KR102532767B1 - composition - Google Patents

Abstract

A composition that maintains adhesion to a surface even after curing is provided. A composition containing the following (P) and (C) to (E). (P) a polymerizable vinyl compound, (C) a photopolymerization initiator, (D) a dicarboxylic acid diester, and (E) a tackifier. An adhesive composition comprising the above composition. (F) You may further contain a thiol and (G) antioxidant. (P) The polymerizable vinyl compound preferably contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate.

Description

composition

The present invention relates to a composition.

BACKGROUND OF THE INVENTION Touch panels mounted on display bodies such as LCDs (liquid crystal displays) include resistive, capacitance, electromagnetic induction, optical, and the like. In some cases, decorative plates for improving appearance design or icon sheets for specifying touch positions are attached to the surfaces of these touch panels. A 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, an adhesive was used for the alignment of a decorative board and a touch panel, the alignment of an icon sheet and a touch panel, and the alignment of a transparent substrate and a transparent board.

In particular, as a typical method of attaching each member to another with a photocurable adhesive composition, after attaching the adhesive to both adherends, the adhesive is cured by irradiating visible light or ultraviolet rays in the front direction of the display to cure both adherends. There is a way to attach it.

Patent Document 1 discloses (A) a (meth)acrylate oligomer having polyisoprene, polybutadiene or polyurethane as a backbone, (B) a softening component, (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 photocurable resin composition comprising a (meth)acrylate monomer selected from tetrahydrofurfuryl (meth)acrylate is described. However, Patent Document 1 does not describe the composition of the present invention, particularly the composition containing the dicarboxylic acid diester (D).

In recent years, the glass of displays such as LCDs has become thinner. As the glass becomes thinner, the LCD becomes more susceptible to deformation due to external stress. When a display body such as an LCD using thin glass and an optical function material such as an acrylic plate or a polycarbonate plate are bonded together, a heat resistance test is performed due to the difference in linear expansion between glass and acrylic or deformation during molding of a plastic molding material such as an acrylic plate or polycarbonate. However, in the moisture resistance test, relief of molding deformation or moisture absorption/drying occurs, and surface precision changes such as dimensional change or warpage occur.

Patent Document 2 describes a cured resin containing urethane-based (meth)acrylate, polybutadiene-based (meth)acrylate, and isoprene-based (meth)acrylate as components. However, when trying to suppress this deformation by the method of patent document 2, the adhesive surface peeled off, the LCD cracked, or the LCD displayed the subject that there was unevenness.

As a solution to the problem of Patent Document 2, a UV curable resin such as Patent Document 3 is described. Since Patent Document 3 is a highly elastic resin based on a rigid skeleton monomer such as isobornyl (meth)acrylate, it could not withstand expansion and contraction of the adherend in a high-temperature reliability test and could cause peeling. The present invention has a design that withstands expansion and contraction of an adherend in a high-temperature reliability test without using a rigid backbone monomer such as isobornyl (meth)acrylate.

Flexible enough to follow the deformation of the adherend in a heated atmosphere that assumes the use environment for applications such as bonding between decorative board and touch panel, bonding between icon sheet and touch panel, and bonding between transparent substrate and transparent board. It is said that it is desirable to have.

On the other hand, since it has flexibility enough to follow the deformation of the adherend in a heated atmosphere assuming a use environment, it is also clear that there are problems such as discoloration and discoloration after the heat resistance test and decrease in strength after the moisture resistance test. As a solution to the above problem, Patent Document 4 contains at least one oligomer selected from the group consisting of polyisoprene (meth) acrylate oligomer, polybutadiene (meth) acrylate oligomer and polyurethane (meth) acrylate oligomer and hindadamine. A photocurable adhesive composition is described. However, Patent Document 4 does not describe the composition of the present invention, particularly the composition containing (D) a dicarboxylic acid diester.

Patent Document 5 describes a photocurable composition comprising a specific sulfur-containing (meth)acrylate compound or a radical reactive composition containing the same, a UV absorber, a photopolymerization initiator, and an antioxidant. However, Patent Document 5 does not describe the composition of the present invention, particularly the composition containing (D) a dicarboxylic acid diester.

In Patent Document 6, urethane (meth)acrylate (A) having two or more functional groups having an unsaturated double bond, a monomer (B) having one functional group having an unsaturated double bond, a photopolymerization initiator (C), and two or more thiol groups As a composition containing a polythiol compound (D), a photocurable transparent adhesive composition in which the weight ratio of urethane (meth)acrylate (A) in the composition is 2% to 30% by weight is described. However, Patent Document 6 does not describe the composition of the present invention, particularly the composition containing (D) a dicarboxylic acid diester.

As a method of maintaining the viscous adhesiveness of the surface even after the adhesive composition is cured, there is a method of adding a tackifier. Patent Document 7 describes an acrylic pressure-sensitive adhesive containing a hydrogenated rosin resin tackifier, an aliphatic completely saturated hydrocarbon resin tackifier, or a hydrogenated terpene resin tackifier as a tackifier. However, Patent Document 7 does not describe the composition of the present invention, particularly the composition containing the dicarboxylic acid diester (D).

