ , R ₂ is an alkyl group having 1 to 18 carbon atoms, R ₃ is an alkylene group having 1 to 10 carbon atoms, and may be the same as or different from _{R 1} and R _{2 .)}

In the compound represented by formula (1), R ₁ and R ₂ are preferably saturated aliphatic hydrocarbon groups. In addition, it is preferable that _{R 1} and R _{2 are unsubstituted.} The above R ₁ and R ₂ are preferably an alkyl group having 2 to 12 carbon atoms, more preferably an alkyl group having 4 to 10 carbon atoms, and most preferably an alkyl group having 8 carbon atoms. In the compound represented by formula (1), R ₃ is preferably a saturated aliphatic hydrocarbon group. In addition, it is preferable that _{R 3 is unsubstituted.} R ₃ is preferably an alkylene group having 4 to 10 carbon atoms, more preferably an alkylene group having 7 to 8 carbon atoms, and most preferably an alkylene group having 8 carbon atoms.

(F) Dicarboxylic acid diester is a compound used to improve the deep curing property and adjust the viscosity. (F) As the dicarboxylic acid diester represented by the general formula (1), dimethyl oxalate, diethyl oxalate, propyl oxalate, diisopropyl oxalate, dibutyl oxalate, dihexyl oxalate, dioctyl oxalate, diisopropyl malonate, di-malonate Butyl, diethyl succinate, dipropyl succinate, diisopropyl succinate, dibutyl succinate, t-butyl succinate, bis succinate (2-ethylhexyl), bis succinate (2-ethoxyethyl), diethyl glutarate, glutaric acid Dibutyl acid, dimethyl adipate, diethyl adipate, dipropyl adipate, diisopropyl adipate, dibutyl adipate, di-t-butyl adipate, bis adipic acid (2-ethylhexyl), diethyl adipic acid Octyl, Dimethyl Pimelate, Diethyl Pimelate, Diisopropyl Pimelate, Dibutyl Pimelate, Dimethyl Suberate, Diethyl Suberate, Dipropyl Suberate, Diisopropyl Suberate, Dimethyl Azelaate, Diethyl Azelalate, Di azelasan Propyl, diisopropyl azelaate, dibutyl azelaic acid, bis azelaic acid (2-ethylhexyl), dimethyl sebacate, diethyl sebacate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, bis sebacic acid ( 2-ethylhexyl) and the like. One or more of these dicarboxylic acid diesters can be used. (F) Among the dicarboxylic acid diesters, bis(2-ethylhexyl) sebacate is most preferred.

(F) The content of the dicarboxylic acid diester is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and most preferably 20 to 40 parts by mass when the total of (P) and (F) is 100 parts by mass. Do. (F) When the content of the dicarboxylic acid diester is 5 parts by mass or more, more excellent viscosity and deep curing properties can be obtained, and when the content is 50 parts by mass or less, more excellent deep curing properties can be obtained. (F) The content of dicarboxylic acid diester is, for example, 5, 6, 7, 8, 9, 10, 11, 15, 20, 21, 25, 29, 30, 31, 35, 39, 40, 41 , 49 or 50 parts by mass may be sufficient, and any two of these may be in the range of values.

The composition of one embodiment of the present invention includes various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, and solvents such as polar organic solvents, and extenders. , Additives such as reinforcing materials, plasticizers, thickeners, dyes, pigments, ignition retardants, silane coupling agents and surfactants may be used.

The cured product bonded with the composition of one embodiment of the present invention can be completely cured and then reworked (recycled). Although there is no particular limitation as a method of rework, the adherends can be disassembled and the adherends after disassembly can be reused by applying a load of 0.01 to 100N between the adhered one or two adherends.

The composition of one embodiment of the present invention is a curable resin composition, and can also be used as an adhesive composition. The composition of one embodiment of the present invention is larger than 3 mm when irradiated with visible or ultraviolet rays at a wavelength of 365 nm at 100 mJ/cm ² , and a composition capable of deep curing of 4 mm or more is preferable. The composition of one embodiment of the present invention is an adhesive composition capable of adhering to an adherend by irradiating visible or ultraviolet light from the front side of the adherend, and then irradiating a point where visible or ultraviolet light does not transmit from the side of the adherend. to be.

The adhesive composition of one embodiment of the present invention can obtain a cured product of the adhesive composition by irradiating with visible light or ultraviolet rays.

