JP2014056122A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition achieving both of elastic recovery characteristics and adhesiveness and having high sensitivity.SOLUTION: In the photosensitive composition, at least one of a radical initiator (A), an acid generator (B) and a base generator (C) generates an active species (H) by irradiation with active 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); and the new active species (I) promotes a polymerization reaction of a polymerizable substance (D) and a metal element-containing compound (E). The active species (H) or (I) is an acid or a base. The composition does not substantially contain any of a colorant, a metal oxide power and a metal powder. The polymerizable substance (D) contains a hydrophilic resin (D1) and a polyfunctional (meth)acrylate monomer (D2). The photosensitive composition contains the metal element-containing compound (E), which has at least one alkoxy group in the molecule.

Description

  The present invention relates to a photosensitive composition having both excellent elastic recovery properties and adhesiveness and high sensitivity.

  In recent years, liquid crystal display elements and organic EL displays have attracted attention, and photosensitive compositions are frequently used in the manufacturing process. In the semiconductor industry, photosensitive resins are also used for the production of ultrafine circuits such as ICs and LSIs, or for insulators and protective films.

For example, as mother glass grows in flat panel display-related liquid crystal display (LCD) production, a drop method (ODF method) (ODF: One Drop Fill) is proposed instead of the conventional liquid crystal inflow method (vacuum suction method) Has been. In this ODF method, since a predetermined amount of liquid crystal is dropped and then sandwiched between two substrates, the liquid crystal is injected, so that the number of processes and the process time can be reduced as compared with the conventional vacuum suction method.
However, in the ODF system, a predetermined amount of liquid crystal calculated from the cell gap is dropped and held, so that a pressure change is applied to the photo spacer arranged on the glass substrate. It is desired for the photo spacer to have a high elastic recovery characteristic so that the shape does not plastically deform with respect to this pressure change.

In order to obtain such high elastic recovery characteristics, a method of nano-dispersing inorganic fine particles such as organosilica sol (for example, Patent Document 1), or a content ratio of a polyfunctional monomer such as dipentaerythritol hexaacrylate is 50% or more. A method (for example, Patent Document 2) for obtaining high elasticity by increasing the thickness is known.
However, in any method, since the adhesiveness between the photospacer and the substrate such as glass is lowered, a photosensitive composition for forming a photospacer capable of achieving both high elasticity and sufficient adhesiveness has not been obtained.

  For example, in touch panels, an increasing number of manufacturers adopt a capacitive method. In the case of the electrostatic capacity method, it is necessary to form a transparent conductive film, for example, an ITO film on a substrate, and to form a protective film on the transparent conductive film in order to protect the transparent conductive film. Performance required for this protective film includes adhesion to transparent electrodes such as substrates, underlayers, and ITO, resistance to ITO etching solutions, heat resistance in the firing process, and transmittance when a laminated substrate is used. Desired. Patent Document 3 discloses a photosensitive composition having good radiation sensitivity, developability and storage stability by combining a radical photopolymerization system and a cationic photopolymerization system. It was difficult to get.

  For example, in recent years, positive photosensitive compositions have been used for semiconductor surface protective films and interlayer insulators in order to simplify the process. Sensitivity is particularly important when utilizing a photosensitive composition. If the sensitivity is low, the exposure time becomes long and the throughput decreases. Therefore, in order to improve the sensitivity of the photosensitive composition, for example, when a large amount of a photosensitive agent is added, the sensitivity becomes high, but scum (development residue) may occur during development. Therefore, a photosensitive composition that is highly sensitive and can be patterned without scum is desired.

Japanese Patent Laid-Open No. 10-274853 Japanese Patent Laid-Open No. 2007-10885 JP 2010-27033 A

  An object of the present invention is to provide a photosensitive composition having both excellent elastic recovery properties and adhesion and high sensitivity.

The inventor of the present invention has arrived at the present invention as a result of studies to achieve the above object. That is, the present invention is the following four inventions.
(I) A photosensitive composition containing the following (1) to (4), wherein at least one of the radical initiator (A), the acid generator (B) and the base generator (C) is an actinic ray. The active species (H) is generated by irradiation with the active species, and the active species (H) reacts with the radical initiator (A), the acid generator (B) or the base generator (C) to form a new active species (I). And the polymerization reaction of the polymerizable substance (D) by the new active species (I) and, if necessary, the metal element-containing compound (E) proceeds, and the active species (H) or (I) is acid or base The polymerizable substance (D) contains the hydrophilic resin (D1) and the polyfunctional (meth) acrylate monomer (D2), and contains substantially no colorant, metal oxide powder or metal powder. The photosensitive composition characterized by the above-mentioned.
(1) Radical initiator (A)
(2) Acid generator (B) and / or base generator (C)
(3) Polymerizable substance (D)
(4) Metal element-containing compound (E)
(II) A radical initiator (A), an acid generator (B), and a base generator (C) are listed below together with the polymerizable substance (D) and the metal element-containing compound (E) represented by the following general formula (1). It is contained in any combination of (1) to (4), the polymerizable substance (D) contains a hydrophilic resin (D1) and a polyfunctional (meth) acrylate) monomer (D2), a colorant, metal oxidation A photosensitive composition characterized by being substantially free of product powder and metal powder.
(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 and / or radicals, acids and It contains a base generator (C2) that generates a base by at least one selected from the group consisting of 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) At least one selected from the group consisting of a base generator (C1) that generates a base 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 an acid generator (B2) that generates an acid depending on the species.
(4) A combination of two or more of (1) to (3) above.
(III) Hardened | cured material formed by hardening | curing said photosensitive composition of (I) or (II) by irradiation of actinic light.
(IV) a colorant in the presence of a radical initiator (A), an acid generator (B) and / or a base generator (C), and a metal element-containing compound (E) represented by the following general formula (1): A method for producing an actinic ray cured product in which a polymerizable substance (D) and, if necessary, a metal element-containing compound (E) are polymerized by irradiation with actinic rays in the absence of both metal oxide powder and metal powder. And 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. React with the initiator (A), the acid generator (B) or the base generator (C) to produce a new active species (I), a polymerizable substance (D) by the new active species (I), and If necessary, the polymerization reaction of the metal element-containing compound (E) proceeds, and the active species (H) or (I) is an acid or a base, and the polymerizable substance (D) contains a hydrophilic resin (D1) and a polyfunctional (meth) acrylate monomer (D2). .

