JP2005146038A - Ultraviolet-curing adhesive and attached body using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet-curing adhesive which is excellent in adhesion property for bonding a thin film such as a film to a foreign material. <P>SOLUTION: The ultraviolet-curing adhesive comprises (A) an alicyclic epoxy compound which has two alicyclic epoxy groups and no ester bond, (B) an epoxy compound different from component (A) and (C) a cation polymerization initiator which releases cations by ultraviolet radiation. Alternatively, the ultraviolet-curing adhesive comprises (D) 1-85 pts.wt. acrylic resin having an epoxy group or an epoxy group and a hydroxy group within a molecule against 100 pts.wt. total weight of components (A) and (B). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an ultraviolet curable adhesive that can be cured by ultraviolet irradiation to form a cured product having excellent adhesion, sealing properties, and adhesive strength, and an adhesive body using the adhesive.

  In recent years, display devices using liquid crystal or organic EL have been mounted on various portable devices, and miniaturization, thinning, and weight reduction of portable devices have been promoted. A substrate or a display portion of a display device using liquid crystal or organic EL uses glass, a metal such as aluminum, a synthetic resin such as PET, or a semi-synthetic resin such as acetylcellulose. Among these materials, a thin film film made of a resin and an adhesive that easily and strongly bonds different types of materials in a short time are desired.

  Conventionally, an ultraviolet curable adhesive has been used to cure and bond easily in a short time. Examples of the ultraviolet curable adhesive include a cationic polymerizable compound having an epoxy group or a vinyl group and a cationic polymerizable type containing a cationic polymerization initiator that generates a cation by ultraviolet irradiation, and a radical polymerizable compound having a radical polymerizable unsaturated group. In addition, those containing a radical polymerization initiator that generates radicals upon irradiation with ultraviolet rays are known.

  However, radical polymerization type adhesives are characterized by a relatively fast curing speed, but they are inferior in surface curability due to insufficient adhesion to materials and processability, and inhibition of curing by oxygen. However, there is a problem that facilities such as nitrogen sealing are necessary.

  On the other hand, cationic polymerization type adhesives have advantages such as better adhesion to materials and workability compared to radical polymerization type adhesives, and do not require equipment such as nitrogen encapsulation. There was a problem that the speed was slow. A technique that solves this problem by using an alicyclic compound containing an oxetanyl group is disclosed (see Patent Document 1), but a cured product having good adhesive strength is desired. In particular, an adhesive having good adhesion by bonding a thin film such as a film is desired.

Further, it has been desired to provide an adhesive having a high curing speed and sufficient adhesive strength by bonding different materials.
JP 2003-213243 A

  The problem of the present invention is that it can be cured quickly by ultraviolet irradiation that does not require equipment such as nitrogen encapsulation, and has excellent adhesion, particularly adhesion of thin films such as films, and adhesion between different materials. It is to provide a curable adhesive.

  As a result of intensive studies, the inventor of the present invention uses an alicyclic epoxy compound having two alicyclic epoxy groups and not having an ester bond, particularly adhesion of a thin film such as a film, In addition, the present inventors have found an ultraviolet curable adhesive having excellent adhesion between different materials and have reached the present invention.

That is, the first of the present invention is (A) an alicyclic epoxy compound having two alicyclic epoxy groups and no ester bond, (B) an epoxy compound different from (A) above, (C) An ultraviolet curable adhesive comprising a cationic polymerization initiator that generates cations by ultraviolet irradiation. The second of the present invention is (A) an alicyclic ring having two alicyclic epoxy groups and no ester bond. 10 to 99 parts by weight of an epoxy compound of formula, (B) 1 to 90 parts by weight of an epoxy compound different from the above (A), and 100 parts by weight of the composition (total of (A) and (B) is 100 parts by weight) (C) An ultraviolet curable adhesive according to the first aspect of the present invention, comprising 0.01 to 20 parts by weight of a cationic polymerization initiator that generates cations by ultraviolet irradiation.

  3rd of this invention made 1-85 weight part of acrylic resin which has an epoxy group or an epoxy group and a hydroxyl group in a molecule | numerator (D) with respect to a total of 100 weight part of (A) and (B). The ultraviolet curable adhesive according to the first aspect of the present invention, wherein 0.1 to 20 parts by weight of (C) is blended with respect to 100 parts by weight of the resin composition.

  According to a fourth aspect of the present invention, a resin containing (E) 1 to 50 parts by weight of a caprolactone-modified polyol compound having 2 to 4 hydroxyl groups in the molecule with respect to 100 parts by weight of (A) and (B) in total. The ultraviolet curable adhesive according to the first aspect of the present invention, wherein 0.1 to 20 parts by weight of (C) is blended with 100 parts by weight of the composition.

  In the fifth aspect of the present invention, (A) an alicyclic epoxy compound having two alicyclic epoxy groups and having no ester bond is represented by the following general formula (1), (3) or (5). The ultraviolet curable adhesive according to any one of the first to fourth aspects of the present invention, wherein the adhesive is an epoxy compound.

（式中でＲ1〜Ｒ18は、それぞれ同一または異なって、水素原子、ハロゲン原子、酸素原子、もしくはハロゲン原子を含んでよい炭化水素基、又は置換基を有してよいアルコキシ基である。）

(In the formula, R1 to R18 are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.)

