JP2015086371A - Active ray-curable adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active ray-curable adhesive composition forming a cured product excellent especially in storage stability even at room temperature, adhesiveness to various base materials (especially heat resistant adhesiveness and moisture resistant adhesiveness) and dimension stability.SOLUTION: There is provided an active ray-curable adhesive composition containing a radical initiator (A), an acid generator (B), and a polymerizable material (C) containing a monofunctional radical polymerizable material (C11) and a monofunctional cationic polymerizable material (C21) and having the total content of the monofunctional radical polymerizable material (C11) and the monofunctional cationic polymerizable material (C21) in the polymerizable material (C) of 60 to 100 wt.%.

Description

  The present invention is cured by irradiation with actinic rays, and actinic ray curable adhesive compositions and actinic ray curable adhesive compositions useful for flat panel displays, touch panels, or electronic component manufacturing are cured. It relates to a cured product.

  At present, flat panel displays (FPDs) represented by liquid crystal displays and organic EL displays are indispensable for many electronic devices such as televisions, tablet terminals, and mobile phones represented by smartphones, and constitute FPDs. The demand for many optical materials is also growing significantly. In addition, most smartphones and tablet terminals are equipped with touch panels in most models, and materials used in electronic devices include light resistance, weather resistance, heat resistance, moisture resistance, and other reliability, adhesion, and adhesion. There are various requirements such as properties and transparency, and there is a demand for a highly reliable resin especially during heat and humidity resistance tests.

  In recent years, cover glasses used for flat panels have become thinner. When the cover glass is thin, when the cover glass and the LCD are bonded to each other using a resin that is cured by actinic ray irradiation as an adhesive, the LCD is likely to bend and deform due to stress generated during the curing. With conventional actinic ray curable compositions (see, for example, Patent Document 1), the cover glass breaks due to dimensional changes during curing, uneven brightness occurs during LCD lighting display, and the adhesive surface peels off during heat and moisture resistance tests. There is a problem that a malfunction such as a problem occurs.

  Therefore, development of an actinic ray curable adhesive composition having high adhesive strength and little dimensional change upon curing is strongly demanded.

  Patent Document 2 discloses an epoxy resin composition containing an epoxy compound, an acrylic compound, an amine curing agent and a photoinitiator. It is described that the epoxy resin composition is preferably used for curing a portion where light does not reach such as adhesion of an electronic component such as a hard disk drive. However, a composition comprising a cationically polymerizable substance such as an epoxy compound and a latent thermosetting agent such as an amine curing agent has poor storage stability at room temperature and poor handling properties.

  Therefore, development of an actinic ray curable adhesive composition having high storage stability at room temperature is strongly demanded.

  On the other hand, a light-shielding portion is formed at the peripheral portion of the light-transmitting cover base material in order to improve the brightness and contrast of the display image. For this reason, sufficient actinic rays do not reach the portion of the actinic ray curable resin composition that is shaded by the light shielding portion, resulting in poor curing. For this reason, sufficient adhesive strength cannot be obtained, and problems such as separation of substrates and deterioration of image quality due to moisture intrusion between the substrates occur.

  Therefore, development of an actinic ray curable adhesive composition having high light-shielding part curability is strongly demanded.

  As a technique for improving the curability of the light-shielding portion, a method utilizing the delayed curability of a cationic polymerizable actinic ray curable resin has been proposed (see, for example, Patent Document 3). In this method, sufficient initial adhesion can be obtained for both the light-shielding part and the non-light-shielding part, but the flexibility and elongation of the cured resin are inferior, and there is a concern that the adhesion after the durability test is insufficient.

JP 2013-020258 A JP 2010-013507 A JP 2010-248387 A

  The present invention has been made in view of the above-mentioned problems, and the object of the present invention is high storage stability at room temperature, high adhesive strength (particularly heat-resistant adhesiveness, moisture-resistant adhesiveness), and good extensibility. It is an object to provide an actinic ray curable adhesive composition with little dimensional change upon curing.

  As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention provides a polymerizable substance (C) containing a radical initiator (A), an acid generator (B), and a monofunctional radical polymerizable substance (C11) and a monofunctional cationic polymerizable substance (C21). Actinic ray curing characterized in that the total content of the monofunctional radical polymerizable substance (C11) and the monofunctional cationic polymerizable substance (C21) in the polymerizable substance (C) is 60 to 100% by weight Mold adhesive composition; and a cured product obtained by curing the actinic ray curable adhesive composition by irradiation with actinic rays.

  By using the actinic ray curable adhesive composition of the present invention, the storage stability at room temperature is high, the adhesive strength (especially heat-resistant adhesiveness, moisture-resistant adhesiveness) is high, the stretchability is good, and the dimensions when cured. A cured product with little change can be produced. Moreover, since the actinic-light curable adhesive composition of this invention is excellent also in the sclerosis | hardenability of a light-shielding part, it can be used conveniently also for bonding of the optical base material which has a light-shielding part.

The actinic ray curable adhesive composition of the present invention contains the following (1) to (3) as essential components;
(1) Radical initiator (A)
(2) Acid generator (B)
(3) Polymerizable substance (C)

  Hereinafter, (A), (B), and (C), which are essential components of the actinic ray curable adhesive composition of the present invention, will be described in order.

In the present invention, the radical initiator (A) means a compound that generates radicals by at least one of actinic rays and acids.
As the radical initiator (A), a radical is generated by either a photoradical initiator (A1) that generates radicals by actinic rays, an acid radical initiator (A2) that generates radicals by acids, or actinic rays or acids. It is possible to use known compounds such as an initiator (A12) that can be used. In the following examples, initiators capable of generating radicals by either actinic rays or acids will be described in the photoradical initiator (A1) according to the above classification.

Examples of the photoradical initiator (A1) include a radical initiator (A12) that generates radicals with actinic rays or acids, for example, acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization. Initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124), benzoin derivative polymerization initiator (A125), oxime ester derivative polymerization initiator (A126) And titanocene derivative polymerization initiator (A127).
As the photoradical initiator (A1), radical initiators (A121) to (A127) that generate radicals with any of the actinic rays and acids exemplified below can be preferably used.

