JPWO2014175129A1 - Adhesive for low polarity resin and molded product using the same - Google Patents

Abstract

An object of the present invention is to provide an adhesive for low polarity resin having high-speed curability, high heat resistance (low linear expansion coefficient, high Tg), low viscosity, and excellent adhesion strength to low polarity resin. Is to provide. The adhesive for low-polarity resins of the present invention is an adhesive for adhering low-polarity resins (X), and the adhesive comprises an alicyclic diepoxy compound (A) having a crosslinked cyclic hydrocarbon group. And the content of the bridgehead carbon in the adhesive is 0.01 to 25.0 mmol / g, and the solubility parameter of the resin constituting the low polarity resin (X) is 6.2 to 10.0. .

Description

  The present invention relates to an adhesive for low-polarity resins and a molded product using the same.

Conventionally, various resin adhesives are used for assembling display members such as liquid crystal and organic EL. As typical ones, a cationic polymerization type containing an epoxy monomer and a vinyl monomer and a radical polymerization type containing a (meth) acryl monomer are known. However, there is a problem that the adhesive strength is not sufficient in the adhesion of low-polarity resins such as polyolefin resins and silicone resins, particularly in the adhesion of low-polarity resin films.
Therefore, as a technique for improving the adhesive strength to low polarity resin films (silicone resin film, polyethylene resin film, etc.), radical polymerization type resin adhesive comprising isostearyl (meth) acrylate, thermoplastic elastomer and photoinitiator. Is known (Patent Document 1). However, the radical polymerization type resin adhesive has a problem that curing shrinkage is large and adhesiveness is insufficient. Furthermore, since hardening is inhibited by oxygen, there is a problem that facilities such as nitrogen sealing are necessary.
In addition, as a cationic polymerization type resin adhesive, an adhesive containing an epoxy monomer is generally used, and a specific alicyclic epoxy compound is a highly polar resin such as a PET resin film or an acetylcellulose resin film. It is known that a film can be firmly bonded to glass or aluminum (Patent Document 2). However, it is not known about adhesiveness with a low polarity resin film.
Moreover, the resin adhesive containing an epoxy monomer has a problem that the curing speed is slow, and a resin adhesive having a high curing speed is required.

  In recent years, adhesives excellent in low-viscosity thin film coating properties have been demanded as various devices have been reduced in size, thickness and weight. In order to reduce the viscosity of the adhesive, measures such as diluting the adhesive with an organic solvent or increasing the blending ratio of the low-viscosity monomer in the adhesive are usually taken. However, the use of organic solvents has a problem of adverse environmental impact. In addition, since low viscosity monomers generally have low concentrations of aromatic rings, polar groups and epoxy groups, increasing these compounding ratios decreases the mechanical strength and heat resistance of the adhesive layer, and decreases the adhesive strength. There's a problem.

Japanese Patent Laying-Open No. 2005-307082 Japanese Patent No. 4553572

  An object of the present invention is to provide an adhesive for low polarity resin having high-speed curability, high heat resistance (low linear expansion coefficient, high Tg), low viscosity, and excellent adhesion strength to low polarity resin. It is to provide.

  The adhesive for low polarity resin of the present invention is an adhesive for bonding the low polarity resin (X), and the adhesive contains an alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group. In addition, the content of bridgehead carbon in the adhesive is 0.01 to 25.0 mmol / g, and the solubility parameter of the resin constituting the low polarity resin (X) is 6.2 to 10.0. A resin adhesive; and a molded article using the same.

  The adhesive for low polarity resins of the present invention has high-speed curability, high heat resistance (low linear expansion coefficient, high Tg), low viscosity, and excellent adhesive strength with respect to low-polar resin films.

  The adhesive for low polarity resin of the present invention is an adhesive for bonding the low polarity resin (X), and the adhesive contains an alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group. In addition, the content of bridgehead carbon in the adhesive is 0.01 to 25.0 mmol / g, and the solubility parameter of the resin constituting the low polarity resin (X) is 6.2 to 10.0. It is an adhesive for resin.

In the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group, the bridged cyclic hydrocarbon is a saturated alicyclic ring in which two or more rings are bonded by sharing two or more atoms. The “alicyclic diepoxy compound having a bridged cyclic hydrocarbon group” is an epoxy compound having the above bridged cyclic hydrocarbon group, in which the oxygen atom of the epoxy group is bridged A compound directly bonded to adjacent carbon atoms forming a ring in a cyclic hydrocarbon.
The ring includes a 3- to 10-membered ring or higher, and from the viewpoint of adhesive strength, a 3- to 10-membered ring is preferable, and a 5- to 7-membered ring is more preferable.
Bridged cyclic hydrocarbons include those having 6 to 20 carbon atoms, specifically, those having two rings {hydroindane, decalin, bicyclo [6.3.0] undecane, bicyclo [5 4.0] undecane, bicyclo [5.3.1] undecane, bicyclo [4.4.1] undecane, bicyclo [4.3.2] undecane, etc.} and having three or more rings {decahydrocyclo Penta [cd] pentalene, tricyclo [3.3.2.0 ^2,4 ] decane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [3.3.2.0 ^2,8 ] decane , Tricyclo [4.2.1.1 ^2,5 ] decane, tetrahydrodicyclopentadiene, tricyclo [4.2.2.0 ^1,4 ] decane, etc.}.
The number of rings of the bridged cyclic hydrocarbon is preferably 2 or 3 from the viewpoints of low viscosity and adhesive strength.

  As an alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group, from the viewpoint of low viscosity, adhesive strength, high Tg, low linear expansion coefficient and curing shrinkage, the following general formula (1) and / or A compound represented by the following general formula (2) is preferred.

［一般式（１）中、Ｒ^１〜Ｒ^１４はそれぞれ水素原子、ハロゲン原子、炭素数１〜１８の炭化水素基又は炭素数１〜１８のアルコキシ基である。炭化水素基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。アルコキシ基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。また、一般式（１）中ａ、ｂ、ｃ及びｄはそれぞれ０又は１〜４の整数である。］

In General Formula ^{(1), R} 1 ~R ¹⁴ each represents a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. The carbon atom in the hydrocarbon group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. The carbon atom in the alkoxy group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. Moreover, in general formula (1), a, b, c, and d are 0 or an integer of 1-4, respectively. ]

［一般式（２）中、Ｒ^１５〜Ｒ^２８はそれぞれ水素原子、ハロゲン原子、炭素数１〜１８の炭化水素基又は炭素数１〜１８のアルコキシ基である。炭化水素基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。アルコキシ基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。また、一般式（２）中ｅ及びｈはそれぞれ１〜４の整数であり、ｆ及びｇはそれぞれ０又は１〜４の整数である。］

In General formula ^(2), each of R 15 ^{to R 28} hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. The carbon atom in the hydrocarbon group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. The carbon atom in the alkoxy group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. In general formula (2), e and h are each an integer of 1 to 4, and f and g are 0 or an integer of 1 to 4, respectively. ]

  The compound represented by the general formula (1) can be produced by oxidizing the unsaturated compound represented by the following general formula (3) with an oxidizing agent {hydroperoxide, organic peracid, etc.}.

