JP5989469B2 - Photosensitive composition - Google Patents

Description

  The present invention relates to a photosensitive composition that forms a transparent cured product by light irradiation.

So-called UV coating, which is cured by light irradiation and coats the surface, is expanding its application range such as coating agents and adhesives from the viewpoint of workability (rapid curing) and low VOC.
Generally, a photocurable coating agent and a photocurable adhesive are composed of a photopolymerization initiator, a radical polymerizable monomer, an oligomer or a polymer, and various additives depending on applications.

In photocurable coating agents, radical polymerization is subject to inhibition of curing by oxygen, poor curability near the surface, and insufficient hardness and scratch resistance. In order to solve this problem, it has been proposed to use specific inorganic particles (see, for example, Patent Document 1).
However, the invention described in Patent Document 1 uses inorganic particles having a specific structure in combination, and is improved in terms of satisfying hardness and scratch resistance, but the adhesion to the substrate becomes poor, And when obtaining hardened | cured materials, such as a transparent coating film, there exists a problem that transparency cannot be hold | maintained.

  In addition, an image display unit and a front plate for improving the contrast and brightness of a flat panel display (FPD) represented by a liquid crystal display (LCD), a plasma display (PDP), etc. Applications such as an adhesive for filling between and the like have been proposed (for example, Patent Document 2). However, no photocurable filling adhesive that satisfies the required high heat resistance, adhesion to various substrates and high transparency is known.

JP 2011-076002 A JP 2009-186957 A

  The present invention has been made in view of the above-mentioned problems, and the object of the present invention is excellent in hardness, scratch resistance, adhesion to various substrates, heat resistance, and a transparent cured product (coating film, etc.). Is to provide a photosensitive composition.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention is the following six inventions.
[1] A combination of the polymerizable substance (D) and the radical initiator (A) and the acid generator (B) in any combination of the following (1) to (3), a colorant, a metal oxide powder, It is a photosensitive composition characterized by not containing a metal powder substantially, and the said polysynthetic substance (D) is only any one of a radically polymerizable compound (D1) or an ionic polymerizable compound (D2). The following radical initiator (A1) that generates radicals with actinic rays, or the following radical initiator (A2) that generates radicals with an acid and / or a base, is an acylphosphine oxide derivative. Systemic 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), titanocene derivative polymerization initiator (A127), and azo compound polymerization initiator (A22) A photosensitive composition which is at least one radical initiator selected from the group consisting of:
(1) A radical initiator (A1) that generates radicals by actinic rays and an acid generator (B2) that generates acids by at least one selected from the group consisting of radicals, acids and bases.
(2) At least one selected from the group consisting of an acid generator (B1) that generates an acid by actinic rays, a radical initiator (A2) that generates a radical by an acid and / or a base, and, if necessary, a radical, an acid and a base Contains a base generator (C2) that generates bases by seeds.
(3) A combination of two or more of (1) to (2) above.
[2] A cured product obtained by curing the photosensitive composition of the above [1] by irradiation with actinic rays.
[3] A photosensitive composition containing the following (1) to (3), wherein at least one of the radical initiator (A12) and the base generator (C) is activated by irradiation with actinic rays (H ), And the active species (H) reacts with the radical initiator (A12) or the base generator (C) to generate a new active species (I), which is caused by the new active species (I). The polymerization reaction of the polymerizable substance (D) proceeds, the active species (H) or (I) is a base, and substantially does not contain any of a colorant, a metal oxide powder, and a metal powder. A photosensitive composition.
(1) Acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124) ), A benzoin derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126), and a titanocene derivative polymerization initiator (A127), which is at least one radical initiator selected from the group consisting of radical initiators (A12)
(2) Base generator (C)
(3) Polymerizable substance (D)
[4] Acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxy together with polymerizable substance (D) At least one selected from the group consisting of an acetophenone derivative polymerization initiator (A124), a benzoin derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126), and a titanocene derivative polymerization initiator (A127). The radical initiator (A12) and the base generator (C), which are radical initiators, are contained in any combination of the following (1) to (3), and substantially contain a colorant, a metal oxide powder, and a metal powder. A photosensitive composition characterized by not containing.
(1) A radical initiator (A12) that generates radicals with actinic rays and a base generator (C2) that generates bases with at least one selected from the group consisting of radicals, acids and bases.
(2) At least one selected from the group consisting of a base generator (C1) that generates a base by actinic rays, a radical initiator (A12) that generates a radical by an acid and / or a base, and a radical, an acid, and a base if necessary. Contains an acid generator (B2) that generates an acid depending on the species.
(3) A combination of two or more of (1) to (2) above.
[5] A cured product obtained by curing the photosensitive composition of [3] or [4] by irradiation with actinic rays.
[6] Acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124) ), A benzoin derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126), and a titanocene derivative polymerization initiator (A127), which is at least one radical initiator selected from the group consisting of radical initiators (A12) and the activity of polymerizing the polymerizable substance (D) by irradiation with actinic rays in the presence of the base generator (C) and in the absence of any of the colorant, metal oxide powder and metal powder. A method for producing a photocured product, including a radical initiator (A12) and a base generator (C). At least one of the active species (H) is generated by irradiation with actinic rays, and the active species (H) reacts with the radical initiator (A12) or the base generator (C) to generate a new active species (I). A process for producing an actinic ray-cured product which is generated and undergoes a polymerization reaction of the polymerizable substance (D) with the new active species (I), and the active species (H) or (I) is a base.

  In the present invention, an actinic ray is a ray having a wavelength of 360 nm to 830 nm.

  By using the photosensitive composition of the present invention, it is possible to produce a cured product that is excellent in hardness, scratch resistance, adhesion to various substrates, and heat resistance.

The photosensitive composition of the present invention contains the following (1) to (3);
(1) Radical initiator (A)
(2) Acid generator (B) and / or base generator (C)
(3) Polymerizable substance (D)

In the photosensitive composition of the first invention , the third invention, the fourth invention , and the actinic ray cured product of the sixth invention, the radical initiator (A), the acid generator (B) and the base are used. At least one of the generators (C) generates active species (H) by irradiation with actinic rays, and the active species (H) generates radical initiator (A), acid generator (B) and / or base. It reacts with the agent (C) to generate new active species (I), and the polymerization reaction of the polymerizable substance (D) with the new active species (I) proceeds. Here, examples of the active species (H) and (I) include radicals, acids, and bases. In the above reaction, either of the active species (H) or (I) is an acid or a base. is necessary. Due to the diffusion of the active species (H), it is difficult to cure with a general photopolymerization initiator, and it is possible to cure a narrow gap such as between the image display unit of the FPD and the front plate or a portion where light does not reach. It becomes possible. Moreover, the transparency of the obtained cured product and the adhesion to the substrate are improved. These characteristics are thought to be due to uniform curing. In order for the active species (H) to diffuse easily, it is preferable to use a polymerizable substance (D) that does not react with the active species (H).

  In general cationic polymerization using an acid generator alone or anionic polymerization using a base generator alone, it is difficult to use a wavelength at which the generator does not absorb. However, in the present invention, an acid generator or a base generator is used. It is possible to use a wavelength that does not have absorption by combining it with a radical initiator that absorbs at that wavelength.

In the present invention, the radical initiator (A) means a compound that generates radicals by at least one of actinic rays, acids, and bases, radical initiator (A1) that generates radicals by actinic rays, and acids. In addition, a known compound such as a radical initiator (A2) that generates radicals with a base can be used.
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). The benzoin derivative polymerization initiator (A125), the oxime ester derivative polymerization initiator (A126), the titanocene derivative polymerization initiator (A127), etc. can generate radicals by any of actinic rays, acids and bases. It can be applied as either (A1) or (A2).
The organic peroxide polymerization initiator (A21), the azo compound polymerization initiator (A22), the other radical initiator (A23), and the like can generate radicals with an acid and / or a base. .
(A) may be used independently and may use 2 or more types together.
In addition, (A121) shows that it is the 1st example of the compound (A12) applicable as both (A1) and (A2).

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

  As the α-aminoacetophenone derivative-based polymerization initiator (A122), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF (IRGACURE 907)], 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF (IRGACURE 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [ 4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF (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 (IRGACURE 651)].

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

  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 (IRGACURE OXE 01)] and ethanone -1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [manufactured by BASF (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. Titanium [manufactured by BASF (IRGACURE 784)] and the like.