[In Formula (1), M is a metal element, and A ¹ and A ² are each independently an alkyl group, a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, or hydrogen. A ³ and A ⁴ are each independently an alkyl group, alkoxy group, aryl group, mercaptoalkyl group, aminoalkyl group, (meth) acryloyloxyalkyl group, (meth) acryloyloxyalkoxy group or (meth) acryloyloxy group In the case where a plurality of A ³ and A ⁴ are contained in one molecule depending on the repeating unit, they may be the same or different groups. However, at least one of n A ³ and n A ⁴ is an alkoxy group. n is an integer of 2-20. ]

  The present invention provides a photosensitive composition having both excellent elastic recovery properties and adhesion and high sensitivity.

The photosensitive composition of the present invention contains the following (1) to (4).
(1) Radical initiator (A)
(2) Acid generator (B) and / or base generator (C)
(3) Polymerizable substance (D)
(4) Metal element-containing compound (E) having a specific composition
The polymerizable substance (D) contains a hydrophilic resin (D1) and a polyfunctional (meth) acrylate monomer (D2).
In the present specification, “(meth) acrylate” means “acrylate or methacrylate”.

  In the method for producing the photosensitive composition of the first invention and the actinic ray cured product of the fourth invention, at least one of the radical initiator (A), the acid generator (B) and the base generator (C). One generates active species (H) by irradiation with actinic rays, and the active species (H) reacts with the radical initiator (A), acid generator (B) and / or base generator (C) to form new species. The active species (I) is generated, and the polymerization reaction of the polymerizable substance (D) by the new active species (I) and, if necessary, the metal element-containing compound (E) 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.

  Below, (A)-(E) which is an essential structural component of the photosensitive composition of this invention is demonstrated in order.

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 relative to the total weight of the polymerizable substance (D) and the metal element-containing compound (E) from the viewpoint of photocurability. 0.05 to 30% by weight, more preferably 0.1 to 20% by 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 (2) or the following general formula (3).

In General Formula (2) or (3), A ¹ is a divalent or trivalent group represented by any of General Formulas (4) to (11), 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 (6) to (9) 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 (3), groups represented by the general formula (6) and the general formulas (8) to (11) are preferable from the viewpoint of acid generation efficiency. Groups represented by 9) to (11) are more preferred.

Ar ^{1 to} Ar ⁷ in the general formula (2) and the general formula (3) are groups in which the compound represented by the general formula (2) or the general formula (3) 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 (2) or (3) 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 (12) to (15) are preferable, and compounds represented by the following general formulas (12) to (15) are more preferable.

(X ³ ) ⁻ to (X ⁶ ) ⁻ in the general formulas (12) to (15) represent anions, specifically, (X ¹ ) ⁻ or (X ² ) in the general formula (2) or (3). ) ^- 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 (16) or the following general formula (17).

In the formula, A ² is a divalent or trivalent group represented by any one of the general formulas (4) to (11), 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 (2) and General formula (3) is illustrated.

As A ² in the general formula (17), a group represented by the general formula (6) and the general formulas (8) to (11) is preferable from the viewpoint of the efficiency of generating an acid. And groups represented by (9) to (11) are more preferred.

Ar ^{8 to} Ar ¹² in the general formula (16) or the general formula (17) are groups in which the compound represented by the general formula (16) or the general formula (17) 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 (2) or general formula (3). 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 (2) or (3). 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 formulas (18) to (21) are preferred, and compounds represented by the following general formulas (18) to (21) (including exemplified compounds) are more preferable.

In the general formulas (18) to (21), 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 (2) and General formula (3) 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} general formulas (18) to (21) are the same as those exemplified as (X ¹ ) ⁻ or (X ² ) ^{− in} general formula (2) or (3). 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 (3) or the general formula (17), an adverse effect 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 of the following general formulas (22) to (24).

R ^{14 to} R ⁴¹ in the general formulas (22) to (24) 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 (25) An atom or a substituent selected from the group consisting of the substituent represented by formula (26) and the substituent represented by formula (26), wherein any one of R ^{14 to} R ²³ is represented by formula (25) or formula ( 26), and any one of R ^{24 to} R ³¹ is a substituent represented by general formula (25) or general formula (26), and any one of R ^{32 to} R ⁴¹ One is a position represented by the general formula (25) or the general formula (26). It is a substituent.