［一般式（３）中、Ｒ^１〜Ｒ^１４はそれぞれ水素原子、ハロゲン原子、炭素数１〜１８の炭化水素基又は炭素数１〜１８のアルコキシ基である。炭化水素基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。アルコキシ基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。また、一般式（３）中ａ、ｂ、ｃ及びｄはそれぞれ０又は１〜４の整数である。］

[In General Formula (3), R < ¹ > -R < ¹⁴ > is a hydrogen atom, a halogen atom, a C1-C18 hydrocarbon group, or a C1-C18 alkoxy group, respectively. The carbon atom in the hydrocarbon group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. The carbon atom in the alkoxy group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. Moreover, in general formula (3), a, b, c, and d are 0 or an integer of 1-4, respectively. ]

In the general formula (1), R ^{1 to} R ¹⁴ are preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, from the viewpoint of adhesive strength.
In general formula (1), from the viewpoint of adhesive strength, preferred combinations of a, b, c and d are (a = 1, b = 0, c = 1, d = 0), (a = 1, b = 1, c = 1, d = 0), (a = 1, b = 1, c = 2, d = 0), (a = 1, b = 1, c = 1, d = 1) or (a = 2, b = 1, c = 2, d = 1), more preferably (a = 1, b = 0, c = 1, d = 0), (a = 1, b = 1, c = 1, d = 0) or (a = 1, b = 1, c = 1, d = 1), and most preferably (a = 1, b = 1, c = 1, d = 0).

  Specific examples of the compound represented by the general formula (1) include 1,2: 5,6-diepoxyhexahydroindane.

  The compound represented by the general formula (2) can be produced by oxidizing the unsaturated compound represented by the following general formula (4) with an oxidizing agent {hydroperoxide, organic peracid, etc.}.

［一般式（４）中、Ｒ^１５〜Ｒ^２８はそれぞれ水素原子、ハロゲン原子、炭素数１〜１８の炭化水素基又は炭素数１〜１８のアルコキシ基である。炭化水素基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。アルコキシ基中の炭素原子は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよい。また、一般式（４）中ｅ及びｈはそれぞれ１〜４の整数であり、ｆ及びｇはそれぞれ０又は１〜４の整数である。］

In General formula ^(4), each of R 15 ^{to R 28} hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. The carbon atom in the hydrocarbon group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. The carbon atom in the alkoxy group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. Moreover, in general formula (4), e and h are the integers of 1-4, respectively, and f and g are the integers of 0, or 1-4, respectively. ]

In General Formula (2), R ^{15 to} R ²⁸ are preferably a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, from the viewpoint of adhesive strength.
In the general formula (2), from the viewpoint of adhesive strength, preferable combinations of e, f, g, and h are (e = 1, f = 1, g = 0, h = 1), (e = 1, f = 1, g = 1, h = 1) or (e = 1, f = 2, g = 1, h = 1), most preferably (e = 1, f = 1, g = 0, h = 1).

  Specific examples of the compound represented by the general formula (2) include 1,2: 5,6-diepoxydicyclopentadiene.

  As the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group, one type may be used, or two or more types may be used.

As the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group, from the viewpoint of low viscosity, adhesive strength, high Tg, low linear expansion coefficient and curing shrinkage, the above general formula (1) and / or The alicyclic diepoxy compound represented by the above general formula (2) is preferable, and more preferably, the compound in which a, b and d are 1 and c is 0 in the above general formula (1) and the above general formula (2) In which e, h and f are 1 and g is 0, particularly preferably 1,2: 5,6-diepoxyhexahydroindane and 1,2: 5,6-diepoxydicyclopentadiene And most preferred is 1,2: 5,6-diepoxydicyclopentadiene.
From the viewpoint of the curing rate, the alicyclic diepoxy compound represented by the general formula (1) and / or the general formula (2) is preferable, and more preferably, a, b, and d are 1 in the general formula (1). And a compound in which c is 0 and a compound in which e, h and f are 1 and g is 0 in the above general formula (2), particularly preferably 1,2: 5,6-diepoxyhexahydroindane And 1,2: 5,6-diepoxydicyclopentadiene, most preferably 1,2: 5,6-diepoxyhexahydroindane.

Examples of the oxidizing agent include hydroperoxide and organic peracid.
Examples of the hydroperoxide include hydrogen peroxide, tertiary butyl hydroperoxide and cumene hydroperoxide.
Examples of organic peracids include organic percarboxylic acids having 1 to 20 carbon atoms. Specific examples include performic acid, peracetic acid, perpropionic acid, perbenzoic acid, trifluoroperacetic acid, and perphthalic acid. It is done.
As the oxidizing agent, peracetic acid is preferable from the viewpoint of being industrially usable in large quantities.

In the oxidation reaction, a catalyst can be used as necessary.
In the case of hydroperoxide, a catalytic effect is obtained by a combination of a mixture of tungstic acid and caustic soda and hydrogen peroxide, a combination of an organic acid and hydrogen peroxide, or a combination of molybdenum hexacarbonyl and tertiary butyl hydroperoxide. be able to.
In the case of an organic peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.
The oxidation reaction is preferably carried out by adjusting the presence or absence of catalyst and solvent and the reaction temperature.

The adhesive for low polarity resins of the present invention is an epoxy compound (B) other than the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group (hereinafter also simply referred to as “epoxy compound (B)”). May be contained.
The epoxy compound (B) includes a compound having one or more epoxy groups in the molecule, and is preferably a compound having 1 to 2 epoxy groups from the viewpoint of low viscosity, adhesive strength and flexibility. .
As the epoxy compound (B), a cycloaliphatic epoxy compound (B-1), an aromatic epoxy compound (B-2), an acyclic aliphatic epoxy compound having no bridged cyclic hydrocarbon group in the molecule ( B-3) and a silicon compound (B-4) having an epoxy group are included.