Patent Document 1: International Publication No. 2010/027041 Patent Document 2: Japanese Unexamined Patent Publication No. 2004-77887 Patent Document 3: Japanese Unexamined Patent Publication No. 64-85209 Patent Document 4: Japanese Unexamined Patent Publication No. 2012-46658 Patent Document 5: Japanese Unexamined Patent Publication No. 2002-097224 Patent Document 6: Japanese Unexamined Patent Publication No. 2009-001655 Patent Document 7: Japanese Unexamined Patent Publication No. 2006-225531

In the present invention, for example, when bonding decorative plates and icon sheets used for display bodies such as touch panels, when bonding transparent substrates and transparent substrates, and when bonding display bodies and optical function materials, the adhesive surface is peeled off. Provided is a curable resin composition that solves the prior art problems of cracking or cracking of glass of a display body, discoloration after heat resistance and moisture resistance tests, and reduction in strength.

That is, the present invention is a composition containing the following (P), (C) to (E),

(P) polymerizable vinyl compound

(C) photopolymerization initiator

(D) dicarboxylic acid diesters

(E) tackifier

(D) is the above composition wherein dicarboxylic acid diester represented by formula (1);

(Wherein, R ₁ and R ₂ are an alkyl group having 1 to 18 carbon atoms, R ₃ is an alkylene group having 1 to 10 carbon atoms, and R ₁ and R ₂ may be the same or different);

(D) is the composition wherein (D) is a sebacic acid diester, (F) is the composition further contains a thiol, (F) is the composition wherein the thiol is a polythiol, and (G) is the composition further contains an antioxidant; , The above composition in which the (P) polymerizable vinyl compound contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, and (A) polyfunctional (meth)acrylate is urethane (Meth) acrylate composition, (B) monofunctional (meth) acrylate is a group consisting of phenolalkylene oxide-modified (meth) acrylate, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate (D) is the composition in which the amount of (D) is 5 to 50 parts by mass based on the total of 100 parts by mass of (P) and (D), and (E) the tackifier is a fully hydrogenated rosin resin, an aromatic The above composition is at least one of the group consisting of a modified terpene resin and a terpene phenol resin, a curable resin composition comprising the above composition, an adhesive composition comprising the above composition, and a cured body of the adhesive composition, wherein an adherend is coated or A touch panel in which the adherend is at least one selected from the group consisting of triacetyl cellulose, fluorine-based polymer, polyester, polycarbonate, polyolefin, glass, and metal, and the adherend is bonded together by the adhesive composition. A laminate, a liquid crystal panel laminate in which adherends are bonded together by the adhesive composition, a display using the touch panel laminate, a display using the liquid crystal panel laminate, and the (P) polymerizable vinyl compound ( A) contains polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, (A) polyfunctional (meth)acrylate is urethane (meth)acrylate, (B) monofunctional (meth)acrylate ) acrylate is at least one selected from the group consisting of phenolalkylene oxide-modified (meth)acrylates, alkyl (meth)acrylates, and hydroxyalkyl (meth)acrylates, (A) polyfunctional (meth)acrylic The amount of the rate used is 10 to 90 parts by mass out of 100 parts by mass of the total amount of (A), (B) and (D), and the amount of the monofunctional (meth)acrylate (B) is (A), (B) and ( 3 to 80 parts by mass in 100 parts by mass of the total amount of D), (D) the amount of dicarboxylic acid diester used is 1 to 50 parts by mass with respect to 100 parts by mass in total of (P) and (D), (E) The tackifier is at least one of the group consisting of a fully hydrogenated rosin resin, an aromatic modified terpene resin, and a terpene phenol resin, and (E) the amount of tackifier used is 1 to 100 parts by mass in total of (P) and (D) It is 40 parts by mass, and further contains 0.1 to 10 parts by mass of (F) polythiol with respect to 100 parts by mass of the total of (P) and (D), and further contains (G) antioxidant.

The present invention can provide a composition that maintains adhesion to a surface even after curing, for example.

(P) As a polymeric vinyl compound, (meth)acrylate is preferable, and what contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate is more preferable. (A) Multifunctional (meth)acrylate refers to (meth)acrylate having two or more (meth)acryloyl groups. Examples of the polyfunctional (meth)acrylate include oligomers/polymers of polyfunctional (meth)acrylates in which two or more (meth)acryloyls are formed at the oligomer/polymer terminals or side chains.

As the oligomer/polymer of the polyfunctional (meth)acrylate, 1,2-polybutadiene terminal urethane (meth)acrylate, 1,2-hydrogenated polybutadiene terminal urethane (meth)acrylate (for example, Nippon Soda Co., Ltd. "TEAI -1000”), 1,4-polybutadiene terminal urethane (meth)acrylate, polyisoprene terminal (meth)acrylate, polyester urethane (meth)acrylate, polyether urethane (meth)acrylate, bisphenol A Type epoxy (meth)acrylate etc. are mentioned. In polybutadiene-terminated (meth)urethane acrylate or hydrogenated polybutadiene-terminated urethane (meth)acrylate, the terminal of the molecular structure is (meth)acrylate. Among these, urethane (meth)acrylate is preferred because of its high effect. Among the urethane (meth)acrylates, polybutadiene-based urethane (meth)acrylates, hydrogenated polybutadiene terminal urethane (meth)acrylates, polyester-based urethane (meth)acrylates, and polyether-based urethane (meth)acrylates At least one of the groups is preferred, and at least one of the group consisting of hydrogenated polybutadiene-based urethane (meth)acrylates and polyester-based urethane (meth)acrylates is more preferred. Among the hydrogenated polybutadiene-based urethane (meth)acrylates, 1,2-hydrogenated polybutadiene terminal urethane (meth)acrylates are preferred.