（式中でＲ1〜Ｒ12は、それぞれ同一または異なって、水素原子、ハロゲン原子、酸素原子、もしくはハロゲン原子を含んでよい炭化水素基、又は置換基を有してよいアルコキシ基である。）

(In the formula, R1 to R12 are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.)

（式中でＲ1〜Ｒ12は、それぞれ同一または異なって、水素原子、ハロゲン原子、酸素原子、もしくはハロゲン原子を含んでよい炭化水素基、又は置換基を有してよいアルコキシ基である。）
本発明の第６は、一般式（１）、（３）または（５）で表わされる脂環式エポキシ化合物におけるＲ1〜Ｒ18の全てが水素原子である本発明第５に記載の紫外線硬化型接着剤、である。

(In the formula, R1 to R12 are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.)
A sixth aspect of the present invention is the ultraviolet curable adhesive according to the fifth aspect of the present invention, wherein all of R1 to R18 in the alicyclic epoxy compound represented by the general formula (1), (3) or (5) are hydrogen atoms. Agent.

  According to a seventh aspect of the present invention, the alicyclic epoxy compound represented by the general formula (1), (3) or (5) epoxidizes the corresponding diolefin compound with an organic percarboxylic acid substantially free of moisture. The ultraviolet curable adhesive according to the fifth or sixth aspect of the present invention,

  An eighth aspect of the present invention is the ultraviolet curable adhesive according to the seventh aspect of the present invention, wherein the water content in the organic percarboxylic acid is 0.8% by weight or less.

  A ninth aspect of the present invention is the ultraviolet curable adhesive according to the seventh or eighth aspect of the present invention, wherein the organic percarboxylic acid is an organic solvent solution.

  A tenth aspect of the present invention is an adhesive body formed using the ultraviolet curable adhesive according to any one of the first to ninth aspects of the present invention.

  The ultraviolet curable adhesive of the present invention can be quickly and efficiently cured by cationic polymerization even in the presence of a cationic polymerization initiator, without requiring facilities such as nitrogen encapsulation, and even by irradiation with a low dose of ultraviolet light. Bonding of thin films such as films, that is, bonding of PET films / PET films, bonding between different materials, that is, inorganic materials such as glass and resins such as PET and acetylcellulose, and their thin films, aluminum Excellent adhesion in adhesion of metal materials such as PET and resin such as PET and its thin film.

  Hereinafter, the present invention will be described in detail.

  Typical examples of the alicyclic epoxy compound having two alicyclic epoxy groups and having no ester bond used in the present invention are those represented by the general formula (1), (3) or (5). It is an epoxy compound represented. For example, an epoxy compound of the general formula (1) is obtained by oxidizing an unsaturated compound represented by the general formula (2) having a bicyclohexyl-3,3′-diene skeleton with an organic percarboxylic acid or a hydroperoxide. Manufactured.

一般式(１)および一般式（２）において、Ｒ¹〜Ｒ¹⁸は、それぞれ同一であっても異なっていてもよい。これらは、水素原子、ハロゲン原子、あるいは酸素原子もしくはハロゲン原子を含んでよい炭化水素基、又は置換基を有してよいアルコキシ基である。

In General Formula (1) and General Formula (2), R ^{1 to} R ¹⁸ may be the same or different from each other. These are a hydrogen atom, a halogen atom, a hydrocarbon group that may contain an oxygen atom or a halogen atom, or an alkoxy group that may have a substituent.

The epoxy compound represented by the general formula (3) is produced by oxidizing an unsaturated compound represented by the general formula (IV) having a cyclooctadiene skeleton with an organic percarboxylic acid or a hydroperoxide. .

一般式（３）および一般式（４）において、Ｒ¹〜Ｒ¹²は、それぞれ同一であ
っても異なっていてもよい。これらは、水素原子、ハロゲン原子、あるいは酸素原子もしくはハロゲン原子を含んでよい炭化水素基、又は置換基を有してよいアルコキシ基である。

In General Formula (3) and General Formula (4), R ^{1 to} R ¹² may be the same or different from each other. These are a hydrogen atom, a halogen atom, a hydrocarbon group that may contain an oxygen atom or a halogen atom, or an alkoxy group that may have a substituent.

  Furthermore, the epoxy compound represented by the general formula (5) is produced by oxidizing the unsaturated compound represented by the general formula (VI) having an alicyclic indene skeleton with a hydroperoxide or an organic percarboxylic acid. The

一般式（６）および一般式（５）において、Ｒ¹〜Ｒ¹²は、それぞれ同一であっても異なっていてもよい。これらは、水素原子、ハロゲン原子、あるいは酸素原子もしくはハロゲン原子を含んでよい炭化水素基、又は置換基を有してよいアルコキシ基である。

In General Formula (6) and General Formula (5), R ^{1 to} R ¹² may be the same or different from each other. These are a hydrogen atom, a halogen atom, a hydrocarbon group that may contain an oxygen atom or a halogen atom, or an alkoxy group that may have a substituent.

Among them, since the epoxy compound R ¹ to R ¹⁸ is a hydrogen atom in the general formula (1) to (4) are industrially produced, preferred.

  Hydroperoxides that can be used include hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, and the like.

Organic peracids that can be used include organic percarboxylic acids, more specifically, formic acid,
There are peracetic acid, perpropionic acid, perbenzoic acid, trifluoroperacetic acid, and perphthalic acid. Among them, it is preferable to use peracetic acid that is used industrially in large quantities.