A composite to which an adherend is coated or bonded can be obtained from the cured product of one embodiment of the present invention. In addition, the adherend is not particularly limited, but it is preferable to include at least one selected from the group consisting of triacetyl cellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal.

A touch panel laminate can be obtained by bonding the adherends by a known method using the adhesive composition of one embodiment of the present invention.

Further, it is possible to obtain a touch panel laminate obtained by bonding the adherends to each other by a known method using the adhesive composition of one embodiment of the present invention. In addition, a display can be obtained using the touch panel laminate.

Further, a liquid crystal panel laminate can be obtained in which the adherend is bonded by a known method using the adhesive composition of one embodiment of the present invention. In addition, a display can be obtained by using the liquid crystal panel laminate.

[Example]

Hereinafter, the present invention will be described in more detail from the experimental examples, but the present invention is not limited thereto.

(Experimental example)

Unless otherwise specified, the experiment was conducted at 23°C. Curable resin compositions of the compositions shown in Tables 1 and 2 were prepared and evaluated. The results are shown in Tables 3 and 4.

As each component in the curable resin composition described in the experimental example, the following compounds were selected.

However, KRM-8776 in the table describes the amount of urethane acrylate contained in "KRM-8776" manufactured by Daicel Cytec. NOAA in the table describes the amount of n-octyl acrylate contained in "KRM-8776" manufactured by Daicel Cytec. When "KRM-8776" manufactured by Daiserucitec was not used, n-octyl acrylate manufactured by Osaka Organic Chemicals Co., Ltd. was used.

<(P) Polymerizable vinyl monomer (A) polyfunctional (meth)acrylate>

As the polyfunctional (meth)acrylate of the component (A), the following compounds were selected.

(A-1) Polyester urethane acrylate oligomer (The structure of "KHP-11" manufactured by Negami Kogyo is as follows, and the polyol compound is polyester polyol, ethylene, which is a condensate between 1,4-butanediol and adipic acid. A compound having a glycol and a polyester polyol that is a condensation product of adipic acid (polyol polyol that is a condensation product between 1,4-butanediol and adipic acid, and a polyester polyol that is a condensation product between ethylene glycol and adipic acid = 2: 3 (molar ratio), the organic polyisocyanate compound is isopolone diisocyanate, the hydroxy (meth)acrylate is 2-hydroxyethyl acrylate, the weight average molecular weight in terms of polystyrene by GPC is 25000)

(A-2) Polyester-based urethane acrylate oligomer ("UV-3000B" manufactured by Nippon Koosei Chemical, the structure is as follows, the polyol compound is a polyester polyol that is a condensate between hydrogenated polybutadiene polyol and adipic acid) , The organic polyisocyanate compound is isopolone diisocyanate, the hydroxy (meth) acrylate is 4-hydroxybutyl acrylate, the weight average molecular weight in terms of polystyrene by GPC is 15000, and the hydrogenated polybutadiene polyol is represented by formula (3). Compound (n is an integer))

(A-3) Polybutadiene-based urethane acrylate ("KRM-8776" manufactured by Daicel-Cytech, a urethane acrylate having a hydrogenated polybutadiene skeleton. The structure is as follows, and the polyol compound is hydrogenated polybutadiene polyol, an organic organic compound). The polyisocyanate compound is isopolone diisocyanate, the hydroxy (meth)acrylate is 2-hydroxyethyl acrylate, the weight average molecular weight in terms of polystyrene by GPC is 19000, and the hydrogenated polybutadiene polyol is a compound represented by formula (3). (n is an integer), however, as a diluted monomer, containing 30% by mass of n-octyl acrylate)

<(P) Monofunctional (meth)acrylate of polymerizable vinyl monomer>

As the monofunctional (meth)acrylate of the component (B), the following compounds were selected.

(B-1) lauryl acrylate ("LA" manufactured by Osaka Organic Chemicals)

(B-2) 2-hydroxybutyl acrylate ("HOB-A" manufactured by Kyei Chemical Co., Ltd.)

(B-3) n-octyl acrylate (hereinafter abbreviated as "NOAA")

<(C) Photoinitiator>

As the photoinitiator of the component (C), the following compounds were selected.

(C-1) 1-hydroxy-cyclohexylphenyl ketone ("Irgacure184" manufactured by BASF, hereinafter abbreviated as "I-184")

(C-2) 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("LucirinTPO" manufactured by BAS Corporation, hereinafter abbreviated as "TPO")

<(D) antioxidant>

As the antioxidant of the component (D), the following compounds were selected.