Here, the urethane (meth)acrylate is, for example, a reaction of a polyol compound (hereinafter referred to as X), an organic polyisocyanate compound (hereinafter referred to as Y), and a hydroxy (meth)acrylate (hereinafter referred to as Z). It refers to urethane (meth)acrylate having a urethane bond in the molecule obtained by (for example, 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, polytrimethylolpropane, pentaerythritol Polyhydric alcohols such as polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide having at least one structure of block or random copolymerization Polyether polyols, caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, polyolefin-based polyols, polycarbonate-based polyols, polybutadiene polyols, polyisoprene polyols, hydrogenated polybutadiene polyols, and polydiene-based polyols such as hydrogenated polyisoprene polyols and silicone polyols such as polydimethylsiloxane polyol. and polyester polyols which are condensates of the above polyhydric alcohols or the above polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid.

Among these, as the polyol compound (X), at least one member from the group consisting of polybutadiene polyol, hydrogenated polybutadiene polyol, polyether polyol, and polyester polyol is preferred, and one member from the group consisting of hydrogenated polybutadiene polyol and polyester polyol is preferred. The above is more preferable. Among the hydrogenated polybutadiene polyols, compounds represented by formula (2) (n is a positive number) are preferred.

(In the formula, n is a positive number.)

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

Although there is no need to specifically limit as organic polyisocyanate compound (Y), For example, aromatic, aliphatic, cyclic aliphatic, alicyclic, etc. polyisocyanate can be used. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (natural 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(isocyanatemethyl)cyclohexane (H6XDI), and trimer compounds of these polyisocyanates. , reaction products of these polyisocyanates and polyols, and the like are suitably used. Among these, hydrogenated xylylene diisocyanate (H-XDI) and/or isophorone diisocyanate (IPDI) are preferred.

Examples of the hydroxy (meth)acrylate (Z) include hydroxyl such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Alkyl (meth)acrylate, 2-hydroxyethyl (meth)acryloyl phosphate, 4-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxy ethyl-2-hydroxypropyl phthalate, glycerin Di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, di Pentaerythritol penta(meth)acrylate, caprolactone modified 2-hydroxyethyl (meth)acrylate, etc. are mentioned. Among these, hydroxyalkyl (meth)acrylates are preferred.

Among hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates represented by formula (3) are preferred.

ZO-(R ₄ -O-) _p -H Equation (3)

(In the formula, Z is a (meth)acryloyl group, R ₄ is an alkylene group, and p represents an integer of 1 to 10.)

1-8 are preferable and, as for carbon number of the alkylene group of R _<4> in Formula (3), 2-6 are more preferable.

Among the hydroxyalkyl (meth)acrylates, at least one of the group consisting of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate is used. desirable. The production method of urethane (meth)acrylate is disclosed in, for example, Japanese Unexamined Patent Publication No. 7-25957, Japanese Unexamined Patent Publication No. 2002-173515, Japanese Unexamined Patent Publication No. 7-292048, Japanese Unexamined Patent Publication No. 2000-351819, etc. are listed.

1000-60000 are preferable and, as for the weight average molecular weight of polyfunctional (meth)acrylate, 1500-40000 are more preferable. The weight average molecular weight is obtained by drawing a calibration curve with commercially available standard polystyrene using tetrahydrofuran as a solvent under the following conditions and using a GPC system (SC-8010 manufactured by Tosoh Corporation) or the like.

Flow Rate: 1.0ml/min

Set temperature: 40℃

Column composition: Tosoh Corporation 「TSK guardcolumn MP(×L)」 6.0mmID×4.0cm 1ea and Tosoh company 「TSK-GELMULTIPOREHXL-M」 7.8mmID×30.0cm (theoretical plate number 16,000) 2ea, total 3ea (32,000 theoretical stages in total)

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

Feeding pressure: 39kg/cm2

Detector: RI detector

(P) When the polymerizable vinyl compound contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, the amount of (A) polyfunctional (meth)acrylate used is (A) , (B) and (D) of 100 parts by mass of the total amount, preferably 10 to 90 parts by mass, more preferably 30 to 90 parts by mass, still more preferably 40 to 85 parts by mass, even more preferably 30 to 80 parts by mass, 40 to 75 parts by mass is most preferred. When it is 10 parts by mass or more, there is no fear of deterioration in adhesiveness, and when it is 90 parts by mass or less, good curability can be obtained.

(B) Monofunctional (meth)acrylate refers to (meth)acrylate having one (meth)acryloyl group. (B) Among the monofunctional (meth)acrylates, at least one of the group consisting of phenolalkylene oxide-modified (meth)acrylates, alkyl (meth)acrylates, and hydroxyalkyl (meth)acrylates is preferred.

Among the phenolalkylene oxide-modified (meth)acrylates, the phenolalkylene oxide-modified (meth)acrylate represented by formula (4) is preferable.

(In the formula, R ¹ is hydrogen or an alkyl group having 1 to 16 carbon atoms. R ² is an alkylene group. R ³ is hydrogen or a methyl group. m is 1 to 6.)

