JP2014108974A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition capable of being cured with low energy amount even when materials which reduce or shield an irradiated light, such as coloring agent exist at high concentration or even in the case of a thick film.SOLUTION: A photosensitive composition contains following (1) to (4) and a polymerizable material (D) contains (D1) urethane (meth)acrylate having at least one (meth)acryloyl group in a molecule and (D2) monofunctional (meth)acrylate other than (D1). (1) a radical initiator (A). (2) an acid generator (B) and/or a base generator (C). (3) the polymerizable material (D). (4) at least one filler (E) selected from a coloring agent (E1), a metal oxide powder (E2) and a metal powder (E3).

Description

  The present invention relates to a composition that is cured 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, paints and printing inks from the viewpoint of workability (fast curing) and low VOC.
In general, a photocurable coating agent comprises a photopolymerization initiator, a radical polymerizable monomer, an oligomer or a polymer, and a colorant and an additive depending on applications. Colorants are roughly divided into pigments and dyes, and are blended to color the coating film. The colorant has a light absorption characteristic according to its color and absorbs a part of the irradiated light to attenuate the light or shield the irradiated light. The light may not reach. In order to solve this problem, it has been proposed to use a specific photopolymerization initiator (see, for example, Patent Document 1).

  However, the invention described in Patent Document 1 is a combination of a photopolymerization initiator and a sensitizer having a specific structure, and can be cured with a smaller amount of energy irradiation than conventionally used photopolymerization initiator systems. Is improved, but there is a problem that the curability is insufficient when the colorant concentration in the ink composition is increased or the film thickness is increased.

In addition, lenticular lenses conventionally used for projection screens such as projection televisions are formed by arranging a large number of cylindrical lenses, and the recesses between the cylindrical lenses reflect outside light such as room lights or sunlight. In order to suppress and improve the image contrast, a light-absorbing black stripe is provided. Such black stripes are required to have sufficient shielding properties and appearance black.
The black stripe is obtained by pouring a photosensitive composition in which a black pigment is dispersed into a concave portion of a transparent resin lens provided with a cylindrical lens shape with a mold, and scraping off the photosensitive composition protruding above the concave portion. It is formed by irradiating and curing with ultraviolet rays.

A photosensitive composition in which a black pigment is dispersed is used, for example, as a paint or an ink. As the black pigment, resin particles in which carbon black is dispersed in a resin such as polymethyl methacrylate are known.
However, in the application of black stripes, if the resin particles having a large average primary particle diameter are simply dispersed in the photosensitive composition as a black pigment, a smooth coated surface cannot be obtained after scraping off the protruding resin.
Further, in order to obtain sufficient shielding properties, it is necessary to increase the amount of resin particles added. However, in that case, there is a problem that penetration into the concave portion of the lens is deteriorated or curability is insufficient.

  In order to solve the smoothness and shielding properties of the coated surface, a black pigment having a reduced average primary particle diameter has been proposed (see, for example, Patent Document 2).

  However, the method of Patent Document 2 has a problem that the dispersion stability with respect to a photosensitive composition such as a black pigment is poor, and aggregation of the black pigment occurs.

JP 2009-19142 A JP 2009-237464 A

  The present invention has been made in view of the above problems, and the object of the present invention is small even when a substance such as a colorant that attenuates or shields irradiated light is present in a high concentration or has a large film thickness. An object of the present invention is to provide a photosensitive composition that can be cured with an energy amount, is excellent in dispersion stability of a coloring material, and is excellent in smoothness after coating.

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 a photosensitive composition containing the following (1) to (4), wherein the polymerizable substance (D) has at least one (meth) acryloyl group in the molecule (meth). A photosensitive composition comprising an acrylate (D1) and a monofunctional (meth) acrylate (D2) other than (D1); and a cured product obtained by curing the composition with actinic rays. .
(1) Radical initiator (A)
(2) Acid generator (B) and / or base generator (C)
(3) Polymerizable substance (D)
(4) At least one filler (E) selected from the colorant (E1), the metal oxide powder (E2), and the metal powder (E3);
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, a thick film can be cured with a small amount of energy even if a substance such as a colorant that attenuates or blocks irradiated light is present in a high concentration.
In addition, since the dispersion of the colorant is excellent and the smoothness after coating is excellent, when black resin particles are used as the colorant, the black stripe can be easily formed by light irradiation. Become.

In the photosensitive composition of the present invention, at least one of the radical initiator (A), the acid generator (B) and the base generator (C) generates an active species (H) by irradiation with actinic rays, The active species (H) reacts with the radical initiator (A), the acid generator (B), or the base generator (C) to generate a new active species (I) to produce the new active species (I). It is preferable that the polymerization reaction of the polymerizable substance (D) 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. The diffusion of the active species (H) facilitates curing of a portion where active light is attenuated or a portion where light does not reach, which is difficult to be photocured with a general photopolymerization initiator. In order for the active species (H) to diffuse, it is preferable to use a polymerizable substance (D) that does not react with the active species (H).
When the active species (H) is an acid, the active species (I) is not a base, and when the active species (H) is a base, the active species (I) is not an acid.

  In cationic polymerization that initiates polymerization with a general acid generator alone, or anionic polymerization that initiates polymerization with a base generator alone, it was difficult to use a wavelength at which the generator does not absorb, Can be used in combination with a radical initiator that absorbs at a wavelength where the acid generator or base generator does not absorb.

