WO2016039289A1

WO2016039289A1 - Composition

Info

Publication number: WO2016039289A1
Application number: PCT/JP2015/075321
Authority: WO
Inventors: 泰則石田; 啓之栗村; 佑基比舎
Original assignee: 電気化学工業株式会社
Priority date: 2014-09-08
Filing date: 2015-09-07
Publication date: 2016-03-17
Also published as: TW201624124A; JPWO2016039289A1; TWI679498B; JP6767869B2

Abstract

Provided is a composition which has high curability in a deep portion and high thermal yellowing resistance. A composition which contains the following (A)-(E). (A) a (meth)acrylate having a hydrogenated conjugated diene structure, (B) a monofunctional (meth)acrylate, (C) a radical photopolymerization initiator, (D) a plasticizer and (E) an antioxidant. It is preferable that the plasticizer (D) is composed of one or more compounds selected from the group consisting of monoester compounds having no (meth)acryloyl group, polyester compounds having no (meth)acryloyl group, monoether compounds having no (meth)acryloyl group, polyether compounds having no (meth)acryloyl group, monocarbonate compounds having no (meth)acryloyl group, polycarbonate compounds having no (meth)acryloyl group and hydrogenated conjugated diene compounds having no (meth)acryloyl group.

Description

Composition

The present invention relates to a composition.

There are a resistive film type, a capacitance type, an electromagnetic induction type, an optical type and the like as a touch panel mounted on a display body such as an LCD (liquid crystal display). There is a case where a decorative board for improving the appearance design and an icon sheet for designating a touch position are pasted on the surface of these touch panels. The capacitive touch panel has a structure in which a transparent electrode is formed on a transparent substrate, and the transparent substrate is bonded to the transparent electrode.

Conventionally, an adhesive is used for bonding a decorative plate and a touch panel, bonding an icon sheet and a touch panel, and bonding a transparent substrate and a transparent substrate.

These icon sheets and touch panels cover the shading frame by printing, etc. in order to hide the display element drive IC, wiring, and LCD frame sealant so that only the display area is visible and to improve design. There is. When this light-shielding frame is present, the photocurable adhesive composition under the light-shielding frame is shielded from light by the light-shielding frame, and is not cured without being exposed to light, resulting in insufficient adhesion.

In order to solve the problem of inadequate adhesion due to uncured, a method of adjusting the light irradiation angle by irradiating light obliquely or from the side, or adding a thermosetting catalyst to the photocurable adhesive composition. In addition to photocuring property, a method of imparting thermosetting property and curing with light and heat has been practiced.

However, in the method of adjusting the light irradiation angle, if the width of the light shielding frame is increased, it becomes difficult to sufficiently cure all of the photocurable adhesive composition under the light shielding frame, and uncured portions are likely to remain. There was a problem. A method for imparting thermosetting to a photocurable adhesive composition and curing with light and heat requires heating a display panel such as an LCD, an EL display, and an LED display to 60 to 80 ° C. for 30 to 60 minutes. For this reason, there has been a problem of quality deterioration and shortening of product life.

Also, in applications such as bonding of decorative plates and touch panels, bonding of icon sheets and touch panels, bonding of transparent substrates and transparent substrates, etc., follow the deformation of the adherend in a heated atmosphere assuming the usage environment. It is desirable to have as much flexibility as possible.

Patent Document 1 discloses (A) a (meth) acrylate oligomer having a polyisoprene, polybutadiene, or polyurethane as a skeleton, (B) a plasticizer, and (C1) phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2 (Meth) acrylate selected from hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, nonylphenol EO adduct (meth) acrylate, methoxytriethylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate A photocurable resin composition containing a monomer is described.

Patent Document 2 describes a cured resin containing urethane (meth) acrylate, polybutadiene (meth) acrylate, and isoprene (meth) acrylate as components.

Patent Document 3 is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth) acrylate.

For applications such as bonding of decorative plates and touch panels, bonding of icon sheets and touch panels, bonding of transparent substrates and transparent substrates, etc., the degree to which the adherend can be deformed in a heated atmosphere assuming the usage environment It is desirable to have the flexibility.

On the other hand, it is clear that there are problems such as coloring and discoloration after the heat resistance test and strength reduction after the moisture resistance test because it has flexibility enough to follow the deformation of the adherend in a heated atmosphere assuming the use environment. It has become. As a solution to the above problem, Patent Document 4 contains at least one oligomer selected from the group consisting of a polyisoprene (meth) acrylate oligomer, a polybutadiene (meth) acrylate oligomer, and a polyurethane (meth) acrylate oligomer, and a hindered amine. A photocurable adhesive composition is described.

Patent Document 5 discloses a liquid resin composition having photocurability containing (A) a compound having a (meth) acryloyl group, (B) a photopolymerization initiator, (C) a plasticizer, and (D) an antioxidant. A liquid resin composition having photocurability is described in which the component (D) includes a compound (D1) having a hindered phenol structure in the molecule.

Patent Document 6 describes (a) at least one monomer selected from the group consisting of (meth) acrylic acid, (meth) acrylate, and (meth) acrylamide, (b) an antioxidant, and (c) initiation of photopolymerization. A photocurable adhesive composition comprising an agent, (d) an oligomer having no (meth) acryloxy group, and optionally an oligomer having (e) (meth) acryloxy group is described. *

Patent Document 7 describes (A) (a-1) a monofunctional (meth) acrylate having a hydrocarbon group having 6 to 20 carbon atoms, (a-2) a monofunctional (meth) acrylate containing a hydroxyl group, (a-3) A monofunctional (meth) acrylate containing a monofunctional (meth) acrylate having a carboxyl group or a phosphate ester group, (B) an oligomer having two or more (meth) acryloyl groups in the molecule, (C) a diene type An energy ray-curable resin composition containing a core / shell type graft copolymer and (D) a photoradical polymerization initiator is described.

In Patent Document 8, (A) a hydrogenated 1,2-polybutadiene polyol or a hydrogenated polyisoprene polyol is reacted with a polyfunctional isocyanate compound to leave a residual hydroxyl group or isocyanate group, a (meth) acryloyl group, an isocyanate group, or (Meth) acryloyl group-containing hydrogenated 1,2-polybutadiene compound or (meth) acryloyl group-containing hydrogenated polyisoprene compound 25 to 45 having a weight average molecular weight of 50,000 to 200,000 obtained by reacting a compound having a hydroxyl group % By weight, (B) 8 to 20% by weight of (meth) acrylic acid ester having a hydroxyl group, (C) 20 to 61.8% by weight of polymerizable monomer other than (meth) acrylic acid ester having a hydroxyl group, (D) 0.2-5% by mass of a photopolymerization initiator, and (E) a softening point of 90-150. Alicyclic tackifier resin 5 to photocurable transparent adhesive sheet composition containing 20 wt% are described is.