R ¹ is preferably an alkyl group. 5-13 are preferable and, as for carbon number of an alkyl group, 9 is preferable. R ² is preferably an ethylene group. As for m, 4 is preferable. Examples of the nonylphenol alkylene oxide-modified (meth)acrylate in which R ¹ is an alkyl group having 9 carbon atoms include nonylphenol ethylene oxide-modified (meth)acrylate, nonylphenol (ethylene oxide-modified 4 moles) (meth)acrylate, and nonylphenol (ethylene oxide). oxide 8 mol modified) (meth)acrylate, nonylphenol (propylene oxide 2.5 mol modified) (meth)acrylate, etc. are mentioned.

Among the alkyl (meth)acrylates, alkyl (meth)acrylates having an alkyl group of 2 to 16 carbon atoms are preferable. The alkyl group is preferably a saturated aliphatic hydrocarbon group. It is preferable that an alkyl group is unsubstituted.

Examples of the alkyl (meth)acrylate having an alkyl group having 2 to 16 carbon atoms include ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and normal octyl (metha)acrylate. )Acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate A rate etc. are mentioned. Among these, from the viewpoint of adhesiveness or moisture resistance, octyl (meth)acrylate is preferred, and normaloctyl (meth)acrylate is more preferred.

Among the hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates represented by the formula (3) described above are preferable.

ZO-(R ₄ -O-) _p -H Equation (3)

(Z is a (meth)acryloyl group, R ₄ is an alkylene group, and p represents an integer of 1 to 10.)

1-8 are preferable and, as for carbon number of the alkylene group of R _<4> in Formula (3), 2-6 are more preferable.

Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol (meth)acrylate, and the like. Among these, 4-hydroxybutyl (meth)acrylate is preferable in terms of adhesiveness and moisture resistance.

(P) When the polymerizable vinyl compound contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, the amount of (B) monofunctional (meth)acrylate used is (A) , (B) and (D) in 100 parts by mass, preferably 3 to 80 parts by mass, more preferably 5 to 80 parts by mass, still more preferably 15 to 65 parts by mass, and most preferably 20 to 60 parts by mass. If it is 3 parts by mass or more, good curability can be obtained, and if it is 80 parts by mass or less, there is no fear that adhesiveness will decrease.

(C) The photopolymerization initiator is used to promote photocuring of the resin composition by sensitizing with actinic rays of visible light or ultraviolet rays. Examples of the photopolymerization initiator include benzophenone and derivatives thereof, benzyl and derivatives thereof, anthraquinone and derivatives thereof, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal. Phosphorus derivatives, acetophenone derivatives such as diethoxyacetophenone and 4-t-butyltrichloroacetophenone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and derivatives thereof , camphorquinone, 7,7-dimethyl-2,3-dioxicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxicyclo[2.2.1]heptane-1 -Carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxyl Camphorquinone derivatives such as sobicyclo[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-trimethylbenzoyl dimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyl diethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- Acylphosphine oxide derivatives such as phenylphosphine oxide, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[ 2-hydroxy-ethoxy]-ethyl ester, 1-hydroxy-cyclohexyl-phenyl-ketone, and the like. A photoinitiator can be used singly or in combination of two or more. Among these, at least one kind from the group consisting of benzoin derivatives, 1-hydroxy-cyclohexyl-phenyl-ketones, and acylphosphine oxide derivatives is preferred in terms of high effect. Among the benzoin derivatives, benzyldimethylketal is preferred. Among the acylphosphine oxide derivatives, at least one of the group consisting of 2,4,6-trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is preferred.

(C) The amount of photopolymerization initiator used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass in total of (A), (B) and (D). If it is 0.01 parts by mass or more, good curability can be obtained, and if it is 10 parts by mass or less, good deep-side curability can be obtained.

(D) As the dicarboxylic acid diester, an aliphatic dibasic acid diester is preferable. As an aliphatic dibasic acid diester, the compound represented by Formula (1) is preferable.

(In the formula, the definitions of R ₁ , R ₂ and R ₃ are as described above.)

As for _{R1 and R2} of the compound represented by Formula (1), a saturated aliphatic hydrocarbon group is preferable. In addition, it is preferable that the above R ₁ and R ₂ are unsubstituted. As for R ₁ and R ₂ , an alkyl group having 2 to 12 carbon atoms is preferable, an alkyl group having 4 to 10 carbon atoms is more preferable, and an alkyl group having 8 carbon atoms is most preferable. R ₃ of the compound represented by Formula (1) is preferably a saturated aliphatic hydrocarbon group. Also, R ₃ is preferably unsubstituted. The 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.

(D) Dicarboxylic acid diesters are compounds used, for example, to improve deep curability and adjust viscosity.

(D) Dicarboxylic acid diesters represented by Formula (1) include dimethyl oxalate, diethyl oxalate, dipropyl oxalate, diisopropyl oxalate, dibutyl oxalate, dihexyl oxalate, dioctyl oxalate, diisopropyl malonate, and horse Dibutyl ronate, diethyl succinate, dipropyl succinate, diisopropyl succinate, dibutyl succinate, dit-butyl succinate, bis(2-ethylhexyl) succinate, bis(2-ethoxyethyl) succinate, diethyl glutarate , dibutyl glutalate, dimethyl adipate, diethyl adipate, dipropyl adipate, diisopropyl adipate, butyl adipate, dit-butyl adipate, bis(2- adipate) Ethylhexyl), Dioctyl Adipate, Dimethyl Pimelate, Diethyl Pimelate, Diisopropyl Pimelate, Dibutyl Pimelate, Dimethyl Suberate, Diethyl Suberate, Dipropyl Suberate, Suberic Acid Diisopropyl, Dimethyl Azelaate, Diethyl Azelaate, Dipropyl Azelaate, Diisopropyl Azelaate, Dibutyl Azelaate, Dimethyl Sebacate, Diethyl Sebate, Dipropyl Sebacate, Dipropyl Sebacate, Sebacic Acid Diisopropyl, dibutyl sebacate, bis(2-ethylhexyl) sebacate, etc. are mentioned. These dicarboxylic acid diesters can use 1 type, or 2 or more types. (D) Among dicarboxylic acid diesters, sebacic acid diesters are preferred. Among the sebacic acid diesters, bis(2-ethylhexyl) sebacic acid is preferred.