The cycloaliphatic epoxy compound (B-1) having no bridged cyclic hydrocarbon group in the molecule is a C5-C30 cycloaliphatic having no bridged cyclic hydrocarbon group in the molecule. Epoxy compounds are included, specifically, those having an alicyclic epoxy group in the molecule {limonene dioxide, di (3,4-epoxycyclohexyl) adipate, (3,4-epoxycyclohexyl) methyl-3, 4-epoxycyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3,4-epoxy-6-methylcyclohexanecarboxylate and ethylene-1,2-di (3,4-epoxycyclohexanecarboxylic acid ) Ester etc.} and epoxy compound {1 having a cycloaliphatic skeleton having an epoxy group which is not an alicyclic epoxy group in the molecule Diglycidyl ether of 4-cyclohexanedimethanol (commercially available product is DME-100 (manufactured by Shin Nippon Rika Co., Ltd.)), bisphenol-type epoxy resin nuclear hydrogenated product (commercially available product is HBE-100 (New Japan) Rika Co., Ltd.), YX-4000 (Mitsubishi Chemical Co., Ltd., etc.)) and 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of alcohol (commercially available products include EHPE-3150 (( Etc., manufactured by Daicel Corporation).
Of the cycloaliphatic epoxy compound (B-1) having no bridged cyclic hydrocarbon group in the molecule, it has a bridged cyclic hydrocarbon group in the molecule from the viewpoint of adhesive strength and flexibility. A cycloaliphatic epoxy compound having 5 to 30 carbon atoms, more preferably a cycloaliphatic epoxy compound having a cycloaliphatic epoxy group having no bridged cyclic hydrocarbon group in the molecule. And more preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexylethyltrimethoxysilane and 1,4-cyclohexane Diglycidyl ether of dimethanol.
The cycloaliphatic epoxy compound (B-1) having no bridged cyclic hydrocarbon group in the molecule may be used alone or in combination of two or more.

  Aromatic epoxy compounds (B-2) having 9 to 300 carbon atoms {Diglycidyl ethers of various bisphenol types such as bisphenol A type and F type (commercially available products include jER828 and 806 (Mitsubishi Chemical Corporation) And YD-128 (manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd.)) and polycyclic aromatic glycidyl ethers such as naphthalene}, aromatic epoxy resins {glycolyl ethers of novolac-type phenol resins, etc.] It is done.

As the acyclic aliphatic epoxy compound (B-3), a glycidyl etherified product of an acyclic aliphatic polyhydric alcohol {ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether and sorbitol polyglycidyl ether, etc.}, glycidyl esterified product of acyclic fatty acid polycarboxylic acid {diglycidyl adipate etc.}, containing an epoxy group ( Polymer having {meth) acrylate monomer (i1) as essential constituent monomer {of (meth) acrylate monomer (i1) containing epoxy group] Compound, copolymer of epoxy group-containing (meth) acrylate monomer (i1) and hydroxyl group-containing (meth) acrylate monomer (i2), epoxy group-containing (meth) acrylate monomer (i1) and alkyl (meth) Copolymer of acrylate (i3), copolymer of (meth) acrylate monomer (i1) containing epoxy group, (meth) acrylate monomer (i2) containing hydroxyl group and alkyl (meth) acrylate (i3)} Etc.
The (meth) acrylate monomer (i1) containing an epoxy group includes a (meth) acrylate monomer containing an epoxy group that does not contain a cyclic aliphatic group having 5 to 30 carbon atoms, specifically, glycidyl (meth). Examples include acrylate and 2-methyl-glycidyl (meth) acrylate.
The (meth) acrylate monomer (i2) containing a hydroxyl group includes a (meth) acrylate monomer containing a hydroxyl group not containing a cyclic aliphatic group having 4 to 30 carbon atoms, specifically, hydroxyethyl (meth) acrylate. And hydroxypropyl (meth) acrylate.
Examples of the alkyl (meth) acrylate (i3) include alkyl (meth) acrylates containing no cyclic aliphatic groups having 4 to 30 carbon atoms, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, Examples thereof include n-, i- or t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate.
In the present specification, “(meth) acrylate” means “acrylate or methacrylate”.

  As the silicon compound (B-4) having an epoxy group, specifically, 3,4-epoxycyclohexylethyltrimethoxysilane, a silane coupling agent having an epoxy group (as a commercially available product, A-186 (Nihon Unicar) (Made by Co., Ltd.), KBM303, KBM403, KBM42 (made by Shin-Etsu Chemical Co., Ltd.), etc.).

  The epoxy compound (B) is preferably a cycloaliphatic epoxy compound (B-1) having no bridged cyclic hydrocarbon group in the molecule, more preferably from the viewpoints of low viscosity, adhesive strength and flexibility. Is preferably a C5-C30 cyclic aliphatic epoxy compound having no bridged cyclic hydrocarbon group in the molecule, more preferably an alicyclic epoxy having no bridged cyclic hydrocarbon group in the molecule. A cyclic aliphatic epoxy compound having 5 to 30 carbon atoms having a group, particularly preferably 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl alcohol and 1,4- Diglycidyl ether of cyclohexanedimethanol.

The adhesive for low-polarity resins of the present invention preferably contains an epoxy compound (B) from the viewpoint of flexibility.
When the epoxy compound (B) is contained, the content of the alicyclic diepoxy compound (A) having a crosslinked cyclic hydrocarbon group in the low polar resin adhesive of the present invention is low viscosity, adhesive strength, high Tg, From the viewpoint of a low linear expansion coefficient and flexibility, the content is preferably 10 to 99% by weight, more preferably 60 to 90% by weight, and particularly preferably 70 to 80% by weight based on the weight of the adhesive.
The content of the epoxy compound (B) is preferably 0.9 to 89.9% by weight based on the weight of the adhesive from the viewpoints of low viscosity, adhesive strength, high Tg, low linear expansion coefficient and flexibility. More preferably, it is 9.85 to 39.85% by weight, and particularly preferably 15 to 29.8% by weight.
In addition, as content of the said alicyclic diepoxy compound (A) which has a bridged cyclic hydrocarbon group, and the said epoxy compound (B), the alicyclic diepoxy compound which has the said bridged cyclic hydrocarbon group (A ) And the total weight of the epoxy compound (B), the content of the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group is 0.1 to 99% by weight, and the epoxy compound (B ) Is preferably 1 to 99.9% by weight.

  In the adhesive for low-polarity resins of the present invention, in addition to the alicyclic epoxy compound (A) having a crosslinked cyclic hydrocarbon group, a photoacid generator (C) that generates an acid upon irradiation with active energy rays. ), Or at least one selected from the group consisting of a thermal acid generator (D) that generates an acid by heating and another epoxy curing agent (E).

  The photoacid generator (C) is a compound that initiates polymerization by generating an acid upon irradiation with active energy rays, and includes a sulfonium salt (C1) and an iodonium salt (C2). A photo-acid generator (C) may be used individually by 1 type, and may use 2 or more types together.

  As the sulfonium salt (C1), triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, [p- (phenyl mercapto) Phenyl] diphenylsulfonium hexafluorophosphate [commercially available products include CPI-100P (manufactured by San Apro Co., Ltd.)] and [p- (phenylmercapto) phenyl] diphenylsulfonium [tri (perfluoroethyl)] trifluorophosphate, etc. Is mentioned.

  As the iodonium salt (C2), iodonium (4-methylphenyl) {4- (2-methylpropyl) phenyl} -hexafluorophosphate [as a commercial product, DAROCUR 250 (manufactured by BASF Japan Ltd.)], iodonium [Bis (4-t-butylphenyl)] hexafluorophosphate, iodonium [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] phosphate, iodonium [bis (4-methoxyphenyl)] Examples include trifluoro [tris (perfluoroethyl)] phosphate and iodonium [bis (4-methoxyphenyl)] [tetrakis (perfluorophenyl)] borate.