  Among the organic percarboxylic acids, those obtained by oxidation of the corresponding aldehyde with air or oxygen have a low water content, specifically, the water content is 0.8% by weight or less, and the epoxy compound in the present invention It is particularly preferable when manufacturing. The reason is that, since water is not substantially present, the epoxy group is ring-opened to form a hydroxyl group, or an esterification reaction between a carboxylic acid and an epoxy group generated from an organic percarboxylic acid that easily occurs in the presence of moisture. This is because a high epoxidation rate is obtained. In the oxidation reaction, a catalyst can be used as necessary. For example, 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.

  In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. it can. It can also be oxidized using alkali metal salts such as hydrogen peroxide and tungstic acid and sodium, and salts of phosphoric acid or phosphate esters, phosphates, phosphonic acids and alkylammonium and inorganic acids such as sulfuric acid. The oxidation reaction is carried out by adjusting the presence or absence of a catalyst and a solvent and the reaction temperature.

  The reaction temperature range that can be used is determined by the reactivity of the oxidizing agent used.

  Speaking of peracetic acid which is a preferable oxidizing agent, it is 0-70 degreeC, Preferably, it is 10-60 degreeC, More preferably, it is 20-50. The reaction is slow at 0 ° C. or lower, and peracetic acid is decomposed at 70 ° C., which is not preferable.

  Moreover, in the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system which is an example of hydroperoxide, it is 20 degreeC-150 degreeC for the same reason, Preferably it is 25-120 degreeC.

  When the organic percarboxylic acid having a low water content as described above is used as the oxidizing agent, a solvent can be used for stabilizing the organic percarboxylic acid. If the organic percarboxylic acid is peracetic acid, ethyl acetate is often used.

  Among the epoxy compounds represented by the general formula (1), (3), or (5), the corresponding diolefins represented by the general formula (2), (4), or (6), respectively. High epoxidation of compounds obtained using organic percarboxylic acids that are substantially free of moisture, specifically 0.8% by weight or less, preferably 0.6% by weight or less Therefore, it is preferable in that the stability of the insulating oil can be maintained over a long period of time. This organic percarboxylic acid substantially free of water is produced by air oxidation of aldehydes, for example, acetaldehyde. For example, peracetic acid is disclosed in German Patent Publication No. 1418465 and Japanese Patent Laid-Open No. 54-30006. Manufactured by the method described in 1. above. According to this method, it is possible to synthesize organic percarboxylic acid in a large amount continuously, compared with the case where organic percarboxylic acid is synthesized from hydrogen peroxide and extracted with a solvent to produce organic percarboxylic acid. Therefore, it can be obtained substantially inexpensively.

  Techniques for producing each epoxy compound represented by the general formula (1), (3) or (5) using the organic percarboxylic acid not containing water as described above are disclosed in Japanese Patent Application No. 2002-260490, respectively. And Japanese Patent Application No. 2002-351437. Specifically, the method is as follows.

  There is no strict limitation on the amount of epoxidizing agent, and the optimum amount in each case depends on variable factors such as the reactivity of the individual epoxidizing agent and cycloaliphatic olefin compound used, and the desired epoxidation ratio. .

  The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the apparatus and the physical properties of the raw material. As the solvent, it can be used for the purpose of lowering the viscosity of the raw material, stabilizing by diluting the epoxidizing agent, and in the case of peracetic acid, esters, aromatic compounds, ethers and the like can be used. Particularly preferred solvents are ethyl acetate, hexane, cyclohexane, toluene, benzene and the like, and ethyl acetate is particularly preferred. The reaction temperature is determined by the reactivity of the epoxidizing agent used and the unsaturated group-containing compound.

  For example, the reaction temperature when using peracetic acid, which is a preferred epoxidizing agent, is preferably 20 to 70 ° C. If it is less than 20 ° C., the reaction is slow, and if it exceeds 70 ° C., peracetic acid decomposes with heat generation, which is not preferable.

  The epoxidizing agent is preferably added in an amount of 1.0 to 3.0 mol, more preferably 1.05 to 1.5 mol per mol of the unsaturated group. From the viewpoint of economy and side reaction, it is usually disadvantageous to exceed 3.0 times mole.

No special operation is required for the crude liquid obtained by the reaction. For example, the crude liquid may be aged by stirring for 1 to 5 hours. Isolation of the epoxy compound from the obtained crude liquid is an appropriate method, for example, a method of precipitating with a poor solvent, a method of pouring the epoxidized product into hot water with stirring and distilling off the solvent, a direct desolvation method, etc. Can be done.
(B) The epoxy compound different from the above (A) in the present invention is a compound having one or more, preferably 1-2 epoxy groups in the molecule. This epoxy group may be an alicyclic epoxy group or an epoxy group other than the alicyclic epoxy group. Specific examples of the compound having an alicyclic epoxy group in the molecule include limonene dioxide, di (3,4-epoxy). (Cyclohexyl) 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, among others, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexyl Trimethoxysilane is preferred. In addition, these compounds can be used individually or in combination of 2 or more types. In the present invention, an ester type alicyclic epoxy compound may be used for “(B) an epoxy compound different from the above (A)”.