In Patent Document 9, (A) the main chain skeleton is at least one selected from the group consisting of polybutadiene, polyisoprene, and hydrogenated products thereof, and at least one at the terminal or side chain of the main chain skeleton. (Meth) acrylate having a (meth) acryloyl group and having a molecular weight of 500 to 5000, (B) a monofunctional (meth) acrylate having an unsaturated hydrocarbon group having 2 to 8 carbon atoms via an ester bond, (C) hydroxyl group-containing (meth) acrylate, (D) polyfunctional (meth) acrylate, (E) photopolymerization initiator, and (F) antioxidant, an energy ray-curable resin composition Is described.

International Publication No. 2010/027041 Japanese Patent Laid-Open No. 2004-77887 JP-A 64-85209 JP 2012-46658 A International Publication No. 2014/077336 International Publication No. 2013/013568 JP 2014-152190 A International Publication No. 2013/115250 International Publication No. 2006/129678

However, the above prior art has room for further improvement in the following points.

For example, Patent Document 1 describes (UA) “UA-1”, “TE2000”, “UC-102”, etc., manufactured by Light Chemical Co., Ltd. as (meth) acrylate oligomers having polyisoprene, polybutadiene, or polyurethane as a skeleton. However, neither is (A) a (meth) acrylate oligomer having a hydrogenated conjugated diene structure. That is, since Patent Document 1 does not describe (A) (meth) acrylate having a hydrogenated conjugated diene structure, coloring and discoloration after the heat resistance test cannot be suppressed. Therefore, the photocurable resin composition described in Patent Document 1 may have problems such as coloring and discoloration after the heat resistance test. That is, since such a resin composition has flexibility enough to follow the deformation of the adherend in a heated atmosphere assuming the use environment, it can be colored, discolored after the heat test, and strength after the moisture test. There is a problem of reduction.

Patent Document 2 does not describe a composition containing (A) a (meth) acrylate having a hydrogenated conjugated diene structure. Therefore, when trying to suppress this deformation by the method of Patent Document 2, there are problems that the adhesive surface is peeled off, the LCD is cracked, or the LCD becomes uneven in display. In recent years, the glass of display bodies such as LCDs has become thinner. When the glass becomes thinner, the LCD is easily deformed by external stress. Therefore, in such a resin composition, 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 between glass and acrylic or the like In addition, there is a problem in that deformation during molding of a plastic molding material such as an acrylic plate or polycarbonate causes relaxation of molding distortion or moisture absorption / drying in a heat resistance test or moisture resistance test, resulting in changes in surface accuracy such as dimensional change or warpage.

Further, since Patent Document 3 is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth) acrylate, it cannot withstand the expansion and contraction of the adherend in the high-temperature reliability test, and is peeled off. There was a possibility of producing. The present invention has a design that can withstand the expansion and contraction of the adherend in a high-temperature reliability test without using a rigid skeleton monomer such as isobornyl (meth) acrylate.

Patent Document 4 does not describe a composition containing (A) a (meth) acrylate having a hydrogenated conjugated diene structure. Patent Document 5 describes (UC) “UC-102” or the like as a compound having (A) (meth) acryloyl group, and (A) (meth) acrylate oligomer having a hydrogenated conjugated diene structure. is not. That is, Patent Document 5 does not describe (A) (meth) acrylate having a hydrogenated conjugated diene structure. Patent Document 6 describes (UC) “UC-102”, “UC-203”, etc. as (e) an oligomer having a (meth) acryloxy group, all of which have (A) a hydrogenated conjugated diene structure. It is not a (meth) acrylate oligomer. That is, Patent Document 6 does not describe (A) (meth) acrylate having a hydrogenated conjugated diene structure. Therefore, in any case, when pasting a decorative board or icon sheet used for a display body such as a touch panel, when pasting a transparent substrate and a transparent substrate, when pasting a display body and an optical functional material, There existed the subject that the adhesive surface peeled off, the glass of a display body cracked, the subject of discoloration after a heat test or a moisture resistance test, and a strength fall.

Moreover, in the composition of patent document 7, there existed a subject that adhesiveness became small in wet heat resistance evaluation. Moreover, in the composition of patent document 8, there existed a subject that adhesiveness became small in wet heat resistance evaluation. Moreover, in the composition of this patent document 8, there existed a subject that adhesiveness became small in wet heat resistance evaluation.

In view of the above circumstances, for example, when pasting a decorative board or icon sheet used for a display body such as a touch panel, or when pasting a transparent substrate and a transparent substrate, the present invention includes a display body and an optical functional material. To provide a curable resin composition that solves the problems of peeling of the adhesive surface and breaking of the glass of the display body, discoloration after the heat resistance test and after the moisture resistance test, and strength reduction when bonding. Objective.

The present inventors have realized that the composition described in the above patent document cannot solve the problems such as coloring and discoloration after the heat resistance test. In order to solve this problem, the present inventors have intensively studied. As a result, a composition containing a (meth) acrylate having a hydrogenated conjugated diene structure and a specific type of plasticizer does not cause the above problem. I found In particular, the plasticizer is selected from the group consisting of a monoester compound having no (meth) acryloyl group, a polyester compound having no (meth) acryloyl group, and a hydrogenated conjugated diene compound having no (meth) acryloyl group. In the case of one or more kinds, it has been found that problems such as coloring and discoloration after the heat resistance test do not occur as in Examples described later. Based on this discovery, the present invention has been completed.

That is, one aspect of the present invention is a composition containing the following (A) to (E):
(A) (meth) acrylate having hydrogenated conjugated diene structure (B) monofunctional (meth) acrylate (C) radical photopolymerization initiator (D) plasticizer (E) antioxidant (D) plasticizer is ( A monoester compound not having a (meth) acryloyl group, a polyester compound not having a (meth) acryloyl group, a monoether compound having no (meth) acryloyl group, a polyether compound not having a (meth) acryloyl group, It is at least one selected from the group consisting of a monocarbonate compound having no (meth) acryloyl group, a polycarbonate compound having no (meth) acryloyl group, and a hydrogenated conjugated diene compound having no (meth) acryloyl group. It is a composition.