In the present invention, the radical initiator (A) means a compound that generates radicals by at least one of actinic rays, acids, and bases. The radical initiator (A1) that generates radicals by actinic rays, Known compounds such as a radical initiator (A2) that generates radicals and a radical initiator (A3) that generates radicals with a base can be used.
For example, acylphosphine oxide derivative polymerization initiator (A1231), α-aminoacetophenone derivative polymerization initiator (A1232), benzyl ketal derivative polymerization initiator (A1233), α-hydroxyacetophenone derivative polymerization initiator (A1234). The benzoin derivative polymerization initiator (A1235), the oxime ester derivative polymerization initiator (A1236), the titanocene derivative polymerization initiator (A1237) and the like can generate radicals by any of actinic rays, acids and bases. Any of (A1), (A2) and (A3) can be applied.
In addition, the organic peroxide polymerization initiator (A231), the azo compound polymerization initiator (A232), the other radical initiator (A233) and the like can generate radicals with an acid and / or a base (A2 ) Or (A3).
(A) may be used independently and may use 2 or more types together.
In addition, (A1231) shows that it is the 1st example of the compound (A123) applicable as any of (A1), (A2), and (A3). Similarly, (A231) indicates that it is the first example of the compound (A23) applicable as either (A2) or (A3).

  As the acylphosphine oxide derivative-based polymerization initiator (A1231), 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 (A1232), 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 (A1233) include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF (IRGACURE 651)].

  As the α-hydroxyacetophenone derivative polymerization initiator (A1234), 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 (A1235) include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As the oxime ester derivative polymerization initiator (A1236), 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-based polymerization initiator (A1237), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) Titanium [manufactured by BASF (IRGACURE 784)] and the like.

  Examples of the organic peroxide polymerization initiator (A231) include benzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, and 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-butylhydride Peroxide and t- butyl trimethylsilyl peroxide.

  As the azo compound-based polymerization initiator (A232), 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 (A233) include 2,3-dimethyl-2,3-diphenylbutane.

  The radical initiator (A2) that generates radicals with an acid or the radical initiator (A3) that generates radicals with a base includes an organic peroxide polymerization initiator (A231) and / or an azo compound polymerization initiator (A232). ) Is preferred.

The content of the radical initiator (A) in the photosensitive composition of the present invention is preferably 0.1 to 10% by weight, more preferably 1 to 8% by weight, and particularly preferably 2 to 5% by weight.
If it is 1% by weight or more, the photo-curing reactivity can be exhibited more satisfactorily, and if it is 10% by weight or less, the adhesion to the lens can be exhibited well.

In the present invention, the acid generator (B) means a compound that generates an acid by at least one of actinic rays, radicals, and acids. The acid generator (B1) that generates an acid by actinic rays, Well-known compounds, such as an acid generator (B2) which generate | occur | produces an acid, and an acid generator (B3) which generate | occur | produces an acid with an acid, are mentioned.
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 (B31), the acetic acid ester derivative (B32), the phosphonic acid ester (B33) and the like can generate an acid with an acid and can be applied as (B3).
(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 [hexafluorophosphine anion (PF ₆ ⁻ ) And trifluoride tris (perfluoroethyl) phosphorus ani Emissions _{(PF 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, phosphorus anions, substituted by halogen Aliphatic 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 (B31) 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 (B32) include dichloroacetic acid cyclohexyl ester and trichloroacetic acid isopropyl ester.

  Examples of the phosphonic acid ester (B33) 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, and bases, and a base generator (C1) that generates bases with actinic rays. Known compounds such as a base generator (C2) that generates a base or a base generator (C3) that generates a base with a base can be used.
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 (C31) can generate a base with a base and can be applied as (C3).
(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 (C31) 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, an alkoxy group having 1 to 20 carbon atoms, C1-C20 alkylthio group, C1-C20 alkylsilyl group, nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, represented by 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. Is a substitution represented by the general formula (24) or the general formula (25) It is a group.

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 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 base 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 (C31) include 1-Z-4-piperidone.

  The content of the acid generator (B) and / or base generator (C) in the photosensitive composition of the present invention [total of (B) and (C)] is preferably 0 from the viewpoint of photocurability. 0.05 to 20% by weight, more preferably 0.1 to 10% by weight.

In this invention, it is preferable to contain (A1)-(A3), (B1)-(B3) or (C1)-(C3) in any combination of the following (1)-(10).
(1) Contains (A1) and (B2).
(2) Contains (A1), (B2) and (B3).
(3) Contains (B1) and (A2).
(4) Contains (B1), (A2) and (B3).
(5) Contains (C1) and (A3).
(6) Contains (C1), (A3) and (C3).
(7) Contains (A1) and (C2).
(8) Contains (A1), (C2) and (C3).
(9) A combination of two or more of (1) to (4) above.
(10) A combination of two or more of (5) to (8) above.

  In (1) above, radicals are generated as active species (H) by irradiation with actinic rays, and acids are generated as active species (I). The active species (H) diffuses into the portions where the actinic rays are attenuated or shielded, thereby promoting curing in these portions.

  In the above (2), an acid is generated as the active species (I) in the same manner as in the above (1), and when this acid reacts with (B3), the acid is proliferated and the active light is attenuated or shielded. Is further accelerated.

  In the above (3), an acid is generated as the active species (H) and a radical is generated as the active species (I) by irradiation with actinic rays. The active species (H) diffuses into the portions where the actinic rays are attenuated or shielded, thereby promoting curing in these portions.

  In the above (4), an acid is generated as the active species (H) in the same manner as in the above (3), and this acid reacts with (B3), whereby the acid is propagated and the active ray is attenuated or shielded. Is further accelerated.