  On the other hand, as a compound having an epoxy group other than an alicyclic epoxy group in the molecule, various bisphenol type diglycidyl ethers typified by bisphenol A type and F type (Epicoat 828,806 (Japan epoxy YD-128 (manufactured by Resin Co., Ltd.), etc.), hydrogenated products of bisphenol type epoxy resin (commercially available products are HBE-100 (manufactured by Nippon Nippon Chemical Co., Ltd.), YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.) Etc.). In addition, glycidyl ether having a cycloaliphatic skeleton such as diglycidyl ether of cyclohexanedimethanol (commercially available products such as DME-100 (manufactured by Shin Nippon Rika)), glycidyl ether of novolac type phenol resin, DCPD, etc. Polycyclic aromatic glycidyl ether such as glycidyl ether and naphthalene of copolymerized novolak type phenol resin, epoxy resin having terminal epoxy on alicyclic skeleton (commercially available products are EHPE-3150, EHPE-3150CE (Daicel Chemical Industries, Ltd.) Etc.), and silicon resins having an epoxy group (commercially available products such as A-186 (manufactured by Nihon Unicar), KBM303, KBM403, KBM42 (manufactured by Shin-Etsu Chemical Co., Ltd.)).

In the present invention, (D) the acrylic resin having an epoxy group, or the acrylic resin having an epoxy group and a hydroxyl group is polymerized with a monomer containing an epoxy group, or a copolymer containing a monomer containing an epoxy group and a monomer containing a hydroxyl group. You can get it. Examples of the monomer containing an epoxy group include glycidyl ether, a compound having a similar terminal epoxy, and a (meth) acrylic acid ester having an alicyclic epoxy. Specific examples include glycidyl methacrylate, 2-methyl-glycidyl methacrylate, epoxidized isoprenyl methacrylate, CYM M-100, and CYM A-400 (manufactured by Daicel Chemical Industries). Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and monomers obtained by caprolactone modification of these hydroxyl group-containing acrylates (trade names FM-1, FM-3, FM-10, FA-1, FA-3, Daicel Chemical) Commercially available from industry).

  In the acrylic resin having an epoxy group (D) in the present invention or an acrylic resin having an epoxy group and a hydroxyl group, as a monomer, in addition to a monomer containing an epoxy group and a monomer containing a hydroxyl group, a normal alkyl acrylate monomer is used. Can be used for copolymerization.

  Usual alkyl acrylate monomers that can be used for copolymerization include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-, i- or t-butyl acrylate, n-, i- or t-butyl. C1-C24 alkyl or cycloalkyl of acrylic acid or methacrylic acid such as methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, etc. Alkyl ester; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acetate Rate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and other acrylic or methacrylic acid hydroxyalkyl esters having 1 to 8 carbon atoms; acrylic acid, methacrylic acid, maleic acid, itaconic acid, Α, β-ethylenically unsaturated carboxylic acids such as crotonic acid; acrylamide, methacrylamide, N-methylacrylamide, N-ethylmethacrylamide, diacetoneacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethyl Acrylamide or methacrylamide such as acrylamide, N-butoxymethylacrylamide or derivatives thereof; aromatic vinyl such as styrene, vinyltoluene, α-methylstyrene Vinyl propionate, vinyl acetate, acrylonitrile, methacrylonitrile, vinyl pivalate, Veova monomer (manufactured by Shell Chemical Co., Ltd., vinyl ester of branched fatty acid), silaplane FM0711, FM0721, FM0721 Polydimethylsiloxane macromonomer having a methacryloyl group) and other vinyl monomers.

  In producing the acrylic resin having an epoxy group (D) or the acrylic resin having an epoxy group and a hydroxyl group in the present invention from a monomer, a polymerization initiator can be used. Polymerization initiators include potassium persulfate, ammonium persulfate, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide. Oxide, cumene hydroperoxide, t-butyl hydroperoxide, acetyl peroxide, methyl ethyl ketone peroxide, succinic acid peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, AIBN (2,2′-azobis) Isobutyronitrile), ABN-E (2,2′-azobis (2-methylbutyronitrile)), ABN-V (2,2′-azobis (2,4-dimethylvaleronitrile)), perbutyl O ( t-Butylperoxy 2-ethylhexanoate) Rukoto can.

  The usage-amount of a polymerization initiator is 1-10 weight part with respect to 100 weight part of monomers, Preferably, it is 3-6 weight part. A part of the polymerization initiator may be charged in the reactor in advance, or may be added to the monomer or dropped separately without being added. Further, an initiator may be additionally charged after the monomer is charged.

  A preferable polymerization temperature is 90 to 130 ° C, and more preferably 100 to 120 ° C. When the temperature is 130 ° C. or higher, the polymerization becomes unstable and a large amount of high molecular weight compounds are produced, which is not preferable. On the other hand, if it is 90 ° C. or less, the polymerization time becomes long, which is not preferable.

  In the present invention, (D) the amount of epoxy group in the acrylic resin having an epoxy group or the acrylic resin having an epoxy group and a hydroxyl group is a functional group that reacts with an epoxy compound having a cationic polymerizable property and a cationic species as an oxirane oxygen concentration. When the acrylic resin having a group is added up, it is 6 to 11%, preferably 7.5 to 9.5%. Moreover, the amount of the hydroxyl group in the acrylic resin having a hydroxyl group in addition to the epoxy group is preferably from 1 to 300 as a hydroxyl value, and more preferably from 1.5 to 250.

  The (C) cationic polymerization initiator in the present invention is a compound that initiates polymerization by generating cationic species by irradiation with ultraviolet rays. For example, a hexafluoroantimonate salt represented by the following formulas (I) to (XV), penta Mention may be made of fluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts and other cationic polymerization initiators.