In the above composition, (A) the (meth) acrylate having a hydrogenated conjugated diene structure is preferably a polyfunctional (meth) acrylate. Moreover, it is preferable that (A) (meth) acrylate which has a hydrogenated conjugated diene structure is this composition which is urethane (meth) acrylate. In the above composition, the (A) (meth) acrylate having a hydrogenated conjugated diene structure preferably has a molecular weight of 500 to 50,000. In the above composition, it is preferable that the photopolymerization initiator (C) is at least one selected from the group consisting of benzoin derivatives, acylphosphine oxide derivatives, and α-hydroxyketone derivatives. . In the above composition, the (D) plasticizer is preferably a polyester compound having no (meth) acryloyl group and having an alkyl group having 8 to 22 carbon atoms. In the above composition, the total amount of (A), (B) and (D) is 100 parts by mass, the amount of component (A) used is 5 to 70 parts by mass, and the amount of component (B) used is 1 to 50 parts by mass and the amount of component (D) used is preferably 1 to 80 parts by mass. In the above composition, the amount of the component (C) used is 0.001 to 10 parts by mass with respect to the total of 100 parts by mass of (A), (B) and (D), and the component (E) is used. The amount is preferably 0.001 to 5 parts by mass.

Another embodiment of the present invention is a photocurable resin composition comprising the above composition. Another embodiment of the present invention is an adhesive composition comprising the above composition. Another embodiment of the present invention is a coating composition comprising the above composition. Another embodiment of the present invention is a cured product of the above composition.

Another embodiment of the present invention is a composite in which an adherend is coated or bonded with the cured body. In the above composite, the adherend is preferably at least one selected from the group consisting of triacetylcellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal. In the above composite, at least one of the adherends preferably includes a portion having a light transmittance of 0.1 or less.

Another embodiment of the present invention is a touch panel laminate in which an adherend is bonded using the above-described adhesive composition. Another aspect of the present invention is a liquid crystal panel laminate in which an adherend is bonded with the above-described adhesive composition. Another embodiment of the present invention is a display using the touch panel laminate. Another embodiment of the present invention is a display using the above liquid crystal panel laminate.

The present invention can provide, for example, a composition having high deep-part curability and high heat-resistant yellowing. In addition, the present invention can be applied, for example, when a decorative board 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, or when a printed part is bonded. A curable resin composition can be provided in which a portion that is not exposed to visible light or ultraviolet rays from the front side by a light-shielding frame such as printing is cured from the front side by visible light or ultraviolet rays from the side surface. Moreover, according to this invention, the hardening of the curable resin composition under a light-shielding frame is possible, for example, and it has the effect of suppressing the hardening defect of an adhesive composition.

(A) The (meth) acrylate having a hydrogenated conjugated diene structure refers to a (meth) acrylate having a hydrogenated conjugated diene skeleton in the molecule. The hydrogenated conjugated diene refers to, for example, a compound obtained by hydrogenating a conjugated diene. The hydrogenated conjugated diene is preferably at least one selected from the group consisting of hydrogenated polybutadiene, hydrogenated polyisoprene and the like. (A) As (meth) acrylate which has a hydrogenated conjugated diene structure, the polyfunctional (meth) acrylate which has a 2 or more (meth) acryloyl group in the terminal or side chain in a molecule | numerator is preferable. The polyfunctional (meth) acrylate refers to a compound having two or more (meth) acryloyl groups. (A) The (meth) acrylate having a hydrogenated conjugated diene structure preferably does not have a conjugated diene structure (a conjugated diene structure in which a double bond is separated by one single bond). (A) As the (meth) acrylate having a hydrogenated conjugated diene structure, an oligomer is preferable.

(A) As the (meth) acrylate having a hydrogenated conjugated diene structure, urethane (meth) acrylate is preferable. Urethane (meth) acrylates include hydrogenated 1,2-polybutadiene terminal urethane (meth) acrylate (for example, “TEAI-1000” manufactured by Nippon Soda Co., Ltd.), hydrogenated 1,2-polybutadiene terminal urethane (meth) acrylate. (For example, “KRM8792”, “KRM8776” manufactured by Daicel Ornex Co., Ltd.) and the like.

Here, the urethane (meth) acrylate is a reaction between a polyol compound (hereinafter represented by X), an organic polyisocyanate compound (hereinafter represented by Y), and a hydroxy (meth) acrylate (hereinafter represented by Z) (for example, , A urethane (meth) acrylate having a urethane bond in the molecule, obtained by a polycondensation reaction).

Examples of the polyol compound (X) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene 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-diethyl-1,5-pentanediol, 2,2-butylethyl-1,3-propanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, poly At least polyhydric alcohols such as limethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, block or random copolymerization of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide Polyether polyol having one type of structure, a polycondensate of the polyhydric alcohol or polyether polyol and a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid Polyester polyols, caprolactone-modified polytetramethylene polyols and other caprolactone-modified polyols, polyolefin-based polyols, polycarbonate-based poly Lumpur, polybutadiene polyol, polyisoprene polyol, hydrogenated conjugated diene polyol (hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol and the like) polydiene polyols such as silicone polyols such as polydimethylsiloxane polyols and the like.
Among these, a polydiene-based polyol is preferable because it has a hydrogenated conjugated diene structure.

Among the polydiene-based polyols, a hydrogenated conjugated diene polyol is preferable because it has a hydrogenated conjugated diene structure. As the hydrogenated conjugated diene polyol, one or more selected from the group consisting of hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol is more preferable, and hydrogenated polybutadiene polyol (hydrogenated polybutadiene polyol) is most preferable. Of the hydrogenated polybutadiene polyols, hydrogenated 1,2-polybutadiene polyols are preferred.

The organic polyisocyanate compound (Y) is not particularly limited, but for example, aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates can be used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate. (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI) Polyisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), etc. Trimer compounds of polyisocyanates, reaction products of these polyisocyanates with polyols are preferably used. Among these, at least one selected from the group consisting of tolylene diisocyanate (TDI), hydrogenated xylylene diisocyanate (H-XDI), and isophorone diisocyanate (IPDI) is preferable. Tolylene diisocyanate (TDI), isophorone diisocyanate One or more selected from the group consisting of (IPDI) is more preferable, and isophorone diisocyanate (IPDI) is most preferable.

Hydroxy (meth) acrylate (Z) refers to (meth) acrylate having a hydroxyl group. Examples of the hydroxy (meth) acrylate (Z) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 2-hydroxybutyl (meth) acrylate, 2- Hydroxyethyl (meth) acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone Modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate Doors and the like. Of these, hydroxyalkyl (meth) acrylate is preferred. Among the hydroxyalkyl (meth) acrylates, one or more selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate are preferable. Hydroxyethyl (meth) acrylate is more preferred.