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

  As a radical initiator (A2) which generates a radical by an acid and / or a base, an organic peroxide polymerization initiator (A21) and / or an azo compound polymerization initiator (A22) are preferable.

  Among these radical initiators (A), from the viewpoint of the storage stability of the photosensitive composition, organic peroxide polymerization initiators (A21) and azo compound polymerization initiators that generate radicals by heat ( Those other than A22), that is, radical initiators (A1) [including (A12)] that generate radicals by actinic rays are preferred. In particular, when the photosensitive composition contains a base generator (C1) that generates a base by actinic rays, radical generation by the base generated from (C1) is further promoted, and therefore (A12) is used. preferable.

  The content of the radical initiator (A) in the photosensitive composition of the present invention is preferably 0.05 to 30% by weight based on the weight of the polymerizable substance (D), from the viewpoint of photocurability, and further Preferably it is 0.1-20 weight%.

In the present invention, the acid generator (B) means a compound that generates an acid by at least one of actinic rays, radicals, acids, and bases, and an acid generator (B1) that generates an acid by actinic rays, And known compounds such as an acid generator (B2) that generates an acid with at least one selected from the group consisting of radicals, acids and bases.
By containing the acid generator (B), the sensitivity is increased and the macroscopic reaction rate distribution can be suppressed. Therefore, the cured product of the present invention obtained by curing the photosensitive composition of the present invention has high hardness and high It is presumed that scratch resistance and high transparency can be expressed.
For example, the sulfonium salt derivative (B121) and the iodonium salt derivative (B122) can generate an acid by actinic rays or radicals, and can be applied as (B1) or (B2).
In addition, the sulfonic acid ester derivative (B21), the acetic acid ester derivative (B22), the phosphonic acid ester (B23), and the like can generate an acid with an acid and / or a base, and can be applied as (B2).
(B) may be used alone or in combination of two or more.
In addition, (B121) shows that it is the 1st example of the compound (B12) applicable as both (B1) and (B2).

  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 the general formula (1) or (2), A ¹ is a divalent or trivalent group represented by any ^one of the general formulas (3) to (10), and Ar ^{1 to} Ar ⁷ are each independently benzene. Having at least one ring skeleton, halogen atom, C1-C20 acyl group, C1-C20 alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, carbon number 1 to 20 alkylsilyl groups, nitro groups, carboxyl groups, hydroxyl groups, mercapto groups, amino groups, cyano groups, phenyl groups, naphthyl groups, phenoxy groups and phenylthio groups, at least one atom or substituent An aromatic hydrocarbon group or a heterocyclic group which may be substituted with Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, Ar ⁵ is a divalent group, and (X ¹ ) ^- and (X ^{2) -} is an anion And, 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 atom or substituent substituted by Ar ^{1 to} Ar ⁷ , a halogen atom, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, a phenylthio group, or an alkyl group having 1 to 20 carbon atoms is preferable from the viewpoint of acid generation efficiency. , 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 a 2- or 3-chloro group from the viewpoint of acid generation efficiency. A phenylene group.

Examples of the anion represented by (X ¹ ) ⁻ or (X ² ) ⁻ in the general formula (1) or (2) include a halide anion, a hydroxide anion, a thiocyanate anion, and those having 1 to 4 carbon atoms. Dialkyldithiocarbamate anion, carbonate anion, bicarbonate anion, aliphatic or aromatic carboxy anion optionally substituted with halogen (benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion, etc.) , An aliphatic or aromatic sulfoxy anion (such as trifluoromethanesulfonate anion) optionally substituted with halogen, hexafluoroantimonate anion (SbF ₆ ⁻ ), phosphorus anion [phosphorus hexafluoride anion (PF ₆ ⁻ ) And tris (perfluoroethyl) phosphorus anion ( _{F 3 (C 2 F 5)} 3 -) , etc.] and borate anion (tetraphenyl borate and butyl triphenyl borate anion), and the like, from the viewpoint of acid generation efficiency, phosphoric anion, aliphatic substituted with halogen Sulfoxy anions and borate anions are preferred.

  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.

(X ³ ) ⁻ to (X ⁶ ) ⁻ in the general formulas (11) to (14) represent anions, specifically, (X ¹ ) ⁻ or (X ² ) in the general formula (1) or (2). ) ^- it includes the same ones as exemplified as, preferable ones are also same.

  The iodonium salt derivative (B122) in the present invention is 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, wherein Ar ^{8 to} Ar ¹⁰ and Ar ¹² are monovalent groups, Ar ¹¹ is a divalent group, and (X ⁷ ) ⁻ and (X ⁸ ) ⁻ are anions. C is an integer of 0-2, d is 1-3 An integer, 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 the general formula (1) or (2), and preferable ones are also included. 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 ) ⁻ represents 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.

(X ⁹ ) ⁻ to (X ¹² ) ^{− in the} general formulas (17) to (20) are the same as those exemplified as (X ¹ ) ⁻ or (X ² ) ^{− in the} general formula (1) or (2). 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 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 the present invention, the base generator (C) means a compound that generates a base with at least one of actinic rays, radicals, acids and bases, and a base generator (C1) that generates a base with actinic rays, In addition, a known compound such as a base generator (C2) that generates a base by at least one selected from the group consisting of radicals, acids and bases can be used.
By including the base generator (C), the sensitivity is increased and the macroscopic reaction rate distribution can be suppressed. Therefore, the cured product of the present invention obtained by curing the photosensitive composition of the present invention has high hardness and high It is presumed that scratch resistance and high transparency can be expressed.
For example, the oxime derivative (C121), the quaternary ammonium salt derivative (C122), the quaternary amidine salt derivative (C123) and the like can generate a base by actinic rays or radicals, and are applied as (C1) or (C2). it can.
Further, the carbamate derivative (C21) can generate a base with a base and can be applied as (C2).
(C) may be used alone or in combination of two or more.
In addition, (C121) shows that it is the 1st example of the compound (C12) applicable as both (C1) and (C2).

  Examples of the oxime derivative (C121) include O-acyloxime.

  Examples of the carbamate derivative (C21) include 1-Fmoc-4-piperidone and o-nitrobenzoyl carbamate.

  Examples of the quaternary ammonium salt derivative (C122) and the quaternary amidine salt derivative (C123) include compounds represented by any one of the following general formulas (21) to (23).

R ^{14 to} R ⁴¹ in the general formulas (21) to (23) are each a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. , 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, a naphthyl group, represented by the general formula (24) An atom or a substituent selected from the group consisting of the substituent represented by formula (25) and the substituent represented by formula (25), wherein any one of R ^{14 to} R ²³ is represented by formula (24) or formula ( 25), and any one of R ^{24 to} R ³¹ is a substituent represented by the general formula (24) or the general formula (25), and any one of R ^{32 to} R ⁴¹ One is a position represented by the general formula (24) or the general formula (25). It is a substituent.

R ^{42 to} R ⁴⁵ in the general formulas (24) and (25) are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{46 to} R ⁴⁸ are each having 1 to 20 carbon atoms which may be substituted with a hydroxyl group. It is an alkyl group, (X ¹³ ) ⁻ and (X ¹⁴ ) ⁻ represent an anion, and e is an integer of 2 to 4.

  In general formulas (21) to (23), 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 carbon Examples of the alkylsilyl group having 1 to 20 are the same as those described in the description of the general formula (1) and the general formula (2).

The compound represented by the general formula (21) is an anthracene skeleton, the compound represented by the general formula (22) is a thioxanthone skeleton, and the compound represented by the general formula (23) is a compound having a benzophenone skeleton, i-line (365 nm). It is an example of a compound having a maximum absorption wavelength in the vicinity. R ^{14 to} R ²³ are modified in consideration of adjustment of absorption wavelength, adjustment of sensitivity, thermal stability, reactivity, decomposability, etc., and include a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms, Nitro group, carboxyl group, hydroxyl group, mercapto group, alkyl silyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, alkyl group having 1 to 20 carbon atoms, phenyl group, naphthyl group The atom or substituent selected from the group consisting of is modified according to the purpose. However, any one of R < ¹⁴ > -R < ²³ > is a substituent represented by General formula (24) or General formula (25).

R ^{14 to} R ²³ 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.

Specific examples of the above R ^{14 to} R ²³ include the compounds described in the description of R ^{8 to} R ^{13 in} the general formulas (17) to (19).