(D) The amount of dicarboxylic acid diester used is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, most preferably 8 to 20 parts by mass, based on 100 parts by mass of the total of (P) and (D). . If it is 1 part by mass or more, good viscosity can be obtained, and if it is 50 parts by mass or less, good deep part curability can be obtained.

(E) The tackifier is, for example, a compound generally referred to as tackifier or tackifying resin, and is a compound used to maintain tackiness on the surface of the adhesive cured product even after curing. As the tackifier, a tackifier that is resistant to deterioration by ultraviolet rays and has high weather resistance is preferable. As the tackifier, hydrogenated rosin resin (fully hydrogenated rosin resin), aliphatic fully saturated hydrocarbon resin, hydrogenated terpene resin (fully hydrogenated terpene resin), aromatic modified hydrogenated terpene resin, aromatic modified terpene resin, styrene resin, terpene phenol resin, hydrogenated terpene A phenol resin etc. are mentioned. Among these, at least one of the group consisting of fully hydrogenated rosin resins, aromatic modified terpene resins, and terpene phenol resins is preferable.

(E) The amount of tackifier used is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, most preferably 5 to 25 parts by mass, and 10 parts by mass to a total of 100 parts by mass of (P) and (D). -20 parts by mass is even more preferred. When it is 1 part by mass or more, good adhesiveness can be obtained on the surface after curing, and when it is 40 parts by mass or less, good transparency can be obtained.

The composition of the present invention may use (F) thiol. (F) A thiol refers to a compound having one or more thiol groups. Among the thiols, polythiols are preferred from the viewpoint of deep curability. (F) Polythiol refers to a compound having two or more thiol groups. As the polythiol, trimethylolpropane trithiopropionate, pentaerythritol tetrakithiopropionate, dipentaerythritol hexakis(3-mercaptopropionate), tris[(3-mercaptopropionyloxy)- ethyl] isocyanurate, 2-ethylhexyl-3-mercaptopropionate, 3-mercaptobutyrate derivatives and the like. These polythiols can use 1 type, or 2 or more types.

(F) Among the polythiols, at least one of the group consisting of 3-mercaptobutyrate derivatives and mercaptopropionate derivatives is preferred. For example 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6 -(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopro cionate), 2-ethylhexyl-3-mercaptopropionate, and the like. (F) Among the polythiols, primary or secondary polythiols are preferred.

(F) The amount of polythiol used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass in total of (P) and (D). If it is 0.1 parts by mass or more, good deep curability can be obtained, and if it is 10 parts by mass or less, coloring or discoloration due to heat of the curable resin composition is reduced.

In order to improve the storage stability of the composition of the present invention, (G) antioxidant may be used. Examples of antioxidants include methylhydroquinone, hydroquinone, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), 6-tert-butyl-4-[3-[(2,4,8,10 -Tetra-tert-butyl dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]propyl]-2-methylphenol, catechol, hydroquinone monomethyl ether, monoter Sherrybutyl hydroquinone, 2,5-ditertiarybutyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-ditertbutyl-p-benzoquinone, picric acid, citric acid, phenol nothiazine, tert-butyl catechol, 2-butyl-4-hydroxyanisole, and 2,6-di-tertiary butyl-p-cresol; and the like. Among these is 6-tert-butyl-4-[3-[(2,4,8,10-tetra-tert-butyl dibenzo[d,f][1,3,2]dioxaphosphepine-6- yl)oxy]propyl]-2-methylphenol is preferred.

(G) The amount of antioxidant used is preferably 0.001 to 0.5 parts by mass, more preferably 0.005 to 0.1 parts by mass, based on 100 parts by mass in total of (P) and (D). If it is 0.001 parts by mass or more, coloring or discoloration due to heat of the curable resin composition is small, and if it is 0.5 parts by mass or less, good deep curability can be obtained.

The composition of the present invention includes various elastomers such as acrylic rubber, urethane rubber, and acrylonitrile-butadiene-styrene rubber, solvents such as polar organic solvents, extenders, reinforcing materials, You may use additives, such as a plasticizer, a thickener, dye, a pigment, a flame retardant, a silane coupling agent, and surfactant.

A cured product bonded with the composition of the present invention can be reworked (reused) after completely cured. The rework method is not particularly limited, but by applying a load of 0.01 to 100 N between one or two adherends put together, it becomes possible to dismantle the adherends and reuse the adherends after disassembly.