(D-1) 6-tert-butyl-4-[3-[(2,4,8,10-tetra-tert-butyldibenzo[d, f][1,3,2] dioxaphosphepine- 6-yl)oxy]propyl]-2-methylphenol (Sumitomo Chemical Co., Ltd. "Sumilizer GP") (hereinafter abbreviated as "GP")

<(E) Thiol>

As the thiol compound, the following compounds were selected.

(E-1) pentaerythritol tetrakis (3-mercaptobutyrate) (Showa Denko Corporation "Carenz MT PE1") (hereinafter abbreviated as "MT-PE1")

(E-2) Pentaerythritol tetrakis (3-mercaptopropionate) (SC Organic Chemicals "PBMP")

(E-3) 1- Dodecane Thiol ("DDT" by Sigma/Oldrichsha)

<(F) Dicarboxylic acid diester>

About (F) As the dicarboxylic acid diester represented by Formula (1), the following compounds were selected.

(F-1) Sebacic acid bis(2-ethylhexyl) ("Sciencer and DOS" manufactured by Shinnippon Likasha) (hereinafter abbreviated as "DOS")

(F-2) Dibutyl sebacate (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter abbreviated as "DBS")

(F-3) Azelaic acid bis(2-ethylhexyl) (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter abbreviated as "DOZ")

(F-4) Adipic acid bis(2-ethylhexyl) (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter abbreviated as "DOA")

Each physical property was measured as follows.

[Photocurable]

It measured at a temperature of 23°C. Regarding photocurability, a curable resin composition was applied to the surface of TEMPAX glass (25 mm in width x 25 mm in length x 2 mm in thickness) so as to have a thickness of 0.1 mm. Thereafter, using a curing apparatus manufactured by Fusion Corporation using an electrodeless discharge lamp, UV rays having a wavelength of 365 nm were irradiated and cured under conditions ^{of a cumulative amount of light of 2000 mJ/cm 2.}

The curing rate was calculated by the following method using FT-IR. Absorption spectrum of the carbon-carbon double bond is 1600cm ^- used the peak in the vicinity of ^1.

(Curing ratio) = 100-(the intensity of the absorption spectrum of the double bond of carbon and carbon after curing) / (the intensity of the absorption spectrum of the double bond of carbon and carbon before curing) × 100 (%)

[Curing shrinkage rate]

The curable resin composition was filled in a pycnometer, and the mass in the air and the mass in pure water were measured, and the liquid specific gravity was calculated. In addition, the curable resin composition was cured by the method described in [Photocurable] to prepare a cured product having a width of 25 mm x a length of 25 mm x a thickness of 2 mm, and the mass in the air and the mass in pure water were measured to calculate the specific gravity of the cured product. . The cure shrinkage was calculated from the ratio of the specific gravity of the liquid and the specific gravity of the cured product.

Curing shrinkage rate = (specific gravity of cured product-specific gravity of liquid) / specific gravity of cured product) × 100 (%)

[Deep hardenability]

The curable resin composition is filled in a black tube with a diameter of 5 mmφ and a hole of 20 mm, and ^{a light beam of 1 mW/cm 2} (365 nm) is irradiated with a black light from the top for 100 seconds (the cumulative amount of light is 100 mJ/cm ² ). After that, the cured product was removed from the black tube to remove the uncured part, and the cured part was measured in thickness with a micrometer.

[Adhesion evaluation of polyethylene terephthalate (PET) (peel adhesion strength between polyethylene terephthalate test pieces)]

Biaxially stretched PET film (Lumor T60, average thickness 190 μm, manufactured by Toray Corporation) test pieces (width 50 mm × length 10 mm × thickness 0.19 mm) using a curable resin composition as an adhesive composition, and the adhesive area with a thickness of 30 μm of the adhesive layer Was adhered to a length of 40 mm × 10 mm in width. After curing by light irradiation, the initial 180° peel adhesion strength was measured by pulling the ends of the two non-adhered films of the test piece adhered with the adhesive composition to peel off the tightly adhered portions between the films. Light irradiation conditions followed the method described in [Photocurability]. Peel adhesion strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in an environment at a temperature of 23°C and a humidity of 50% using a tensile tester.