The substituent represented by the general formula (24) is a substituent having a cationized amidine skeleton, and e is an integer of 2 to 4. Examples of the substituent include a substituent having a cationized structure of 1,8-diazabicyclo [5.4.0] -7-undecene in which e is 4, and 1,5-diazabicyclo [4. 3.0] -5-Nonene is preferably a substituent having a cationized structure. R ⁴² and R ⁴³ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. It is.

General formula (25) has a quaternary ammonium structure, R ⁴⁴ and R ⁴⁵ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, More preferably, they are a hydrogen atom or a C1-C5 alkyl group. R ^{46 to} R ⁴⁸ represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, and may be linear, branched or cyclic. R ^{46 to} R ⁴⁸ are preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

(X ¹³ ) ⁻ and (X ¹⁴ ) ⁻ in the general formulas (24) and (25) represent anions, specifically, (X ¹ ) ⁻ or (X ² ) in the general formula (1) or (2). ) ^- it includes the same as those exemplified as. Of these, aliphatic or aromatic carboxy ions and borate anions are preferred from the viewpoint of photodegradability.

When the compound represented by the general formula (24) is irradiated with actinic rays, the bond between carbon and nitrogen to which R ⁴² and R ⁴³ are bonded is cleaved to produce a basic compound having an amidine skeleton. In the compound represented by 25), upon irradiation with actinic rays, a bond between carbon and nitrogen to which R ⁴⁴ and R ⁴⁵ are bonded is cleaved to produce a tertiary amine.

  Of these photobase generators (C1), a compound represented by the following general formula (26) is preferred from the viewpoint of photodegradability.

(X ¹⁵ ) ⁻ in the general formula (26) represents an anion, specifically, the same as those exemplified as (X ¹ ) ⁻ or (X ² ) ^{− in the} general formula (1) or (2). Things. Of these, aliphatic or aromatic carboxy ions and borate anions are preferred from the viewpoint of photodegradability.

  Examples of the carbamate derivative (C21) include 1-Z-4-piperidone.

  In the photosensitive composition of the present invention, even if any of the acid generator (B) and the base generator (C) is used, excellent adhesiveness to various substrates and a transparent cured product can be obtained. From the viewpoint of yellowing resistance of the cured product, it is preferable to use the acid generator (B).

  The content of the acid generator (B) and / or the base generator (C) [total of (B) and (C)] in the photosensitive composition of the present invention is a polymerizable substance from the viewpoint of photocurability. Preferably it is 0.05-30 weight% with respect to the weight of (D), More preferably, it is 0.1-20 weight%.

In the present invention, (A1), (A2), (B1), (B2), (C1), or (C2) may be contained in any combination of the following (1) to (4): Preferred [photosensitive compositions of the first and fourth inventions ].
(1) Contains (A1) and (B2) and / or (C2).
(2) Contains (B1), (A2), and (C2) if necessary.
(3) Contains (C1), (A2), and (B2) if necessary.
(4) A combination of two or more of (1) to (3) above.

In (1) above, radicals are generated as active species (H) upon irradiation with actinic rays, and acids and / or bases are generated as active species (I).
In (2) above, an acid is generated as the active species (H) by irradiation with actinic rays, and a radical and a base as required are generated as the active species (I).
In (3) above, a base is generated as an active species (H) by irradiation with actinic rays, and a radical and an acid are generated as necessary as an active species (I).
Among these combinations, more preferred are those containing (A1) and (B2) of (1), (B1) and (A2) of (2) (A1), (A2) A compound containing the compound (A12) applicable as any of the above, and the compound (A12) applicable as any of (A1) and (A2) out of (C1) and (A2) in (3) Particularly preferred are those containing (A1) and (B2), and those containing (B1) and (A12).

  As the polymerizable substance (D) in the present invention, known compounds such as a radical polymerizable compound (D1) and an ionic polymerizable compound (D2) can be used. (D) may be used alone or in combination of two or more. Of these, the radically polymerizable compound (D1) is preferable from the viewpoint of curing speed. Further, if necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be used in combination.

Examples of the radical polymerizable compound (D1) include a (meth) acrylamide compound (D11) having 3 to 35 carbon atoms, a (meth) acrylate compound (D12) having 4 to 35 carbon atoms, and an aromatic vinyl compound having 6 to 35 carbon atoms. (D13), a C3-C35 vinyl ether compound (D14), and other radically polymerizable compounds (D15).
In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.

  Examples of the (meth) acrylamide compound (D11) 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, N, N-dimethyl (meth) ) Other than (meth) acryloylmorpholine such as acrylamide and N, N-diethyl (meth) acrylamide.

Examples of the (meth) acrylate compound (D12) having 4 to 35 carbon atoms include the following monofunctional to hexafunctional (meth) acrylates.
The “monofunctional to hexafunctional (meth) acrylate” means a (meth) acrylate having 1 to 6 (meth) acryloyl groups, and the same description method is used hereinafter.
Monofunctional (meth) acrylates include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (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 Relate, 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, hydroxyalkyl (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, dimethylaminopropyl (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 oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide Monoalkyl ether (meth) acrylate, oligop Pyrene 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 EO) modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, propylene oxide (Hereinafter referred to as PO) vinyl ether groups such as modified nonylphenol (meth) acrylate and EO-modified-2-ethylhexyl (meth) acrylate and / or allyl ether. Such as those having no ether group.

  Examples of the bifunctional (meth) acrylate include 1,4-butanedi (meth) acrylate, 1,6-hexanedi (meth) acrylate, polypropylene di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl 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, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl- Tandiol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (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-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) ) Acrylate and tricyclodecane di (meth) acrylate.

  Trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate , Tri (meth) having 2 to 4 alkylene oxide 30-mole adduct of carbon atoms of the pentaerythritol acrylate, ethoxylated glycerin tri (meth) acrylate.

  As tetrafunctional (meth) acrylates, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetrapropionate ( Examples include tetra (meth) acrylates of 1 to 30 moles of adducts of 2 to 4 carbon atoms of (meth) acrylate and pentaerythritol.

  Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Examples of hexafunctional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) acrylate. It is done.

  Examples of the aromatic vinyl compound having 6 to 35 carbon atoms (D13) include vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro. Styrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, Seo propenyl styrene, butenylstyrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

As a C3-C35 vinyl ether compound (D14), the following monofunctional or polyfunctional vinyl ether is mentioned, for example.
The “monofunctional vinyl ether” means a vinyl ether compound having one vinyl group, and the “polyfunctional vinyl ether” means two or more vinyl groups.
Examples of the monofunctional vinyl ether include 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, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl 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, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether.

  Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, EO-added trimethylolpropane trivinyl ether, PO-added trimethylolpropane trivinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added pentaerythritol tetravinyl ether, EO-added Examples thereof include dipentaerythritol hexavinyl ether and PO-added dipentaerythritol hexavinyl ether.

  Other radical polymerizable compounds (D15) include acrylonitrile, aliphatic vinyl ester compounds (such as vinyl acetate, vinyl propionate and vinyl versatate), aliphatic allyl ester compounds (such as allyl acetate), halogen-containing monomers ( Non-aromatic ester compounds such as vinylidene chloride and vinyl chloride) and olefin compounds (such as ethylene and propylene).

  The radical polymerizable compound (D1) contains a trifunctional or higher functional radical polymerizable compound (Df3) and, if necessary, a monofunctional radical polymerizable compound (Df1) and / or a bifunctional radical polymerizable compound (Df2). A tri- or higher functional radical polymerizable compound (Df3) is preferably a tri- to hexa-functional alcohol tri- to tri-functional (meth) acrylate compound, more preferably pentaerythritol tetra (meth) acrylate, di- Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

  Among these, the (meth) acrylamide compound (D11) having 3 to 35 carbon atoms, the (meth) acrylate compound (D12) having 4 to 35 carbon atoms, and the aroma having 6 to 35 carbon atoms are preferable from the viewpoint of curing speed. Group vinyl compound (D13) and C3-C35 vinyl ether compound (D14), more preferably C3-C35 (meth) acrylamide compound (D11) and C4-C35 (meth) acrylate. It is a compound (D12).

  Examples of the ion polymerizable compound (D2) include an epoxy compound (D21) having 3 to 20 carbon atoms and an oxetane compound having 4 to 20 carbon atoms (D22).