（上記（I）、（II）式中、Ａｒはアリール基、例えばフェニル基を表わし
、Ｘ^- はＰＦ6^-、ＳｂＦ6^- 又はＡｓＦ6^- を表わす。）

(Above (I), (II) wherein, Ar represents an aryl group such as phenyl group, X ^- is PF6 @ ^-, SbF6 @ ^- or AsF6 @ ^- represents a.)

（上記式中、Ｒ20は炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表わし、ｒは０〜３の整数を表わし、Ｘ^- はＰＦ6^-、ＳｂＦ6^- 又はＡｓＦ6^- を表わす）

(In the formula, R20 represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms, r is an integer of 0 to 3, X ^- is PF6 ^-, SbF6 ^- or AsF6 @ ^- represents a )

（上記中、Ｙ^- はＰＦ6^-、ＳｂＦ6^-、ＡｓＦ6^- 又はＳｂＦ5（ＯＨ）^- を表わす。）

(In the above, Y ^- is PF6 ^-, SbF6 ^-, AsF6 ^- or SbF5 (OH) ^- represent.)

（上記式中、Ｘ^- はＰＦ6^-、ＳｂＦ6^- 又はＡｓＦ6^- を表わす。）

(In the formula, X ^- is PF6 ^-, SbF6 ^- or AsF6 @ ^- represents a.)

（上記式中、Ｘ^- はＰＦ6^-、ＳｂＦ6^- 又はＡｓＦ6^- を表わす。）

(In the formula, X ^- is PF6 ^-, SbF6 ^- or AsF6 @ ^- represents a.)

（上記式中、Ｘ^- はＰＦ6^-、ＳｂＦ6^- 又はＡｓＦ6^- を表わす。）

(In the formula, X ^- is PF6 ^-, SbF6 ^- or AsF6 @ ^- represents a.)

（上記式中、Ｒ21は炭素原子数７〜１５のアラルキル基又は炭素原子数３〜９のアルケニル基を表わし、Ｒ22は炭素原子数１〜７の炭化水素基又はヒドロキシフェニル基を表わし、Ｒ23は酸素原子又は硫黄原子を含有していてもよい炭素原子数１〜５のアルキル基を表わし、Ｘ^- はＰＦ6^-、ＳｂＦ6^- 又はＡｓＦ6^- を表わす。）

(In the above formula, R21 represents an aralkyl group having 7 to 15 carbon atoms or an alkenyl group having 3 to 9 carbon atoms, R22 represents a hydrocarbon group or hydroxyphenyl group having 1 to 7 carbon atoms, and R23 represents represents an oxygen atom or an alkyl group having 1 to 5 carbon atoms which may contain a sulfur atom, X ^- is PF6 ^-, SbF6 ^- or AsF6 @ ^- represents a).

（上記式中、Ｒ24及びＲ25はそれぞれ独立に炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表わす。）

(In the above formula, R24 and R25 each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.)

（上記式中、Ｒ24及びＲ25はそれぞれ独立に炭素数１〜１２のアルキル基又は炭素数１〜１２のアルコキシ基を表わす。）

(In the above formula, R24 and R25 each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.)

（Ｃ）カチオン重合開始剤としては市販品を使用することもできる。市販品としては、例えば、UVACURE1591（ダイセルUCB社製）、イルガキュア２６４（チバガイギー社製）、CIT−１６８２（日本曹達（株）製）、サイラキュアＵＶＩ-６９７０、同ＵＶＩ-６９７４、同ＵＶＩ-６９９０（以上いずれも米国ユニオンカーバイド社製）、SＩ−６０Ｌ、ＳＩ−１００Ｌ、（以上三新化学工業製）などを挙げることができる。

(C) A commercial item can also be used as a cationic polymerization initiator. Examples of commercially available products include UVACURE1591 (manufactured by Daicel UCB), Irgacure 264 (manufactured by Ciba Geigy), CIT-1682 (manufactured by Nippon Soda Co., Ltd.), Cyracure UVI-6970, UVI-6974, UVI-6990 (manufactured by Nippon Soda Co., Ltd.) Any of the above can be cited (manufactured by Union Carbide, USA), SI-60L, SI-100L, (manufactured by Sanshin Chemical Industry).

  Examples of the caprolactone-modified polyol compound having 2 to 4 hydroxyl groups in the molecule (E) in the present invention include the following. As those having two hydroxyl groups, PCL-205, PCL-212, PCL-240, PCL-L208AL, PCL-L220AL, PCL-220EC, PCL-CD220PL, PCL-CD210HL (all from Daicel Chemical Industries, Ltd.) Commercially available). PCL-303, PCL-308, and PCL-L320AL (all are commercially available from Daicel Chemical Industries) as those having 3 hydroxyl groups, and PCL-410, PCL as those having 4 hydroxyl groups. -420D (all are commercially available from Daicel Chemical Industries, Ltd.).

<Combination ratio>
The total amount of the (A) alicyclic epoxy compound having two alicyclic epoxies used in the present invention and having no ester bond, and (B) an epoxy compound different from the above (A) is 100. In the ratio of parts by weight, the component (A) is 10 to 99 parts by weight, preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight, and the component (B) is 90 to 1 part by weight, preferably Can be used in the range of 80 to 30 parts by weight, more preferably 70 to 40 parts by weight. When the amount of the component (A) exceeds 99 parts by weight, the curability of the adhesive is inferior in the low irradiation amount of ultraviolet irradiation. Moreover, when the amount of the component (B) is less than 1 part by weight, the hardness and adhesion of the obtained bonded body are inferior. By blending the component A in the above proportion, a three-dimensional crosslinking effect is produced and a good adhesive effect is obtained.