  As the acylphosphine oxide derivative polymerization initiator (A121), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [manufactured by BASF Japan (LUCIRIN TPO)] and bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide [manufactured by BASF Japan Ltd. (IRGACURE 819)] and the like.

  As the α-aminoacetophenone derivative-based polymerization initiator (A122), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan (IRGACURE 907)], 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF Japan (IRGACURE 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -[4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF Japan Ltd. (IRGACURE 379)] and the like.

  Examples of the benzyl ketal derivative polymerization initiator (A123) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF Japan (IRGACURE 651)].

  As the α-hydroxyacetophenone derivative-based polymerization initiator (A124), 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF Japan (IRGACURE 184)], 2-hydroxy-2-methyl-1-phenyl-propane-1 -ON [BASF Japan (DAROCUR 1173)], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [BASF Japan (IRGACURE) 2959)] and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [manufactured by BASF Japan Ltd. (IRGACURE 127 )] And the like.

  Examples of the benzoin derivative polymerization initiator (A125) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As the oxime ester derivative polymerization initiator (A126), 1,2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)] [manufactured by BASF Japan Ltd. (IRGACURE OXE 01)] and Etanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [manufactured by BASF Japan Ltd. (IRGACURE OXE 02)] and the like. .

  As the titanocene derivative polymerization initiator (A127), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) is used. Examples thereof include titanium [manufactured by BASF Japan (IRGACURE 784)].

Examples of the acid radical initiator (A2) include an organic peroxide polymerization initiator (A21), an azo compound polymerization initiator (A22), and other acid radical initiators (A23).

  Examples of the organic peroxide polymerization initiator (A21) include benzoyl peroxide (BPO), tert-butyl peroxyacetate, 2,2-di- (tert-butylperoxy) butane, tert-butyl peroxybenzoate, n-butyl 4,4-di- (tert-butylperoxy) valerate, di- (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, di-tert-hexyl peroxide, 2,5,- Dimethyl-2,5, -di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3 , 3-Tetramethylbutylhydro Chromatography, cumene hydroperoxide, tert- butyl hydroperoxide and tert- butyl trimethylsilyl peroxide.

  As the azo compound-based polymerization initiator (A22), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 Examples include '-azobis (N-cyclohexyl-2-methylpropionamide) and 2,2'-azobis (2,4,4-trimethylpentane).

  Examples of the other polymerization initiator (A23) include 2,3-dimethyl-2,3-diphenylbutane.

  Among these radical initiators (A), from the viewpoint of storage stability, a photoradical initiator (A1) that generates radicals with actinic rays is preferable, and a radical initiator that generates radicals with actinic rays or acids ( A12) is preferred.

Of the photoradical initiator (A1), acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), and benzyl ketal derivative polymerization are preferred from the viewpoint of photocurability. An initiator (A123), an α-hydroxyacetophenone derivative polymerization initiator (A124) and an oxime ester derivative polymerization initiator (A126), more preferably an acylphosphine oxide derivative polymerization initiator (A121) and α -A hydroxyacetophenone derivative-based polymerization initiator (A124).

The content of the radical initiator (A) in the actinic ray curable adhesive composition of the present invention is preferably 0.05 to 30 with respect to the weight of the polymerizable substance (C) from the viewpoint of photocurability. % By weight, more preferably 0.1 to 25% by weight.

In the present invention, the acid generator (B) means a compound that generates an acid by actinic rays, radicals or acids.
Examples of the acid generator (B) include a photoacid generator (B1) that generates an acid by actinic rays, an acid generator (B2) that generates an acid by an acid, and a radical acid generator (B3) that generates an acid by a radical. And publicly known compounds such as In addition, among acid generators, there is an acid generator (B12) that can generate an acid by either actinic rays or radicals. This is exemplified by the above-mentioned classification. It demonstrates in an agent (B1).
In addition, (B) may be used independently and may use 2 or more types together.

Examples of the photoacid generator (B1) include a sulfonium salt derivative (B121) and an iodonium salt derivative (B122), including an acid generator (B12) capable of generating an acid by either actinic rays or radicals. These (B121) and (B122) can be preferably used as the photoacid generator (B1).

  Examples of the sulfonium salt derivative (B121) in the present invention include compounds represented by the following general formula (1) or the following general formula (2).

In General Formula (1) or (2), A ¹ is a divalent or trivalent group represented by any of the following General Formulas (3) to (10), and Ar ^{1 to} Ar ⁷ are each independently Having at least one benzene ring skeleton, halogen atom, C1-C20 acyl group, C1-C20 alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, carbon At least one atom or substitution selected from the group consisting of an alkylsilyl group, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group An aromatic hydrocarbon group or a heterocyclic group which may be substituted with a group, Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, Ar ⁵ is a divalent group, and (X ¹ ) - and (X ) - represents an anion, a is an integer of 0 to 2, b is an integer from 1 to 3, and a + b is an integer equal the valence of ^{A 1} in 2 or 3.

R ^{1 to} R ⁷ in the general formulas (5) to (8) are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom, an acyl group having 1 to 20 carbon atoms, or 1 to carbon atoms. 20 alkyl group, an amino group, a cyano group, a phenyl group, a naphthyl group, at least one atom or optionally substituted phenyl group which is substituted with a group selected from the group consisting of a phenoxy group and a phenylthio group, R ¹ And R ² , R ⁴ and R ⁵ , and R ⁶ and R ⁷ may be bonded to each other to form a ring structure.

As A ¹ in the general formula (2), groups represented by the general formula (5) and the general formulas (7) to (10) are preferable from the viewpoint of acid generation efficiency. The groups represented by 8) to (10) are more preferable.
Ar ^{1 to} Ar ⁷ in the general formula (1) and the general formula (2) are groups in which the compound represented by the general formula (1) or the general formula (2) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar ^{1 to} Ar ⁷ is preferably 1 to 5, and more preferably 1 to 4.
As an example in the case of having one benzene ring skeleton, a residue obtained by removing one or two hydrogen atoms from benzene or a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline, coumarin, and the like can be given.
Examples of the case of having two benzene ring skeletons include one or two hydrogen atoms from heterocyclic compounds such as naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine, and thianthrene. Residues excluded are listed.
As an example in the case of having three benzene ring skeletons, for example, one or two hydrogen atoms are removed from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene, and naphthobenzothiophene. Residue.
As an example in the case of having four benzene ring skeletons, for example, a residue obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like can be mentioned.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.

  Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n- or iso-propylthio group, an n-, sec- or tert-butylthio group, an n-, iso- or neo-pentylthio group, and a hexylthio group. , Heptylthio group, octylthio group and the like.

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

As the atoms or substituents substituted by Ar ^{1 to} Ar ⁷ , preferred from the viewpoint of acid generation efficiency are halogen atoms, cyano groups, phenyl groups, naphthyl groups, phenoxy groups, phenylthio groups, alkyl groups having 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms, more preferably a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, An alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, They are an alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Ar ^{1 to} Ar ⁴ , Ar ⁶ and Ar ⁷ are preferably a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group, a p-tert-butylphenyl group, 2, 4, from the viewpoint of acid generation efficiency. 6-trimethylphenyl group, p- (thioxanthylmercapto) phenyl group and m-chlorophenyl group.

Ar ⁵ is preferably a phenylene group, a 2- or 3-methylphenylene group, a 2- or 3-methoxyphenylene group, a 2- or 3-butylphenylene group, and 2- or 3-chloro, from the viewpoint of acid generation efficiency. A phenylene group.

In the general formula (1) or (2) ^{(X 1)} - or ^{(X 2)} -, as the anion represented, halide anions, hydroxide anions, thiocyanate anions, dialkyl having from 1 to 4 carbon atoms Dithiocarbamate anion, carbonate anion, bicarbonate anion, aliphatic or aromatic carboxy anion optionally substituted with halogen (benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion, etc.), Aliphatic or aromatic sulfoxy anion (trifluoromethanesulfonate anion, etc.) optionally substituted with halogen, hexafluoroantimonate anion (SbF ₆ −), phosphorus anion [phosphorus hexafluoride anion (PF ₆ −) And tris (perfluoroethyl) trifluoride On _{(PF 3 (C 2 F 5} ) 3 -) , etc.] and borate anion (tetraphenyl borate, tetrakis (perfluorophenyl) borate and butyl triphenyl borate anion), and the like, from the viewpoint of efficiency of acid generation, A phosphine anion, an aliphatic sulfoxy anion substituted with a halogen, and a borate anion are preferred. More preferred are hexafluorophosphate anion, trifluoro [tris (perfluoroethyl)] phosphate anion and tetrakis (perfluorophenyl) borate anion, and particularly preferred is trifluoro [tris (perfluoroethyl)] phosphate anion and Tetrakis (perfluorophenyl) borate anion.

  As the sulfonium salt derivative (B121), a compound having a triphenylsulfonium cation, a tri-p-tolylsulfonium cation, or a [p- (phenylmercapto) phenyl] diphenylsulfonium cation as a cation skeleton is preferable from the viewpoint of acid generation efficiency. Compounds represented by the following general formulas (11) to (14) are preferable, and compounds represented by the following general formulas (11) to (14) are more preferable.

Formula (11) to (14) in the ^{(X 3) -~ (X 6} ) - represents an anion, specifically, the general formula (1) or in (2) ^{(X 1)} - or ^(X 2) The thing similar to what was illustrated as-is mentioned, A preferable thing is also the same.

  Examples of the iodonium salt derivative (B122) in the present invention include compounds represented by the following general formula (15) or the following general formula (16).

In the formula, A ² is a divalent or trivalent group represented by any one of the general formulas (3) to (10), and Ar ^{8 to} Ar ¹² each independently have at least one benzene ring skeleton. A halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. , Aromatic group optionally substituted with at least one substituent selected from the group consisting of nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, phenoxy group and phenylthio group A hydrocarbon group or a heterocyclic group, Ar ^{8 to} Ar ¹⁰ and Ar ¹² are monovalent groups, Ar ¹¹ is a divalent group, and (X ⁷ )-and (X ⁸ )-represent anions. , C is 0-2 Integer, d is an integer from 1 to 3, and c + d is an integer equal the valence of ^{A 2} in 2 or 3.

    As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

As A ² in the general formula (16), a group represented by the general formula (5) and the general formulas (7) to (10) is preferable from the viewpoint of the efficiency of generating an acid. And groups represented by (8) to (10) are more preferable.

Ar ^{8 to} Ar ¹² in the general formula (15) or the general formula (16) are groups in which the compound represented by the general formula (15) or the general formula (16) has absorption in the ultraviolet to visible light region. is there.
The number of benzene ring skeletons in Ar ^{8 to} Ar ¹² is preferably 1 to 5, and more preferably 1 to 4. Specific examples of Ar ^{8 to} Ar ¹² include general formula (1) or general formula (2). The thing similar to what was illustrated as Ar < ¹ > -Ar < ⁷ > of these is mentioned, A preferable thing is also the same.

Examples of (X ⁷ )-and (X ⁸ )-include the same as those exemplified as (X ¹ )-or (X ² )-in general formula (1) or (2). It is the same.

  As the iodonium salt derivative (B122), (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium cation, [bis (4-t-butylphenyl)] iodonium are preferable from the viewpoint of acid generation efficiency. Cation, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium cation and [bis (4-methoxyphenyl)] iodonium cation as cation skeleton, and the following other general compounds Compounds represented by the formulas (17) to (20) are preferable, and compounds represented by the following general formulas (17) to (20) (including exemplified compounds) are more preferable.

In the general formulas (17) to (20), R ^{8 to} R ¹³ are a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An atom or substitution selected from the group consisting of an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, and a naphthyl group And (X ⁹ )-to (X ¹² )-represent an anion.

  As a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms The thing similar to what was described by description of General formula (1) and General formula (2) is illustrated.

R ^{8 to} R ¹³ are preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and more preferably a cyano group, A phenyl group, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms. An alkoxy group and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

Formula (17) to the ^{(20) (X 9) -~} (X 12) - As the general formula (1) or in (2) ^{(X 1)} - or ^{(X 2)} - similar to those exemplified for The preferable thing is also the same.