  Among these photoacid generators (C), from the viewpoint of active energy ray curability, the sulfonium salt (C1) is preferable, and [p- (phenylmercapto) phenyl] diphenylsulfonium hexafluorophosphate is more preferable.

  Examples of the thermal acid generator (D) include a sulfonium salt (D1), an iodonium salt (D2), a benzothiazonium salt (D3), an ammonium salt (D4), and a phosphonium salt (D5). However, the compounds mentioned for the sulfonium salt (C1) and the iodonium salt (C2) are not included. A thermal acid generator (D) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the sulfonium salt (D1) include (4-hydroxyphenyl) dimethylsulfonium bis (trifluoromethanesulfonyl) imide, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium bis (trifluoromethanesulfonyl) imide, (4 -Hydroxyphenyl) benzylmethylsulfonium bis (trifluoromethanesulfonyl) imide, (4-hydroxyphenyl) dimethylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium hexafluorophosphate, (4- Hydroxyphenyl) benzylmethylsulfonium hexafluorophosphate, (4-hydroxyphenyl) (4-methylbenzyl) methylsulfonium hexafluorophosphate (4-hydroxyphenyl) dimethylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) benzylmethylsulfonium trifluoromethanesulfonate, (4 -Hydroxyphenyl) (4-methylbenzyl) methylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium hexafluoroantimonate, (4-acetophenyl) dimethylsulfonium hexafluoroantimonate, 4-Benzyloxycarbonyloxyphenyl) dimethylsulfonium hexafluoroantimonate, (4-benzoyloxyphenyl) Methyl sulfonium hexafluoroantimonate, (4-acetoxyphenyl) dimethyl sulfonium hexafluoroarsenate and (4-benzoyloxy-phenyl) dimethyl sulfonium hexafluoroarsenate and the like.

  Examples of the iodonium salt (D2) include diphenyliodonium bis (trifluoromethanesulfonyl) imide and (p-nitrophenyl) phenyliodonium hexafluorophosphate.

  Examples of the benzothiazonium salt (D3) include 3-benzylbenzothiazonium hexafluoroantimonate, 3- (4-methoxybenzyl) benzothiazonium hexafluoroantimonate, and 2-methylsulfanyl-3-benzyl. Benzothiazonium hexafluoroantimonate, 5-chloro-3-benzylbenzothiazonium hexafluoroantimonate; 3-benzylbenzothiazonium hexafluorophosphate; 3-benzylbenzothiazonium tetrafluoroborate Can be mentioned.

  Examples of the ammonium salt (D4) include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) Examples thereof include borate, benzyldimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate and benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate. .

  Examples of the phosphonium salt (D5) include (4-methylphenyl) diphenylphosphonium triflate.

  Of the thermal acid generator (D), a sulfonium salt (D1) is preferable from the viewpoint of curing speed.

Examples of the other epoxy curing agent (E) include ordinary curing agents for epoxy resins, such as an amine curing agent (E1), a carboxylic acid curing agent (E2), a basic active hydrogen compound (E3), Examples include imidazoles (E4), polymercaptan curing agents (E5), phenol resins (E6), urea resins (E7), melamine resins (E8), and latent curing agents (E9).
Other epoxy curing agents (E) may be used alone or in combination of two or more.

  As the amine-based curing agent (E1), polymethylenediamine {ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like}; alicyclic polyamine {mensendiamine, isophoronediamine, bis (4-amino-3- Methyl cyclohexyl) methane, N-aminoethylpiperazine and diaminodicyclohexylmethane, etc .; aliphatic polyamines containing aromatic rings {metaxylylenediamine, etc.}; aromatic polyamines; amine adducts {polyamine epoxy resin adducts, etc.}; and ketimines; Is mentioned.

  Carboxylic acid-based curing agents (E2) include polycarboxylic acid-based curing agents {adipic acid and the like}; and acid anhydride-based curing agents {phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Methyl hexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, trimellitic anhydride, etc.}.

  Examples of the basic active hydrogen compound (E3) include dicyandiamide and organic acid dihydrazide.

  Examples of imidazoles (E4) include 2-methylimidazole.

  Examples of the polymercaptan curing agent (E5), polyhydric phenols (E6), and latent curing agent (E7) include those described in JP-A-2007-262204.

  Among these other epoxy curing agents (E), a carboxylic acid curing agent (E2) is preferable from the viewpoint of curing speed.

In the adhesive for low polarity resins of the present invention, the total content of the photoacid generator (C), thermal acid generator (D) and other epoxy curing agent (E) is from the viewpoint of adhesive strength and curing speed. 0.1-20 weight% is preferable, More preferably, it is 0.15-10 weight%, Most preferably, it is 0.20-5 weight%.
In the adhesive for low polarity resins of the present invention, an alicyclic epoxy compound (A) having a crosslinked cyclic hydrocarbon group in the adhesive, a photoacid generator (C), a thermal acid generator (D) and other Weight ratio with total weight of epoxy curing agent (E) [Cycloaliphatic epoxy compound having bridged cyclic hydrocarbon group (A) / {Photoacid generator (C) + thermal acid generator (D) + others The epoxy curing agent (E)}] is preferably from 1/2 to 990/1, more preferably from 1/1 to 500/1, from the viewpoints of low viscosity, adhesive strength, and flexibility.

In the present invention, the content of bridgehead carbon in the adhesive (in 1 g of the adhesive) is 0.01 to 25.0 mmol / g. From the viewpoint of low viscosity, adhesive strength, high Tg, and low linear expansion coefficient, 5 -20 mmol / g is preferable, More preferably, it is 5-11 mmol / g.
When the content of the bridgehead carbon is in the above range, the mechanical properties and heat resistance of the adhesive for low polarity resins of the present invention become appropriate, so that the adhesive strength can be increased while the viscosity is low.
The content of the bridgehead carbon can be increased by increasing the content ratio of the alicyclic epoxy compound (A) having the above-mentioned bridged cyclic hydrocarbon group, or the fat having a bridged cyclic hydrocarbon group having a lot of bridgehead carbon. It can be increased by using the cyclic epoxy compound (A).
In addition, the content of bridgehead carbon can be calculated from the structure and preparation amount of each component in the adhesive.

  A sensitizer, a pigment, a pigment dispersant, a modified resin, organic resin fine particles, a solvent, and the like can be added to the low polar resin adhesive of the present invention as necessary.

Examples of the sensitizer include anthracene, pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin. These may be used alone or in combination of two or more.
The addition amount of the sensitizer is preferably 0 to 10% by weight, more preferably 0 to 3% by weight, based on the weight of the low-polarity resin adhesive, from the viewpoint of adhesive strength.

Examples of the pigment include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black. These may be used alone or in combination of two or more.
The addition amount of the pigment is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, based on the weight of the low-polarity resin adhesive, from the viewpoint of adhesive strength.