(A) The average molecular weight of the (meth) acrylate having a hydrogenated conjugated diene structure is preferably from 500 to 50,000, more preferably from 1,000 to 40,000 in terms of viscosity adjustment. Examples of the average molecular weight include weight average molecular weight and number average molecular weight. In the case of a weight average molecular weight, it is preferably 10,000 to 50,000, more preferably 15,000 to 40,000. In the case of the number average molecular weight, 500 to 5000 is preferable, and 1000 to 4000 is more preferable. The average molecular weight is obtained by preparing a calibration curve with commercially available standard polystyrene using GPC system (SC-8010 manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent under the following conditions.

Flow rate: 1.0 ml / min
Setting temperature: 40 ° C. Column configuration: “TSK guardcolumn MP (× L)” manufactured by Tosoh Corp. 6.0 mm ID × 4.0 cm 1 and “TSK-GELMULTIPORTHXL-M” 7.8 mm ID × 30.0 cm manufactured by Tosoh Corp. 2 (16,000 stages), 3 in total (32,000 theoretical stages as a whole),
Sample injection volume: 100 μl (sample solution concentration 1 mg / ml)
Liquid feeding pressure: 39 kg / cm ²
Detector: RI detector

(A) The amount of the (meth) acrylate oligomer having a hydrogenated conjugated diene structure is preferably 5 to 70 parts by mass, and preferably 15 to 60 parts by mass, out of a total of 100 parts by mass of (A), (B) and (D). Part is more preferable, and 30 to 50 parts by mass is most preferable. If it is 5 mass parts or more, favorable sclerosis | hardenability will be obtained, and if it is 70 mass parts or less, adhesiveness will not fall.

(B) Monofunctional (meth) acrylate refers to (meth) acrylate having one (meth) acryloyl group.

(B) Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy- 3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified ) Acrylate, phenol (ethylene oxide 2 mol modified) (meth) acrylate, phenol (ethylene oxide 4 mol modified) (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol (Ethylene oxide 4 mol modified) (meth) acrylate, nonylphenol (ethylene oxide 8 mol modified) (meth) acrylate, nonylphenol (propylene oxide 2.5 mol modified) (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, Ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylic Rate, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, (meth) acrylic acid dimer, β- (meth) acryloyloxyethyl hydrogen succinate, n- (meth) Examples include acryloyloxyalkyl hexahydrophthalimide, 2- (1,2-cyclohexadicarboximido) ethyl (meth) acrylate, and 2- (meth) acryloyloxyethyl succinic acid. (B) You may contain (meth) acrylic acid as monofunctional (meth) acrylate. One or more of these can be used. Among these, at least one selected from the group consisting of 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, n-octyl (meth) acrylate, and lauryl (meth) acrylate is preferable. N-octyl (meth) acrylate is most preferred.

(B) 1 to 95 parts by mass of n-octyl (meth) acrylate is preferably contained in 100 parts by mass of monofunctional (meth) acrylate, more preferably 20 to 90 parts by mass, and 40 to 70 parts by mass. It is most preferable to contain.

(B) Monofunctional (meth) acrylate used in combination with n-octyl (meth) acrylate includes 2-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, and lauryl (meth) acrylate One or more selected from the group is preferred, and 2-hydroxybutyl (meth) acrylate is more preferred.

(B) The amount of the monofunctional (meth) acrylate used is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, out of a total of 100 parts by mass of (A), (B) and (D), 15 Most preferred is ˜35 parts by weight. If it is 1 mass part or more, favorable adhesiveness will be obtained, and if it is 50 mass parts or less, there is no possibility that curability will fall.

(C) A radical photopolymerization initiator is used for sensitization with visible light or actinic light such as ultraviolet rays to promote photocuring of the composition. Photopolymerization initiators include benzophenone and derivatives thereof, benzyl and derivatives thereof, anthraquinone and derivatives thereof, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and diethoxy Acetophenone, acetophenone derivatives such as 4-t-butyltrichloroacetophenone, 2-dimethylaminoethyl benzoate, p-dimethylaminoethyl benzoate, diphenyl disulfide, thioxanthone and its derivatives, camphorquinone, 7,7-dimethyl-2,3-di Oxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-ca Boxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-di Camphorquinone derivatives such as oxobicyclo [2.2.1] heptane-1-carboxylic acid chloride, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl Α-aminoalkylphenone derivatives such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine Oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine Acyl, phosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone Α-hydroxy ketone derivatives such as oxy-phenyl-acetic acid 2- [2-o Seo-2-phenyl - acetoxy - ethoxy] - ethyl ester and oxy - phenyl - acetate tic acid 2- [2-hydroxy - ethoxy] - ethyl ester. One or more of these can be used. Among these, at least one selected from the group consisting of benzoin derivatives, acylphosphine oxide derivatives, and α-hydroxyketone derivatives is preferable because it is highly effective. From the group consisting of acylphosphine oxide derivatives and α-hydroxyketone derivatives. One or more selected are more preferable, and it is most preferable to use an acylphosphine oxide derivative and an α-hydroxyketone derivative in combination. When the acylphosphine oxide derivative and the α-hydroxyketone derivative are used in combination, the amount of the α-hydroxyketone derivative used is preferably 100 to 300 parts by mass, and 150 to 250 parts by mass with respect to 100 parts by mass of the acylphosphine oxide derivative. More preferred. Of the benzoin derivatives, benzyl dimethyl ketal is preferred. Of the α-hydroxyketone derivatives, 1-hydroxycyclohexyl phenyl ketone is preferred. Of the acylphosphine oxide derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferred.

(C) The amount of the photopolymerization initiator used is preferably 0.001 to 10 parts by mass, and 0.01 to 8 parts by mass with respect to 100 parts by mass in total of (A), (B) and (D). More preferred is 0.1 to 5 parts by mass. If it is 0.001 mass part or more, favorable adhesiveness will be obtained, and if it is 10 mass parts or less, favorable deep part curability will be obtained.

(D) A plasticizer is a compound used in order to adjust the softness | flexibility of hardened | cured material. (D) Among plasticizers, the boiling point is preferably 150 ° C. or higher. Plasticizers include monoester compounds that do not have (meth) acryloyl groups, polyester compounds that do not have (meth) acryloyl groups, monoether compounds that do not have (meth) acryloyl groups, and those that have (meth) acryloyl groups. Selected from the group consisting of non-polyether compounds, monocarbonate compounds having no (meth) acryloyl group, polycarbonate compounds having no (meth) acryloyl group, and hydrogenated conjugated diene compounds having no (meth) acryloyl group One or more selected from the above are preferred. One or more of these can be used.