  In general, a photopolymerization initiator that can be used for curing in the visible light region (360 nm to 830 nm; see JIS-Z8120) is colored by the initiator itself because it absorbs visible light, which adversely affects the hue of the cured film. However, by using the compound represented by the general formula (2) or the general formula (16), adverse effects on the hue of the cured film can be suppressed.

Examples of the acid generator (B2) that generates an acid by an acid include a sulfonic acid ester derivative (B21), an acetic acid ester derivative (B22), and a phosphonic acid ester (B23).
Examples of the sulfonic acid ester derivative (B21) include methanesulfonic acid cyclohexyl ester, ethanesulfonic acid isopropyl ester, benzenesulfonic acid-t-butyl ester, p-toluenesulfonic acid cyclohexyl ester, and naphthalenesulfonic acid cyclohexyl ester.

  Examples of the acetate derivative (B22) include dichloroacetic acid cyclohexyl ester and trichloroacetic acid isopropyl ester.

  Examples of the phosphonic acid ester (B23) include triphenylphosphonic acid cyclohexyl ester.

  In addition, as a radical acid generator (B3) which generates an acid by radical, what was illustrated by the acid generator (B12) which can generate an acid by either actinic light or a radical corresponds also to this. .

  Among these acid generators (B), a photoacid generator (B1) that generates an acid by active light is preferable, and an acid generator (B12) that can generate an acid by active light or a radical. preferable.

  The content of the acid generator (B) in the actinic ray curable adhesive composition of the present invention is preferably 0.01 to 30 with respect to the weight of the polymerizable substance (C) from the viewpoint of photocurability. % By weight, more preferably 0.02 to 25% by weight.

In the actinic ray curable adhesive composition of the present invention, at least one of the radical initiator (A) and the acid generator (B) generates active chemical species (H) upon irradiation with actinic rays, and this activity The chemical species (H) reacts with the radical initiator (A) or the acid generator (B) to generate a new active chemical species (I), and the new active species (I) generates a polymerizable compound (C ) Proceeds.
Here, the active chemical species (H) and (I) are radicals or acids, respectively. Curing is further promoted by the diffusion of the active chemical species (H), and the curability of the actinic radiation curable adhesive composition including the portion that becomes the light shielding portion is improved. Moreover, the adhesiveness to the base material of the hardened | cured material obtained improves.
In order for the active chemical species (H) to diffuse easily, it is preferable to use a radical initiator (A) that does not react with the active chemical species (H).

The combination of the radical initiator (A) and the acid generator (B) in the actinic ray curable adhesive composition of the present invention is not particularly limited, but the combination of the photo radical initiator (A1) and the photo acid generator (B1). It is preferable that it is contained in a combination of a photo radical initiator (A12) and a photo acid generator (B12).
Specific combinations of (A) and (B) include, for example, α-aminoacetophenone derivative polymerization initiator (A122) and iodonium salt derivative (B122), and sulfonium salt derivative (B121) and acylphosphine oxide derivative polymerization. A combination of initiators (A121) is preferred.

  By containing an acid generator (B), it is highly sensitive and the macroscopic reaction rate distribution can be suppressed, so that a defect hardly occurs and a cured product having excellent homogeneity can be obtained. As a result, it is estimated that the extensibility and the adhesion to the substrate are also improved.

  In the actinic ray curable adhesive composition of the present invention, the essential polymerizable substance (C) contains a monofunctional radical polymerizable substance (C11) and a monofunctional cationic polymerizable substance (C21).

Examples of the monofunctional radically polymerizable substance (C11) include (meth) acrylic acid, monofunctional (meth) acrylamide (C111) having 3 to 35 carbon atoms, and monofunctional (meth) acrylate (C112) having 4 to 35 carbon atoms. ), Monofunctional aromatic vinyl compounds having 6 to 35 carbon atoms (C113), and other monofunctional radically polymerizable substances (C114).
In the present specification, the notation “(meth) acryl” may represent both “acryl” and “methacryl”.

  Examples of the monofunctional (meth) acrylamide (C111) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N -N-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, acryloylmorpholine, N, N -Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc. are mentioned.

  Examples of the monofunctional (meth) acrylate (C112) having 4 to 35 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, and hexyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, tert-octyl (meth) acrylate, 2,3-dimethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) ) Acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, 2-decyltetradecanyl (meth) acrylate, cyclohexyl (Meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) Acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene mono (meth) acrylate, 3-methoxybutyl (meth) acrylate, alkoxymethyl (Meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, alkoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl ( (Meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) Acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3- Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethyl Aminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene Oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene Xoxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl Ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide (hereinafter referred to as ethylene oxide EO) Modified phenol (meth) acrylate, EO-modified cresol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, propylene oxide (hereinafter, propylene oxide may be abbreviated as PO) modified nonylphenol (meth) Examples thereof include those having no vinyl ether group and / or allyl ether group such as acrylate and EO-modified 2-ethylhexyl (meth) acrylate.

  Monofunctional aromatic vinyl compound having 6 to 35 carbon atoms (C113) [excluding vinyl ether (C211) described later]. ] Are vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid. Methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4- Hexyl styrene, 3-octyl styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, Kute alkenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

  Other monofunctional radically polymerizable substances (C114) include N-vinyl-2-pyrrolidone, acrylonitrile, aliphatic vinyl esters (such as vinyl acetate, vinyl propionate and vinyl versatate), and aliphatic allyl esters (such as allyl acetate). ), Halogen-containing monomers (such as vinylidene chloride and vinyl chloride) and olefins (such as ethylene and propylene).

Among these monofunctional radically polymerizable substances (C11), from the viewpoint of adhesive strength, (meth) acrylic acid, monofunctional (meth) acrylamide (C111) having 3 to 35 carbon atoms, and 4 to 35 carbon atoms are preferable. Monofunctional (meth) acrylate (C112) and N-vinylpyrrolidone.
More preferred are monofunctional (meth) acrylamide (C111) having 3 to 35 carbon atoms and monofunctional alkyl (meth) acrylate having 6 to 35 carbon atoms, and particularly preferred are N, N-diethylacrylamide and tert-butyl. (Meth) acrylate, 2,3-dimethylhexyl (meth) acrylate, stearyl acrylate, isooctyl acrylate, lauryl acrylate and isostearyl acrylate.