  In (5) above, a base is generated as the active species (H) by irradiation with actinic rays, and a radical is generated as the active species (I). The active species (H) diffuses into the portions where the actinic rays are attenuated or shielded, thereby promoting curing in these portions.

  In the above (6), a base is generated as an active species (H) as in the above (5), and the base is proliferated by reacting with this (C3), and the active light is attenuated or shielded. Is further accelerated.

  In (7) above, radicals are generated as active species (H) by irradiation with actinic rays, and bases are generated as active species (I). The active species (H) diffuses into the portions where the actinic rays are attenuated or shielded, thereby promoting curing in these portions.

  In the above (8), a base is generated as an active species (I) in the same manner as in the above (7), and this base reacts with (C3) so that the base is proliferated and the active light is attenuated or shielded. Is further accelerated.

The polymerizable substance (D) in the present invention is essential for urethane (meth) acrylate (D1) having at least one (meth) acryloyl group in the molecule and monofunctional (meth) acrylate (D2) other than (D1). Contains as a component.
In addition, said (meth) acryloyl group means an acryloyl group and / or a methacryloyl group, (meth) acrylate means an acrylate and / or a methacrylate, respectively, and the same description method is used hereafter.

  Further, if necessary, a polymerization inhibitor such as hydroquinones may be used in combination.

  The urethane (meth) acrylate (D1) in the present invention contains at least one (meth) acryloyl group in the molecule. For example, polyisocyanate (D1a), polyol (D1b), and hydroxyl group-containing (meth) acrylate ( Obtained by reacting D1c).

The polyisocyanate (D1a) that is the raw material of the urethane (meth) acrylate (D1) in the present invention includes aromatic polyisocyanate (D1a1), aliphatic polyisocyanate (D1a2), alicyclic polyisocyanate (D1a3), and aromatic fat. Group polyisocyanate (D1a4), and nurateated products (D1a5) of (D1a1) to (D1a4).
Two or more of these may be combined.

  Examples of the aromatic polyisocyanate (D1a1) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4, 4′- or 2,4 ′. -Diphenylmethane diisocyanate (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3 ' -Divalent isocyanates such as dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate; or crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate ), 4, 4 ', 4 "-tri Trifunctional or higher functional triisocyanates such as phenylmethane triisocyanate.

Examples of the aliphatic polyisocyanate (D1a2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4. -And / or 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate, Divalent isocyanates such as bis (2-isocyanatoethyl) carbonate and trimethylhexamethylene diisocyanate (TMDI);
1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, lysine ester triisocyanate (phosgenated product of reaction product of lysine and alkanolamine, etc. And trifunctional or higher functional triisocyanates.

Examples of the alicyclic polyisocyanate (D1a3) include isophorone diisocyanate (IPDI), 2,4- or 2,6-methylcyclohexane diisocyanate (hydrogenated TDI), and dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI). , Cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, dimer acid diisocyanate (DDI) Divalent isocyanates such as
And trifunctional or higher functional triisocyanates such as bicycloheptane triisocyanate.

  Examples of the araliphatic polyisocyanate (D1a4) include m- or p-xylylene diisocyanate (XDI), diethylbenzene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like. .

  Examples of the nurated product (D1a5) include isocyanurate-modified isophorone diisocyanate and isocyanurate-modified hexamethylene diisocyanate.

  As polyisocyanate (D1a), alicyclic polyisocyanate (D1a3) and araliphatic polyisocyanate (D1a4) are preferable.

  The polyol (D1b) which is a raw material of the urethane (meth) acrylate (D1) in the present invention includes an aliphatic dihydric alcohol (D1b1), a dihydric alcohol having an alicyclic skeleton (D1b2), and an araliphatic dihydric alcohol. (D1b3), alkylene oxide 1-50 mol adduct (D1b4) of these (D1b1)-(D1b3), etc. are mentioned. Two or more of these may be combined.

Examples of the aliphatic dihydric alcohol (D1b1) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, and 1,4-butanediol. 1,6-hexanediol, neopentyl glycol, 3-methylpentanediol, dodecanediol, and the like.
Examples of the dihydric alcohol (D1b2) having an alicyclic skeleton include 1,3- and 1,4-cyclohexanediol and cyclohexanedimethanol.
As the araliphatic dihydric alcohol (D1b3), resorcinol ethylene oxide (hereinafter abbreviated as EO) 4 mol adduct, dihydroxynaphthalene propylene oxide (hereinafter abbreviated as PO) 4 mol adduct, bisphenol An EO2 molar adduct of A, an EO2 molar adduct of bisphenol-F, an EO2 molar adduct of bisphenol-S, and the like.

  As the hydroxyl group-containing (meth) acrylate (D1c) which is a raw material of the urethane (meth) acrylate (D1) in the present invention, an alkylene oxide (hereinafter abbreviated as AO) adduct of (meth) acrylic acid, and a mono diol. (Meth) acrylate, reaction product of (meth) acrylic acid and a tri- or higher functional polyol and its AO adduct, and a mixture of two or more of these.

  Specific examples of the hydroxyl group-containing (meth) acrylate (D1c) include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, and these AO adduct, etc .; polycarbonate diol mono (meth) acrylate, polyether diol mono (meth) acrylate, polyester diol mono (meth) acrylate, etc .; glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, And AO adducts thereof.

  The NCO / OH equivalent ratio in the reaction of the polyisocyanate (D1a), the polyol (D1b), and the hydroxyl group-containing (meth) acrylate (Ac) is not particularly limited, but is preferably 1 / 0.5 to from the viewpoint of storage stability. 1/10, more preferably 1 / 0.7 to 1/5, particularly preferably 1/1 to 1/2.