Monoester compounds not having (meth) acryloyl groups or polyester compounds not having (meth) acryloyl groups include isostearyl isostearate, isocetyl isostearate, isopropyl isostearate, 2-hexyldecyl isostearate, isostearic acid 2 -Octyldodecyl, isopropyl myristate, octyldodecyl myristate, isocetyl myristate, isopropyl myristate, isostearyl lactate, polyglyceryl monoisostearate, hexyl laurate, hexyl decyl laurate, isononyl isononanoate, 2-ethylhexyl isononanoate, isononane Isodecyl acid, isotridecyl isononanoate, nonyl isononanoate, cetostearyl isononanoate, decyl oleate, olei Oleyl acid, cetyl palmitate, polyglyceryl diisostearate, polyglyceryl triisostearate, polyglyceryl tetraisostearate, di-2-ethylhexyl succinate, ethyl olive oleate, isocetyl stearate, isopropyl palmitate, diisopropyl dimer, diisostearyl dimer , Dicapryl carbonate, ethyl linoleate, isopropyl linoleate, diisostearyl malate, neopentyl glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, (2-hexyldecanoic acid / sebacic acid) diglyceryl oligoester, (adipine Acid, 2-ethylhexanoic acid, stearic acid) diglyceryl oligoester, hexyldecyl dimethyloctanoate, octanoate dimethyloctanoate Ludodecyl, caprylic / capric acid palm oil alkyl, glyceryl tri (capryl / caprylate), glyceryl tricaprylate, glyceryl tri (capryl / caprin / myristin / stearate), glyceryl 2-ethylhexanoate, glyceryl triisostearate, tripalmitin Glyceryl acid, triiso long-chain fatty acid (C10-37, C is carbon number) glyceryl, glyceryl tripalmitate, tetra-2-ethylhexanoic acid pentaerythritol, tetra-2-isostearic acid pentaerythritol, dimethyl oxalate, Diethyl oxalate, dipropyl oxalate, diisopropyl oxalate, dibutyl oxalate, dihexyl oxalate, dioctyl oxalate, diisopropyl malonate, dibutyl malonate, diethyl succinate, dipro succinate Pill, diisopropyl succinate, dibutyl succinate, di-t-butyl succinate, bis (2-ethylhexyl) succinate, bis (2-ethoxyethyl) succinate, diethyl glutarate, dibutyl glutarate, dimethyl adipate, adipic acid Diethyl, dipropyl adipate, diisopropyl adipate, dibutyl adipate, di-t-butyl adipate, bis (2-ethylhexyl) adipate, dioctyl adipate, dimethyl pimelate, diethyl pimelate, diisopropyl pimelate, dibutyl pimelate, Dimethyl suberate, Diethyl suberate, Dipropyl suberate, Diisopropyl suberate, Dimethyl azelate, Diethyl azelate, Dipropyl azelate, Diisopropyl azelate, Dibutyl azelate, Dimethyl bacinate, diethyl sebacate, dipropyl sebacate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, dioctyl sebacate, tributyl acetyl citrate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, phthalate Dihexyl acid, diheptyl phthalate, dioctyl phthalate, bis (2-ethylhexyl) phthalate, diisononyl phthalate, diisotridecyl phthalate, dipentadecyl phthalate, dioctyl terephthalate, diisononyl isophthalate, decyl toluate, bis (2) camphorate Ethylhexyl), 2-ethylhexyl cyclohexyl carboxylate, diisobutyl fumarate, diisobutyl maleate, triglyceride caproate, benzoic acid -Ethylhexyl, dipropylene glycol dibenzoate, pentaisolitria tetraisostearate, pentaerythritol 2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, trimethylolpropane triisostearate, glyceryl triisopalmitate, tri Examples include glyceryl-2-ethylhexanoate, trimethylolpropane trioctanoate, and tri (capryl / capric acid) glycerin. One or more of these can be used. In these, the polyester compound which does not have a (meth) acryloyl group is preferable. Of the polyester compounds having no (meth) acryloyl group, polyester compounds having an alkyl group having 8 to 22 carbon atoms are preferred. Among the polyester compounds having an alkyl group having 8 to 22 carbon atoms, one or more selected from the group consisting of polyglyceryl triisostearate and dioctyl sebacate are preferred.

As a monoether compound having no (meth) acryloyl group or a polyether compound having no (meth) acryloyl group, didodecyl ether, ditetradecyl ether, dihexadecyl ether, dioctadecyl ether, dieicosyl ether, Didocosyl ether, ditetracosyl ether, dihexacosyl ether, dioctacosyl ether, ditriacontyl ether, didotriacontyl ether and mixtures thereof, as well as cyclic ethers to polyhydric alcohols, sugars, alkanolamines and other initiators, Particularly, polyethers obtained by adding alkylene oxides such as propylene oxide and ethylene oxide can be mentioned.

Monocarbonate compounds not having (meth) acryloyl groups or polycarbonate compounds not having (meth) acryloyl groups include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, diphenyl carbonate, dinaphthyl carbonate , Dimethyl carbonate, diethyl carbonate and the like.

Examples of hydrogenated conjugated diene compounds having no (meth) acryloyl group include hydrogenated 1,2-polybutadiene, hydrogenated 1,4-polybutadiene, terminal hydroxylated hydrogenated 1,2-polybutadiene, and terminal hydroxylated hydrogenated 1,4. -Polybutadiene and the like. Of these, hydrogenated 1,2-polybutadiene is preferred.

Examples of the polyisoprene compound having no (meth) acryloyl group include polyisoprene, a maleic anhydride adduct of an isoprene polymer, a maleic anhydride adduct and a methanol adduct of an isoprene polymer, and the like.

Examples of the polyolefin compound having no (meth) acryloyl group include ethylene-α olefin co-oligomer and polybutene.

(D) One or more selected from the group consisting of a polyester compound not having a (meth) acryloyl group and a hydrogenated conjugated diene compound not having a (meth) acryloyl group in terms of great effect among plasticizers Is preferred, and a polyester compound having no (meth) acryloyl group is more preferred. Of the polyester compounds having no (meth) acryloyl group, polyester compounds having an alkyl group having 8 to 22 carbon atoms are preferred.

(D) The amount of plasticizer used is preferably 1 to 80 parts by weight, more preferably 15 to 75 parts by weight, and more preferably 30 to 50 parts by weight in a total of 100 parts by weight of (A), (B) and (D). Is most preferred. If it is 1 mass part or more, favorable adhesiveness will be obtained, and if it is 80 mass parts or less, curability will not fall.

(E) Antioxidants are used for improving storage stability and heat resistance of cured products. (E) Antioxidants include methylhydroquinone, hydroquinone, 2,2-methylene-bis (4-methyl-6-tertiarybutylphenol), 6-tert-butyl-4- [3-[(2,4,4 8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] propyl] -2-methylphenol, catechol, hydroquinone monomethyl ether, monotercia Libutylbutylquinone, 2,5-ditertiarybutylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertiarybutyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butyl Catechol, 2-butyl-4-hydroxyanisole and 2,6 Ditertiary butyl -p- cresol. One or more of these can be used. Among these, 6-tert-butyl-4- [3-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl) oxy] propyl] -2-methylphenol is preferred.