As a C3-C20 epoxy compound (D21), the following monofunctional or polyfunctional epoxy compounds are mentioned, for example.
The “monofunctional epoxy compound” means an epoxy compound having one epoxy group, and the “polyfunctional epoxy compound” means an epoxy compound having two or more epoxy groups.
Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 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 polyfunctional epoxy compound 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-epoxycyclohexyl) Til) 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, Serine triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-di Examples include epoxy octane and 1,2,5,6-diepoxycyclooctane.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of curing speed, and alicyclic epoxides are particularly preferable.

  Examples of the oxetane compound (D22) having 4 to 20 carbon atoms include compounds having 1 to 6 oxetane rings.

  Examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) 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-oxetanyl) Methyl) ether, 2-ethylhexyl (3-ethyl-3-o Cetanylmethyl) 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-tetrabromophenoxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) Ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether and bornyl (3-ethyl-3-oxetanylmethyl) ether.

  Examples of the compound having 2 to 6 oxetane rings 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, dicyclopentenyl bis (3-ethyl-3-oxetanyl) Methyl) 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 Bis (3-ethyl-3-oxetanylmethyl) ether and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether are mentioned.

  Of these, compounds having 1 to 2 oxetane rings are preferred from the viewpoint of curing speed.

  The photosensitive composition of the present invention includes a coloring material (a pigment such as an inorganic pigment and an organic pigment, a dye), a metal oxide, and a metal powder, from the viewpoint of transparency of the resulting cured product. It is necessary to not contain substantially. Here, the phrase “not substantially contained” means that the content in the photosensitive composition is less than 1% by weight. The content of the coloring material in the photosensitive composition is preferably 0.8% by weight or less, more preferably 0% by weight.

  The photosensitive composition of the present invention can contain a solvent, a sensitizer, an adhesion-imparting agent (such as a silane coupling agent) and the like as necessary.

Solvents include glycol ethers (ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether). Acetate and propylene glycol alkyl ether acetate), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.) and ethers (tetrahydrofuran) And 1,8-cineole). These may be used alone or in combination of two or more.
The content of the solvent in the photosensitive composition is preferably 0 to 99% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 90% by weight.

  Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, substituted anthracene, and the like other than (C). 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 photosensitive composition.

  Adhesion imparting agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltri Examples include ethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. The content of the adhesion-imparting agent is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight, based on the photosensitive composition.

  The photosensitive composition of the present invention further includes a dispersant, an antifoaming agent, a leveling agent, a thixotropy imparting agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant, an ultraviolet absorber, etc. according to the purpose of use. In addition to (meth) acrylic resin, it can contain.

  The photosensitive composition of the present invention comprises a radical initiator (A), a polymerizable substance (D), an acid generator (B) and / or a base generator (C), and, if necessary, a solvent and other components. Can be obtained by kneading with a ball mill or a three-roll mill. The kneading temperature is usually 10 ° C to 40 ° C, preferably 20 ° C to 30 ° C.

  Since the photosensitive 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, a high power metal halide lamp, etc. The latest trends in EB curing technology, edited by Radtech Research Association, CMC Publishing, 138, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently. Heating may be performed for the purpose of diffusing the base generated from the photobase generator during and / or after irradiation with actinic rays. The heating temperature is usually 30 ° C to 200 ° C, preferably 35 ° C to 150 ° C, more preferably 40 ° C to 120 ° C.

  Examples of the method for applying the photosensitive composition of the present invention to a substrate include known coating methods such as spin coating, roll coating, and spray coating, and planographic printing, carton printing, metal printing, offset printing, screen printing, and gravure printing. A known printing method can be applied. In addition, the present invention can also be applied to ink jet type coating in which fine droplets are continuously discharged.

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”. In the following, Examples 6 to 9 are referred to as Reference Examples 1 to 4, respectively.

[Production of acid generator (B)]
Production Example 1
[Synthesis of Acid Generator (B121-1) {Compound Represented by Chemical Formula (27)}]

(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 acid generator (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, charged into 65 parts of 10% aqueous potassium tris (pentafluoroethyl) trifluorophosphate, and stirred at room temperature (about 25 ° C.) for 2 hours. After washing with water three times, the organic solvent was distilled off under reduced pressure to obtain 5.5 parts of an acid generator (B121-1) (yellow solid).

Production Example 2
[Synthesis of Acid Generator (B121-2) {Compound Represented by Chemical Formula (28)}]

  IRGACURE 819 [manufactured by BASF Corp.] 4.2 parts, p-tolyl sulfoxide [manufactured by Tokyo Chemical Industry Co., Ltd.] 2.8 parts, potassium nonafluoro-1-butanesulfonate [manufactured by Tokyo Chemical Industry Co., Ltd.] 4.1 parts, 1.2 parts of sulfuric acid [manufactured by Wako Pure Chemical Industries, Ltd.] and 100 parts of acetonitrile were charged and dissolved, followed by stirring at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the solvent was distilled off from the organic layer under reduced pressure to obtain 6.7 parts of an acid generator (B121-2) (yellow solid). .

Production Example 3
[Synthesis of Acid Generator (B121-3) {Compound Represented by Chemical Formula (29)}]

  In a reaction vessel, LUCIRIN TPO [manufactured by BASF] 3.5 parts, diphenyl sulfoxide [manufactured by Tokyo Chemical Industry Co., Ltd.] 2.4 parts, potassium hexafluorophosphate [manufactured by Tokyo Chemical Industry Co., Ltd.] 2.2 parts, 1.2 parts of sulfuric acid [manufactured by Wako Pure Chemical Industries, Ltd.] and 100 parts of acetonitrile were charged and dissolved, followed by stirring at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the solvent was distilled off from the organic layer under reduced pressure to obtain 5.4 parts of an acid generator (B121-3) (yellow solid). .

Production Example 4
[Synthesis of Acid Generator (B121-4) {Compound Represented by Chemical Formula (30)}]

  In a reaction vessel, 2.8 parts IRGACURE 907 [manufactured by BASF], 1.7 parts bromobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.3 parts silver tetrafluoroborate [manufactured by Tokyo Chemical Industry Co., Ltd.] 100 parts of tetrahydrofuran was charged and dissolved, and the mixture was stirred at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the solvent was distilled off from the organic layer under reduced pressure to obtain 3.3 parts of an acid generator (B121-4) (light yellow solid). It was.

Production Example 5
[Synthesis of Acid Generator (B122-1) {Compound Represented by Chemical Formula (31)}]

  8.1 parts of t-butylbenzene [manufactured by Tokyo Chemical Industry Co., Ltd.], 5.35 parts of potassium iodide [manufactured by Tokyo Chemical Industry Co., Ltd.] and 20 parts of acetic anhydride are dissolved in 70 parts of acetic acid, and the mixture is dissolved up to 10 ° C. The mixture was cooled and a mixed solution of 12 parts of concentrated sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour while maintaining the temperature at 10 ± 2 ° C. 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 3 times with water, and the organic solvent was distilled off under reduced pressure to obtain 14.0 parts of the target acid generator (B122-1) (light yellow liquid). It was.

Production Example 6
[Synthesis of Acid Generator (B122-2) {Compound Represented by Chemical Formula (32)}]

  “8.1 parts of t-butylbenzene” was changed to 7.5 parts of “methoxybenzene [manufactured by Tokyo Chemical Industry Co., Ltd.]” and “118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate} was changed to“ Except having changed to 80 parts of potassium hexafluorophosphate [manufactured by Tokyo Chemical Industry Co., Ltd.], 12.1 parts of an acid generator (B122-2) (light yellow liquid) was obtained in the same manner as in Production Example 5.

Production Example 7
[Synthesis of Acid Generator (B122-3) {Compound Represented by Chemical Formula (33)}]

  “8.1 parts of t-butylbenzene” was replaced with “9.2 parts of methyl phenoxyacetate [manufactured by Tokyo Chemical Industry Co., Ltd.]” and “118 parts of potassium {trifluoro [tris (perfluoroethyl)] phosphate}” Except for changing to 140 parts of potassium tetrakis (perfluorophenyl) borate [manufactured by Tokyo Chemical Industry Co., Ltd.], 13.3 parts of acid generator (B122-3) (light yellow liquid) was prepared in the same manner as in Production Example 5. Obtained.