R ^{42 to} R ⁴⁵ in the general formulas (25) and (26) are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{46 to} R ⁴⁸ have 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 (22) to (24), 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 (2) and the general formula (3).

The compound represented by the general formula (22) is an anthracene skeleton, the compound represented by the general formula (23) is a thioxanthone skeleton, and the compound represented by the general formula (24) 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 (25) or General formula (26).

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 (18) to (20).

The substituent represented by the general formula (25) 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.

The general formula (26) 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 (25) and (26) represent anions, specifically, (X ¹ ) ⁻ or (X ² ) in the general formula (2) or (3). ) ^- 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 (25) 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), the compound represented by the following general formula (27) is preferred from the viewpoint of photodegradability.

(X ¹⁵ ) ⁻ in the general formula (27) represents an anion, specifically, the same as those exemplified as (X ¹ ) ⁻ or (X ² ) ^{− in the} general formula (2) or (3). 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).

Content of acid generator (B) and / or base generator (C) in the photosensitive composition of the present invention [(B
) And (C)] is preferably 0.05 to 30% by weight, more preferably, based on the total weight of the polymerizable substance (D) and the metal element-containing compound (E), from the viewpoint of photocurability. Is 0.1 to 20% by 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 composition of the second invention].
(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, if necessary, a base 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).

  The polymerizable substance (D) in the present invention is a radical polymerizable compound, contains a hydrophilic resin (D1) and a polyfunctional (meth) acrylate monomer (D2), and is other than the metal element-containing compound (E) described later. is there.

The hydrophilicity index in the hydrophilic resin (D1) in the present invention is defined by HLB. Generally, the larger this value, the higher the hydrophilicity.
The HLB value of (D1) is preferably 4 to 19, more preferably 5 to 18, and particularly preferably 6 to 17. When it is 4 or more, the developing property is further improved when developing the photospacer, and when it is 19 or less, the water resistance of the cured product is further improved.

Here, “HLB” is an index indicating a balance between hydrophilicity and lipophilicity, and is described in, for example, “Introduction to Surfactants” (published by Sanyo Chemical Industries, Ltd., 2007, Takehiko Fujimoto), page 212. It is known as the calculated value by the Oda method, not the calculated value by the Griffin method.
The HLB value can be calculated from the ratio between the organic value and the inorganic value of the organic compound.
HLB≈10 × inorganic / organic The organic value and the inorganic value for deriving HLB can be calculated by using the values in the table described in “Introduction of Surfactant” on page 213.

Further, the solubility parameter (hereinafter referred to as SP value) [(unit is (cal / cm ³ ) ^1/2 ]) of the hydrophilic resin (D1) is preferably 7 to 14, more preferably 8 to 13, particularly preferably. Is from 9 to 13. If it is 7 or more, the developability can be further improved, and if it is 14 or less, the water resistance of the cured product is further improved.

The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
“POLYMER ENGINEERING AND SCIENCE, February, 1974, Vol. 14, No. 2, Robert F. Fedors (pp. 147-154)”
Those with close SP values are likely to mix with each other (highly dispersible), and those with a distant numerical value are difficult to mix.

  From the viewpoint of alkali developability, the hydrophilic functional group contained in the molecule of the hydrophilic resin (D1) is preferably a carboxyl group, an epoxy group, a sulfonic acid group, or a phosphoric acid group, and more preferably a carboxyl group.

  Specific examples of the hydrophilic resin (D1) that can be used in the present invention include a hydrophilic epoxy resin (D11) and a hydrophilic (meth) acrylic resin (D12).

It is essential that the hydrophilic epoxy resin (D11) contains a (meth) acryloyl group or a carboxyl group in the molecule.
For example, in order to introduce a (meth) acryloyl group into a molecule, a novolak type epoxy resin having an epoxy group in the molecule may be reacted with acrylic acid or methacrylic acid, or a (meth) acryloyl group and a carboxyl group. For the hydrophilic epoxy resin containing both of these, there can be mentioned a method in which (meth) acrylic acid is first reacted with a novolak-type epoxy resin and then a polyvalent carboxylic acid or polyvalent carboxylic acid anhydride is added.

  The hydrophilic (meth) acrylic resin (D12) of the present invention can be obtained by polymerizing a (meth) acrylic acid derivative by an existing method.

  As a method for producing the hydrophilic (meth) acrylic resin (D12), radical polymerization is preferable, and a solution polymerization method is preferable because the molecular weight can be easily adjusted.

  Examples of the monomer constituting the hydrophilic (meth) acrylic resin (D12) include (meth) acrylic acid (d121) and (meth) acrylic acid ester (d122).

  (D122) is preferably methyl (meth) acrylate or hydroxyethyl (meth) acrylate.

  As a monomer constituting the hydrophilic (meth) acrylic resin (D12), an aromatic ring-containing vinyl compound (d123) is used in combination with (d121) and (d122) from the viewpoint of elastic recovery characteristics of the photosensitive composition. Also good. Styrene is mentioned as such (d123).

  In the hydrophilic (meth) acrylic resin (D12), it is preferable to introduce a (meth) acryloyl group into a side chain or a terminal as necessary for the purpose of further improving the elastic recovery property of the photospacer.

  Examples of the method for introducing a (meth) acryloyl group into the side chain include the following methods (1) and (2).