Examples of the pigment dispersant include pigment dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184 and 2020). Etc.), pigment dispersants (Ajisper PB711, PB821, PB814, PN411, PA111, etc.) manufactured by Ajinomoto Fine Techno Co., and pigment dispersants (Solspers 5000, 12000, 32000, 33000, 39000, etc.) manufactured by Lubrizol. These pigment dispersants may be used alone or in combination of two or more.
The addition amount of the pigment dispersant is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, based on the weight of the low-polarity resin adhesive, from the viewpoint of adhesive strength.

Examples of the modified resin include polyol resin, phenol resin, acrylic resin, polyester resin, polyolefin resin, epoxy resin, and epoxidized polybutadiene resin. These may be used alone or in combination of two or more.
The amount of the modified resin added to the low-polar resin adhesive is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, based on the weight of the low-polar resin adhesive, from the viewpoint of adhesive strength. is there.

Examples of the organic resin fine particles include acrylic resin fine particles.
Organic resin fine particles are obtained by pulverizing an organic polymer into fine particles; those obtained by drying and pulverizing polymer fine particles obtained by emulsion polymerization in water in the presence of an emulsifier; in the presence of a polymer stabilizer. Examples thereof include those obtained by drying and pulverizing polymer fine particles obtained by dispersion polymerization in an organic solvent.
The organic resin fine particles are preferably organic resin fine particles having a number average particle diameter of 50 to 500 nm from the viewpoint of dispersibility in an adhesive.
The addition amount of the organic resin fine particles of the low-polar resin adhesive is preferably 0 to 50% by weight, more preferably 0 to 10% by weight, based on the weight of the low-polar resin adhesive, from the viewpoint of adhesive strength. is there.

Solvents include glycol ethers (ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether acetate, lactic acid) Methyl and propylene glycol alkyl ether acetates), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.), amides (N, N- Dimethylacetamide and N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide) Fine ether (tetrahydrofuran, 1,3-dioxane and 1,8-cineole and the like) and the like. These may be used alone or in combination of two or more.
The addition amount of the solvent is preferably 0 to 400% by weight, more preferably 3 to 350% by weight, and particularly preferably 5 to 300% by weight with respect to the weight of the low-polarity resin adhesive from the viewpoint of viscosity. %.

  The low-polarity resin adhesive of the present invention is preferably prepared by mixing the above components so as to form a uniform adhesive. For example, it can prepare by mixing each component, making it the temperature of 25-80 degreeC as needed, and stirring until it becomes uniform with stirrers, such as a dissolver.

The low polar resin adhesive of the present invention can be applied by a method such as roll coating, spray coating, brush coating, bar coating, roller coating, silk screen printing, and the like.
When the adhesive for low-polarity resin of the present invention contains a solvent, after the adhesive is applied, the solvent is removed by heating and then cured by heating and / or active energy ray irradiation, etc. The irradiation conditions can be appropriately changed according to the type of adhesive applied, the film thickness, and the like.

  The coating film thickness is preferably 0.5 to 20 μm, more preferably 1.0 to 5.0 μm from the viewpoint of adhesive strength and weight reduction as the film thickness after drying and curing.

Examples of the active energy rays for curing the adhesive for low polarity resins of the present invention by irradiating with active energy rays include actinic rays and electron beams.
As an actinic ray source for curing the adhesive for low polarity resin of the present invention by actinic ray irradiation, in addition to a commonly used high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, etc. (UV・ Latest trends in EB curing technology, edited by Radtech Research Association, CM Publishing, 138 pages, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently.
The irradiation condition to the coating film is preferably 10 to 1,000 mJ / cm ² , more preferably 50 to 500 mJ / ^second , from the viewpoint of promoting curing of the coating film and avoiding photodegradation of the coating film and the adherend. cm ² .

As an electron beam source for curing the low-polarity resin adhesive of the present invention by electron beam irradiation, a generally used electron beam irradiation apparatus can be used.
The irradiation amount (Mrad) of the electron beam is preferably 0.5 to 20 and more preferably 1 to 15 from the viewpoints of curability and flexibility of the adhesive.

Moreover, you may heat an adhesive agent as needed after active energy ray irradiation. By heating, unreacted substances in the adhesive can be reduced, and curability of the coating film by irradiation with active energy rays and distortion generated by molding can be reduced.
In some cases, the heating can improve the hardness and adhesion of the adhesive. The heating is preferably performed at an ambient temperature of 150 to 200 ° C. for 1 to 30 minutes from the viewpoint of promoting the reaction of unreacted substances and avoiding thermal degradation of the adherend.

  The conditions for curing the low-polarity resin adhesive of the present invention by heating are as follows: from the viewpoint of promoting the curing of the coating film and avoiding thermal degradation of the coating film and the adherend. It is preferable that it is 200 degreeC, and it is more preferable that it is 80-150 degreeC. Moreover, it is preferable that heating time is 30 to 180 minutes, and it is more preferable that it is 60 to 120 minutes.

From the viewpoint of thin film coating properties, the low polar resin adhesive of the present invention preferably has a viscosity at 25 ° C. of 1 to 50 mPa · s, more preferably 2 to 30 mPa · s.
The viscosity can be measured with a B-type viscometer.

In the present specification, the low polar resin (X) is a resin having a solubility parameter (hereinafter abbreviated as SP value) of 6.2 to 10.0 (cal / cm ³ ) ^1/2 .
In this specification, SP value is calculated | required by following Formula.
SP = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of molar evaporation (cal / mol), and V represents the molar volume (cm ³ / mol). ΔH and V are the heat of molar evaporation (Δe) of the atomic group described in “POLYMER ENGINEERING AND SCIENCE, February, 1974, Vol. 14, No. 2, Robert F. Fedors. (Pp. 147 to 154)”. The total (ΔH) and the total molar volume (Δv) (V) can be used.
In the low polar resin (X), the SP value {(cal / cm ³ ) ^1/2 } of the resin is preferably 7.0 to 9.5, more preferably 8.0 to 9.9 from the viewpoint of adhesive strength. 3.

Examples of the low polar resin (X) include amorphous polyolefin resin, poly (meth) acrylic resin, crystalline polyolefin resin, fluororesin, polydimethylsilicone resin, polyisoprene resin, polybutadiene resin, polystyrene resin, and polycarbonate resin. Is included.
Examples of the amorphous polyolefin resin include cyclic olefins having 3 to 20 carbon atoms {cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, 1,5-cyclooctadiene, norbornene, tetracyclododecene, and hydrogen atoms thereof. Or a copolymer obtained by copolymerizing a chain olefin and / or an aromatic vinyl compound with a cyclic olefin. Good. When a double bond remains, a hydrogenated resin is preferable from the viewpoint of oxidation stability.
A typical example of the amorphous polyolefin resin is a thermoplastic saturated norbornene resin. Commercially available amorphous polyolefin resins include “Arton” from JSR Corporation, “ZEONEX” and “ZEONOR” from Nippon Zeon Corporation, “APO” and “Apel” from Mitsui Chemicals, Inc. is there.