(E) The amount of the antioxidant used is preferably 0.001 to 0.5 parts by mass, and preferably 0.005 to 0.1 with respect to 100 parts by mass in total of (A), (B) and (D). Part by mass is more preferable. If it is 0.001 mass part or more, the coloring and discoloration by the heat | fever of a curable resin composition are small, and if it is 0.5 mass part or less, favorable deep part sclerosis | hardenability will be obtained.

The composition of the present invention includes various types of elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, solvents such as polar organic solvents, fillers, reinforcements, and the like, as long as the object of the present invention is not impaired. Additives such as materials, thickeners, dyes, pigments, flame retardants, silane coupling agents and surfactants may be used.

The cured product bonded with the composition of the present invention can be reworked (reused) after being completely cured. The rework method is not particularly limited, but the adherends are disassembled by applying a load of 0.01 to 100 N between the one or two kinds of adherends bonded together, and the adherend after disassembly The body can be reused.

The composition of the present invention is, for example, a photocurable resin composition, and can be used as an adhesive composition or a coating composition.

In the present invention, a composite can be produced by bonding or covering an adherend with a cured product of an adhesive composition or a coating composition. The various materials of the adherend are preferably at least one selected from the group consisting of triacetylcellulose, fluoropolymer, polyester, polycarbonate, polyolefin, glass, and metal. Polyester, glass, polyolefin, triacetylcellulose, fluoropolymer One or more selected from the group consisting of polycarbonate is more preferred. As the polyester, polyethylene terephthalate is preferable. As the polyolefin, a cycloolefin polymer is preferable.

The composition of the present invention can be cured at a depth of 3 mm or more when irradiated with 1000 mJ / cm ^{2 of} visible light or ultraviolet light at a wavelength of 365 nm, for example. The composition of the present invention, for example, after irradiating visible light or ultraviolet light from the front side of the adherend, irradiates the side where the visible light or ultraviolet light does not transmit from the side surface of the adherend, and bonds the adherend together. Is possible.

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

(Experimental example)
Unless otherwise stated, experiments were conducted at 23 ° C. A curable resin composition having the composition shown in Table 1 was prepared and evaluated.
The following compounds were selected as each component in the curable resin composition described in the experimental examples.
However, KRM-8792 and KRM-8776 in the table indicate the amount of urethane acrylate contained in “KRM-8772” and “KRM-8776” manufactured by Daicel Cytec. “NOAA” in the table indicates the amount of n-octyl acrylate contained in “KRM-8792” and “KRM-8776” manufactured by Daicel Cytec. When “KRM-8792” and “KRM-8776” manufactured by Daicel Cytec were not used, n-octyl acrylate manufactured by Osaka Organic Chemical Co., Ltd. was used.

The following compounds were selected as the (A) component (meth) acrylate having a hydrogenated conjugated diene structure.

(A-1) Hydrogenated 1,2-polybutadiene terminal urethane (meth) acrylate (“KRM-8792” manufactured by Daicel Cytec, the structure is as follows, the polyol compound is a hydrogenated conjugated diene polyol, hydrogenated 1, 2-polybutadiene polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, polystyrene equivalent weight average molecular weight of 31000, but contains 20% by mass of n-octyl acrylate as a diluting monomer)

(A-2) Hydrogenated 1,2-polybutadiene terminal urethane (meth) acrylate (“KRM-8777” manufactured by Daicel Cytec, the structure is as follows, and the polyol compound is a hydrogenated 1,2-polybutadiene hydrogenated conjugated diene polyol. 2-polybutadiene polyol, organic polyisocyanate compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, polystyrene equivalent weight average molecular weight of 19000, but contains 30% by mass of n-octyl acrylate as a diluting monomer)

(A-3) Hydrogenated 1,2-polybutadiene terminal urethane (meth) acrylate (“TEAI-1000” manufactured by Nippon Soda Co., Ltd., the structure is as follows, and the polyol compound is a hydrogenated 1,2-polybutadiene polyol) Polybutadiene polyol, organic polyisocyanate compound is tolylene diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, polystyrene equivalent number average molecular weight is 1300)

(Comparative A-4) 1,2-polybutadiene terminal urethane (meth) acrylate (“TE-2000” manufactured by Nippon Soda Co., Ltd., the structure is as follows, the polyol compound is 1,2-polybutadiene polyol, which is a polybutadiene polyol, (Organic polyisocyanate compound is tolylene diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, weight average molecular weight 9200 in terms of polystyrene by GPC)

(Comparative A-5) Isoprene oligomer (“UC-102” manufactured by Kuraray Co., Ltd., number average molecular weight 17,000 in terms of polystyrene by GPC, esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate, formula In (1), Y is an ethylene group, and R is a methyl group)

(Comparative A-6) Polyester urethane acrylate oligomer (“KHP-11” manufactured by Negami Kogyo Co., Ltd., the structure is as follows, the polyol compound is a polyester polyol which is a condensate of 1,4-butanediol and adipic acid, , A compound having a polyester polyol which is a condensate of ethylene glycol and adipic acid (polyester polyol which is a condensate of 1,4-butanediol and adipic acid: a polyester polyol which is a condensate of ethylene glycol and adipic acid = 2: 3 (molar ratio)), the organic polyisocyanate compound is isophorone diisocyanate, the hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, and the weight average molecular weight in terms of polystyrene by GPC is 25000)

The following compounds were selected as the water monofunctional (meth) acrylate of the component (B).
(B-1) 2-hydroxybutyl acrylate (“Light acrylate HOB-A” manufactured by Kyoeisha Chemical Co., Ltd.)
(B-2) 2-Methacryloyloxyethyl succinic acid (“Light Ester HO-MS” manufactured by Kyoeisha Chemical Co., hereinafter abbreviated as HO-MS)
(B-3) Lauryl acrylate (“LA” manufactured by Osaka Organic Chemical Company, hereinafter abbreviated as LA)
(B-4) n-octyl acrylate (Osaka Organic Chemical Co., Ltd., hereinafter abbreviated as NOAA)

The following compounds were selected as the radical photopolymerization initiator of component (C).
(C-1) 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by BASF, hereinafter abbreviated as I-184)
(C-2) 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin TPO” manufactured by BASF, hereinafter abbreviated as TPO)

The following compounds were selected as the plasticizer for component (D).
(D-1) Polyglyceryl triisostearate (Nisshin Oilio “Cosmol 43V”, hereinafter abbreviated as 43V)
(D-2) Dioctyl sebacate (“DOS” manufactured by Toyokuni Oil)
(D-3) Hydrogenated 1,2-polybutadiene (“BI-2000” manufactured by Nippon Soda Co., Ltd.)
(Comparison D-4) 1,2-polybutadiene (not hydrogenated, “B-2000” manufactured by Nippon Soda Co., Ltd.)