  The amount of the cationic polymerization initiator (C) that generates a cation upon irradiation with ultraviolet rays is as follows: (A) an alicyclic epoxy compound having two alicyclic epoxies and no ester bond; and (B) the above ( The total amount of the epoxy compound different from A) is 0.01 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight. .

  In the third embodiment of the present invention, (D) an acrylic resin having an epoxy group or an epoxy group and a hydroxyl group in the molecule is used. (D) The usage-amount of a component is 1-85 weight part with respect to a total of 100 weight part of (A) component and (B) component, Preferably it is 3-70 weight part, More preferably, it is 5-60 weight part. When the amount of component (D) used is less than 1 part by weight, there is no effect of using component (D), while when the amount of component (D) used exceeds 85 parts by weight, the adhesive strength of the resulting cured product is reduced. .

  The amount of the cationic polymerization initiator (C) used is 0 with respect to 100 parts by weight of the composition obtained by adding 1 to 85 parts by weight of (D) to 100 parts by weight of the total of components (A) and (B). 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight.

  In the fourth embodiment of the present invention, (E) a caprolactone-modified polyol compound having 2 to 4 hydroxyl groups in the molecule is used. (E) The usage-amount of a component is 1-50 weight part with respect to a total of 100 weight part of (A) component and (B) component, Preferably it is 3-45 weight part, More preferably, it is 5-40 weight part. When the amount of component (E) used is less than 1 part by weight, there is no effect of using component (E). On the other hand, when the amount of component (E) used exceeds 50 parts by weight, the adhesive strength of the resulting cured product decreases. .

The amount of the cationic polymerization initiator (C) used is based on 100 parts by weight of the resin composition obtained by adding 1 to 50 parts by weight of (E) to 100 parts by weight of the total of the components (A) and (B). 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight. In the second embodiment of the present invention, as a blending ratio as the whole adhesive, (A) Component 40-99 parts by weight, (B) Component 1-60 parts by weight, (C) Component 0.3-10 parts by weight, preferably (A) Component 50-98 parts by weight, (B) Component 2 -50 parts by weight, (C) component 0.5-8 parts by weight, more preferably (A) component 60-95 parts by weight, (B) component 5-40 parts by weight, (C) component 1-5 parts by weight Range.

  In the third embodiment of the present invention, (A) component 5 to 95 parts by weight, (B) component 5 to 85 parts by weight, (C) component 0.3 to 10 parts by weight, and (D) component 1 to 85 parts by weight. The component (A) is preferably 10 to 90 parts by weight, the component (B) is 10 to 75 parts by weight, the component (C) is 0.5 to 8 parts by weight, and the component (D) is 1 to 75 parts by weight, more preferably. , (A) 20-80 parts by weight, (B) 17-17 parts by weight, (C) 1-5 parts by weight, and (D) components 3-60 parts by weight.

  In the fourth embodiment of the present invention, (A) component 5 to 95 parts by weight, (B) component 3 to 85 parts by weight, (C) component 0.3 to 10 parts by weight, and (E) component 1 to 50 parts by weight. The component (A) is 10 to 95 parts by weight, the component (B) is 5 to 80 parts by weight, the component (C) is 0.5 to 8 parts by weight, and the component (E) is 3 to 25 parts by weight, more preferably. , (A) 20-90 parts by weight, (B) 10-70 parts by weight, (C) 1-5 parts by weight, and (E) 5-20 parts by weight.

  In the adhesive of the present invention, in addition to the components (A), (B), (C) and (D), (E), if necessary, a sensitizer; an amount of coloring pigment that does not significantly inhibit curing Pigments such as extender pigments, dyes; polyol resins, phenol resins, acrylic resins, polyester resins, polyolefin resins, epoxy resins, epoxidized polybutadiene resins and other modified resins; organic resin fine particles; solvents and the like can be blended .

  The sensitizer is blended for the purpose of further improving curability by ultraviolet rays, and examples thereof include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin. The blending amount of the sensitizer is usually 10 parts by weight or less, preferably 3 parts by weight or less with respect to 100 parts by weight of the total amount of the components (A) and (B).

  Moreover, when mix | blending a modified resin, this modified resin is 0.1-50 weight part normally with respect to the total amount of 100 weight part of (A) component and (B) component, Especially 5-20 weight part. It is preferable to use within the range of parts.

  Various surfactants can be added to prevent leveling and improve coating performance. Silicon-based compounds and fluorine-based compounds can be used as the surfactant.

  It is also possible to use organic resin fine particles. These are preferably organic resin fine particles having a particle diameter in the range of 50 to 500 nm, and examples thereof include acrylic resin fine particles whose inside is three-dimensionally cross-linked. Organic resin fine particles are obtained by pulverizing an organic polymer into fine particles; polymer fine particles obtained by emulsion polymerization in water in the presence of an emulsifier; dried and pulverized; organic in the presence of a polymer stabilizer. Examples thereof include those obtained by drying and pulverizing polymer fine particles obtained by dispersion polymerization in a solvent. By blending organic resin fine particles with the adhesive of the present invention, the adhesion and workability of the coating film can be improved. When organic resin fine particles are blended, the amount of the organic resin fine particles is usually 0.1 to 50 parts by weight, particularly 1 to 10 parts per 100 parts by weight of the total amount of the component (A) and the component (B). It is preferably within the range of parts by weight.