The composition of the present invention is, for example, a curable resin composition and can be used as an adhesive composition. The composition of the present invention is a composition that maintains sufficient adhesiveness and tackiness for bonding of various adherends even in the state of a cured product having a curing rate of 90% or more. The composition of the present invention, for example, by irradiating visible light or ultraviolet rays to the adhesive composition applied on one adherend and then attaching it to the other adherend, thereby curing regardless of the location where visible light or ultraviolet rays do not transmit, It is an adhesive composition to which a complex can be bonded.

The adhesive composition of the present invention can be obtained as a cured product of the adhesive composition by, for example, irradiating visible light or ultraviolet light.

With the cured product of the present invention, a composite in which an adherend is coated or bonded can be obtained. The adherend is not particularly limited, but at least one selected from the group consisting of triacetyl cellulose, fluorine-based polymers, polyesters, polycarbonates, polyolefins, glass, and metals is preferable.

Using the adhesive composition of the present invention, a touch panel laminate in which adherends are bonded together can be obtained.

Using the adhesive composition of the present invention, a touch panel laminate in which adherends are bonded together can be obtained. A display can be obtained using the touch panel laminate.

Using the adhesive composition of the present invention, a liquid crystal panel laminate in which adherends are bonded together can be obtained. A display can be obtained using the liquid crystal panel laminate.

Example

The present invention will be described in more detail below with reference to experimental examples, but the present invention is not limited thereto. Unless otherwise specified, experiments were conducted at 23°C.

(Experimental Example 1)

A curable resin composition having a composition shown in Table 1 was prepared and evaluated. The results are shown in Table 1.

As each component in the curable resin composition described in Experimental Examples, the following compounds were selected.

(A) The following compounds were selected as the polyfunctional (meth)acrylate of the component.

(A-2) polyester urethane acrylate oligomer ("Oligomer 2", the structure is as follows, the polyol compound is a polyester polyol that is a condensate of 1,4-butanediol and adipic acid, ethylene glycol and adipic acid A compound having a polyester polyol that is a condensate of (polyester polyol that is a condensate of 1,4-butanediol and adipic acid: polyester polyol that is a condensate of ethylene glycol and adipic acid = 2:3 (molar ratio)), organic polyisocyanate Compound is isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, weight average molecular weight in terms of polystyrene by GPC 18000)

(A-1) polyester urethane acrylate oligomer ("Oligomer 1", the structure is as follows, the polyol compound is a polyester polyol that is a condensate of hydrogenated polybutadiene polyol and adipic acid, the organic polyisocyanate compound is isophorone di Isocyanate and hydroxy (meth) acrylate are 4-hydroxybutyl acrylate, weight average molecular weight of 25000 in terms of polystyrene by GPC, and hydrogenated polybutadiene polyol are compounds represented by formula (3) (n is a positive number)

(A-3) Hydrogenated polybutadiene-based urethane acrylate ("Oligomer 3", urethane acrylate having a hydrogenated polybutadiene skeleton. The structure is as follows, and the polyol compound is hydrogenated polybutadiene polyol, and the organic polyisocyanate compound is Isophorone diisocyanate, hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, weight average molecular weight 19000, hydrogenated polybutadiene polyol is a compound represented by formula (2) (n is a positive number))

(A-4) Hydrogenated polybutadiene-based urethane acrylate ("Oligomer 4", however, is a urethane acrylate containing 20% by mass of n-octyl acrylate as a dilute monomer and having a hydrogenated polybutadiene skeleton. The structure is as follows The same, the polyol compound is hydrogenated polybutadiene polyol, the organic polyisocyanate compound is isophorone diisocyanate, the hydroxy (meth) acrylate is 2-hydroxyethyl acrylate, the weight average molecular weight is 35000, the hydrogenated polybutadiene polyol is formula (2) Compound represented by (n is a positive number)

(B) The following compounds were selected as monofunctional (meth)acrylates of component.

(B-1) Nonylphenoxy polyethylene glycol acrylate (m = 4 in Formula (4)) ("M-113" manufactured by Toa Seong Co., Ltd.)

(B-2) Lauryl acrylate (“LA” manufactured by Osaka Yugi Co., Ltd.)

(B-3) 4-hydroxybutyl (meth)acrylate ("4HBA" manufactured by Nippon Kasei)

(B-4) n-octyl acrylate (hereinafter referred to as "NOAA")

(C) The following compounds were selected as photopolymerization initiators of the component.

(C-1) 1-hydroxycyclohexylphenyl ketone ("Irgacure184" manufactured by BASF)

(C-2) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“LucirinTPO” manufactured by BASF)

(C-3) bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure819" manufactured by BASF)

The following compounds were selected as dicarboxylic acid diesters of component (D).

(D-1) Bis(2-ethylhexyl) sebacic acid ("Sansosizer DOS" manufactured by New Japan Rica Co., Ltd.) (hereinafter referred to as "DOS")

(D-2) bis(2-ethylhexyl) adipic acid (hereinafter referred to as "DOA")

(E) The following compounds were selected as the tackifier of the component.

(E-1) Haritac F85 (fully hydrogenated rosin resin) manufactured by Harima Chemicals

(E-2) Yasuhara Chemical YS Resin TR105 (aromatic modified terpene resin)

(E-3) Yasuhara Chemical YS Polyster TH130 (Terpenephenol Resin)

(F) As a thiol compound of component, the following compounds were selected.

(F-1) pentaerythritol tetrakis(3-mercaptobutyrate) ("Karenz MT PE1" manufactured by Showa Denko Co., Ltd.) (hereinafter referred to as "MT-PE1")

(F-2) 2-ethylhexyl-3-mercaptopropionate (SC Organic Chemicals "EHMP")

(G) The following compounds were selected as antioxidants of component.