Production Example 8
[Synthesis of Acid Generator (B122-4) {Compound Represented by Chemical Formula (34)}]

  In a reaction vessel, IRGACURE 651 (BASF) 2.4 parts, potassium iodide [Tokyo Chemical Industry Co., Ltd.] 4.0 parts, hexafluoroantimonate silver [Tokyo Chemical Industry Co., Ltd.] 8.2 parts Then, 2.4 parts of sulfuric acid [manufactured by Wako Pure Chemical Industries, Ltd.], 5.0 parts of benzene and 100 parts of acetonitrile were charged and dissolved, followed by stirring at 60 ° C. for 6 hours. 200 parts of dichloromethane was added, the organic layer was washed three times with 200 parts of ion-exchanged water, and the organic solvent was distilled off under reduced pressure to obtain 10.7 parts (light yellow solid) of an acid generator (B122-4).

Production Example 9
[Synthesis of Acid Generator (B122-5) {Compound Represented by Chemical Formula (35)}]

  Except for changing “t-butylbenzene 8.1 parts” to “toluene [Tokyo Chemical Industry Co., Ltd.] 6.5 parts” and “isopropylbenzene [Tokyo Chemical Industry Co., Ltd.] 8.1 parts”, In the same manner as in Production Example 5, 5.0 parts of an acid generator (B122-5) (light yellow liquid) was obtained.

[Production of base generator (C)]
Production Example 10
[Synthesis of Base Generator (C122-1) {Compound Represented by Chemical Formula (36)}]

  Dissolve 2.0 parts of 9-chloromethylanthracene (manufactured by Aldrich) in chloroform and add 3.1 parts of trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] little by little (slightly exothermic after addition) The mixture was stirred at room temperature (about 25 ° C.) for 1 hour to obtain a reaction solution. The reaction solution is dropped little by little into an aqueous solution consisting of 4.0 parts of sodium tetraphenylborate salt and 40 parts of water, and the mixture is further stirred for 1 hour at room temperature (about 25 ° C.). The layer was washed 3 times with water. The organic solvent was distilled off under reduced pressure to obtain 7.1 parts of a white solid. This white solid was recrystallized from acetonitrile to obtain 6.2 parts of a base generator (C122-1) (white solid).

Production Example 11
[Synthesis of Base Generator (C122-2) {Compound Represented by Chemical Formula (37)}]

(1) Synthesis of methylthioxanthone [intermediate (C122-2-1)]:
10 parts of dithiosalicylic acid [manufactured by Wako Pure Chemical Industries, Ltd.] was dissolved in 139 parts of sulfuric acid, stirred for 1 hour at room temperature (about 25 ° C.), and then cooled in an ice bath to obtain a cooled solution. Next, 25 parts of toluene was dropped little by little while keeping the liquid temperature of this cooling solution at 20 ° C. or lower, and then returned to room temperature (about 25 ° C.) and further stirred for 2 hours to obtain a reaction solution. The reaction solution was added little by little to 815 parts of water, and the precipitated yellow solid was filtered off. This yellow solid is dissolved in 260 parts of dichloromethane, 150 parts of water is added, 6.7 parts of 24% KOH aqueous solution is further added to make the aqueous layer alkaline, and the mixture is stirred for 1 hour, and then the aqueous layer is removed by a liquid separation operation. The organic layer was washed 3 times with 130 parts of water. Then, the organic layer was dried over anhydrous sodium sulfate, and then the organic solvent was distilled off under reduced pressure to obtain 8.7 parts of intermediate (C122-2-1) (yellow solid). The intermediate (C122-2-1) is a mixture of 2-methylthioxanthone and 3-methylthioxanthone.

(2) Synthesis of 2-bromomethylthioxanthone [intermediate (C122-2-2)]:
An intermediate (C122-2-1) (2.1 parts) was dissolved in cyclohexane (120 parts), and N-bromosuccinimide [Wako Pure Chemical Industries, Ltd.] 8.3 parts and benzoyl peroxide [Wako Pure Chemical Industries, Ltd.] Made by Co., Ltd.] After adding 0.1 part and reacting under reflux for 4 hours (3-methylthioxanthone does not react), the solvent (cyclohexane) was distilled off, and then 50 parts of chloroform was added to the residue. Redissolved to obtain a chloroform solution. The chloroform solution was washed with 30 parts of water three times, and the aqueous layer was removed by a liquid separation operation. Then, the organic solvent was distilled off under reduced pressure to obtain 1.7 parts of a brown solid. This was recrystallized from ethyl acetate (3-methylthioxanthone was removed here) to obtain 1.5 parts of intermediate (C122-2-2) (yellow solid).

(3) Synthesis of N- (9-oxo-9H-thioxanthen-2-yl) methyl-N, N, N-tris (2-hydroxyethyl) ammonium bromide [intermediate (C122-2-3)]
After dissolving 1.0 part of intermediate (C122-2-2) (2-bromomethylthioxanthone) in 85 g of dichloromethane, 0.5 part of triethanolamine [manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise thereto. The mixture was stirred at room temperature (about 25 ° C.) for 1 hour, and the organic solvent was distilled off under reduced pressure to obtain 2.2 parts of a white solid. This white solid was recrystallized with a tetrahydrofuran / dichloromethane mixed solution to obtain 1.0 part of an intermediate (C122-2-3) (brown solid).

(4) Synthesis of base generator (C122-2):
Sodium tetraphenylborate salt [manufactured by Nacalai Tesque Co., Ltd.] 0.8 parts of an intermediate (C122-2-3) was dissolved in 50 parts of chloroform in an aqueous solution in which 17 parts of water was dissolved. After the solution was added dropwise little by little, the mixture was stirred for 1 hour at room temperature (about 25 ° C.), the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with 30 parts of water three times. The organic solvent was distilled off under reduced pressure to obtain a yellow solid. This yellow solid was recrystallized with an acetonitrile / ether mixed solution to obtain 1.3 parts of a base generator (C122-2) (slightly yellow powder).

Production Example 12
[Synthesis of Base Generator (C122-3) {Compound Represented by Chemical Formula (38)}]

(1) Synthesis of N- (9-oxo-9H-thioxanthen-2-yl) methyl-N, N-dimethyl-N- (2-hydroxyethyl) ammonium bromide [intermediate (C122-3-3)] :
Except for changing “triethanolamine [manufactured by Wako Pure Chemical Industries, Ltd.] 0.5 part” to “dimethylethanolamine [manufactured by Wako Pure Chemical Industries, Ltd.] 0.3 part”, (1 of Production Example 11) ) To (3), 0.8 part of an intermediate (C122-3-3) (brown solid) was obtained.

(2) Synthesis of base generator (C122-3):
A base generator in the same manner as in (4) of Production Example 11 except that 1.0 part of “intermediate (C122-2-3)” was changed to 0.8 part of “intermediate (C122-3-3)” 1.0 part of (C122-3) (white powder) was obtained.

Production Example 13
[Synthesis of Base Generator (C122-4) {Compound Represented by Chemical Formula (39)}]

  Except that “trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] 3.1 parts” was changed to “1-azabicyclo [2.2.2] octane 1.0 part”, in the same manner as in Production Example 10. , 4.4 parts of a base generator (C122-4) (white solid) were obtained.

Production Example 14
[Synthesis of Base Generator (C123-1) {Compound Represented by Chemical Formula (40)}]

  “Trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] 3.1 parts” is replaced with “1,8-diazabicyclo [5.4.0] -7-undecene [San Apro Co., Ltd.“ DBU ”] 1.3. 4.7 parts of a base generator (C123-1) (white solid) was obtained in the same manner as in Production Example 10, except that it was changed to “parts”.

Production Example 15
[Synthesis of Base Generator (C123-2) {Compound Represented by Chemical Formula (41)}]

  “Trioctylamine [manufactured by Wako Pure Chemical Industries, Ltd.] 3.1 parts” was replaced with “1,5-diazabicyclo [4.3.0] -5-nonene [San Apro Co., Ltd.“ DBN ”] 1.1. Except for the change to "parts", 4.6 parts of base generator (C123-2) (white solid) were obtained in the same manner as in Production Example 10.

Production Example 16
[Synthesis of Base Generator (C123-3) {Compound Represented by Chemical Formula (42)}]

(1) Preparation of silver phenylglyoxylate:
3.9 parts of phenylglyoxylic acid (manufactured by Aldrich) is dissolved in 20 parts of methanol, and 0.9 part of sodium hydroxide [manufactured by Wako Pure Chemical Industries, Ltd.] is added little by little (the heat generation due to neutralization is observed). The mixture was stirred for 1 hour, and after adding 10.4 parts of a 1 mol / L aqueous silver nitrate solution [manufactured by Wako Pure Chemical Industries, Ltd.], the precipitated gray solid was filtered off, washed with methanol, and dried. As a result, 4.4 parts of silver phenylglyoxylate (gray solid) was obtained.