As the poly (meth) acrylic resin, a polymer (j1) having (meth) acrylic acid ester having 3 to 35 carbon atoms and / or (meth) acrylic acid amide having 3 to 35 carbon atoms as an essential constituent monomer. (Hereinafter simply referred to as “polymer (j1)”), specifically, polymethyl methacrylate and the like.
(Meth) acrylic acid ester and / or (meth) acrylic acid amide, which are essential constituent monomers of the polymer (j1), and types and weight fractions of constituent monomers other than these essential constituent monomers Can be freely selected as long as the SP value of the polymer (j1) satisfies 6.2 to 10.0 (cal / cm ³ ) ^1/2 , and as a constituent monomer other than the essential constituent monomers Includes (meth) acrylic acid, meth (acrylonitrile), styrene, maleic anhydride, and the like.

  Examples of the crystalline polyolefin resin include polymers of olefins having 2 to 20 carbon atoms, and specific examples include polyethylene and polypropylene.

  Examples of the fluororesin include polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, and polyvinyl fluoride resin.

Polystyrene resins include, in addition to polystyrene, high impact polystyrene (HIPS) in which rubber particles are dispersed in a polystyrene matrix phase, and a copolymer of styrene and maleic anhydride (k1) (hereinafter simply referred to as “co-polymer”). Also referred to as polymer (k1) ”).
The weight fraction of maleic anhydride in the copolymer (k1) can be freely selected as long as the SP value of the copolymer (k1) satisfies 6.2 to 10.0 (cal / cm ³ ) ^1/2. Is possible.

  As the low polarity resin (X), from the viewpoint of adhesive strength, an amorphous polyolefin resin, a poly (meth) acrylic resin, and a crystalline polyolefin resin are preferable, and an amorphous polyolefin resin is more preferable.

The molded product of the present invention is a molded product in which two members are bonded via an adhesive, at least one of which is a member made of a low polarity resin (X), and the adhesive is the low polarity of the present invention. It is a molded product that is an adhesive for resin.
In the molded product of the present invention, the material of the other member is not particularly limited as long as at least one member is made of the low polarity resin (X).
Examples of the material of the other member include polyvinyl alcohol resin, PET resin, polyacetal resin, and polyamide resin.
The two members are preferably both low-polar resins (X) from the viewpoint of adhesive strength.

  In the molded product of the present invention, from the viewpoint of adhesive strength, it is preferable that at least one of the two members is a film and the molded product is a polarizing plate.

  When the molded product of the present invention is a polarizing plate, the two members are both films, and the polarizing plate is formed by bonding the two films via an adhesive, and at least one of the two films. Is a low polarity resin (X), and the adhesive is preferably the adhesive for a low polarity resin of the present invention.

  In such a polarizing plate, as long as at least one of the two films is made of a low polarity resin (X), the other film may be any film. For example, the following resin film (Y) may be sufficient. From the viewpoint of adhesive strength, both of the two films are preferably films made of a low polarity resin (X).

Examples of the resin film (Y) include a polyvinyl alcohol resin film, a PET resin film, a polyacetal resin film, and a polyamide resin film.
The polyvinyl alcohol resin film includes a conventional polyvinyl alcohol resin film and a polyvinyl alcohol resin film in which a dichroic dye is adsorbed and oriented.
A polyvinyl alcohol resin film is obtained by saponifying a polyvinyl acetate resin. The polyvinyl acetate resin may be a polyvinyl acetate which is a homopolymer of vinyl acetate, or a copolymer of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers and unsaturated sulfonic acids.
The polyvinyl alcohol resin may be further modified, for example, polyvinyl formal or polyvinyl acetal modified with an aldehyde may be used.

In the case of producing a polarizing plate which is a kind of the molded product of the present invention, the coating layer of the low-polarity resin adhesive is formed on the bonding surface of the film-like low-polarity resin (X), and One film may be bonded. Moreover, the coating layer of the said adhesive agent for low polar resins may be formed on the bonding surface of the other film, and film-like low polar resin (X) may be bonded together. Furthermore, the coating layer of the adhesive agent for low polarity resin is formed on both the bonding surface of the film-like low polarity resin (X) and on the bonding surface of the other film, and the coating layer is formed. A film-like low-polarity resin (X) may be bonded to the other film. The uncured coating layer thus formed can be cured by irradiation with active energy rays and / or heating to fix both films.
The coating layer can be formed by the above-described coating method. Also, while continuously supplying the film-like low-polarity resin (X) and the other film so that the bonding surface of both is on the inside, the adhesive for low-polarity resin is cast and applied between them. A method of forming a layer can also be adopted.

  Thus, in the polarizing plate produced by adhering two films, the film thickness of the low-polarity resin adhesive between the two films is preferably 0.5 to 20 μm from the viewpoint of adhesive strength and weight reduction. More preferably, it is 1.0-5.0 micrometers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.

<Production Example 1>
1,2: 5,6-diepoxyhexahydroindane (a1) was produced by the method described in Synthesis Example 3 of Patent Document 2 (Japanese Patent No. 4553572).

<Production Example 2>
In the same manner as in Production Example 1, except that “1,2: 5,6-dicyclopentadiene” is used instead of “1,2: 5,6-diepoxyhexahydroindane”, 6-diepoxydicyclopentadiene (a2) was produced.

<Production Example 3>
A 15% aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval 117) was applied on an aluminum plate and dried in hot air at 100 ° C. to obtain a polyvinyl alcohol resin film (y1).

<Comparative Production Example 1>
1,2: 6,7-diepoxycyclooctane (p1) was produced by the method described in Patent Document (Patent No. 4553572).

<Comparative Production Example 2>
3,4: 3′4′-diepoxybicyclohexane (p2) was produced by the method described in Patent Document (Patent No. 4553572).

<Examples 1 to 10>
Composition ratios shown in Table 1 for the alicyclic diepoxy compound (A), epoxy compound (B) and photoacid generator (C) having a crosslinked cyclic hydrocarbon group in a 200 mL flask equipped with a stirrer and a thermometer And stirred at 25 ° C. for 30 minutes to obtain active energy ray-curable adhesives for low polarity resins (1) to (10).

<Examples 11 to 20>
Composition ratios shown in Table 2 for the alicyclic diepoxy compound (A), epoxy compound (B) and thermal acid generator (D) having a bridged cyclic hydrocarbon group on a 200 mL flask equipped with a stirrer and a thermometer And stirred at 25 ° C. for 30 minutes to obtain thermosetting low-polarity resin adhesives (11) to (20).

<Comparative Examples 1-6>
Composition shown in Table 1 for an alicyclic diepoxy compound (P) having no epoxy compound (B), a photoacid generator (C) and a bridged cyclic hydrocarbon group in a 200 mL flask equipped with a stirrer and a thermometer The resultant was stirred at 25 ° C. for 30 minutes to obtain comparative active energy ray-curable adhesives for low polarity resins (1 ′) to (6 ′).