  In the production of urethane (meth) acrylate (D1) obtained by reacting polyisocyanate (D1a), polyol (D1b), and hydroxyl group-containing (meth) acrylate (D1c), a urethanization catalyst may be used. Urethane catalysts include metal compounds (organic bismuth compounds, organic tin compounds, organic titanium compounds, etc.) and quaternary ammonium salts.

  The urethanization reaction can be carried out at normal pressure, reduced pressure or increased pressure. The progress of the urethanization reaction can be judged, for example, by measuring the NCO% and hydroxyl value of the reaction system.

The number average molecular weight (hereinafter sometimes abbreviated as Mn) of the urethane (meth) acrylate (D1) is preferably 1,000 from the viewpoint of flowability into the lens recess and prevention of dripping during coating. To 10,000, more preferably 1,300 to 9,000, particularly preferably 1,500 to 8,000.
When Mn is 1,000 or more, there is no problem of dripping at the time of coating, the variation due to temperature is small, and when it is 10,000 or less, the flowability into the lens recess is good.
In addition, Mn in this invention is a number average molecular weight by a gel permeation chromatography (GPC) method, uses HLC-8320GPC (made by Tosoh Corporation), THF solvent, TSK standard polystyrene (Tosoh Corporation made). ) As a reference substance, measurement temperature: 40 ° C., column: Alliance (manufactured by Waters). Moreover, GPC workstation EcoSEC-WS (made by Tosoh Corporation) was used as analysis software.

The content of the urethane (meth) acrylate (D1) in the photosensitive composition of the present invention is preferably 5 to 60% by weight, more preferably 10 to 55% by weight, and particularly preferably 15 to 15% from the viewpoint of adhesion. 50% by weight.
If the content is 5% by weight or more, the curing shrinkage is small, so that the adhesion is better. Moreover, handling property is favorable in it being 60 weight% or less.

The monofunctional (meth) acrylate (D2) in the present invention is other than urethane (meth) acrylate (D1), and includes aliphatic monofunctional (meth) acrylate (D21), alicyclic monofunctional (meth) acrylate ( D22), and aromatic monofunctional (meth) acrylate (D23).
Two or more of these may be combined.

  Examples of the aliphatic monofunctional (meth) acrylate (D21) include methyl (meth) acrylate, ethyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and the like. Is mentioned.

  Examples of the alicyclic monofunctional (meth) acrylate (D22) include cyclohexyl (meth) acrylate.

  Examples of the aromatic monofunctional (meth) acrylate (D23) include phenoxyethyl (meth) acrylate, orthophenylphenol mono (meth) acrylate, mono (meth) acrylate of nonylphenol EO2 to 10 mol adduct, and the like. .

  Of the above (D21) to (D23), (D21) and (D23) are preferable from the viewpoint of adhesion.

  The molecular weight (or Mn) of the monofunctional (meth) acrylate (D2) in the present invention is preferably from 86 to 1,000, more preferably from 100 to 500, from the viewpoint of smoothness after coating.

The viscosity of monofunctional (meth) acrylate (D2) at 25 ° C. [when using a plurality of (D2) (D2) overall viscosity] is preferably 5 to 1,000 mPa from the viewpoint of smoothness after coating. · S, more preferably 10 to 500 mPa · s, particularly preferably 15 to 300 mPa · s.
The viscosity in the present invention is measured by a Brookfield type rotational viscometer (BL type viscometer).

  The content of the monofunctional (meth) acrylate (D2) in the photosensitive composition of the present invention is preferably 10 to 80% by weight, more preferably 15 to 70% by weight, from the viewpoint of the strength and curability of the cured product. Particularly preferred is 20 to 60% by weight. If content is 10 weight% or more, it is excellent in photocurability, and if it is 80 weight% or less, dripping at the time of coating can be prevented.

The weight ratio (D1) / (D2) of urethane (meth) acrylate (D1) and monofunctional (meth) acrylate (D2) other than (D1) in the photosensitive composition of the present invention is preferably 5 / It is 95-95 / 5, More preferably, it is 10 / 90-83 / 17, Most preferably, it is 22 / 78-60 / 40.
When the weight ratio of (D1) is 5 or more, the adhesion is better, and when it is 95 or less, the handling property is good.

In the photosensitive composition of the present invention, as the polymerizable substance (D), a urethane (meth) acrylate (D1) having at least one (meth) acryloyl group in the molecule, and a monofunctional (meth) other than (D1) In addition to the acrylate (D2), other commonly used polymerizable substances (particularly radical polymerizable substances) (D3) may be contained.
Examples of the polymerizable substance (D3) include (meth) acrylamide (D31) having 3 to 35 carbon atoms, 2 to 6 functional (meth) acrylate (D32) other than (D1) having 10 to 35 carbon atoms, and carbon. Examples include an aromatic vinyl compound (D33) having 6 to 35 carbon atoms, a vinyl ether compound (D34) having 3 to 35 carbon atoms, and other radical polymerizable substances (D35).
The “2-6 functional (meth) acrylate” means (meth) acrylate having 2 to 6 (meth) acryloyl groups, and the same description method is used hereinafter.

  Examples of the (meth) acrylamide compound (D31) having 3 to 35 carbon atoms include (meth) acrylamide and N-methyl (meth) acrylamide.