(2) Synthesis of base generator (C123-3):
2.0 parts of 9-chloromethylanthracene (manufactured by Aldrich) was dissolved in 40 g of methanol, and 1,8-diazabicyclo [5.4.0] -7-undecene ["DBU" manufactured by San Apro Co., Ltd.] 1 .3 parts were added little by little (a slight exotherm was observed after the addition), and the mixture was stirred at room temperature (about 25 ° C.) for 1 hour to obtain a reaction solution. The reaction solution was added dropwise to a dispersion composed of 3.0 parts of silver phenylglyoxylate and 20 parts of methanol, and the mixture was further stirred for 1 hour at room temperature (about 25 ° C.), and then the resulting gray solid was removed by filtration. Was distilled off under reduced pressure to obtain 4.5 parts of a brown solid. This brown solid was recrystallized with an ether / hexane mixed solution to obtain 2.6 parts of a base generator (C123-3) (yellow solid).

Production Example 17
[Synthesis of Base Generator (C123-4) {Compound Represented by Chemical Formula (43)}

(1) 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide [intermediate (C123-4-3) ]:
Manufactured except that “Triethanolamine [Wako Pure Chemical Industries, Ltd.]” was changed to “1,8-diazabicyclo [5.4.0] -7-undecene [San Apro Co., Ltd.“ DBU ”]”. In the same manner as in Example 11 (1) to (3), 2.2 parts of intermediate (C123-4-3) (white solid) was obtained.

(2) Synthesis of base generator (C123-4):
A base generator (C123-4) (light yellowish white) was prepared in the same manner as in Production Example 11 (4) except that “Intermediate (C122-2-3)” was changed to “Intermediate (C123-4-3)”. 1.3 parts of powder) was obtained.

Production Example 18
[Synthesis of Base Generator (C123-5) {Compound Represented by Chemical Formula (44)}]

(1) Synthesis of 2,4-di-tert-butyl-7-methylthioxanthone [intermediate (C123-5-1)]:
Intermediate (C122-2-1) (2.1 parts) was dissolved in dichloromethane (85 parts), and aluminum (III) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) (0.5 parts) and 2-chloro-2-methyl 1.9 parts of propane [manufactured by Wako Pure Chemical Industries, Ltd.] was added and stirred at room temperature (about 25 ° C.) for 23 hours. The aqueous layer was removed by a liquid separation operation, and the organic layer was washed 3 times with 30 parts of water. The organic solvent was distilled off under reduced pressure to obtain a pale yellow solid. This pale yellow solid was recrystallized with an ethyl acetate / hexane mixed solution to obtain 0.5 part of an intermediate (C123-5-1) (yellow powder).

(2) Synthesis of 2,4-di-tert-butyl-7-bromomethylthioxanthone [intermediate (C123-5-2)]:
In the same manner as in (2) of Production Example 11, except that 2.1 parts of “Intermediate (C122-2-1)” was changed to 1.0 part of “Intermediate (C123-5-1)” C123-5-2) (yellow powder) 1.2 parts were obtained.

(3) 8- (2,4-Di-tert-butyl-9-oxo-9H-thioxanthen-7-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide Synthesis of [Intermediate (C123-5-3)]:
Intermediate (C123-5-3) (Fine) was prepared in the same manner as in Production Example 11 (3) except that "Intermediate (C122-2-2)" was changed to "Intermediate (C123-5-2)". 1.3 parts of a yellow powder) were obtained.

(4) Synthesis of base generator (C123-5):
Base generator as in (4) of Production Example 11 except that 1.0 part of “Intermediate (C1222-2-2)” was changed to 0.8 part of “Intermediate (C123-5-3)” 1.0 part of (C123-5) (slightly yellow powder) was obtained.

Production Example 19
[Synthesis of Base Generator (C123-6) {Compound Represented by Chemical Formula (45)}]

(1) Synthesis of 4-bromomethylbenzophenone [intermediate (C123-6-1)]:
4-methylbenzophenone (manufactured by Aldrich) 25.1 parts, N-bromosuccinimide [Wako Pure Chemical Industries, Ltd.] 22.8 parts, benzoyl peroxide [20% water content: Wako Pure Chemical Industries, Ltd.] 0.54 parts and 80 parts of acetonitrile were added, heated to 80 ° C., reacted under reflux for 2 hours, cooled, the organic solvent was distilled off under reduced pressure, and recrystallized from 160 parts of methanol to obtain an intermediate (C123 -6-1) 26 parts (white crystals) were obtained.

(2) Synthesis of 8- (4-benzoylphenyl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide [intermediate (C123-6-2)]:
25.8 parts of the intermediate (C123-6-1) was dissolved in 100 parts of acetonitrile, and 1,8-diazabicyclo [5.4.0] -7-undecene [“DBU” manufactured by San Apro Co., Ltd.] 14 After dropwise addition of 6 parts (heat generation after dropping), the mixture was stirred at room temperature (about 25 ° C.) for 18 hours, and the organic solvent was distilled off under reduced pressure to obtain a brown solid. This brown solid was recrystallized from acetonitrile to obtain 28.2 parts of intermediate (C123-6-2) (white solid).

(3) Synthesis of base generator (C123-6):
A solution of 0.8 parts of sodium tetraphenylborate salt [manufactured by Nacalai Tesque Co., Ltd.] dissolved in 17 parts of water and 6.8 parts of intermediate (C123-6-2) dissolved in 50 parts of chloroform in advance After dropwise addition, the reaction solution was obtained by stirring at room temperature (about 25 ° C.) for 2 hours. The reaction solution was filtered, and the yellow liquid obtained by evaporating the filtrate under reduced pressure was dissolved in acetonitrile and recrystallized to obtain 7.6 parts of a base generator (C123-6) (white solid).

Production Example 20
[Synthesis of Base Generator (C123-7) {Compound Represented by Chemical Formula (46)}]

(1) Synthesis of 8- (9-naphthalylmethyl) -1,8-diazabicyclo [5.4.0] -7-undecenium bromide [(C123-7-1)]
Except having changed "intermediate (C123-6-1) 25.8 parts" into "2-bromomethylnaphthalene [Tokyo Chemical Industry Co., Ltd.] 1.1 parts", it was carried out similarly to manufacture example 19 (2). Intermediate part (C123-7-1) (white powder) was obtained.

(2) Synthesis of base generator (C123-7):
A base generator in the same manner as in Production Example 19 (3) except that “6.8 parts of intermediate (C123-6-2)” was changed to “0.8 parts of intermediate (C123-7-1)”. 1.3 parts of (C123-7) (slightly yellow powder) were obtained.

Examples 1 to 22 (examples of radical polymerization)
Dipentaerythritol pentaacrylate as a radical polymerizable compound [“Neomer DA-600” manufactured by Sanyo Chemical Industries, Ltd.] 96.5 parts, radical initiator (A) shown in Table 1, and acid generator (B) Alternatively, “3 parts of radical initiator (A) and 0.5 part of acid generator (B) or base generator (C)” are kneaded at 25 ° C. for 3 hours using a base generator (C). Thus, photosensitive compositions (Q-1) to (Q-22) of the present invention were produced.
However, the breakdown of 0.5 part (B) in Example 10 is 0.3 part (B1) and 0.2 part (B2), and the breakdown of 0.5 part (C) in Example 22 is (C1) 0.4 part and (C2) 0.1 part.

Examples 23 to 28 (examples of cationic polymerization)
Using 96.5 parts of cyclohexene oxide as an ion polymerizable compound and the radical initiator (A) and acid generator (B) shown in Table 2, 3 parts of radical initiator (A), acid generator (B) 0.5 parts "was kneaded at 25 ° C. for 3 hours using a ball mill to prepare photosensitive compositions (Q-23) to (Q-28) of the present invention.
However, the breakdown of (A) 3 parts in Example 28 is (A1) 2 parts and (A2) 1 part, and (B) 0.5 parts breakdown is (B1) 0.3 parts and (B2 ) 0.2 parts.