  As the essential component polymerizable substance (C), the monofunctional cationic polymerizable substance (C21) used in combination with the monofunctional radical polymerizable substance (C11) includes monofunctional vinyl ether (C211) having 3 to 20 carbon atoms, carbon number Examples thereof include a monofunctional epoxy compound having 3 to 20 carbon atoms (C212) and a monofunctional oxetane compound having 4 to 20 carbon atoms (C213).

  Examples of the C3-C20 monofunctional vinyl ether (C211) include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, stearyl. Vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether , Ethoxyethoxyethyl vinyl Ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, Examples include chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, and phenoxypolyethylene glycol vinyl ether.

  Examples of the monofunctional epoxy compound having 3 to 20 carbon atoms (C212) include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, and 1,2-butylene. Oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide And 3-vinylcyclohexene oxide.

  Examples of the monofunctional oxetane compound (C213) having 4 to 20 carbon atoms include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, and (3-ethyl-3-oxetanyl). Methoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3 -Ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl 3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl- 3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) Ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3- Xetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Examples include pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, and bornyl (3-ethyl-3-oxetanylmethyl) ether.

  Among these monofunctional cation polymerizable substances (C21), from the viewpoint of curing speed and flexibility, monofunctional vinyl ethers having 3 to 20 carbon atoms (C211) are preferred, such as 2-ethylhexyl vinyl ether and 2-ethylhexyl glycidyl ether. And lauryl vinyl ether are particularly preferred.

  From the viewpoint of adhesive strength, the polymerizable substance (C) needs to contain a total of 60 to 100% by weight of the monofunctional radically polymerizable substance (C11) and the monofunctional cation polymerizable substance (C21). It is preferable to contain 9% by weight.

  In addition to the monofunctional radically polymerizable substance (C11) and the monofunctional cation polymerizable substance (C21), the polyfunctional radically polymerizable substance (C12) and the polymerizable substance (C) may be used as necessary in addition to the monofunctional radically polymerizable substance (C11) and the monofunctional cation polymerizable substance (C21). You may use a polyfunctional cation polymeric substance (C22) together.

  As the polyfunctional radically polymerizable substance (C12) that can be used in combination, 2 to 8 functional groups are preferable, and examples thereof include polyfunctional (meth) acrylates (C121) of 2- to 6-valent alcohols.

  As the polyfunctional (meth) acrylate (C121) of a divalent to hexavalent alcohol, 1,6-hexanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, neopentyl hydroxypivalate Recall di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipen Tris of adducts of 1 to 30 mol of alkylene oxide having 2 to 4 carbon atoms of erythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, sorbitol tri (meth) acrylate, pentaerythritol (Meth) acrylate, ethoxylated glycerin tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Erythritol tetra (meth) acrylate, dipentaerythritol propionate tetra (meth) acrylate, pentaerythritol alkylene oxide 1-30 mol adduct tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, caprolactone modified dipenta Erythritol hexa (meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde modified dimethylolpropane tri (meth) acrylate, and phosphazene modified with alkylene oxide Examples include hexa (meth) acrylate.

  As the polyfunctional cationic polymerizable substance (C22) that can be used in combination, 2 to 8 functional groups are preferable. For example, polyfunctional vinyl ether (C221) of 2-6 valent alcohol, polyfunctional epoxy compound (C222), and polyfunctional oxetane compound. (C223) and the like.

  Examples of the polyfunctional vinyl ether (C221) of a divalent to hexavalent alcohol include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, and alkylene oxide modified. Bisphenol A divinyl ether, alkylene oxide modified bisphenol F divinyl ether, trimethylol ethane trivinyl ether, trimethylol propane trivinyl ether, glycerin trivinyl ether EO-added trimethylol propane trivinyl ether, PO-added trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, Intererythritol tetravinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, EO-added diester Examples thereof include pentaerythritol hexavinyl ether and PO-added dipentaerythritol hexavinyl ether.

  Examples of the polyfunctional epoxy compound (C222) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S. Diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxysilane) (Rohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy -6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl Ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8 -Diepoxyoctane, 1,2,5,6-diepoxycyclooctane and the like.

  Examples of the polyfunctional oxetane compound (C223) include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene). )) Bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) Ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4 -Bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis ( 3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO Modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A Examples thereof include bis (3-ethyl-3-oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

In addition to the essential component monofunctional radical polymerizable substance (C11) and monofunctional cationic polymerizable substance (C21), from the viewpoint of curability and resin strength (toughness, heat resistance and moisture resistance are improved), It is preferable to use together a polymerizable substance (C3) having both a radical polymerizable functional group and a cationic polymerizable group.
Examples of the polymerizable substance (C3) having both a radical polymerizable group and a cationic polymerizable group in the molecule used for this purpose include, for example, one radical polymerizable functional group and one cationic polymerizable functional group. A substance (C311) or the like can be used.
The number of (C3) is not particularly limited as long as it has at least one radical polymerizable functional group and one cationic polymerizable group in the molecule.