Among the bifunctional to hexafunctional (meth) acrylate (D32) having 10 to 35 carbon atoms, the bifunctional (meth) acrylate includes 1,4-butanedi (meth) acrylate and 1,6-hexanedi (meth) acrylate. , Polypropylene di (meth) acrylate, AO of bisphenol A (EO and / or PO, etc., the same shall apply hereinafter) 2 to 10 mol adduct di (meth) acrylate and the like.
Examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol AO 1-30 mol adduct tri ( And (meth) acrylate.
Examples of tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tetra (meth) acrylate of pentaerythritol AO 1 to 30 mol adduct, and the like. Is mentioned.
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 and sorbitol hexa (meth) acrylate.

  Examples of the aromatic vinyl compound (D33) having 6 to 35 carbon atoms include styrene, methylstyrene, chlorostyrene and the like.

As a C3-C35 vinyl ether compound (D34), 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, ethoxyethyl vinyl ether, diethylene glycol monovinyl ether, and the like.
Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, polyethylene glycol divinyl ether, pentaerythritol tetravinyl ether, and the like. ,

  Examples of the other radical polymerizable substance (D35) include acrylonitrile, vinyl chloride, ethylene, propylene and the like.

  Among these, from the viewpoint of the curing rate, 2 to 6 functional (meth) acrylate (D32) other than (D1) having 10 to 35 carbon atoms is preferable.

  The amount of the other polymerizable substance (D3) in (D) is preferably 40% by weight or less, more preferably 5 to 30% by weight.

  As the filler (E) in the present invention, at least one selected from a colorant (E1), a metal oxide powder (E2) and a metal powder (E3) can be used.

  As the colorant (E1), pigments and dyes such as inorganic pigments and organic pigments conventionally used in paints and inks can be used.

  Examples of inorganic pigments include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine, carbon black, graphite, titanium black, and Fe.

  Organic pigments include β-naphthol, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone and other soluble azo pigments, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid Insoluble azo pigments such as anilide, acetoacetanilide monoazo, acetoacetate anilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, iso Examples thereof include polycyclic or heterocyclic compounds such as sindrinone, quinacridone, dioxazine, perinone, and perylene.

  Specific examples of dyes include yellow dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones or open-chain active methylene compounds as coupling components, open-chain activity as coupling components Examples thereof include azomethine dyes having a methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes.

  For magenta dyes, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) are used as coupling components. Aryl or heteryl azo dyes having, azomethine dyes having pyrazolones or pyrazolotriazoles as coupling components, arylidene dyes, styryl dyes, merocyanine dyes such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes Examples thereof include carbonium dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes Examples of the coupling component include phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives, aryl or heteryl azo dyes (such as CI Direct Blue 14), and indigo / thioindigo dyes.

As the colorant (E1), resin beads (E1 ′) containing the colorant (E1) can also be used. In the present invention, (E1 ′) is also included in the colorant (E1).
When the resin beads (E1 ′) containing the colorant (E1) having a volume average primary particle diameter of 1 to 20 μm are used as the colorant (E1), the colorant (E1) is preferably used for forming a black stripe for a lens sheet. be able to.

  When used for forming black stripes, the colorant (E1) contained in the resin beads is usually a black inorganic pigment, preferably carbon black and titanium black, particularly preferably carbon black.

  Examples of the carbon black include known carbon blacks such as channel black, furnace black, thermal black, and lamp black. Of these, channel black is preferable from the viewpoint of shielding properties.

As the resin beads, melamine beads, urethane beads, acrylic beads, acrylic styrene beads, polycarbonate beads, polyethylene beads, polystyrene beads, polyvinyl chloride beads and the like can be used.
Among these, from the viewpoint of dispersibility in the ink composition, urethane beads and acrylic beads are preferable, and acrylic beads are particularly preferable.

Furthermore, in order to exhibit sufficient shielding properties as black stripes and smoothness of the concave portions after scraping, the volume average primary particle diameter of the resin beads (E1 ′) containing the colorant (E1) is 1 to 20 μm. More preferably, it is 1-10 micrometers, Most preferably, it is 2-6 micrometers.
In addition, the volume average primary particle diameter in the present invention is a value measured by a Coulter counter method.

  The colorant (E1) and the resin beads are used in the form of black resin particles obtained by uniformly dispersing with a known mixing device or the like. As a mixing apparatus, for example, a planetary mixer, a bead mill, a three roll, a two roll, or the like can be used. The stirring and mixing time is, for example, the time until most of the aggregates contained in the black resin particles disappear, and is appropriately determined. The obtained composition may remove aggregates and the like by filtration, if necessary.

  When the metal oxide powder (E2) or the metal powder (E3) is contained as the filler (E), it can be used for green sheet formation and electrode layer formation of ceramic electronic components, for example.

  The metal oxide powder (E2) is used when forming the dielectric layer. Examples of (E2) include barium titanate, calcium zirconate, niobium oxide, and lead zirconate titanate, and barium titanate is preferred.

  The particle diameter of (E2) is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm, as a volume average primary particle diameter, from the viewpoint of dielectric constant.

The metal powder (E3) is a noble metal and a base metal used when forming the conductor layer, and specifically includes palladium, nickel, copper, silver, gold, etc., preferably palladium, nickel, and copper. It is.
The volume average primary particle diameter of (E3) is preferably 0.01 μm to 10 μm.

Although content of the filler (E) in the photosensitive composition of this invention is not specifically limited, Preferably it is 0.5 to 60 weight%.
The content when the filler (E) is resin beads (E1 ′) is preferably 0.5 to 40% by weight, more preferably 5 to 35% by weight, particularly preferably 10 to 30% by weight. is there.
If it is 0.5% by weight or more, the shielding property can be exerted satisfactorily, and if it is 60% by weight or less, photocurability can be satisfactorily exhibited.