[Glass adhesion evaluation (tensile adhesion strength between heat-resistant glass specimens)]

Heat-resistant glass test pieces (25 mm wide x 25 mm long x 2.0 mm thick) were bonded to each other using a Teflon (registered trademark) tape having a thickness of 80 μm x a width of 11.5 mm x a length of 25 mm as a spacer, and a curable resin composition as an adhesive composition ( Bonding area 3cm ² ). Light irradiation conditions followed the method described in [Photocurability]. After curing the adhesive composition under the above conditions, a galvanized steel sheet (width 100 mm × length 25 mm × thickness 2.0 mm, manufactured by Engineering Test Service) is adhered to both sides of the test piece using the adhesive composition "G-55" manufactured by Electrochemical Industry Co., Ltd. Made it. After curing, the galvanized steel sheet was checked using a test piece bonded with the adhesive composition, and the initial tensile shear bonding strength was measured. Shear adhesion strength (unit: MPa) was measured at a tensile speed of 10 mm/min in an environment at a temperature of 23°C and a humidity of 50% using a tensile tester.

[Cycloolefin polymer (COP) adhesion evaluation (peel adhesion strength between cycloolefin polymer test pieces)]

A curable resin composition was used as the adhesive composition between the test pieces (50mm width x 10mm length x 0.04mm thickness) of COP film (ZEONOR, average thickness 40μm, made by Japan Xeon Corporation), and the adhesive area was 40mm vertically with the thickness of the adhesive layer 10μm. It was adhered to a width of 10 mm. After curing by light irradiation, the initial 180° peel adhesion strength was measured by pulling the ends of the two non-closed films of the test piece adhered with an adhesive to separate the tightly adhered portions between the films. Light irradiation conditions followed the method described in [Photocurability]. Peel adhesive strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in an environment at a temperature of 23°C and a humidity of 50% using a tensile tester.

[Triacetyl cellulose adhesion evaluation (peel adhesion strength between triacetyl cellulose test pieces)]

A curable resin composition was used as the adhesive composition between the specimens (50 mm width x 10 mm length x 0.04 mm thickness) of a triacetylcellulose (TAC) film (average thickness of 40 μm, manufactured by Fuji Film Corporation), and the adhesive area was adjusted to a thickness of 10 μm of the adhesive layer. It was bonded at a length of 40 mm x a width of 10 mm. The initial 180° peel adhesion strength was measured by pulling the ends of the two non-adhered films of the test piece bonded with the adhesive composition to separate the adhered portions between the films. After curing by light irradiation, the initial 180° peel adhesion strength was measured by pulling the ends of the two non-closed films of the test piece adhered with the adhesive composition to separate the tightly adhered portions between the films. Light irradiation conditions followed the method described in [Photocurability]. Peel adhesion strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in an environment at a temperature of 23°C and a humidity of 50% using a tensile tester.

[Fluorine-based polymer adhesion evaluation (peel adhesion strength between fluorine polymer test pieces)]

PVDF (Polyvinylidene fluoride) film (average thickness 40μm, Denki Chemical Co., Ltd. "DX Film") between the test pieces (width 50mm × length 10mm × thickness 0.04mm) between the curable resin composition used as the adhesive composition, the thickness of the adhesive layer The adhesive area of 10 μm was adhered to a length of 40 mm x a width of 10 mm. The initial 180° peel adhesion strength was measured by pulling the ends of the two non-closed films of the test piece adhered with the adhesive composition to separate the tightly adhered portions between the films. After curing by light irradiation, the initial 180° peel adhesion strength was measured by pulling the ends of the two non-adhered films of the test piece adhered with the adhesive composition to separate the tightly adhered portions between the films. Light irradiation conditions followed the method described in [Photocurability]. Peel adhesion strength (unit: N/cm) was measured at a tensile speed of 50 mm/min in an environment at a temperature of 23°C and a humidity of 50% using a tensile tester.

[Polycarbonate adhesion evaluation (tensile adhesion strength between polycarbonate specimens)]

Polycarbonate ("Panlite" manufactured by Teijin Corporation) Test specimens (25mm wide x 25mm long x 2.0mm thick) are 80μm thick x 12.5mm wide x 25mm long Teflon (registered trademark) tape used as a spacer as a spacer, and curable resin composition Was adhered using the adhesive composition (adhesive area 3 cm ² ). Light irradiation conditions followed the method described in [Photocurability]. Shear adhesion strength (unit: MPa) was measured at a tensile speed of 10 mm/min in an environment at a temperature of 23°C and a humidity of 50% using a tensile tester.