  The ultraviolet curable adhesive of the present invention can be prepared by mixing the components described above and stirring the mixture so as to form a uniform adhesive. For example, each component can be mixed, heated as necessary, for example, at about 50 ° C., and stirred for about 10 minutes until uniform with a stirrer such as a dissolver. .

  The ultraviolet curable adhesive of the present invention can be applied by a method such as roll coating, spray coating, brush coating, bar coating, roller coating or silk screen printing. When the adhesive contains a solvent, after application, the solvent is removed by heating or the like, and then cured by ultraviolet irradiation, but the irradiation conditions are appropriately changed according to the type of adhesive applied, film thickness, etc. be able to. The wavelength of the ultraviolet rays to be irradiated is usually within the range of 200 to 600 nm, and an irradiation source having a high sensitivity wavelength can be appropriately selected and used depending on the type of the cationic polymerization initiator. .

Examples of the ultraviolet irradiation source include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. Irradiation condition to the coating film is usually within the range dose is 10~1,000mJ / cm ^2, in particular 50 to 500 mJ / cm ² is suitable.

  Moreover, you may heat an adhesive agent as needed after ultraviolet irradiation. Unreacted substances in the adhesive can be reduced by heating, and the curability of the coating film by ultraviolet irradiation and the distortion generated by the molding process can be reduced. In some cases, the heating can improve the hardness and adhesion of the adhesive. The said heating can be normally performed on the conditions for 1 to 30 minutes at 150-200 degreeC atmospheric temperature.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. “%” And “part” indicate “% by weight” and “part by weight”, unless otherwise specified.
[Synthesis Example 1]
406 g of bicyclohexyl-3,3′-diene, which is the compound of the formula (2), and 1217 g of ethyl acetate are charged into the reactor, and the temperature in the reactor is adjusted to 37.5 while flowing nitrogen into the gas phase portion. While maintaining the temperature, 457 g of a 30 wt% peracetic acid ethyl acetate solution (water content 0.41 wt%) was added dropwise over about 3 hours. After completion of the dropwise addition of peracetic acid in ethyl acetate, the mixture was stirred at 40 ° C. for 1 hour to complete the reaction. Subsequently, the reactor was cooled to 30 ° C., and the reaction crude liquid was washed with water. Thereafter, low boiling components were removed from the reaction crude liquid at 70 ° C./20 mmHg to obtain 415 g of an epoxy compound. The obtained epoxy compound had an oxirane oxygen concentration of 14.7% by weight and a yield of 85%.

When the obtained epoxy compound was analyzed using ¹ HNMR, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton derived from an epoxy group in the vicinity of δ2.9 to 3.1 ppm disappeared. Peak generation was confirmed. Therefore, it was confirmed that the epoxy compound is a non-ester type alicyclic epoxy compound having the structure of the formula (1).
[Synthesis Example 2]
About 108 g of cyclooctadiene, which is the compound of the above formula (4), and 108 g of ethyl acetate were charged into a reactor, and nitrogen was passed through the gas phase portion, and the temperature in the reactor was kept at 30 ° C. Over a period of 3 hours, 532 g of a 30 wt% ethyl acetate solution of peracetic acid was added dropwise. After completion of the dropwise addition of peracetic acid in ethyl acetate, the reaction was terminated by stirring at 30 ° C. for 5 hours. Subsequently, the reactor was cooled to 20 ° C., 86.9 g of sodium carbonate was added to the stirred reaction crude liquid, 219 g of 10% NaOH aqueous solution was further added, the stirring was stopped, and the reaction crude liquid was allowed to stand. After separation into two phases, the lower aqueous phase was extracted. After repeating this operation three times, 250 g of deionized water was added to the remaining organic phase, and the remaining neutralized salt was washed twice. Thereafter, low boiling components were removed from the reaction crude liquid at 60 ° C./20 mmHg to obtain 112.3 g of a diepoxy compound. The yield of the obtained diepoxy compound was 80.2%.
[Synthesis Example 3]
The reactor was charged with 240 g of tetrahydroindene, which is a compound of the above formula (6), and 480 g of ethyl acetate, and while flowing nitrogen into the gas phase part and maintaining the temperature in the reactor at 30 ° C., about 3 Over a period of time, 1220 g of a 30 wt% peracetic acid ethyl acetate solution was added dropwise. After completion of the dropwise addition of peracetic acid in ethyl acetate, the mixture was stirred at 30 ° C. for 6 hours to complete the reaction. Subsequently, the reactor was cooled to 20 ° C., 398 g of sodium carbonate was added to the stirred reaction crude liquid, and then 1500 g of 10% NaOH aqueous solution was added, stirring was stopped and the reaction crude liquid was separated into two phases. Was separated, the lower aqueous phase was extracted. Subsequently, 1000 g of deionized water was added to the remaining organic phase to wash the remaining neutralized salt. Thereafter, the low boiling component was removed from the reaction crude liquid at 40 ° C./10 mmHg to obtain 243 g of a diepoxy compound. The yield of the obtained diepoxy compound was 80%.
[Synthesis Examples 4 to 5] Synthesis of (D) 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate shown in Table 1 in a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. (Trade name CEL-2021P: manufactured by Daicel Chemical Industries, Ltd.) is charged with 233 g. And it heated up to 105-110 degreeC, blowing air, and the monomer and initiator which are shown in Table 1 were dripped over 3 hours. After completion of dropping, the reaction was completed by stirring for 1 hour. Table 1 shows the hydroxyl value and oxirane oxygen concentration of the acrylic resin having an epoxy group and a hydroxyl group obtained in Synthesis Example 4, and the hydroxyl value and oxirane oxygen concentration of the acrylic resin having an epoxy group and a hydroxyl group obtained in Synthesis Example 5 respectively. Indicated.