The surface tension at 25 ° C. of the photosensitive composition of the present invention is preferably 38 mN / m or less, more preferably 36 mN / m or less, and particularly preferably 35 mN / m or less.
When the surface tension is 38 mN / m or less, smoothness after coating is better.

The viscosity of the photosensitive composition of the present invention at 25 ° C. is preferably 1,500 to 5,000 mPa · s, more preferably 2,000 to 4,500 mPa · s, particularly preferably 2, 500 to 4,000 mPa · s.
When the viscosity at 25 ° C. is 1,500 mPa · s or more, the handleability is good, and when it is 5,000 mPa · s or less, the smoothness after coating becomes better.

  As a method of adjusting the viscosity of the photosensitive composition to the above preferred range, a method of adjusting the molecular weight of the urethane (meth) acrylate (D1), a method of adjusting the content of the urethane (meth) acrylate (D1), and The method etc. which adjust the molecular weight of monofunctional (meth) acrylate (D2) are mentioned. Among these, from the viewpoint of ease of adjustment, a method of adjusting the molecular weight of the urethane (meth) acrylate (D1) and a method of adjusting the content of the urethane (meth) acrylate (D1) are preferable.

  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, and particularly preferably 2 to 10% by weight with respect to the photosensitive composition.

  The photosensitive composition of the present invention further comprises inorganic fine particles, a dispersant, an antifoaming agent, a leveling agent, a thixotropic agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant and an ultraviolet ray in accordance with the purpose of use. An absorbent or the like can be contained.

  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 a filler (E) as necessary. It can be obtained by kneading a solvent or other components 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 base 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.

As a method of forming a black stripe for a lens sheet, the photosensitive composition of the present invention is poured into a concave portion of a transparent lens sheet provided with a concave cylindrical lens shape by a mold, and the photosensitive composition above the concave portion is poured. After scraping off an object, it is formed by irradiating with ultraviolet rays and photocuring. These operations may be performed a plurality of times.

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

[Production of acid generator (B)]
Production Example 1
[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 (B122-1) {Compound Represented by Chemical Formula (28)}]

  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 of base generator (C)]
Production Example 3
[Synthesis of Base Generator (C122-1) {Compound Represented by Chemical Formula (29)}]

  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.] in small portions (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 4
[Synthesis of Base Generator (C123-1) {Compound Represented by Chemical Formula (30)}]

  “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 9 except that it was changed to “parts”.

Production Example 5 [Synthesis of Urethane (meth) acrylate (D1-1)]
In a reaction vessel equipped with a stirrer and an air introduction tube, 277 parts of a PO2 molar adduct of bisphenol A was charged and dehydrated by heating at 70 ° C. under reduced pressure. After dehydration, 500 parts of ethyl acetate was added and homogenized, and then the temperature was lowered to 50 ° C. or lower.
Next, 135 parts of isophorone diisocyanate (IPDI) [trade name: VESTANAT IPDI, manufactured by BASF], 65 parts of xylylene diisocyanate (XDI) [trade name: Takenate 500, manufactured by Mitsui Takeda Chemical Co., Ltd.], and bismuth as a urethanization catalyst A urethane prepolymer having isocyanate groups at both ends was obtained by adding 0.4 parts of a system catalyst [trade name: Neostan U-600, manufactured by Nitto Kasei Co., Ltd.] and reacting at 75 ° C. for 10 hours with stirring.
After adding 23 parts of 2-hydroxyethyl acrylate [BHEA, Nippon Shokubai Co., Ltd.] to the obtained urethane prepolymer and reacting at 75 ° C. for 4 hours while ventilating air, the temperature was lowered to 50 ° C. or lower, Ethyl acetate was removed under reduced pressure to obtain urethane (meth) acrylate (D1-1) having acryloyl groups at both ends. This urethane (meth) acrylate (D1-1) contained two acrylate groups, and Mn by GPC was 3,300.

Production Example 6 [Production of Urethane (meth) acrylate (D1-2)]
A glass reaction vessel equipped with a stirrer and a thermometer was charged with 59.7 parts of polytetramethylene glycol [trade name: PTMG-1000, manufactured by Mitsubishi Chemical Corporation] and confirmed that the water content was 500 ppm. Thereafter, 26.5 parts of IPDI and 0.5 part of a 50% 2-ethylhexanoic acid solution of bismuth tri (2-ethylhexanoate) as a catalyst were added and stirred to obtain a homogeneous solution. The temperature was raised to. While adjusting the temperature in the container to 110 ° C., the first stage urethanization reaction was carried out for 6 hours.
In the first urethanization reaction, after confirming that the isocyanate content was 5.85% or less, nitrogen and oxygen mixed gas with oxygen concentration adjusted to 8% was passed through the liquid for the purpose of inhibiting polymerization. Then, 13.8 parts of hydroxyethyl acrylate was added and reacted at 75 ° C. for 2 hours. The second stage urethanization reaction confirmed that the isocyanate content became 0.01% or less, and then cooled to 60 ° C. to obtain urethane (meth) acrylate (D1-2). This urethane (meth) acrylate contained two acrylate groups, and Mn by GPC was 1,750.

Production Example 7 [Method for producing urethane (meth) acrylate (D1-3)>
As a polyol component, urethane (meta) was prepared under the same conditions as in Production Example 5, except that 200 parts of PO2 molar adduct of bisphenol A and 200 parts of PO2 molar adduct of bisphenol A and 221 parts of PTMG-1000 were combined. ) Acrylate (D1-3) was obtained.
This urethane (meth) acrylate contained two acrylate groups, and Mn by GPC was 4,500.