Examples 29 to 34 (examples of anionic polymerization)
Using 96.5 parts of cyclohexene oxide as an ion polymerizable compound and the radical initiator (A) and the base generator (C) shown in Table 3, “3 parts of radical initiator (A), base generator (C)” 0.5 parts "was kneaded at 25 ° C. for 3 hours using a ball mill to prepare photosensitive compositions (Q-29) to (Q-34) of the present invention.
However, the breakdown of (A) 3 parts in Example 34 is (A1) 2 parts and (A2) 1 part, and (C) 0.5 parts breakdown is (C1) 0.25 parts and (C2 ) 0.25 part.

Examples 35 to 42 (examples of radical polymerization)
Monofunctional radical polymerizable compound (Df1), bifunctional radical polymerizable compound (Df2), trifunctional or higher functional radical polymerizable compound (Df3), radical initiator (A), and acid generator (B) shown in Table 4 Alternatively, “5 parts of radical initiator (A) and 0.5 part of acid generator (B) or base generator (C)” are kneaded at 25 ° C. for 3 hours using a base generator (C). Thus, photosensitive compositions (Q-35) to (Q-42) of the present invention were produced.

Comparative Examples 1-2 (examples of radical polymerization)
Comparative photosensitivity in the same manner as in Example 1 except that no acid generator (B) was used and 3.5 parts of the radical initiator (A) shown in Table 5 was used as the radical initiator (A). Compositions (Q′-1) and (Q′-2) were produced.

Comparative Examples 3 to 8 (Examples of cationic polymerization)
A comparative example was used in the same manner as in Examples 23 to 28 except that the radical initiator (A) was not used and 3.5 parts of the acid generator (B) shown in Table 6 was used as the acid generator (B). Photosensitive compositions (Q′-3) to (Q′-8) were produced.
However, the breakdown of (B) 3.5 parts in Comparative Example 8 is (B1) 2.5 parts and (B2) 1 part.

Comparative Examples 9 to 14 (Examples of anionic polymerization)
Comparative Example 29-34 was used except that the radical initiator (A) was not used and 3.5 parts of the base generator (C) shown in Table 7 was used as the base generator (C). Photosensitive compositions (Q′-9) to (Q′-14) were produced.
However, the breakdown of (C) 3.5 parts in Comparative Example 14 is (C1) 2.5 parts and (C2) 1 part.

Comparative Examples 15 to 16 (when inorganic particles are used)
Photosensitive compositions (Q′-15) to (Q′-16) for comparison were prepared in the same manner as Comparative Examples 1 and 2, except that 5 parts by weight of silica sol (“Nanocyl C130” manufactured by Nanoresin Co., Ltd.) was further added. Manufactured.

  Regarding the compounds described in Tables 1 to 8, LUCIRIN TPO as (A121) is manufactured by BASF, 1-Fmoc-piperidone as (C21) is manufactured by Aldrich, and BPO (benzoyl peroxide) as (A21) is “Nyper BW” made of oil, p-toluenesulfonic acid cyclohexyl ester as (B21) was a product manufactured by Tokyo Chemical Industry Co., Ltd.

[Adhesion]
Each photosensitive composition obtained in Examples 1 to 42 and Comparative Examples 1 to 16 was subjected to a surface treatment of a PET (polyethylene terephthalate) film having a thickness of 100 μm [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd. The same thing was used. ] And a 125 μm-thick PMMA (polymethylmethacrylate) film [Acryprene HBS010P manufactured by Mitsubishi Rayon Co., Ltd.] using an applicator so that the film thickness becomes 20 μm, and a belt conveyor type UV irradiation device (Igraphics Co., Ltd.) The exposure was carried out using the company “ECS-151U”, which was also used for the following evaluation. The exposure amount was 150 mJ / cm ² at 365 nm.
About the coating film after hardening apply | coated to PET film and PMMA film, based on JISK-5600-5-6, adhesiveness was evaluated by the cross cut cellophane tape peeling test.

[Transparency (transmittance and haze)]
Each photosensitive composition obtained in Examples 1-42 and Comparative Examples 1-16 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 150 mJ / cm ² at 365 nm.
Based on JIS-K7105, the cured coating film was measured for transmittance and haze using a total light transmittance measuring device [trade name “haze-garddual” manufactured by BYK Gardner Co., Ltd.] (PET film of substrate) Was subtracted as a blank). In both cases, the unit is%.

[Pencil hardness]
Each photosensitive composition obtained in Examples 1-42 and Comparative Examples 1-16 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 150 mJ / cm ² at 365 nm.
About the coating film after hardening, pencil hardness was measured based on JISK-5400.

[Abrasion resistance]
Each photosensitive composition obtained in Examples 1-42 and Comparative Examples 1-16 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was carried out using a belt conveyor type UV irradiation device. The exposure amount was 150 mJ / cm ² at 365 nm.
The cured coating film was evaluated by the following criteria by visual inspection after steel reciprocal scratches using steel wool # 0000 with a load of 250 g per cm ² and 30 reciprocal scratches.
A: Not scratched at all.
○: Some scratches are recognized.
X: Many scratches are recognized and the surface becomes cloudy.

[Heat-resistant]
Each photosensitive composition obtained in Examples 1-42 and Comparative Examples 1-16 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was performed using the belt conveyor type UV irradiation apparatus. The exposure amount was 150 mJ / cm ² at 365 nm.
The cured coating film was placed in a blast constant-temperature thermostatic chamber (DKN302: manufactured by Yamato Scientific Co., Ltd.) at 85 ° C. and temperature-controlled for 100 hours or 300 hours. The temperature-controlled resin film was visually observed and observed at 50 times using a shape measurement microscope (ultra-deep shape measurement microscope VK-8550, manufactured by Keyence Corporation), and evaluated according to the following criteria.
A: Appearance change is not recognized at all before temperature control, and there is no discoloration.
○: Appearance change is not recognized at all before temperature adjustment, but there is discoloration.
Δ: There is no change visually, but a change is observed with a microscope before temperature adjustment.
X: Visual change before temperature control is recognized

[Curing property]
Each photosensitive composition obtained in Examples 1-42 and Comparative Examples 1-16 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm or 80 μm. . About the exposure, it implemented using the following 2 types of irradiation apparatuses.
(1) It exposed using the said belt conveyor type | mold UV irradiation apparatus. The exposure amount was 150 mJ / cm ² at 365 nm.
(2) Exposure was performed using a spot type LED irradiation device (“RX FireFlex” manufactured by Foseon Technology). The exposure amount was 150 mJ / cm ² at 395 nm.
The curability immediately after light irradiation of the coated film after curing was evaluated by the following evaluation criteria by scratching with a finger and nails.
A: There is no tack on the surface and it is not damaged by the nail.
○: There is no tack on the surface, but the nail is damaged.
Δ: There is tack on the surface and it is damaged by the nail.
X: Uncured.

[Yellowing resistance]
Each photosensitive composition obtained in Examples 1-42 and Comparative Examples 1-16 was applied to the above PET film having a thickness of 100 μm using an applicator so as to have a film thickness of 20 μm. Exposure was performed using the belt conveyor type UV irradiation apparatus. The exposure amount was 10,000 mJ / cm ² at 365 nm. The appearance was visually observed and evaluated according to the following criteria.
A: No yellowing.
○: Slightly yellowed when observed on white paper.
Δ: Yellowing is observed under fluorescent light.
X: Severe yellowing is observed.

[Storage stability]
Each photosensitive composition obtained in Examples 1-42 and Comparative Examples 1-16 was allowed to stand at 40 ° C. for 1 week, the appearance was visually observed, and the following criteria were evaluated.
A: Viscosity change and discoloration are not recognized at all before temperature control.
○: No change in viscosity is observed before temperature adjustment, but there is a slight discoloration.
Δ: Viscosity change was observed before temperature adjustment, and there was discoloration.
X: Completely solidified and discolored after temperature adjustment.

  The evaluation results are shown in Table 9 and Table 10.

  The photosensitive composition of the present invention is excellent in hardness, scratch resistance, adhesion to various substrates, heat resistance, and can be cured with a small amount of energy to form a transparent cured product. Extremely as a buffer layer between the image display unit of a liquid crystal display, plasma display, electroluminescence display, touch panel, flat panel display and front plate, for flat panel display, coating agent, ink, adhesive or resist pattern formation Useful.