(1) A polymer is produced using a monomer having a group capable of reacting with an isocyanate group (such as a hydroxyl group or a primary or secondary amino group) in at least a part of (d121) or (d122), and then A method of reacting a compound having a (meth) acryloyl group and an isocyanate group (such as (meth) acryloyloxyethyl isocyanate).

(2) A polymer is produced using a monomer having a group capable of reacting with an epoxy group (hydroxyl group, carboxyl group, primary or secondary amino group, etc.) in at least part of (d121) or (d122). And then reacting a compound having a (meth) acryloyl group and an epoxy group (such as glycidyl (meth) acrylate).

  The content of the hydrophilic resin (D1) in the photosensitive composition of the present invention is preferably 5 to 60% by weight, more preferably 15 to 50% by weight, based on the total weight of (A) to (E). Particularly preferred is 20 to 50% by weight. If it is 5% by weight or more, the alkali developability of the photosensitive composition is improved, so that formation of a photospacer is facilitated. If it is 60% by weight or less, the elastic recovery property of the photospacer is better.

The polyfunctional (meth) acrylate monomer (D2) is not particularly limited as long as it is a known polyfunctional (meth) acrylate monomer.
As such polyfunctional (meth) acrylate monomer (D2), bifunctional (meth) acrylate (D21), trifunctional (meth) acrylate (D22), 4-6 functional (meth) acrylate (D23) and 7- A 10 functional (meth) acrylate (D24) is mentioned.

  Examples of the bifunctional (meth) acrylate (D21) include esterified products of polyhydric alcohol and (meth) acrylic acid [for example, di (meth) acrylate of glycol, di (meth) acrylate of glycerin, dimethyl of trimethylolpropane. (Meth) acrylate, di (meth) acrylate of 3-hydroxy-1,5-pentanediol, di (meth) acrylate of 2-hydroxy-2-ethyl-1,3-propanediol]; alkylene oxide of polyhydric alcohol Adducts and esterified products of (meth) acrylic acid [for example, di (meth) acrylate of trimethylolpropane ethylene oxide adduct, di (meth) acrylate of glycerin ethylene oxide adduct]; OH group-containing both-end epoxy acrylate; Polyhydric alcohol and (meth) ac Ester [example hydroxypivalic acid neopentyl glycol di (meth) acrylate] Le acid and hydroxycarboxylic acid, and the like.

  Trifunctional (meth) acrylate (D22) includes tri (meth) acrylate of glycerin, tri (meth) acrylate of trimethylolpropane, tri (meth) acrylate of pentaerythritol; and trioxide of ethylene oxide adduct of trimethylolpropane. (Meth) acrylate etc. are mentioned.

  The tetra- to hexa-functional (meth) acrylate (D23) includes pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; dipentaerythritol ethylene oxide addition Tetra (meth) acrylate of a product, penta (meth) acrylate of an ethylene oxide adduct of dipentaerythritol, penta (meth) acrylate of a propylene oxide adduct of dipentaerythritol, and the like.

  As the (meth) acrylate compound having 7 or more functional groups, for example, a compound obtained by a reaction of dipentaerythritol penta (meth) acrylate and hexamethylene diisocyanate is obtained by reacting a diisocyanate compound with a hydroxyl group-containing polyfunctional (meth) acrylate compound. be able to.

The content of the polyfunctional (meth) acrylate monomer (D2) of the present invention is preferably 20 to 90% by weight, more preferably 25 to 80% by weight, in particular, based on the total weight of (A) to (E). Preferably it is 30 to 70% by weight.
If it is 20% by weight or more, the elastic recovery property of the photospacer is better, and if it is 90% by weight or less, the developability of the photosensitive composition is improved and the formation of the photospacer becomes easy.

The metal element-containing compound (E) preferably improves the elastic recovery characteristics of the spacer by forming clusters of 1 nm to 100 nm in the resin after curing.
The size of the cluster is more preferably 10 to 80 nm, particularly preferably 12 to 70 nm. If it is 1 nm or more, the elastic recovery property of the spacer can be expressed more favorably, and if it is 100 nm or less, developability and transparency are better.

In addition, as a measuring method of the cluster size in this invention, it can measure with the following conditions with a scanning probe microscope (SII nanotechnology Co., Ltd. product E-sweep SPI4000) Measurement mode: DFM mode Cantilever model number: SI-DF40 (Spring constant 42N / m)
Scanning distance: 150 μm

  The metal element-containing compound (E) is an alkoxy-containing metal compound represented by the following general formula (1).

[In Formula (1), M is a metal element, and A ¹ and A ² are each independently an alkyl group, a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, or hydrogen. A ³ and A ⁴ are each independently an alkyl group, alkoxy group, aryl group, mercaptoalkyl group, aminoalkyl group, (meth) acryloyloxyalkyl group, (meth) acryloyloxyalkoxy group or (meth) acryloyloxy group In the case where a plurality of A ³ and A ⁴ are contained in one molecule depending on the repeating unit, they may be the same or different groups. However, at least one of n A ³ and n A ⁴ is an alkoxy group. n is an integer of 2-20. ]

  In the formula (1), the metal element M is an element selected from titanium, zirconium, aluminum, silicon, boron, vanadium, manganese, iron, cobalt, germanium, yttrium, niobium, lanthanum, cerium, tantalum, tungsten, and magnesium. Is mentioned. Among these, silicon, zirconium, aluminum, and titanium are preferable, and silicon is particularly preferable.