As the polymerizable substance (C311) having one radical polymerizable functional group and one cationic polymerizable functional group, for example, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, (meta ) 2-vinyloxypropyl acrylate, 1-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate 2-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1-methyl-2 (meth) acrylate -Vinyloxypropyl, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, ( T) 6-vinyloxyhexyl acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, (meth) 2-vinyloxymethylcyclohexylmethyl acrylate, 4-vinyloxymethylphenylmethyl (meth) acrylate, 3-vinyloxymethylphenylmethyl (meth) acrylate, 2-vinyloxymethylphenylmethyl (meth) acrylate, ( 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- (2-vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (2-vinyloxyethoxy) propyl (meth) acrylate, (meta ) Acrylic acid 2- (2-vinyloxyisopropoxy) propiate , (Meth) acrylic acid 2- (2-vinyloxyethoxy) isopropyl, (meth) acrylic acid 2- (2-vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- {2- (2-vinyloxyethoxy) ) Ethoxy} ethyl, 2- {2- (2-vinyloxyisopropoxy) ethoxy} ethyl (meth) acrylate, 2- {2- (2-vinyloxyisopropoxy) isopropoxy} ethyl (meth) acrylate, 2- (2- (2- (2-vinyloxyethoxy) ethoxy) propyl (meth) acrylate, 2- {2- (2-vinyloxyethoxy) isopropoxy} propyl (meth) acrylate, 2- (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) ethoxy} propyl, (meth) acrylic acid 2- {2- (2-vinyloxyisopropoxy) isopropyl Ropoxy} propyl, 2- (2- (2-vinyloxyethoxy) ethoxy} isopropyl (meth) acrylate, 2- {2- (2-vinyloxyethoxy) isopropoxy} isopropyl (meth) acrylate, (meth) 2- {2- (2-vinyloxyisopropoxy) ethoxy} isopropyl acrylate, 2- {2- (2-vinyloxyisopropoxy) isopropoxy} isopropyl (meth) acrylate, 2- [meth) acrylic acid 2- [ 2- {2- (2-vinyloxyethoxy) ethoxy} ethoxy] ethyl, (meth) acrylic acid 2- [2- {2- (2-vinyloxyisopropoxy) ethoxy} ethoxy] ethyl, (meth) acrylic acid 2- (2- [2- {2- (2-vinyloxyethoxy) ethoxy} ethoxy] ethoxy) ethyl; and the like.
Among these polymerizable substances (C311), from the viewpoints of curability and resin strength, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxyethyl (meth) acrylate, and 2-vinyloxy (meth) acrylate are preferable. Propyl, 4-vinyloxybutyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- {2- (2) (meth) acrylate -Vinyloxyethoxy) ethoxy} ethyl.

By containing a polymerizable substance (C3) having both a radical polymerizable group and a cationic polymerizable group in these molecules, the curability and the toughness of the cured product can be further improved. Moreover, when the optical base material which has a light shielding part is bonded together, the sclerosis | hardenability of a light shielding part improves.
The content of (C3) is preferably 0.01 to 40% by weight, more preferably 0.01 to 25% by weight, and particularly preferably 0.1 to 40% by weight with respect to the polymerizable substance (C). 25% by weight.

  In the actinic ray curable adhesive composition of the present invention, the content of the radical initiator (A) is 0.05 to 30% by weight based on the total amount of (A), (B), and (C). The content of the acid generator (B) is 0.01 to 30% by weight based on the total amount of (A), (B) and (C), and the content of the polymerizable compound (C) is (A ), (B), (C) based on 40 to 99.94% by weight.

  The actinic ray curable adhesive composition of the present invention is a coloring material (pigments such as inorganic pigments and organic pigments, dyes), metal oxides, and metal powders from the viewpoint of transparency of the resulting cured product. It is preferable that none of these are substantially contained. Here, the phrase “not substantially contained” means that the content in the actinic ray curable adhesive composition is less than 1% by weight.

  If necessary, the actinic ray curable adhesive composition of the present invention may contain a polymerization inhibitor such as hydroquinones.

The actinic ray curable adhesive composition of the present invention can contain a sensitizer if necessary.
Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The content of the sensitizer is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 2 to 10% by weight with respect to the actinic ray curable adhesive composition.

  The actinic ray curable adhesive composition of the present invention further has an adhesion-imparting agent (such as a silane coupling agent), a tackifier, a dispersant, an antifoaming agent, a leveling agent, and thixotropy according to the purpose of use. An imparting agent, slip agent, flame retardant, antistatic agent, antioxidant, ultraviolet absorber and the like can be contained.

  The actinic ray curable adhesive composition of the present invention is polymerizable including a radical initiator (A), an acid generator (B), a monofunctional radical polymerizable substance (C11), and a monofunctional cationic polymerizable substance (C21). It can be obtained by kneading the substance (C) and, if necessary, a sensitizer, other components, etc. with a rotation / revolution stirrer, a ball mill or a three roll mill. The kneading temperature is preferably 10 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.

Examples of the actinic rays used for curing the actinic ray curable adhesive composition of the present invention include visible rays and ultraviolet rays.
Since the actinic ray curable adhesive composition of the present invention can be photocured by irradiation with an actinic ray of 360 nm to 830 nm, in addition to a commonly used high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a high power metal halide lamp (Latest trends in UV / EB curing technology, edited by Radtech Research Association, CM Publishing, page 138, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Furthermore, sunlight, a low-pressure mercury lamp, a semiconductor laser, etc. can be used. Heating may be performed for the purpose of diffusing and accelerating curing of the acid generated from the photoacid generator (B) during and / or after irradiation with actinic rays. The heating temperature is preferably 30 ° C to 200 ° C, more preferably 35 ° C to 150 ° C, and particularly preferably 40 ° C to 120 ° C.

  As an application method to the substrate of the actinic ray curable adhesive composition of the present invention, known coating methods such as spin coating, roll coating and spray coating, nanoimprint process, lithographic printing, carton printing, metal printing, offset printing Printing methods such as screen printing and gravure printing can be applied. Further, the present invention can also be applied to coating using an ink jet method or a liquid fixed quantity discharge device that discharges fine droplets continuously.

  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 of acid generator (B)]
Production Example 1
[Sulphonium Salt Derivative (B121-1) {Compound Represented by Chemical Formula (21)} that Generates Acid by Active Light]

(1) Synthesis of 2- (phenylthio) thioxanthone [intermediate (B121-1-1)]:
11.0 parts of 2-chlorothioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours. The product was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. Purification by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) yielded 3.1 parts of intermediate (B121-1-1) (yellow solid).

(2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone [intermediate (B121-1-2)]:
While stirring 11.2 parts of the intermediate (B121-1-1), 215 parts of acetonitrile, and 0.02 part of sulfuric acid at 40 ° C., 4.0 parts of 30% aqueous hydrogen peroxide was gradually added dropwise thereto. After reacting at ˜45 ° C. for 14 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: ethyl acetate / toluene = 1/3: volume ratio) to obtain 13.2 parts of intermediate (B121-1-2) (yellow solid).