Claims (12)

A radical initiator (A) and an acid generator (B) are contained in any combination of the following (1) to (3) together with the polymerizable substance (D), and a colorant, a metal oxide powder and a metal powder In which the polysynthetic substance (D) is composed of only one of the radical polymerizable compound (D1) and the ion polymerizable compound (D2). The following radical initiator (A1) which is a photosensitive composition and generates radicals by actinic rays, or the following radical initiator (A2) which generates radicals by acid and / or base, is an acylphosphine oxide derivative-based polymerization. Initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative From systematic polymerization initiator (A124), benzoin derivative polymerization initiator (A125), oxime ester derivative polymerization initiator (A126), titanocene derivative polymerization initiator (A127), and azo compound polymerization initiator (A22) A photosensitive composition which is at least one radical initiator selected from the group consisting of:
(1) A radical initiator (A1) that generates radicals by actinic rays and an acid generator (B2) that generates acids by at least one selected from the group consisting of radicals, acids and bases.
(2) At least one selected from the group consisting of an acid generator (B1) that generates an acid by actinic rays, a radical initiator (A2) that generates a radical by an acid and / or a base, and, if necessary, a radical, an acid and a base Contains a base generator (C2) that generates bases by seeds.
(3) A combination of two or more of (1) to (2) above.
The acid generator (B1) that generates an acid by the actinic ray or the acid generator (B2) that generates an acid by at least one selected from the group consisting of the radical, acid and base is a sulfonium salt derivative (B121). , iodonium salt derivatives (B 122), a sulfonic acid ester derivative (B21), No placement claim 1 Symbol is at least one acid generator selected from the group consisting of acetic acid ester derivative (B22) and phosphonic acid ester (B23) Photosensitive composition.
The photosensitive composition according to claim 2, wherein the sulfonium salt derivative (B121) is a compound represented by the general formula (1) or the general formula (2).
[Wherein, A ¹ is a divalent or trivalent group represented by any ^one of the general formulas (3) to (10);
Ar ^{1 to} Ar ⁷ 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, carbon 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, a naphthyl group, a phenoxy group, and a phenylthio group. Aromatic hydrocarbon group or heterocyclic group which may be substituted with at least one selected atom or substituent, Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, Ar ⁵ is 2 (X ¹ )-and (X ² )-each represents an anion; a is an integer from 0 to 2, b is an integer from 1 to 3, and a + b is 2 or 3, and A same as ¹ of valence Is a number. ]
[Wherein, R ^{1 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, amino Represents a phenyl group optionally substituted by at least one atom or substituent selected from the group consisting of a group, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, and a phenylthio group, and R ¹ , R ² , R ⁴ And R ⁵ , and R ⁶ and R ⁷ may be bonded to each other to form a ring structure. ]
The photosensitive composition according to claim 2 or 3, wherein the iodonium salt derivative (B122) is a compound represented by the general formula (15) or the general formula (16).
[Wherein, A ² is a divalent or trivalent group represented by any one of the general formulas (3) to (10);
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, carbon 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, a naphthyl group, a phenoxy group, and a phenylthio group. An aromatic hydrocarbon group or a heterocyclic group optionally substituted with at least one selected atom or substituent, wherein Ar ^{8 to} Ar ¹⁰ and Ar ¹² are a monovalent group, and Ar ¹¹ is a divalent group. (X ⁷ )-and (X ⁸ )-each represents an anion; c is an integer from 0 to 2, d is an integer from 1 to 3, and c + d is 2 or 3, and A ² Same as valence Is a number. ]
Hardened | cured material formed by hardening the photosensitive composition in any one of Claims 1-4 by irradiation of actinic light.
A photosensitive composition containing the following (1) to (3), wherein at least one of the radical initiator (A12) and the base generator (C) generates an active species (H) upon irradiation with actinic rays. Then, the active species (H) reacts with the radical initiator (A12) or the base generator (C) to produce a new active species (I), and a polymerizable substance by the new active species (I). A photosensitive reaction characterized in that the polymerization reaction of (D) proceeds, the active species (H) or (I) is a base, and substantially does not contain any of a colorant, metal oxide powder and metal powder. Sex composition.
(1) Acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative polymerization initiator (A124) ), A benzoin derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126), and a titanocene derivative polymerization initiator (A127), which is at least one radical initiator selected from the group consisting of radical initiators (A12)
(2) Base generator (C)
(3) Polymerizable substance (D)
The radical initiator (A12) is an acylphosphine oxide derivative polymerization initiator (A121), an α-aminoacetophenone derivative polymerization initiator (A122), a benzyl ketal derivative polymerization initiator (A123), an α-hydroxyacetophenone derivative. At least one radical initiation selected from the group consisting of a systemic polymerization initiator (A124), a benzoin derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126) and a titanocene derivative polymerization initiator (A127). Agent,
The base generator (C) is a base generator (C1) that generates a base by actinic rays, or a base generator (C2) that generates a base by at least one selected from the group consisting of radicals, acids and bases. The photosensitive composition according to claim 7, wherein (A12), (C1), or (C2) is contained in any combination of the following (1) to (3).
(1) Contains (A12) and (C2).
(2) It contains an acid generator (B2) that generates an acid by at least one selected from the group consisting of (C1) and (A12) and, if necessary, a radical, an acid, and a base.
(3) A combination of two or more of (1) to (2) above.
Along with the polymerizable substance (D), acylphosphine oxide derivative polymerization initiator (A121), α-aminoacetophenone derivative polymerization initiator (A122), benzyl ketal derivative polymerization initiator (A123), α-hydroxyacetophenone derivative system At least one radical initiator selected from the group consisting of a polymerization initiator (A124), a benzoin derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126) and a titanocene derivative polymerization initiator (A127). The radical initiator (A12) and the base generator (C) are in any combination of the following (1) to (3) and are substantially free of colorant, metal oxide powder and metal powder. A photosensitive composition characterized by the above.
(1) A radical initiator (A12) that generates radicals with actinic rays and a base generator (C2) that generates bases with at least one selected from the group consisting of radicals, acids and bases.
(2) At least one selected from the group consisting of a base generator (C1) that generates a base by actinic rays, a radical initiator (A12) that generates a radical by an acid and / or a base, and if necessary, a radical, an acid, and a base Contains an acid generator (B2) that generates an acid.
(3) A combination of two or more of (1) to (2) above.
The base generator (C1) that generates a base by the active light, or the base generator (C2) that generates a base by at least one selected from the group consisting of the radical, acid, and base is an oxime derivative (C121), The photosensitive composition according to claim 7 or 8, which is at least one base generator selected from the group consisting of a quaternary ammonium salt derivative (C122), a quaternary amidine salt derivative (C123) and a carbamate derivative (C21).
The base generator (C1) that generates a base by the actinic ray or the base generator (C2) that generates a base by at least one selected from the group consisting of the radical, acid, and base is represented by the general formulas (21) to (21). The photosensitive composition according to any one of claims 7 to 9 , which is a compound represented by any one of (23).
[Wherein, R ^{14 to} R ⁴¹ are each 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, or an alkyl group having 1 to 20 carbon atoms. Alkylthio group, C1-C20 alkylsilyl group, nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, substituent represented by formula (24) and formula An atom or a substituent selected from the group consisting of the substituent represented by (25), wherein any one of R ^{14 to} R ²³ is a substitution represented by the general formula (24) or the general formula (25) Any one of R ^{24 to} R ³¹ is a substituent represented by General Formula (24) or General Formula (25); and any one of R ^{32 to} R ⁴¹ is General Formula (24 ) Or a substituent represented by the general formula (25) A. ]
[Wherein, R ^{42 to} R ⁴⁵ are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R ^{46 to} R ⁴⁸ are each an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group. Each of (X ¹³ )-and (X ¹⁴ )-represents an anion; e is an integer of 2-4. ]
Cured product photosensitive composition is formed by curing upon irradiation with an actinic ray according to any one of claims 6-10.
  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 A radical initiator (A12) which is at least one radical initiator selected from the group consisting of a derivative polymerization initiator (A125), an oxime ester derivative polymerization initiator (A126) and a titanocene derivative polymerization initiator (A127). In addition, an actinic ray cured product in which the polymerizable substance (D) is polymerized by irradiation with actinic rays in the presence of the base generator (C) and in the absence of any of the colorant, the metal oxide powder, and the metal powder. Of the radical initiator (A12) and the base generator (C). At least one of the active species (H) is generated by irradiation with actinic rays, and the active species (H) reacts with the radical initiator (A12) or the base generator (C) to form a new active species (I). Is produced, the polymerization reaction of the polymerizable substance (D) with the new active species (I) proceeds, and the active species (H) or (I) is a base.