In formula (1), A ¹ and A ² are each independently an alkyl group, a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, or hydrogen.
Examples of the alkyl group used for A ¹ and A ² include a linear alkyl group and a branched alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a butyl group, and an octyl group, and examples of the branched alkyl chain include an isopropyl group, an isobutyl group, and a 2-ethylhexyl group.

Examples of the (meth) acryloyl group used for A ¹ and A ² include an acryloyl group and a methacryloyl group.

Examples of the (meth) acryloyloxyalkyl group used for A ¹ and A ² include a 1-acryloyloxypropyl group and a 1-methacryloyloxypropyl group.

In formula (1), A ³ and A ⁴ are each independently an alkyl group, alkoxy group, aryl group, mercaptoalkyl group, aminoalkyl group, (meth) acryloyloxyalkyl group, (meth) acryloyloxyalkoxy group or It is a (meth) acryloyloxy group, and when a plurality of A ³ and A ⁴ are contained in one molecule by repeating units, they may be the same or different groups. However, at least one of n A ³ and n A ⁴ is an alkoxy group.
The alkyl group used for A ³ and A ⁴ is the same as that described for A ¹ and A ² above.

Examples of the alkoxy group used for A ³ and A ⁴ include a methoxy group, an ethoxy group, a butoxy group, and an octoxy group. Of these, a methoxy group is preferably used from the viewpoint of curability.

Examples of the aryl group used for A ³ and A ⁴ include a phenyl group, a biphenyl group, and a naphthyl group. Of these, a phenyl group is preferably used from the viewpoint of reactivity.

Examples of the mercaptoalkyl group used for A ³ and A ⁴ include a mercaptomethyl group, a mercaptoethyl group, and a mercaptobutyl group.

Examples of the aminoalkyl group used for A ³ and A ⁴ include an aminomethyl group, an aminoethyl group, and an aminobutyl group.

The (meth) acryloyloxyalkyl group used for A ³ and A ⁴ is the same as that described for A ¹ and A ² above.

Examples of the (meth) acryloyloxyalkoxy group used for A ³ and A ⁴ include a 1-acryloyloxypropoxy group and a 1-methacryloyloxypropoxy group.

Examples of the (meth) acryloyloxy group used for A ³ and A ⁴ include an acryloyloxy group and a methacryloyloxy group.

  The repeating unit n of the formula (1) is 2 to 20 and preferably 3 to 15 from the viewpoint of the reactivity and storage stability of the compound.

  From the viewpoint of curability of the photosensitive composition, the metal element-containing compound (E) preferably contains a (meth) acryloyloxy group or a (meth) acryloyloxyalkoxy group.

The content of the metal element-containing compound (E) in the photosensitive composition of the present invention is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the total weight of (A) to (E). %.
If it is 1% by weight or more, the elastic recovery property of the photospacer is better, and if it is 40% by weight or less, the developability of the photosensitive composition is further improved and the formation of the photospacer becomes easy.

The content of carbon-carbon double bonds (C = C) based on the total weight of (A) to (E) of the photosensitive composition of the present invention is preferably 3.0 to 8.0 mmol / g, more preferably Is in the range of 3.5 to 7.5 mmol / g, particularly preferably 4.0 to 7.4 mmol / g.
If it is 3.0 mmol / g or more, the photocurability is sufficient, so that the elastic recovery property is better, and if it is 8.0 mmol / g or less, the adhesion of the photospacer to a glass substrate or the like is better.

  The photosensitive composition concerning this invention may contain the other component further as needed. Other components include sensitizers, polymerization inhibitors, solvents, thickeners, surface conditioners, and other additives (eg, silane coupling agents, fluorescent brighteners, yellowing inhibitors, antioxidants). , Defoaming agents, deodorants, fragrances, bactericides, antibacterial agents, fungicides, and the like.

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 comprises a radical initiator (A), a polymerizable substance (D), a metal element-containing compound (E), an acid generator (B) and / or a base generator (C). If 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 preferably 10 ° C to 40 ° C, more 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.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

[Production of sulfonium salt derivative (B121-1)]
Production Example 1
[Sulphonium Salt Derivative (B121-1) {Compound Represented by Chemical Formula (28)} that Generates Acid by Active Light]

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

(2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone [intermediate (B121-1-2)]:
While stirring 11.2 parts of the intermediate (B121-1), 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 to the mixture. After reaction at 14 ° 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 (B-1-2) (yellow solid).

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

Production Example 2
[Synthesis of Iodonium Salt Derivative (B122-1) {Compound Represented by Chemical Formula (29)} that Generates Acid by Actinic Light]

  6.5 parts of toluene [manufactured by Tokyo Chemical Industry Co., Ltd.], 8.1 parts of isopropylbenzene [manufactured by Tokyo Chemical Industry Co., Ltd.], 5.35 parts of potassium iodide [manufactured by Tokyo Chemical Industry Co., Ltd.] and acetic anhydride 20 parts were dissolved in 70 parts of acetic acid, cooled to 10 ° C., 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 with water three times, and the organic solvent was distilled off under reduced pressure to obtain 14.0 parts of the target iodonium salt derivative (B122-1) (light yellow liquid). It was.

Production Example 3
[Synthesis of Base Generator (C122-1) {Compound Represented by Chemical Formula (30)}]

  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 (31)}]

  “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”.