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

Various physical properties were measured as follows.

[Photocurable]

It was measured at a temperature of 23°C. Regarding photocurability, a curable resin composition was applied to the surface of Tempax glass (25 mm wide x 25 mm long x 2 mm thick) to a thickness of 0.1 mm. Thereafter, UV light having a wavelength of 365 nm was irradiated and cured under conditions of a cumulative light amount of 1500 mJ/cm 2 using a curing device manufactured by Fusion Co. using an electrodeless discharge lamp.

The curing rate was calculated by the following formula using FT-IR. For the absorption spectrum of carbon and the carbon double bond, a peak around 1600 cm ^-1 was used.

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

[Evaluation of glass adhesion (evaluation of tensile strength of glass)]

A curable resin composition was applied in a circular shape with a radius of 4 mm using a Teflon (registered trademark) tape having a thickness of 200 μm × width 20 mm × length 20 mm as a spacer at the center of a slide glass test piece (commercial product, width 20 mm × length 76 mm × thickness 1.1 mm). After that, it was cured by irradiating light. For light irradiation conditions, after curing the curable resin composition according to the method described on the [Photocuring] page, it was attached to a slide glass test piece of the same size in a cross shape and bonded by applying a pressure of 1 kgf / cm 2 (bonding area 50 mm 2). After the slide glass test pieces were adhered to each other under the above conditions, the tensile strength (unit: kPa) was measured by applying pressure to only one of the slide glass test pieces bonded in a cross shape using a universal tester. Tensile strength was measured at a speed of 10 mm/min under an environment of a temperature of 23° C. and a humidity of 50%.

[Evaluation of polycarbonate adhesiveness (evaluation of polycarbonate tensile strength)]

A Teflon (registered trademark) tape with a thickness of 200 μm × width 20 mm × length 20 mm was used as a spacer at the center of a polycarbonate test piece (“Panlite” manufactured by Teijin, width 25 mm × length 25 mm × thickness 2.0 mm), and a curable resin composition was applied to the radius. After applying in a circular shape of 4 mm, it was cured by irradiating light. For light irradiation conditions, after curing the curable resin composition according to the method described on the [Photocurable] page, it was attached to a polycarbonate test piece of the same size in a cross shape and bonded by applying a pressure of 1 kgf / cm 2 (adhesion area 50 mm 2). After the polycarbonate test pieces were bonded to each other under the above conditions, the tensile strength (unit: kPa) was measured by applying pressure to only one of the polycarbonate test pieces bonded in a cross shape using a universal tester. Tensile strength was measured at a speed of 10 mm/min under an environment of a temperature of 23° C. and a humidity of 50%.

[Evaluation of heat and moisture resistance (observation of appearance (yellowing degree))]

EAGLE XG (registered trademark) glass (50 mm in width x 70 mm in length x 0.7 mm in thickness) was bonded to each other using a curable resin composition with a thickness of the curable resin composition layer of 200 µm, and cured. Light irradiation conditions followed the method described in the above [Photocurable] page. After curing, this adhesive test piece was exposed to an environment of a temperature of 85°C and a relative humidity of 95% for 1000 hours using a constant temperature and humidity chamber. After exposure, the Δb value of this adhesive test piece was measured with a color measuring device ("UV-VISIBLE SPECTROPHOTOMETER" manufactured by SHIMADZU) to determine the degree of yellowing.

The following was recognized from Table 1. The present invention has excellent effects. When no tackifier is used (Comparative Example 1), the adhesiveness is low and the effect of the present invention is not obtained. When there are many tackifiers, transparency becomes small and hardenability becomes small (Example 6).

(Experimental Example 2)

Deep curability was evaluated using the curable resin composition having the composition shown in Table 2. The results are shown in Table 2.

[deep curing]

A 20 mm long black tube with a diameter of 5 mm ? was filled with the curable resin composition, and 1 mW/cm 2 (365 nm) light was irradiated from the top with a black light for 100 seconds (integrated light amount: 100 mJ/cm 2 ). Then, the cured product was taken out from the black tube, the uncured portion was removed, and the thickness of the cured portion was measured with a micrometer.

From Table 2, the following was recognized. When thiol is used, it has deep curability.

(Experimental Example 3)

Viscosity was evaluated using the curable resin composition of the composition shown in Table 3. The results are shown in Table 3.

〔viscosity〕

The viscosity of the composition was measured using an E-type viscometer under conditions of a temperature of 25°C and a rotation speed of 20 rpm.

The following was recognized from Table 3. The present invention has excellent effects. When no dicarboxylic acid diester is used (Comparative Example 2), the viscosity is high. When the viscosity is low, it is easy to apply to the adherend and the application workability is excellent.

The present invention can provide a composition that maintains adhesion to a surface even after curing, for example. Furthermore, it has the following effects.

An icon sheet or touch panel, which is an adherend, may cover the light-shielding portion with printing or the like to improve design by hiding the driving IC or wiring of the display body or the edge sealant of the LCD so that only the display area is visible. Conventional photocurable adhesive compositions have a tendency to decrease the point adhesive force (also called tack force, unified as point adhesive force in this paper) on the surface as curing progresses. For this reason, in order to adhere the adherends to each other, the adhesive is applied on one adherend, and then the adhesive is cured in an uncured liquid state or to the extent that the adhesive is not completely cured (also called "semi-cured" or "temporarily cured"). After bonding the adherend on the other side of the adhesive, a method of curing by irradiating ultraviolet light is often taken. At this time, if the light-shielding portion is present, the photocurable adhesive composition under the light-shielding portion is not exposed to light and is not cured, so adhesion may be insufficient.