The following compounds were selected as the antioxidant for component (E).
(E-1) 6-tert-butyl-4- [3-[(2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl) oxy] propyl] -2-methylphenol (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd., hereinafter abbreviated as GP)

Various physical properties were measured as follows.

[Photocurability] Measured at a temperature of 23 ° C. Regarding photocurability, a curable resin composition was applied to a surface of Tempax glass (width 25 mm × length 25 mm × thickness 2 mm) to a thickness of 0.1 mm. Thereafter, using a curing device manufactured by Fusion Corporation using an electrodeless discharge lamp, UV light having a wavelength of 365 nm was irradiated and cured under the condition of an integrated light quantity of 2000 mJ / cm ² .
The curing rate was calculated by the following formula using FT-IR. For the absorption spectrum of carbon-carbon double bond, a peak around 1600 cm ⁻¹ was used.
(Curing rate) = 100- (Intensity of absorption spectrum of carbon-carbon double bond after curing) / (Intensity of absorption spectrum of carbon-carbon double bond before curing) × 100 (%)

[Curing Shrinkage] The specific gravity bottle was filled with the curable resin composition, and the mass in the air and the mass in pure water were measured to calculate the liquid specific gravity. Furthermore, the curable resin composition is cured by the method described in [Photocurability] to produce a cured product having a width of 25 mm × length of 25 mm × thickness of 2 mm, and the mass in the air and the mass in pure water are measured. It measured and computed hardened | cured material specific gravity. The cure shrinkage was calculated from the ratio of liquid specific gravity and cured product specific gravity.
Curing shrinkage = ((cured product specific gravity−liquid specific gravity) / (cured product specific gravity)) × 100 (%)

[Depth Curability] A 20 mm long black tube with a diameter of 5 mmφ was filled with the curable resin composition, and 100 mW / cm ² (365 nm) of light was applied from the top with black light for 10 seconds (1000 mJ / cm ² ) Irradiation. Then, the hardened | cured material was taken out from the black tube, the uncured part was removed, and the thickness of the hardened part was measured with the micrometer.

[Polyethylene terephthalate (PET) adhesion evaluation (peel adhesion strength between polyethylene terephthalate test pieces)] Test pieces (width 50 mm × length 10 mm) of biaxially stretched PET film (Lumirror T60, average thickness 190 μm, manufactured by Toray Industries, Inc.) × thickness 0.19 mm) were bonded using a curable resin composition as an adhesive composition, with an adhesive layer thickness of 30 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Glass Adhesion Evaluation (Tensile Adhesive Strength Between Heat-Resistant Glass Test Pieces)] Heat-resistant glass test pieces (width 25 mm × length 25 mm × thickness 2.0 mm) are 80 μm thick × 11.5 mm wide × 25 mm long. The Teflon (registered trademark) tape was used as a spacer, and the curable resin composition was used as an adhesive composition for adhesion (adhesion area 3 cm ² ). The light irradiation conditions followed the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on both sides of the test piece, and a galvanized steel sheet (width 100 mm × length 25 mm × A thickness of 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered. After the curing, using the test piece bonded with the adhesive composition, the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Cycloolefin polymer (COP) adhesion evaluation (peel adhesion strength between cycloolefin polymer test pieces)] COP film (ZEONOR, average thickness 40 μm, manufactured by Nippon Zeon Co., Ltd.) test piece (width 50 mm × length 10 mm × A thickness of 0.04 mm was bonded to each other using a curable resin composition as an adhesive composition, with an adhesive layer thickness of 10 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Triacetylcellulose Adhesion Evaluation (Peeling Adhesive Strength Between Triacetylcellulose Test Pieces)] Triacetylcellulose (TAC) film (average thickness 40 μm, manufactured by Fuji Film) test piece (width 50 mm × length 10 mm × A thickness of 0.04 mm was bonded to each other using a curable resin composition as an adhesive composition, with an adhesive layer thickness of 10 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Evaluation of Fluoropolymer Adhesion (Peeling Adhesive Strength Between Fluoropolymer Specimens)] PVDF (Polyvinylidene fluoride) film (average thickness 40 μm, “DX film” manufactured by Denki Kagaku Kogyo Co., Ltd.) (width 50 mm × length) 10 mm in thickness x 0.04 mm in thickness) were bonded using a curable resin composition as an adhesive composition, with an adhesive layer thickness of 10 μm and an adhesive area of 40 mm long × 10 mm wide. After curing by light irradiation, by pulling the two end portions of the film that are not in close contact with the test piece bonded with the adhesive composition, the portions where the films are in close contact are peeled off, and the initial 180 ° peeling is performed. The bond strength was measured. The light irradiation conditions followed the method described in [Photocurability]. The peel adhesive strength (unit: N / cm) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 50 mm / min.

[Polycarbonate Adhesion Evaluation (Tensile Adhesive Strength Between Polycarbonate Specimens)] Polycarbonate (“Panlite” manufactured by Teijin Limited) Specimens (width 25 mm × length 25 mm × thickness 2.0 mm), thickness 80 μm × width A Teflon (registered trademark) tape of 12.5 mm × length 25 mm was used as a spacer and a curable resin composition was used as an adhesive composition (adhesion area 3 cm ² ). The light irradiation conditions followed the method described in [Photocurability]. After the adhesive composition was cured under the above conditions, an adhesive composition “G-55” manufactured by Denki Kagaku Kogyo Co., Ltd. was used on both sides of the test piece, and a galvanized steel sheet (width 100 mm × length 25 mm × A thickness of 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was adhered. After the curing, using the test piece bonded with the adhesive composition, the galvanized steel sheet was chucked, and the initial tensile shear bond strength was measured. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Heat and heat resistance evaluation (tensile bond strength between heat-resistant glass test pieces after exposure to high temperature and high humidity)] Tempax (registered trademark) glass (width 25 mm × length 25 mm × thickness 2 mm) and curable resin composition Was used as an adhesive composition, and was adhered and cured with an adhesive layer thickness of 100 μm and an adhesive area of 1.0 cm ² . The light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was exposed to an environment of 85 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. The tensile shear bond strength was measured using the test piece after exposure. The tensile shear bond strength (unit: MPa) was measured using a tensile tester at a temperature of 23 ° C. and a humidity of 50% at a tensile speed of 10 mm / min.