[Manufacture of hydrophilic resin]
Production Example 5
A glass Kolben equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introduction tube, cresol novolac type epoxy resin “EOCN-102S” (Epoxy equivalent 200 from Nippon Kayaku Co., Ltd.) and propylene 245 parts of glycol monomethyl ether acetate was charged and heated to 110 ° C. to dissolve uniformly. Subsequently, 76 parts of acrylic acid (1.07 mol part), 2 parts of triphenylphosphine and 0.2 part of p-methoxyphenol were charged and reacted at 110 ° C. for 10 hours. The reaction product was further charged with 91 parts (0.60 mol part) of tetrahydrophthalic anhydride and further reacted at 90 ° C. for 5 hours, and then the content of hydrophilic epoxy resin with propylene glycol monomethyl ether acetate was 50% by weight. As a hydrophilic resin having an acryloyl group and a carboxyl group, a 50% solution (D11-1) of an acryloyl group and a carboxyl group-containing cresol novolac type epoxy resin was obtained.
In addition, it was the number average molecular weight (Mn) by GPC as pure part conversion of this resin: 2,200, SP value: 11.3, and HLB value: 9.8.

[Production of siloxane compound (E-1) having two or more hydrolyzable alkoxy groups]
Production Example 6
To a glass Kolben equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 46 parts (0.2 mole part) of 3-acryloyloxypropyltrimethoxysilane, 160 parts of diphenyldimethoxysilane (0 .65 mol parts), 45 g (2.5 mol parts) of ion-exchanged water, and 0.1 part (0.001 mol parts) of oxalic acid, and heated and stirred at 60 ° C. for 6 hours. Using, methanol by-produced by hydrolysis was removed under reduced pressure over 2 hours to obtain acrylic-modified polysiloxane (E-1) (Mn: 2,100).

[Production of titanium oxide compound (E-2) having two or more hydrolyzable alkoxy groups]
Production Example 7
In a glass Kolben equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introduction pipe, 46 parts (0.2 mol part) of 3-acryloyloxypropyltrimethoxytitanium, 160 parts of diphenyldimethoxytitanium (0 .65 mol parts), 45 g (2.5 mol parts) of ion-exchanged water, and 0.1 part (0.001 mol parts) of oxalic acid, and heated and stirred at 60 ° C. for 6 hours. The methanol by-produced by hydrolysis was removed over 2 hours under reduced pressure to obtain acrylic modified titanium oxide (E-2) (Mn: 2,100).

[Production of photosensitive composition]
Examples 1-5 and Comparative Examples 1-6
According to the number of parts in Table 1, a glass container was charged with the photoacid generator or photobase generator produced in Production Examples 1 to 4, and the hydrophilic resin solution produced in Production Examples 5 and 6, and further Production Example 3 The metal-containing compound (E-1) or (E-2) produced in Step 1, the following (A-1), (A-2), (A-3), (D23-1), (D23-2) The mixture was stirred and stirred until uniform, and an additional solvent (propylene glycol monomethyl ether acetate) was added to obtain the photosensitive compositions of Examples 1 and 2 and Comparative Examples 1 to 4. .

The details of the abbreviated chemicals in Table 1 are as follows.
(A-1): “Lucirin TPO” (trimethylbenzoyldiphenylphosphine oxide: manufactured by BASF)
(A-2): “Irgacure 907” (2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone: manufactured by BASF)
(A-3) “Kayacure DETX-S” (2,4-diethylthioxanthen-9-one: manufactured by Nippon Kayaku Co., Ltd. (D23-1): “Neomer DA-600” (dipentaerythritol pentaacrylate) : Sanyo Chemical Industries, Ltd.)
(D23-2): “Neomer EA-300” (pentaerythritol tetraacrylate; manufactured by Sanyo Chemical Industries, Ltd.)

The performance evaluation method will be described below.
[Production of photo spacer]
A 10 cm × 10 cm square glass substrate was coated with a spin coater and dried to form a coating film having a dry film thickness of 5 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes.
The resulting coating film was irradiated with 60 mJ / cm ^{2 of} light from an ultrahigh pressure mercury lamp through a plurality of masks for forming a photospacer having 10,000 openings per cm ² and diameters of 7, 8, 9 and 10 μm (i Illuminance 22 mW / cm ^{2 in} line conversion).
In addition, it exposed with the space | interval (exposure gap) of a mask and a board | substrate 100 micrometers.
Thereafter, alkali development was performed using a 0.05% aqueous KOH solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes to form 10,000 photospacers per 1 cm ² on the glass substrate.
Note that a photo spacer having a desired lower base diameter can be formed by adjusting the mask opening diameter.

[Evaluation of adhesion]
With the miniaturization and high definition of the LCD, the size of the photo spacer manufactured on the substrate is required to be 10 μm or less. However, the smaller the ground contact area between the substrate and the photo spacer, the higher the adhesion is required.
In other words, a photo spacer with higher adhesion is more excellent in performance that is less likely to be peeled off by rubbing or the like even if the lower bottom diameter of the spacer is smaller.
Therefore, the adhesiveness was evaluated by setting the bottom bottom diameter of the spacer to 8 μm in diameter and performing the following swab rubbing test.