(3) Synthesis of sulfonium salt derivative (B121-1):
While stirring 4.3 parts of intermediate (B121-1-2), 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was gradually added dropwise to After reacting at 45 ° C. for 1 hour, the reaction solution is cooled to room temperature (about 25 ° C.), poured into 150 parts of distilled water, extracted with chloroform, and washed with water until the pH of the aqueous phase becomes neutral. did. After the chloroform phase was transferred to a rotary evaporator and the solvent was distilled off, 50 parts of toluene was added, dispersed in toluene with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the supernatant was removed three times to produce The washed solid was washed, and the residue was dried under reduced pressure. This residue was dissolved in 212 parts of dichloromethane, poured into 65 parts of 10% potassium {trifluoro [tris (perfluoroethyl)] phosphate} aqueous solution, and stirred at room temperature (about 25 ° C.) for 2 hours. After washing three times with water by a liquid separation operation, the organic solvent was distilled off under reduced pressure to obtain 5.5 parts of a sulfonium salt derivative (B121-1) (yellow solid).

Production Example 2
[Synthesis of Iodonium Salt Derivative (B122-1) {Compound Represented by Chemical Formula (22)} that Generates Acid by Actinic Light]

  6.5 parts of toluene, 8.1 parts of isopropylbenzene, 5.35 parts of potassium iodide and 20 parts of acetic anhydride are dissolved in 70 parts of acetic acid, cooled to 10 ° C., and kept at a temperature of 10 ± 2 ° C. A mixed solution of 12 parts of sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour. It heated up to 25 degreeC and stirred for 24 hours. Thereafter, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and diethyl ether was distilled off under reduced pressure. An aqueous solution in which 118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate} was dissolved in 100 parts of water was added to the residue, followed by stirring at 25 ° C. for 20 hours. Thereafter, 500 parts of ethyl acetate was added to the reaction solution, washed with water three times, and the organic solvent was distilled off under reduced pressure to obtain 14.0 parts of the target iodonium salt derivative (B122-1) (light yellow liquid). It was.

Examples 1-18
The number of radical initiators (A), acid generators (B), monofunctional radical polymerizable substances (C11), monofunctional cationic polymerizable substances (C21) and, if necessary, polyfunctional radical polymerizable substances (as shown in Table 1) C12), a polyfunctional radically polymerizable substance (C22) and a polymerizable substance (C3) having both a radically polymerizable group and a cationically polymerizable group in the molecule are blended in the number of parts shown in Table 1, and rotation and revolution stirring is performed. The actinic ray curable adhesive compositions (Q-1) to (Q-18) of the present invention were produced by mixing at 25 ° C. for 10 minutes using an apparatus.

Comparative Examples 1-6
The number of radical initiators (A), acid generators (B), monofunctional radical polymerizable substances (C11), monofunctional cationic polymerizable substances (C21) and, if necessary, polyfunctional radical polymerizable substances (as shown in Table 1) C12), polyfunctional radically polymerizable substance (C22), polymerizable substance (C3) having both radically polymerizable group and cationically polymerizable group in the molecule, and latent thermosetting agent, as shown in Table 1. Then, it was mixed at 25 ° C. for 10 minutes using a rotation / revolution stirrer to produce comparative actinic ray curable adhesive compositions (Q′-1) to (Q′-6).

The composition of the trade names in the table is as follows.
“Irgacure 819”: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [manufactured by BASF Japan Ltd.]
“Irgacure 907”: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan Ltd.]
“Irgacure 184”: 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF Japan Ltd.]
“VEEA”: 2- (2-vinyloxyethoxy) ethyl acrylate [manufactured by Nippon Shokubai Co., Ltd.]
“Amicure VDH”: Hydrazide compound [Ajinomoto Fine Techno Co., Ltd.]

The physical properties and performance of each actinic ray curable adhesive composition obtained in Examples 1 to 18 and Comparative Examples 1 to 6 and the cured product were evaluated by the following methods.

[Viscosity change rate]
The viscosity (p) at 25 ° C. of the actinic ray curable adhesive composition was measured using an E type viscometer [manufactured by Toki Sangyo Co., Ltd., TVE-25 type viscometer].
Next, 5 g of each actinic ray curable adhesive composition was placed in a polyethylene brown container (manufactured by NALGENE, 30 mL), sealed, allowed to stand at 25 ° C. for 2 weeks, and viscosity at 25 ° C. after 2 weeks. (Q) was measured.
The viscosity change rate was calculated from the following formula.
Viscosity change rate (%) = {(q / p) -1} × 100

[Adhesive strength]
About 0.1 mL of the actinic ray curable adhesive composition was applied on a 1 mm thick slide glass, and another slide glass was prepared using a gap gauge [manufactured by Nagai Gauge Manufacturing Co., Ltd., 0.10 mm]. And was formed into a circular shape so as to have a film thickness of 100 μm.
The exposure was performed using a belt conveyor type UV irradiation apparatus [“ECS-151U” manufactured by Eye Graphics Co., Ltd., and the same applies hereinafter]. The exposure amount was 1500 mJ / cm ² at 365 nm.
Based on JIS K-6849, the adhesive strength of the round test piece after curing was evaluated using a tensile tester [Autograph AG-IS, manufactured by Shimadzu Corporation, the same applies hereinafter].

[Adhesive strength after heat test]
A test piece for measuring adhesive strength is prepared using an actinic ray curable adhesive composition.
After the 1000 hr test piece was subjected to a heat resistance test at 85 ° C., the test piece after the heat test was evaluated for adhesive strength with a tensile tester in accordance with JIS K-6849.

[Adhesive strength after moisture resistance test]
After preparing a test piece for measuring the adhesive strength and subjecting the 1000 hr test piece to a moisture resistance test at 60 ° C. and 90% RH, the test piece after the moisture resistance test is based on JIS K-6849. Evaluated.