Examples 1-9 and Comparative Examples 1-5
Urethane (meth) acrylate (D1), monofunctional (meth) acrylate (D2), radical initiator (A), acid generator (B) or base generator (C) shown in Table 1, (D1) and ( Polymeric substances (D3) other than D2) were blended together and stirred with a disperser until uniform. Further, with stirring, the black resin particles as the resin beads (E1 ′) containing the colorant (E1) were equally added in three portions to obtain the photosensitive composition of the present invention.

In addition, the symbol of the compound described in Table 1 represents the following compounds. The viscosity of (D2) at 25 ° C. is shown in the table.
(D2-1): Isobornyl acrylate [trade name “Light acrylate IBX-A”, manufactured by Kyoeisha Chemical Co., Ltd.]
(D2-2): 2-ethylhexyl acrylate [trade name “2-ethylhexyl acrylate” manufactured by Tokyo Chemical Industry Co., Ltd.]
(D2-3): Phenoxyethyl acrylate [trade name “Light acrylate PO-A”, manufactured by Kyoeisha Chemical Co., Ltd.]
(D2-4): Methoxypolyethylene glycol acrylate [trade name “Light Acrylate 130A”, manufactured by Kyoeisha Chemical Co., Ltd.]
(D2-5): Nonylphenol EO 4 mol adduct acrylate [trade name “Light Acrylate NP-4EA”, manufactured by Kyoeisha Chemical Co., Ltd.]
(D2-6): Nonylphenol EO 8 mol adduct acrylate [trade name “Light Acrylate NP-8EA”, manufactured by Kyoeisha Chemical Co., Ltd.]
(E1′-1): Black resin particles, volume average primary particle diameter of 4 μm [trade name: “Ganz Pearl GMB-04S-B2”, manufactured by Ganz Kasei Co., Ltd.]
(E1′-2): black resin particles, volume average primary particle diameter of 6 μm [trade name: “Ganz Pearl GM-06S-B5”, manufactured by Ganz Kasei Co., Ltd.]
(A-1): 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 184”, manufactured by BASF Corporation]
(A-2): 1,3,5-trimethylbenzoyldiphenylphosphine oxide [trade name “LUCIRIN TPO”, manufactured by BASF Corporation]
(A-3): Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide [trade name “Irgacure 819”, manufactured by BASF Corporation]
(D3-1): Diacrylate of ethylene oxide 4 mol adduct of bisphenol A [trade name: “Neomer BA-641”, manufactured by Sanyo Chemical Industries, Ltd.]
(D3-2): Diacrylate of 20 mol adduct of bisphenol A with ethylene oxide [trade name: “New Frontier BPE-20”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.]

[Performance evaluation]
Static surface tension at 25 ° C., viscosity at 25 ° C., coating of the photosensitive composition of the present invention prepared in Examples 1 to 9 and the comparative photosensitive composition prepared in Comparative Examples 1 to 5 Film curability, dispersion stability of the filler (black resin particles), and smoothness after coating were measured by the following methods.

[Static surface tension]
The static surface tension (mN / m) of the photosensitive composition was measured by a Wilhelmy method using a platinum plate at 25 ° C. using a surface tension meter (CBVB-A3: manufactured by Kyowa Science Co., Ltd.).

[viscosity]
The viscosity of the photosensitive composition at 25 ° C. was measured using a BL type viscometer (TVB-10: manufactured by Toki Sangyo Co., Ltd.) and rotor No3.

[Evaluation of coating curability]
Each photosensitive composition obtained in Examples 1 to 9 and Comparative Examples 1 to 5 was subjected to a surface treatment on a 100 μm thick PET (polyethylene terephthalate) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.]. The film was applied so as to have a film thickness of 60 μm, and was exposed using a belt conveyor type UV irradiation device (“EICS-151U”, iGraphics Co., Ltd.). The exposure amount was 200 mJ / cm ² at 365 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.

[Dispersion stability of filler (black resin particles)]
The photosensitive composition was applied on a slide glass “S1225, manufactured by Matsunami Glass Industry Co., Ltd.” having a thickness of 1.2 mm with an applicator so as to have a film thickness of 10 μm. Furthermore, the same slide glass was put so that air could not be caught from above, and a sample in which the photosensitive composition was sandwiched was prepared.
This sample was observed using a microspectroscope (MCPD2000: manufactured by Otsuka Electronics Co., Ltd.) immediately after forming the coating film and after standing for 30 minutes.
An area of 100 μm square was observed at a magnification of 1000 times to confirm the presence or absence of aggregates.
The dispersion stability of the black resin particles was evaluated according to the following criteria.
○: Increase in the number of particles having a particle size of 20 μm or more is within 5%.

[Smoothness after coating]
The photosensitive composition was applied to a PET film “A4300, manufactured by Toyobo Co., Ltd.” cut into 15 cm × 15 cm using an applicator. Then, 1000 mJ / cm < ² > was irradiated with the said ultraviolet irradiation device, and the light shielding material was formed.
The smoothness of a 10 cm square resin 2.5 cm inside from the edge of this film was measured using a shape measuring microscope at a magnification of 1000 times the centerline average roughness described in Appendix 2 of JIS B0601: 2001 ( Ra) was measured at five locations, and the average value was evaluated based on the following criteria.
A: Center line average roughness Ra is less than 0.15 μm O: Center line average roughness Ra is 0.15 μm or more and 0.3 μm or less ×: Center line average roughness Ra exceeds 0.3 μm

  Table 1 shows the evaluation results of the photosensitive compositions obtained in Examples and Comparative Examples.