Select only a mask having a bottom base diameter of 8 μm from the photo spacers prepared using a plurality of masks for forming photo spacers having openings with diameters of 7, 8, 9 and 10 μm, and have the following adhesion properties: A test was conducted.
(1) A cross mark of 1 cm in length and 1 cm in width is marked with an oil-based pen on the back side of the glass substrate on which the photospacer is formed.
(2) First, rubbing the surface of the front side of the glass substrate marked with a cross with a cotton swab soaked with acetone 10 times from the top of the vertical line downward at a speed of 2 cm per second.
Next, rub it 10 times from the left to the right of the horizontal line.
(3) Count the number of remaining photospacers without peeling off the point where the rubbed portions in (2) intersect with an optical microscope.
In addition, when even one piece is not peeled off, 100 pieces per mm ² (10 pieces × 10 pieces on the glass substrate)
Spacers).

Judgment criteria are as follows.
○: The number of peeled spacers is 9 or less ×: The number of peeled spacers is 10 or more

[Evaluation of elastic recovery characteristics]
The elastic recovery characteristic of the photospacer can be evaluated by the “elastic recovery rate” when a certain pressure defined by the following formula (1) is applied. The higher the elastic recovery rate (%), the better the elastic recovery characteristics.
The elastic recovery characteristic was evaluated by measuring the elastic recovery rate under a pressure condition of 0.5 mN / μm ² .

(1) A micro hardness tester (Fischer Instruments, Inc .; “Fischer Scope H-100”) and a planar indenter having a square cross section for one photo spacer selected arbitrarily from among photo spacers formed on a glass substrate. (50 μm × 50 μm) was used to measure the amount of deformation when a load was applied and when the load was returned.
At this time, a load was applied to 0.5 mN / μm ² over 30 seconds at a load speed of 0.017 mN / μm ² · sec and held for 5 seconds.
The amount of deformation from the initial position of the photospacer in a state where a load was applied was measured. The amount of change at this time is defined as a total deformation amount T ₀ (μm).
(2) Next, the load was released to 0 over 30 seconds at an unloading speed of 0.017 mN / μm ² · sec, and the state was maintained for 5 seconds. The deformation amount of the photo spacer at this time is defined as a plastic deformation amount T ₁ (μm).
(3) From the T ₀ and T ₁ measured as described above, the elastic recovery rate was calculated using the following formula (1).

Elastic recovery rate (%) = [(T ₀ −T ₁ ) / T ₀ ] × 100 (1)

From the value of the elastic recovery rate, the elastic recovery characteristics were determined as follows according to the following criteria.
○: 70% or more ×: less than 70%

[Resolution evaluation]
As LCDs have become smaller and higher definition, and the pixel size has become smaller, fine photo spacers can be formed. That is, patterning with a resolution of 10 μm or less is required as the resolution. It has become.
That is, the higher the resolution, the better the performance of forming a photo spacer having the same size as the mask opening diameter even if the mask opening diameter is reduced.
Therefore, the resolution was evaluated by measuring the lower base diameter of the photo spacer when the photo spacer was formed by the above method with the opening diameter of the mask set to 10 μm.

In the production of the photospacer, a photospacer was formed on a glass substrate by the same method as described above except that a photomask having a pattern having an opening diameter of 10 μm was used instead of 9 μm in diameter.
The lower base diameter of the photo spacer was measured with a laser microscope, and this was used as an evaluation of resolution. It can be said that the smaller the bottom diameter, the higher the resolution.

Criteria based on the lower base diameter of the spacer are as follows.
○: Less than 11 μm ×: 11 μm or more

As shown in Table 1, the photosensitive compositions of Examples 1 to 5 of the present invention are excellent in all points of adhesion, elastic recovery characteristics, and resolution.
On the other hand, Comparative Example 1 that does not satisfy the initiator system of the present invention does not satisfy all of the adhesion, elastic recovery rate, and resolution. In Comparative Examples 2 and 3, the adhesion and resolution are not satisfied. In Comparative Example 4, the resolution is not satisfied. Comparative Examples 5 and 6 do not satisfy the elastic recovery rate.

  The photosensitive composition of the present invention can be suitably used for a photospacer. Furthermore, it is also suitable as a photosensitive composition for various other resist materials such as a photo solder resist, a photosensitive resist film, a photosensitive resin relief plate, a screen plate, a photoadhesive or a hard coat material.

Claims (14)

The photosensitive composition containing the following (1) to (4), wherein at least one of the radical initiator (A), the acid generator (B) and the base generator (C) is irradiated with actinic rays. The active species (H) is generated, and 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). Polymerization reaction of the polymerizable substance (D) by the new active species (I) and, if necessary, the metal element-containing compound (E) proceeds, and the active species (H) or (I) is an acid or a base, The polymerizable substance (D) contains a hydrophilic resin (D1) and a polyfunctional (meth) acrylate monomer (D2), and contains substantially no colorant, metal oxide powder, or metal powder. A photosensitive composition.
(1) Radical initiator (A)
(2) Acid generator (B) and / or base generator (C)
(3) Polymerizable substance (D)
(4) Metal element-containing compound (E) represented by the following general formula (1)