[Flexibility]
The actinic ray curable adhesive composition was poured into a cylindrical mold so as to have a film thickness of 1 cm, and exposed using a belt conveyor UV irradiation device to obtain a test piece for flexibility evaluation. The exposure amount was 3000 mJ / cm ² at 365 nm.
Using this test piece, in accordance with JIS-K7215, the durometer E hardness was measured using a durometer hardness meter (type E) [product name Asker rubber hardness meter, manufactured by Kobunshi Keiki Co., Ltd.].
A: Less than 10 (very excellent flexibility)
○: 10 or more and less than 16 (excellent flexibility)
X: 16 or more (flexibility is inferior)

[Elongation]
Another actinic ray curable adhesive composition was prepared on a 25 μm thick PP (polypropylene) film [Wintech WFX4TA manufactured by Nippon Polypro Co., Ltd.] using a silicon spacer [manufactured by ASONE Co., Ltd., 1 mm]. Molded so as to have a width of 5.0 mm, a length of 40 mm, and a film thickness of 1.0 mm with the PP film, exposed using a belt conveyor UV irradiation device, and a test piece for evaluation of extensibility. Obtained.
The test piece was reinforced by winding a vinyl tape around each of the 10 mm ends on the long side, and a tensile test was performed at a tensile rate of 10 mm / s using a tensile tester, and the elongation was calculated according to the following formula.
Elongation rate (%) = L / L ₀ × 100
In the formula, L is the displacement length until breakage, and L ₀ is the length of the sheet before the test (L ₀ = 20 mm).

[Curing shrinkage]
About actinic-light curable adhesive composition, liquid specific gravity [a] was measured based on JISZ-8804 using a 25 mL specific gravity bottle.
In addition, a gap gauge [manufactured by Nagai Gauge Manufacturing Co., Ltd., 1.00 mm] is used on a 25 μm thick PP (polypropylene) film [Nippon Polypro Co., Ltd. Wintech WFX4TA]. Then, it was molded so as to have a film thickness of 1.0 mm with another PP film prepared.
Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 1500 mJ / cm ² at 365 nm. Using the cured coating film, the specific gravity [b] of the cured product was measured by an underwater substitution method in accordance with JIS K-7112.
From the specific gravity [a] of the liquid and the specific gravity [b] of the cured product, the cure shrinkage was calculated from the following formula.
Curing shrinkage (%) = {1- (a / b)} × 100

[Curability of light shielding part]
Apply thermosetting black ink [MRX ink, Teikoku Mfg. Co., Ltd.] to the entire periphery of a glass plate [Gorilla Glass, Corning (50 mm x 100 mm x thickness 0.7 mm)] by screen printing. By drying, a glass plate having a light-shielding part having a width of 5 mm was prepared. Each actinic ray curable adhesive composition was applied to the entire surface of the glass plate having the light-shielding portion using a resin dispenser so that the thickness became an average of 150 μm. UV light with an illuminance of 100 mW / cm ^{2 is applied} from the glass plate side using a belt conveyor type UV irradiation device using a belt conveyor type UV irradiation device, with the application surface overlapped with the surface on which the polarizing plate of the liquid crystal module [50 mm × 80 mm × thickness 0.9 mm] is laminated. Was irradiated for 30 seconds to obtain a light-shielding part curability evaluation test piece in which the glass plate and the liquid crystal module were in close contact with each other.
The glass plate was peeled off from this test piece, the resin layer of the light shielding part was washed with methanol, and the uncured resin composition in the resin layer was removed. The resin layer after methanol washing was visually observed and evaluated according to the following criteria.
A: There is no evidence that the uncured resin composition has been removed. (Fully cured)
◯: Although there is a trace that a partially uncured resin composition has been removed, a cured product having a width of 2 mm or more remains.
(Triangle | delta): There exists a trace by which the partially uncured resin composition was removed, and the width | variety which hardened | cured material remains is less than 2 mm.
X: Hardened | cured material does not remain at all. (Uncured)

  These evaluation results are shown in Table 1.

  In Comparative Examples 1 and 5, the resin was not cured even after exposure, and performance evaluation could not be performed. In Comparative Examples 3 and 6, the curing shrinkage rate was too large, so that the glass was broken during exposure, and the adhesive strength could not be evaluated.

  The actinic ray curable adhesive composition of the present invention has high adhesive strength, excellent heat resistance and moisture resistance, and low curing shrinkage, so that it is used for flat panel displays, touch panels, and electronic component manufacturing. In particular, it is extremely useful for flat panel displays and touch panels.

Claims (8)

  A polymerizable substance containing a polymerizable substance (C) containing a radical initiator (A), an acid generator (B), and a monofunctional radical polymerizable substance (C11) and a monofunctional cationic polymerizable substance (C21) The actinic ray curable adhesive composition, wherein the total content of the monofunctional radically polymerizable substance (C11) and the monofunctional cation polymerizable substance (C21) in (C) is 60 to 100% by weight.   The actinic ray curable adhesive according to claim 1, wherein the anion moiety of the acid generator (B) is a hexafluorophosphate anion, a trifluoro [tris (perfluoroethyl)] phosphate anion, or a tetrakis (perfluorophenyl) borate anion. Composition.   The monofunctional radical polymerizable substance (C11) is (meth) acrylic acid, monofunctional (meth) acrylamide (C111) having 3 to 35 carbon atoms, or monofunctional (meth) acrylate (C112) having 4 to 35 carbon atoms. The actinic ray curable adhesive composition according to claim 1 or 2.   The actinic ray curable adhesive composition according to any one of claims 1 to 3, wherein the monofunctional cationic polymerizable substance (C21) is a monofunctional vinyl ether (C211) having 3 to 20 carbon atoms.   The actinic ray curable adhesive composition according to any one of claims 1 to 4, further comprising a polymerizable substance (C3) having both a radical polymerizable group and a cationic polymerizable group in the molecule.   The content of the radical initiator (A) with respect to the polymerizable substance (C) is 0.05 to 30% by weight, and the content of the acid generator (B) with respect to the polymerizable substance (C) is 0.01 to 30% by weight. The actinic ray curable adhesive composition according to claim 1, wherein the composition is%.   The actinic ray curable adhesive composition according to any one of claims 1 to 6, which is used for flat panel displays, touch panels, or electronic component manufacturing.   Hardened | cured material formed by hardening | curing the actinic-light curable adhesive composition in any one of Claims 1-7 by irradiation of actinic light.