  As is apparent from Table 1, the photosensitive compositions of Examples 1 to 9 of the present invention have good coating film curability and filler dispersion stability. Moreover, since it is excellent in the smoothness after coating, it turns out that it is excellent in an optical characteristic.

On the other hand, in Comparative Examples 1 to 3 in which neither the acid generator (B) nor the base generator (C) was used, the coating curability at a low exposure amount was lowered.
The comparative example 4 which does not use a urethane (meth) acrylate (D1) has a problem in the dispersion stability of a filler.
Moreover, the comparative example 5 which does not use a monofunctional (meth) acrylate (D2) has a problem in the smoothness after coating.

Since the photosensitive composition of the present invention can be cured with a thick film at a high colorant concentration even with a small amount of energy, it is for flat panel displays, coating agents, inks, paints, adhesives, resist patterns, or It is extremely useful as a material for manufacturing ceramic electronic components.
In addition, when the photosensitive composition of the present invention is used as a light-shielding material, the dispersion stability of the colorant such as black resin particles is good, the smoothness after coating is good, and the productivity is excellent. It is suitable as a light shielding material.

Claims (11)

A photosensitive composition containing the following (1) to (4), wherein the polymerizable substance (D) is a urethane (meth) acrylate (D1) having at least one (meth) acryloyl group in the molecule, and A photosensitive composition comprising a monofunctional (meth) acrylate (D2) other than (D1).
(1) Radical initiator (A)
(2) Acid generator (B) and / or base generator (C)
(3) Polymerizable substance (D)
(4) At least one filler (E) selected from colorant (E1), metal oxide powder (E2) and metal powder (E3)   At least one of the radical initiator (A), the acid generator (B) and the base generator (C) generates an active species (H) by irradiation with actinic rays, and the active species (H) is a radical initiator. (A), reacting with the acid generator (B) or the base generator (C) to produce a new active species (I), and the polymerization reaction of the polymerizable substance (D) with the new active species (I) The photosensitive composition according to claim 1, wherein the active species (H) or (I) is an acid or a base.   The photosensitive composition according to claim 1, wherein the viscosity at 25 ° C. is 1,500 to 5,000 mPa · s.   The photosensitive composition according to claim 1, wherein the filler (E) is a resin bead (E1 ′) containing a colorant (E1) and having a volume average primary particle diameter of 1 to 20 μm. The radical initiator (A) is a radical initiator (A1) that generates radicals with actinic rays, a radical initiator (A2) that generates radicals with an acid, or a radical initiator (A3) that generates radicals with a base, The acid generator (B) is an acid generator (B1) that generates acid by actinic rays, an acid generator (B2) that generates acid by radicals, or an acid generator (B3) that generates acid by acid, The base generator (C) is a base generator (C1) that generates a base by actinic rays, a base generator (C2) that generates a base by radicals, or a base generator (C3) that generates a base by a base. , (A1) to (A3), (B1) to (B3) or (C1) to (C3) are contained in any combination of the following (1) to (10): Sensitivity described Composition.
(1) Contains (A1) and (B2).
(2) Contains (A1), (B2) and (B3).
(3) Contains (B1) and (A2).
(4) Contains (B1), (A2) and (B3).
(5) Contains (C1) and (A3).
(6) Contains (C1), (A3) and (C3).
(7) Contains (A1) and (C2).
(8) Contains (A1), (C2) and (C3).
(9) A combination of two or more of (1) to (4) above.
(10) A combination of two or more of (5) to (8) above.   A radical initiator (A1) that generates radicals with actinic rays, a radical initiator (A2) that generates radicals with an acid, or a radical initiator (A3) that generates radicals with a base is polymerized with an acylphosphine oxide derivative. Initiator (A1231), α-aminoacetophenone derivative polymerization initiator (A1232), benzyl ketal derivative polymerization initiator (A1233), α-hydroxyacetophenone derivative polymerization initiator (A1234), benzoin derivative polymerization initiator ( A1235), an oxime ester derivative polymerization initiator (A1236), a titanocene derivative polymerization initiator (A1237), an organic peroxide polymerization initiator (A231), and an azo compound polymerization initiator (A232). At least one radical polymerization The photosensitive composition according to claim 5, which is an initiator.   The acid generator (B1) that generates acid by the active light, the acid generator (B2) that generates acid by the radical, or the acid generator (B3) that generates acid by the acid is a sulfonium salt derivative (B121). 7. An acid generator selected from the group consisting of iodonium salt derivative (B122), sulfonic acid ester derivative (B31), acetic acid ester derivative (B32), and phosphonic acid ester (B33). Photosensitive composition.   The base generator (C1) that generates a base by the active light, the base generator (C2) that generates a base by the radical, or the base generator (C3) that generates a base by the base is an oxime derivative (C121), The photosensitivity according to any one of claims 5 to 7, 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 (C31). Composition.   The content of the radical initiator (A) is 0.1 to 10% by weight, the total content of the acid generator (B) and the base generator (C) is 0.05 to 20% by weight, urethane (meth) acrylate ( The content of D1) is 5 to 60% by weight, the content of monofunctional (meth) acrylate (D2) is 10 to 80% by weight, and the content of filler (E) is 0.5 to 60% by weight. Item 9. The light composition according to any one of Items 1 to 8.   The photosensitive composition according to any one of claims 1 to 9, which is used for flat panel displays, coating agents, inks, paints, adhesives, resist patterns, or ceramic electronic parts.   Hardened | cured material formed by hardening | curing the composition in any one of Claims 1-10 with actinic light.