This invention is an invention which also solved the said subject, and has the following effects, for example. In the present invention, the curable resin composition can be cured without being affected even if a light-shielding portion exists in the adherend by bonding the adherends together after curing the adhesive composition applied on one adherend in advance. The curing shrinkage of the present invention is small, and surface accuracy change such as dimensional change or warpage does not occur. The present invention can withstand expansion and contraction of an adherend in a high-temperature reliability test. In the present invention, problems such as discoloration and discoloration after a heat resistance test and decrease in strength after a moisture resistance test do not occur.

The present invention is applied, for example, to light-shielding parts such as printing in the case of gluing decorative plates or icon sheets used in display bodies such as touch panels, in the case of gluing transparent substrates and transparent substrates, in the case of piecing together printed parts. Even in places where visible light or ultraviolet rays do not reach from the front of the adherend, before bonding each adherend, the adhesive applied on one adherend is irradiated with visible light or ultraviolet rays in advance and cured, regardless of the presence or absence of a light-shielding part. It is possible to provide a curable resin composition in which the adhesive of the cotton is cured in the same way. The present invention has an effect of enabling curing of the curable adhesive resin under the light-shielding portion and suppressing poor curing of the adhesive.

Claims (21)

A composition containing the following (P), (C) to (E):
(P) a polymerizable vinyl compound;
(C) a photopolymerization initiator;
(D) aliphatic dibasic acid diesters other than adipic acid diesters and cyclohexane dicarboxylic acid diesters;
(E) a tackifier. The method of claim 1,
A composition in which (D) is an aliphatic dibasic acid diester represented by formula (1).
[Formula 1]

(In the formula, R ₁ and R ₂ are alkyl groups having 1 to 18 carbon atoms, R ₃ is an alkylene group having 1 to 10 carbon atoms, and R ₁ and R ₂ may be the same or different.) The method of claim 2,
(D) is a sebacic acid diester. The method of claim 1,
(F) A composition further containing a thiol. The method of claim 4,
The composition (F) wherein the thiol is a polythiol. The method of claim 1,
(G) A composition further containing an antioxidant. The method of claim 1,
A composition in which the (P) polymerizable vinyl compound contains (A) a multifunctional (meth)acrylate and (B) a monofunctional (meth)acrylate. The method of claim 7,
(A) A composition in which the polyfunctional (meth)acrylate is urethane (meth)acrylate. The method of claim 7,
(B) A composition in which the monofunctional (meth)acrylate is at least one selected from the group consisting of phenolalkylene oxide-modified (meth)acrylates, alkyl (meth)acrylates, and hydroxyalkyl (meth)acrylates. The method of claim 1,
A composition in which the amount of (D) used is 5 to 50 parts by mass in 100 parts by mass of the total of (P) and (D). The method of claim 1,
(E) A composition in which the tackifier is at least one of the group consisting of fully hydrogenated rosin resins, aromatic modified terpene resins, and terpene phenol resins. A curable resin composition comprising the composition according to any one of claims 1 to 11. An adhesive composition comprising the composition according to any one of claims 1 to 11. A cured product of the adhesive composition according to claim 13. A composite in which an adherend is coated or bonded with the cured body according to claim 14. The method of claim 15
A composite wherein the adherend is at least one member selected from the group consisting of triacetyl cellulose, fluorine-based polymers, polyesters, polycarbonates, polyolefins, glass, and metals. A touch panel laminate in which adherends are bonded together with the adhesive composition according to claim 13. A liquid crystal panel laminate in which adherends are bonded together with the adhesive composition according to claim 13. A display using the touch panel laminate according to claim 17. A display using the liquid crystal panel laminate according to claim 18. The (P) polymerizable vinyl compound contains (A) polyfunctional (meth)acrylate and (B) monofunctional (meth)acrylate, and (A) polyfunctional (meth)acrylate is urethane (meth)acrylic acid. rate, and (B) monofunctional (meth)acrylate is at least one selected from the group consisting of phenolalkylene oxide-modified (meth)acrylates, alkyl (meth)acrylates, and hydroxyalkyl (meth)acrylates. , (A) the amount of polyfunctional (meth)acrylate used is 10 to 90 parts by mass out of 100 parts by mass of the total amount of (A), (B) and (D), and (B) the amount of monofunctional (meth)acrylate used Silver is 3 to 80 parts by mass in 100 parts by mass of the total amount of (A), (B) and (D), and the amount of the aliphatic dibasic acid diester (D) is 100 parts by mass in total of (P) and (D) 5 to 50 parts by mass, (E) the tackifier is at least one of the group consisting of fully hydrogenated rosin resin, aromatic modified terpene resin, and terpene phenol resin, (E) the amount of tackifier used is (P) and (D ) 1 to 40 parts by mass relative to 100 parts by mass in total, and further contains 0.1 to 10 parts by mass of (F) polythiol relative to 100 parts by mass in total of (P) and (D), and (G) antioxidant An adhesive composition comprising the composition according to any one of claims 1 to 11 further contained.