<Comparative Examples 7-12>
The composition which showed the alicyclic diepoxy compound (P) which does not have an epoxy compound (B), a thermal acid generator (D), and a bridged cyclic hydrocarbon group in a 200 mL flask provided with a stirrer and a thermometer is shown in Table 2. The mixture was added at a ratio and stirred at 25 ° C. for 30 minutes to obtain comparative thermosetting adhesives for low polarity resins (7 ′) to (12 ′).

In Tables 1 and 2, the following components were used.
(A1); 1,2: 5,6-diepoxyhexahydroindane (a2) obtained in Production Example 1; 1,2: 5,6-diepoxydicyclopentadiene (b1) obtained in Production Example 2; Diglycidyl ether of 1,4-cyclohexanedimethanol [Product name “DME-100”, manufactured by Shin Nippon Rika Co., Ltd.]
(B2); Bisphenol A diglycidyl ether [Product name “jER828”, manufactured by Mitsubishi Chemical Corporation]
(C1); [p- (phenylmercapto) phenyl] diphenylsulfonium hexafluorophosphate [product name “CPI-100P”, manufactured by San Apro Co., Ltd.], which is a photoacid generator
(D1); (4-hydroxyphenyl) (2-methylbenzyl) methylsulfonium hexafluoroantimonate (p1) which is a thermal acid generator; 1,2: 6,7-diepoxycyclo obtained in Comparative Production Example 1 Octane (p2): 3,4: 3 ′, 4′-diepoxybicyclohexane (p3) obtained in Comparative Production Example 2: 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate [Product Name "Celoxide 2021P", manufactured by Daicel Corporation]
(X1): Amorphous polyolefin resin film (SP value 9.0 (cal / cm ³ ) ^1/2 ), [Product name “Zeonor ZF141”, manufactured by Nippon Zeon Co., Ltd., film thickness 100 μm]
(X2): Polypropylene resin film (SP value 8.1 (cal / cm ³ ) ^1/2 ), [Product name “Trephan NL10”, manufactured by Toray Industries, Inc., film thickness 27.5 μm]
(X3); polymethyl methacrylate resin film (SP value 9.2 (cal / cm ³ ) ^1/2 ), [product name “Acryprene HBS010P”, manufactured by Mitsubishi Rayon Co., Ltd., film thickness 125 μm]
(X4): polycarbonate resin film (SP value 9.8 (cal / cm ³ ) ^1/2 ), [product name “Iupilon NF-2000”, manufactured by Mitsubishi Gas Chemical Co., Inc., film thickness 300 μm]
(Y1): Polyvinyl alcohol resin film (SP value 18.9 (cal / cm ³ ) ^1/2 ) obtained in Production Example 3, [film thickness 50 μm]
(Y2): PET resin film (SP value 10.7 (cal / cm ³ ) ^1/2 ), [Product name “Cosmo Shine A4300”, manufactured by Toyobo Co., Ltd., film thickness 100 μm]

<Measurement of viscosity of adhesive liquid>
For each of the adhesives prepared in Examples 1 to 20 and Comparative Examples 1 to 12, a B-type viscometer [product name “digital viscometer DVL-BII type, LCH-400”, manufactured by Advantech Toyo Co., Ltd.] Used to measure the viscosity at 25 ° C. The results are shown in Tables 1 and 2.

<Photocurability test>
After coating the active energy ray-curable adhesive for low polarity resin obtained in Examples 1 to 10 and Comparative Examples 1 to 6 on a glass plate with a film thickness of 10 μm using a bar coater, an ultraviolet irradiation device [belt Conveyor type, product name “ECS-151U” manufactured by Eye Graphics Co., Ltd.], UV irradiation is performed in units of 10 mJ / cm ² (UV-B), finger touch test is performed, and no contact with fingers The integrated irradiation exposure amount was determined as the exposure amount required for curing. The results are shown in Table 1.

<Thermosetting test>
The thermosetting low-polarity resin adhesives obtained in Examples 11 to 20 and Comparative Examples 7 to 12 were applied to a glass plate with a film thickness of 10 μm using a bar coater, and then heated with a dryer at 100 ° C. However, the finger touch test was performed every 5 minutes, and the time required for the finger to not adhere to the finger was determined as the time required for curing. The results are shown in Table 2.

<Film adhesion test>
1. Film bonding (1) Photo-curing system Each adhesive obtained in Examples 1 to 10 and Comparative Examples 1 to 6 is a film-like low-polar resin (X) (x1) using a bar coater. Coating was performed with a film thickness. In addition, the adhesives obtained in Comparative Examples 4 to 6 could not be applied to a film thickness of 5 μm because of high viscosity.
Next, the other resin film described in Table 1 was put on the surface coated with the adhesive, and the two films were bonded together with a roller. Then, an ultraviolet irradiation device [belt conveyor type, product name “ECS-151U” was used. ”, Manufactured by iGraphics Co., Ltd.], ultraviolet light was irradiated from the (x1) side with an integrated light amount of 250 mJ / cm ² (UV-B), the adhesive was cured, and the films were bonded together to obtain a laminated film. .

(2) Thermosetting system Each adhesive obtained in Examples 11 to 20 and Comparative Examples 7 to 12 was applied to (x1) which is a film-like low polarity resin (X) with a film thickness of 5 μm using a bar coater. Worked. In addition, the adhesives obtained in Comparative Examples 10 to 12 could not be applied to a film thickness of 5 μm because of high viscosity.
Next, the other resin film described in Table 2 was placed on the surface coated with the adhesive, and the two films were bonded together with a roller, and then heated at 100 ° C. for 1 hour with a dryer, and then further 180 ° C. The adhesive was cured by heating for 2 hours, and the films were bonded together to obtain a laminated film.

2. 180 degree peeling test Each laminated film obtained in “1. Lamination of films” was cut into a size of 200 mm in length × 25 mm in width. Each test piece thus obtained was subjected to a 180 degree peel test in accordance with the description of JIS K 6854-2 (adhesive-peel adhesion strength test method-second part: 180 degree peel). Peeling speed: 300 mm / min). The results are shown in Tables 1 and 2.

<Measurement of glass transition temperature (Tg) and linear expansion coefficient (α ₁ )>
1. Production of cured product for thermomechanical analysis (TMA) (1) Photocuring system Examples 1 to 10 and Comparative Examples 1 to 6 were formed on a stainless steel mold (recess dimensions: 200 mm x 200 mm x 5 mm) with an open top surface. Each adhesive obtained in the above was poured, and ultraviolet rays were irradiated from the upper surface with an integrated light amount of 250 mJ / cm ² (UV-B) using an ultraviolet irradiation device [belt conveyor type, product name “ECS-151U”, manufactured by Eye Graphics Co., Ltd.]. Was cured to produce a cured product for TMA (size: 200 mm × 200 mm × about 5 mm).