[実施例１〜１１及び比較例１，２]
攪拌機、温度計を備えた５００ｍｌのフラスコに表２及び表３に示した各成分を加え３０℃で２０分攪拌して、紫外線硬化型接着剤を得た。このようにして得た各接着剤を、厚さ０．５０ｍｍのＰＥＴ、及び厚さ０．５０ｍｍのガラス板に２０μｍになるように塗布した。
紫外線照射を高圧水銀灯（１２０Ｗ／ｃｍ）を用い、塗装板との距離１５ｃｍから、エネルギー線量が５００ｍＪ／ｃｍ²となるように行ない塗膜を硬化させて試験塗板とした。 得られた各試験塗板について下記の試験方法に基づいて試験を行なった。なお、試験はすべて２３℃において行なった。

[Examples 1 to 11 and Comparative Examples 1 and 2]
Each component shown in Table 2 and Table 3 was added to a 500 ml flask equipped with a stirrer and a thermometer, and stirred at 30 ° C. for 20 minutes to obtain an ultraviolet curable adhesive. Each of the adhesives thus obtained was applied to PET having a thickness of 0.50 mm and a glass plate having a thickness of 0.50 mm so as to be 20 μm.
Ultraviolet irradiation was performed using a high-pressure mercury lamp (120 W / cm) from a distance of 15 cm to the coating plate so that the energy dose was 500 mJ / cm ^2, and the coating film was cured to obtain a test coating plate. Each of the obtained test coated plates was tested based on the following test method. All tests were performed at 23 ° C.

The adhesive force was measured by the following procedure.
In the case of glass, 1 mm thickness, Al plate (aluminum plate) 0.5 mm thickness, PET (polyester film) 200 μm thickness, Ac cell (acetylcellulose film) 200 μm thickness, and prepare 15 mm wide test pieces, Overlap length is 5mm, adhesive is applied to the overlapped part, bonded and fixed while removing bubbles, irradiated with high pressure mercury lamp 120w x 10m x 4 passes (irradiation amount 1200mJ), adhesive strength with tensile tester (Kg / 15 mm) was measured.
The results are shown in Tables 4 and 5.

Claims (10)

  (A) An alicyclic epoxy compound having two alicyclic epoxy groups and no ester bond, (B) an epoxy compound different from the above (A), (C) cationic polymerization generating a cation by ultraviolet irradiation An ultraviolet curable adhesive comprising an initiator.   (A) 10 to 99 parts by weight of an alicyclic epoxy compound having two alicyclic epoxy groups and no ester bond, (B) 1 to 90 parts by weight of an epoxy compound different from the above (A), (( A total of 100 parts by weight of A) and (B) is blended with 0.01 to 20 parts by weight of a cationic polymerization initiator that generates a cation by ultraviolet irradiation (C). Item 4. The ultraviolet curable adhesive according to Item 1.   (D) 100 parts by weight of a resin composition containing 1 to 85 parts by weight of an acrylic resin having an epoxy group or an epoxy group and a hydroxyl group in the molecule with respect to a total of 100 parts by weight of (A) and (B) On the other hand, the ultraviolet curable adhesive according to claim 1, comprising 0.1 to 20 parts by weight of (C).   (E) With respect to 100 parts by weight of the resin composition containing 1 to 50 parts by weight of a caprolactone-modified polyol compound having 2 to 4 hydroxyl groups in the molecule, based on 100 parts by weight of the total of (A) and (B). The ultraviolet curable adhesive according to claim 1, wherein 0.1 to 20 parts by weight of (C) is blended. (A) The alicyclic epoxy compound having two alicyclic epoxy groups and having no ester bond is an epoxy compound represented by the following general formula (1), (3) or (5) The ultraviolet curable adhesive according to claim 1.

(In the formula, R1 to R18 are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.)

(In the formula, R1 to R12 are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.)

(In the formula, R1 to R12 are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent.)   The ultraviolet curable adhesive according to claim 5, wherein all of R1 to R18 in the alicyclic epoxy compound represented by the general formula (1), (3) or (5) are hydrogen atoms.   The alicyclic epoxy compound represented by the general formula (1), (3) or (5) is obtained by epoxidizing a corresponding diolefin compound with an organic percarboxylic acid containing substantially no water. Item 7. The ultraviolet curable adhesive according to Item 5 or 6.   The ultraviolet curable adhesive according to claim 7, wherein the water content in the organic percarboxylic acid is 0.8 wt% or less.   The ultraviolet curable adhesive according to claim 7 or 8, wherein the organic percarboxylic acid is an organic solvent solution. It forms using the ultraviolet curable adhesive as described in any one of Claims 1-9, The adhesive body characterized by the above-mentioned.