[Moisture and heat resistance evaluation (tensile adhesion strength between heat-resistant glass specimens after exposure to high temperature and high humidity)]

A curable resin composition was used as an adhesive composition between TEMPAX (registered trademark) glass (25 mm in width × 25 mm in length × 2 mm in thickness), and the adhesive area was bonded to 1.0 cm ² with a thickness of 100 μm of the adhesive layer, followed by curing. Light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was exposed for 1000 hours in an environment at a temperature of 85°C and a relative humidity of 85% using a thermo-hygrostat. Shear adhesive strength was measured using the test piece after exposure. Shear adhesive strength (unit: MPa) was measured at a tensile speed of 10 mm/min in an environment at a temperature of 23°C and a humidity of 50% using a tensile tester.

[Moisture and heat resistance evaluation (appearance observation (change in surface precision and degree of yellowing))]

Tempax (registered trademark) glass (25 mm in width × 25 mm in length × 2 mm in thickness) was used as an adhesive composition, and the adhesive area was adhered to and cured ^{to 1.0 cm 2 with a thickness of 100 μm of the adhesive layer.} Light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was exposed for 1000 hours in an environment at a temperature of 85°C and a relative humidity of 85% using a constant temperature and humidity device. After exposure, the Δb value of the test piece adhered with the adhesive composition was measured with a color measuring device ("UV-VISIBLE SPECTROPOHOTOMETER" manufactured by Shimadzu Corporation.) After exposure, the appearance of the bonded site was visually observed to determine the change in surface accuracy. As a result, dimensional change, warping, and yellowing were investigated.

In the experimental example, it can be seen the following points. The curable resin composition according to the embodiment of the present invention has excellent deep curing properties. For example, even when light is irradiated in the oblique direction or the transverse direction of the light-shielding frame, the curable resin composition under the light-shielding frame can be cured to the core.

Moreover, the curable resin composition according to the embodiment of the present invention can be cured to the deep part with weak light (for example, light having an accumulated light amount of 1000 to 3000 mJ/cm ^{2) even under the shading edge.}

In the experimental examples of the curable resin composition corresponding to the embodiment of the present invention, since the curing shrinkage rate was low, there was no change in surface precision such as dimensional change or warping after the heat-and-moisture test. In Experimental Example 6, since the number of thiol groups in the component (E) was one, deep curing properties were lower than those of the curable resin compositions using the polythiols of Experimental Examples 2 and 3.

The curable resin composition corresponding to the example of the present invention did not cause problems such as coloring and discoloration after the heat resistance test, and decrease in strength after the moisture resistance test.

Claims (16)

As a composition containing the following (P), (C) to (F),
(P) polymerizable vinyl monomer;
(C) a photoinitiator;
(D) antioxidants;
(E) thiol;
(F) dicarboxylic acid diester,
The content of the (D) antioxidant is 0.001 to 0.5 parts by mass when the total of (P) and (F) is 100 parts by mass. The composition according to claim 1, wherein the (F) dicarboxylic acid diester is a dicarboxylic acid diester represented by formula (1).
Equation (1)

(R ₁ , R ₂ is an alkyl group having 1 to 18 carbon atoms, R ₃ is an alkylene group having 1 to 10 carbon atoms, and may be the same as or different from _{R 1} and R _{2 .)} The composition according to claim 1, wherein the (E) thiol is polythiol. The composition according to claim 1, wherein the (P) polymerizable vinyl monomer contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate. The composition according to claim 4, wherein the (A) polyfunctional (meth)acrylate is a urethane (meth)acrylate. The composition according to claim 4, wherein the (B) monofunctional (meth)acrylate comprises at least one selected from the group consisting of hydroxyalkyl (meth)acrylate and alkyl (meth)acrylate. The content of the (F) dicarboxylic acid diester according to any one of claims 1 to 6, when the total of the (P) polymerizable vinyl monomer and (F) dicarboxylic acid diester is 100 parts by mass. A composition of 5 to 50 parts by mass. Curable resin composition containing the composition of any one of Claims 1-6. An adhesive composition comprising the composition of any one of claims 1 to 6. A cured product of the adhesive composition of claim 9. A composite in which an adherend is coated or bonded by the cured product of claim 10. The composite according to claim 11, wherein the adherend comprises at least one selected from the group consisting of triacetylcellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal. A touch panel laminate in which an adherend is bonded to each other by the adhesive composition of claim 9. A liquid crystal panel laminate in which an adherend is bonded with the adhesive composition of claim 9. A display using the touch panel laminate of claim 13. A display using the liquid crystal panel laminate of claim 14.