(2) Thermosetting system Each adhesive obtained in Examples 11 to 20 and Comparative Examples 7 to 12 is poured into a stainless steel mold having an open top surface (recess dimensions: 200 mm x 200 mm x 5 mm), and a dryer. Then, the adhesive was cured by heating at 100 ° C. for 1 hour and further at 140 ° C. for 2 hours to produce a cured product for TMA (size: 200 mm × 200 mm × about 5 mm).

2. TMA measurement A 10 mm × 4 mm × 4 mm piece was cut out from the cured product obtained in “1. Production of cured product for thermomechanical analysis (TMA)” to obtain a TMA test piece. In accordance with the description of JIS K 7197-1991 (linear expansion coefficient test method by thermomechanical analysis of plastic) for each test piece thus obtained, linear expansion coefficient (α ₁ ) measurement was performed (increase) (Temperature rate: 5 ° C./min). Moreover, Tg was calculated | required from the intersection of the tangent before and behind an inflection point based on the obtained temperature-linear expansion coefficient curve. The results are shown in Tables 1 and 2.

<Curing shrinkage test>
(1) Photocuring system After applying each low-polarity resin adhesive obtained in Examples 1 to 10 and Comparative Examples 1 to 6 on a glass plate with a film thickness of 100 μm using a bar coater, an ultraviolet irradiation device [ By a belt conveyor type, product name “ECS-151U” manufactured by Eye Graphics Co., Ltd.], 250 mJ / cm ² (UV-B) ultraviolet rays are irradiated to cure the adhesive coating film, Obtained.
A 20 cm × 5 cm × 100 μm small piece was cut out from the cured product obtained as described above to obtain a solid specific gravity test piece.
The specific gravity of the low-polarity resin adhesive and the solid specific gravity test piece before curing is measured by the specific gravity bottle method described in JIS K 7232: 1986, and based on the obtained value, the curing shrinkage rate according to the formula (I) Asked. The results are shown in Table 1.
Curing shrinkage (%) = {(specific gravity of cured product−specific gravity of adhesive for low polarity resin before curing) / specific gravity of cured product} × 100 (I)

(2) Thermosetting system Each low-polarity resin adhesive obtained in Examples 11 to 20 and Comparative Examples 7 to 12 was coated on a glass plate with a film thickness of 100 μm using a bar coater, and then dried with a dryer. After heating at 1 ° C. for 1 hour, the coating was further heated at 140 ° C. for 2 hours to cure the adhesive coating film to obtain a cured product.
A 20 cm × 5 cm × 100 μm small piece was cut out from the cured product obtained as described above to obtain a solid specific gravity test piece.
The specific gravity of the low-polarity resin adhesive and the solid specific gravity test piece before curing is measured by the specific gravity bottle method described in JIS K 7232: 1986, and based on the obtained value, the curing shrinkage rate according to the formula (I) Asked. The results are shown in Table 2.
Curing shrinkage (%) = {(specific gravity of cured product−specific gravity of adhesive for low polarity resin before curing) / specific gravity of cured product} × 100 (I)

From the results of Table 1 and Table 2, instead of the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group, an “alicyclic diepoxy compound (P) having no bridged cyclic hydrocarbon group” is obtained. The adhesives (1 ′) to (12 ′) of Comparative Examples 1 to 12 containing at the same time have high-speed curability, low viscosity capable of thin film coating, high adhesive strength, low linear expansion coefficient, high Tg and low cure shrinkage. Not achieved.
On the other hand, the adhesives (1) to (20) for low polarity resins of the present invention containing the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group have a low viscosity suitable for thin film coating. However, it turns out that high adhesive strength is shown with respect to low polar resin (X). Furthermore, the curing speed and heat resistance (low linear expansion coefficient, high Tg) are equal to or higher than those of the comparative example, and the curing shrinkage rate is extremely low.

  The adhesive for low-polarity resin of the present invention has high-speed curability and high heat resistance (low linear expansion coefficient, high Tg), low viscosity, and extremely high adhesion to low-polarity resins. It is useful as an adhesive used for laminating various resins of displays such as, particularly useful as an adhesive used for laminating each resin film, and useful as an adhesive for polarizing plates. For example, it is useful for applications such as bonding an acrylic film or an amorphous olefin resin film as a protective film to a polyvinyl alcohol resin film on which a polarizer is adsorbed during the production of a polarizing plate.

Claims (9)

An adhesive for bonding a low-polarity resin (X), wherein the adhesive contains an alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group, and the bridgehead carbon in the adhesive The adhesive agent for low polar resins whose content is 0.01-25.0 mmol / g and whose solubility parameter of resin which comprises the said low polar resin (X) is 6.2-10.0. The low polarity resin according to claim 1, wherein the alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group is a compound represented by the following general formula (1) and / or the following general formula (2). Adhesive.

In General Formula ^{(1), R} 1 ~R ¹⁴ each represents a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. The carbon atom in the hydrocarbon group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. The carbon atom in the alkoxy group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. Moreover, in general formula (1), a, b, c, and d are 0 or an integer of 1-4, respectively. ]

In General formula ^(2), each of R 15 ^{to R 28} hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. The carbon atom in the hydrocarbon group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. The carbon atom in the alkoxy group may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom. In general formula (2), e and h are each an integer of 1 to 4, and f and g are 0 or an integer of 1 to 4, respectively. ] The alicyclic diepoxy compound (A) having a bridged cyclic hydrocarbon group is 1,2: 5,6-diepoxyhexahydroindane and / or 1,2: 5,6-diepoxydicyclopentadiene. The adhesive for low polarity resins according to claim 1 or 2. Furthermore, the adhesive agent for low polar resins in any one of Claims 1-3 containing epoxy compounds (B) other than the alicyclic diepoxy compound (A) which has the said bridged cyclic hydrocarbon group. The alicyclic diepoxy compound (A) having the bridged cyclic hydrocarbon group based on the total weight of the alicyclic diepoxy compound (A) having the bridged cyclic hydrocarbon group and the epoxy compound (B). The low-polarity resin adhesive according to claim 4, wherein the content of the epoxy compound (B) is 0.1 to 99 wt% and the content of the epoxy compound (B) is 1 to 99.9 wt%. Furthermore, at least one selected from the group consisting of a photoacid generator (C) that generates an acid upon irradiation with active energy rays, a thermal acid generator (D) that generates an acid by heating, and another epoxy curing agent (E). The adhesive agent for low polar resins in any one of Claims 1-5 containing. The low polarity resin according to any one of claims 1 to 6, wherein the low polarity resin (X) is at least one selected from the group consisting of a poly (meth) acrylic resin, an amorphous polyolefin resin, and a crystalline polyolefin resin. Adhesive. A molded product in which two members are bonded via an adhesive, at least one of which is a member made of a low-polarity resin (X), and the adhesive is a low product according to any one of claims 1 to 7. Molded product that is an adhesive for polar resins. The molded product according to claim 8, wherein at least one of the two members is a film, and the molded product is a polarizing plate.