[In Formula (1), M is a metal element, and A ¹ and A ² are each independently an alkyl group, a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, or hydrogen. A ³ and A ⁴ are each independently an alkyl group, alkoxy group, aryl group, mercaptoalkyl group, aminoalkyl group, (meth) acryloyloxyalkyl group, (meth) acryloyloxyalkoxy group or (meth) acryloyloxy group In the case where a plurality of A ³ and A ⁴ are contained in one molecule depending on the repeating unit, they may be the same or different groups. However, at least one of n A ³ and n A ⁴ is an alkoxy group. n is an integer of 2-20. ] The radical initiator (A) is a radical initiator (A1) that generates radicals with actinic rays, or a radical initiator (A2) that generates radicals with an acid and / or a base, and the acid generator (B) Is an acid generator (B1) that generates an acid by actinic rays, or an acid generator (B2) that generates an acid by at least one selected from the group consisting of radicals, acids and bases, and 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, (A1 ), (A2), (B1), (B2), (C1), or (C2) is contained in any combination of the following (1) to (4).
(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. Along with the polymerizable substance (D) and the metal element-containing compound (E) represented by the following general formula (1), the radical initiator (A), the acid generator (B) and the base generator (C) are represented by the following (1). In any combination of (4), the polymerizable substance (D) contains a hydrophilic resin (D1) and a polyfunctional (meth) acrylate) monomer (D2), a colorant, a metal oxide powder, and A photosensitive composition containing substantially no metal powder.
(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 and / or radicals, acids and It contains a base generator (C2) that generates a base by at least one selected from the group consisting of 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) At least one selected from the group consisting of a base generator (C1) that generates a base 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 an acid generator (B2) that generates an acid depending on the species.
(4) A combination of two or more of (1) to (3) above.

[In Formula (1), M is a metal element, and A ¹ and A ² are each independently an alkyl group, a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, or hydrogen. A ³ and A ⁴ are each independently an alkyl group, alkoxy group, aryl group, mercaptoalkyl group, aminoalkyl group, (meth) acryloyloxyalkyl group, (meth) acryloyloxyalkoxy group or (meth) acryloyloxy group In the case where a plurality of A ³ and A ⁴ are contained in one molecule depending on the repeating unit, they may be the same or different groups. However, at least one of n A ³ and n A ⁴ is an alkoxy group. n is an integer of 2-20. ] The metal element-containing compound Formula (1) A ¹ and at least one A ² is according to any one of claims 1 to 3, a (meth) acryloyl group or (meth) acryloyloxy alkyl group of (E) Photosensitive composition. At least one of A ³ and A ⁴ in the formula (1) of the metal element-containing compound (E) is a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxyalkoxy group or ( The photosensitive composition according to claim 1, which is a (meth) acryloyloxy group.   The content of photo-radically polymerizable carbon-carbon double bond (C = C) based on the total weight of (A) to (E) of the photosensitive composition is 3.0 to 8.0 mmol / g. The photosensitive composition in any one of 1-5.   Based on the total weight of (A) to (E) of the photosensitive composition, the hydrophilic resin (D1) is 5 to 60% by weight, and the polyfunctional (meth) acrylate monomer (D2) is 20 to 90% by weight. And 1 to 40% by weight of the metal element-containing compound (E).   The content of the radical initiator (A) with respect to the total weight of the polymerizable substance (D) and the metal element-containing compound (E) is 0.05 to 30% by weight, the polymerizable substance (D) and the metal element-containing compound (E) The content of the acid generator (B) and / or the base generator (C) [total of (B) and (C)] is 0.05 to 30% by weight relative to the total weight of Or a photosensitive composition.   The radical initiator (A1) that generates radicals by the actinic rays or the radical initiator (A2) that generates radicals by the acid and / or base is an acylphosphine oxide derivative polymerization initiator (A121), α-amino Acetophenone 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 initiation An at least one radical initiator selected from the group consisting of an agent (A126), a titanocene derivative polymerization initiator (A127), an organic peroxide polymerization initiator (A21), and an azo compound polymerization initiator (A22). The photosensitive composition according to claim 2.   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). And at least one acid generator selected from the group consisting of an iodonium salt derivative (B122), a sulfonate derivative (B21), an acetate derivative (B22), and a phosphonate (B23). The photosensitive composition in any one.   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 photosensitivity according to any one of claims 2 to 9, 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). Composition.   The photosensitive composition according to claim 1, wherein the photosensitive composition is for a flat panel display, a touch panel, a semiconductor, and a printed wiring board.   Hardened | cured material formed by hardening | curing the photosensitive composition in any one of Claims 1-12 with actinic light. In the presence of a radical initiator (A), an acid generator (B) and / or a base generator (C), and a metal element-containing compound (E) represented by the following general formula (1), a colorant, a metal oxide It is a method for producing an actinic ray cured product in which a polymerizable substance (D) and, if necessary, a metal element-containing compound (E) are polymerized by irradiation with actinic rays in the absence of both powder and metal powder, At least one of the 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) reacts with the acid generator (B) or the base generator (C) to produce a new active species (I), a polymerizable substance (D) by the new active species (I), and optionally a metal The polymerization reaction of the element-containing compound (E) proceeds and the active species (H) or (I) An acid or base, method for producing a photosensitive composition polymerizable substance (D) is characterized by containing a hydrophilic resin (D1) and the polyfunctional (meth) acrylate monomer (D2).

[In Formula (1), M is a metal element, and A ¹ and A ² are each independently an alkyl group, a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, or hydrogen. A ³ and A ⁴ are each independently an alkyl group, alkoxy group, aryl group, mercaptoalkyl group, aminoalkyl group, (meth) acryloyloxyalkyl group, (meth) acryloyloxyalkoxy group or (meth) acryloyloxy group In the case where a plurality of A ³ and A ⁴ are contained in one molecule depending on the repeating unit, they may be the same or different groups. However, at least one of n A ³ and n A ⁴ is an alkoxy group. n is an integer of 2-20. ]