[Moisture and heat resistance evaluation (appearance observation (yellowing degree))] The appearance of the adhesion site was observed to determine whether it was yellowing or not. Tempax (registered trademark) glass (width 25 mm x length 25 mm x thickness 2 mm) using a curable resin composition as an adhesive composition, with an adhesive layer thickness of 1 mm and an adhesive area of 1.0 cm ² Glued and cured. The light irradiation conditions followed the method described in [Photocurability]. After curing, the test piece bonded with the adhesive composition was exposed to an environment of 85 ° C. and 85% relative humidity for 1000 hours using a constant temperature and humidity chamber. After the exposure, the Δb value of the test piece adhered with the adhesive composition was measured with a color measuring device (“UV-VISABLE SPECTROPOHOTOMETER” manufactured by SHIMADZU) to determine the degree of yellowing (after heat and humidity resistance). Measure Δb value before exposure. Yellowness was assumed (initial).

The present invention has the following effects, for example. In the present invention, the curable resin composition under the light shielding frame can be cured to a deep part by irradiating light from an oblique direction or a lateral direction of the light shielding frame. In the present invention, even under a light-shielding frame, it is possible to cure to a deep portion with weak light (for example, light having an integrated light quantity of 1000 to 3000 mJ / cm ² ). In the present invention, for example, when a visible ray or an ultraviolet ray is irradiated with 1000 mJ / cm ² at a wavelength of 365 nm, deep curing of 3 mm or more is possible.

The present invention has a small curing shrinkage rate and does not cause changes in surface accuracy such as dimensional changes and warping. The present invention can withstand the expansion and contraction of the adherend in the high temperature reliability test. In the present invention, problems such as coloring after the heat resistance test, discoloration, and strength reduction after the moisture resistance test do not occur.

In the present invention, for example, in the evaluation of moist heat resistance, the initial Δb value in a cured product having a thickness of 1 mm is 0.1 or less, and the Δb value after standing at 85 ° C. for 500 hours is 0.5 or less. .

When the amount of the radical photopolymerization initiator used was large, the effect of improving the adhesiveness was small in the wet heat resistance evaluation (Experimental Example 8). When (meth) acrylates other than those of the present invention were used, yellowing occurred in the evaluation of heat and moisture resistance, and the effects of the present invention were not shown (Experimental Examples 9 to 11). For example, when (meth) acrylate having a conjugated diene structure without hydrogenation was used, yellowing was observed in the wet heat resistance evaluation, and the effects of the present invention were not shown (Experimental Examples 9 to 10). For example, when (meth) acrylate having no hydrogenated conjugated diene structure was used, it was yellowed in the wet heat resistance evaluation, and the effect of the present invention was not shown (Experimental Example 11). When the plasticizer was not used, the adhesiveness was small in the wet heat resistance evaluation, and the effect of the present invention was not shown (Experimental Example 12). When the antioxidant was not used, in the heat and humidity resistance evaluation, it turned yellow and did not show the effect of the present invention (Experimental Example 13). When non-hydrogenated polybutadiene was used as the plasticizer, the adhesiveness was small and yellowing occurred in the wet heat resistance evaluation, and the effect of the present invention was not shown (Experimental Example 14). Therefore, it became clear that not all of the known plasticizers show the effects of the present invention.

The composition of the present invention can be used for an adhesive composition for a touch panel laminate or a liquid crystal panel laminate. The touch panel laminate and the liquid crystal panel laminate of the present invention can be used as a display. The composition of the present invention can improve curability even when a transparent part or a translucent part is bonded.

Claims

A composition containing the following (A) to (E),
(A) (meth) acrylate having hydrogenated conjugated diene structure (B) monofunctional (meth) acrylate (C) radical photopolymerization initiator (D) plasticizer (E) antioxidant (D) plasticizer is ( A monoester compound not having a (meth) acryloyl group, a polyester compound not having a (meth) acryloyl group, a monoether compound having no (meth) acryloyl group, a polyether compound not having a (meth) acryloyl group, It is at least one selected from the group consisting of a monocarbonate compound having no (meth) acryloyl group, a polycarbonate compound having no (meth) acryloyl group, and a hydrogenated conjugated diene compound having no (meth) acryloyl group. Composition.
(A) The composition according to claim 1, wherein the (meth) acrylate having a hydrogenated conjugated diene structure is a polyfunctional (meth) acrylate.
(A) The composition according to claim 1 or 2, wherein the (meth) acrylate having a hydrogenated conjugated diene structure is urethane (meth) acrylate.
4. The composition according to claim 1, wherein the molecular weight of (A) (meth) acrylate having a hydrogenated conjugated diene structure is 500 to 50,000.
5. The composition according to claim 1, wherein the photopolymerization initiator (C) is at least one selected from the group consisting of benzoin derivatives, acylphosphine oxide derivatives, and α-hydroxyketone derivatives.
(D) From the group which a plasticizer consists of a monoester compound which does not have a (meth) acryloyl group, a polyester compound which does not have a (meth) acryloyl group, and a hydrogenated conjugated diene compound which does not have a (meth) acryloyl group 6. The composition according to claim 1, wherein the composition is one or more selected.
7. The composition according to claim 1, wherein the plasticizer is a polyester compound having no (meth) acryloyl group and having an alkyl group having 8 to 22 carbon atoms.
Of the total 100 parts by mass of (A), (B) and (D), the amount of component (A) used is 5 to 70 parts by mass, the amount of component (B) used is 1 to 50 parts by mass, and component (D) The composition according to any one of claims 1 to 7, wherein the amount of is 1 to 80 parts by mass.
The amount of component (C) used is 0.001 to 10 parts by weight and the amount of component (E) used is 0.001 to 5 parts by weight with respect to a total of 100 parts by weight of (A), (B) and (D). The composition according to one of claims 1 to 8, which is a part.
A photocurable resin composition comprising the composition according to any one of claims 1 to 9.
An adhesive composition comprising the composition according to any one of claims 1 to 9.
A coating composition comprising the composition according to any one of claims 1 to 9.
A cured product of the composition according to any one of claims 1 to 9.
A composite in which an adherend is coated or bonded with the cured body according to claim 13.
The composite_body | complex which the to-be-adhered body of Claim 14 is 1 or more types chosen from the group which consists of a triacetyl cellulose, a fluorine-type polymer, polyester, a polycarbonate, polyolefin, glass, and a metal.
A composite in which at least one of the adherends according to claim 14 includes a portion having a light transmittance of 0.1 or less.
A touch panel laminate in which an adherend is bonded with the composition according to any one of claims 1 to 9.
A liquid crystal panel laminate in which an adherend is bonded with the composition according to any one of claims 1 to 9.
A display using the touch panel laminate according to claim 17.
A display using the liquid crystal panel laminate according to claim 18.