KR20180124831A - Photopolymerization initiator composition and photosensitive composition - Google Patents

Abstract

1 to 99 parts by mass of the following component (A) and 1 to 99 parts by mass of the following component (B) (provided that the total of the components (A) and (B) is 100 parts by mass). (Please refer to specification for details of general formula.)
Component (A): A photopolymerization initiator comprising at least one oxime ester compound represented by the general formulas (1-1) to (1-3), which has an ether structure represented by the general formula (3).
Component (B): A photopolymerization initiator comprising at least one oxime ester compound represented by the general formula (2-1) or (2-2), which has a cycloalkyl structure of the general formula (4).

Description

Photopolymerization initiator composition and photosensitive composition

The present invention relates to a photopolymerization initiator composition useful as an initiator component of photopolymerization used in a photosensitive composition, and a photosensitive composition comprising the photopolymerization initiator composition and a polymerizable compound having an ethylenically unsaturated bond.

The photosensitive composition is a photopolymerizable compound having an ethylenically unsaturated bond added with a photopolymerization initiator and is used for a photocurable ink, a photosensitive printing plate and various photoresists since it can irradiate an energy ray (light) .

As photopolymerization initiators used in the photosensitive composition, it has been proposed to use oxime ester compounds in the following Patent Documents 1 to 7.

However, each of these conventional photopolymerization initiators is not sufficient in sensitivity and can not be satisfactorily satisfactory in resolution when used in an alkali developable photosensitive resin composition or the like.

U.S. Patent Application Publication No. 2004/170924 U.S. Patent Application Publication No. 2007/270522 U.S. Patent Application Publication No. 2009/292039 U.S. Patent Application Publication No. 2011/129778 EP2407456A 1 EP2433927A 1 Japanese Patent Publication No. 2013-543875

Accordingly, an object of the present invention is to provide a photopolymerization initiator composition capable of imparting excellent sensitivity and resolution to a photosensitive composition, and a photosensitive composition using the photopolymerization initiator composition.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an oxime ester compound having a specific ether structure and an oxime ester compound having a specific cycloalkyl structure can be used in combination to impart excellent sensitivity and resolution to a photosensitive composition A photopolymerization initiator composition is obtained, and the present invention has been accomplished.

That is, the present invention relates to a photopolymerizable composition comprising 1 to 99 parts by mass of the following component (A), 1 to 99 parts by mass of the following component (B) (100 parts by mass of the total of the components (A) To provide an initiator composition.

Component (A): A photopolymerization initiator comprising at least one oxime ester compound represented by the following general formulas (1-1) to (1-3), which has an ether structure represented by the following general formula (3)

In the general formulas (1-1) to (1-3), R ¹ , R ² and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or a cyano group, and the alkyl, alkoxy, aryl, the hydrogen atoms of the aryloxy group, aralkyl group and heterocyclic group, and ^{oR 11, COR 11, SR 11} , NR 12 R 13, -NCOR 12 -OCOR 13, CN, halogen atom, -CR ¹¹ = CR ¹² R ¹³ or -CO-CR ¹¹ = CR ¹² R ¹³ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms An aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms and the alkylene moiety of the substituent represented by R ¹ , R ² , R ⁶ , R ¹¹ , R ¹² and R ¹³ is , Unsaturated bond, The alkyl moiety of the substituent may have a branched side chain, and the cyclic moiety (ring (s)) may be present in the alkyl moiety of the substituent, And the alkyl terminal (terminal) of the substituent may be an unsaturated bond, and R ² may form a ring together with the adjacent benzene ring in some cases.

R ³ , R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms An aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and the hydrogen atom of the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group and heterocyclic group It is further substituted by ^{oR 14, COR 14, SR 14} , NR 15 R 16, -NCOR 15 -OCOR 16, CN, halogen atom, -CR ¹⁴ = CR ¹⁵ R ¹⁶ or ^{-CO-CR 14 = CR 15 R} 16 R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, represents a heterocyclic group of 2 to 20 carbon atoms, the alkylene portion of the substituent represented by the above ^{R 3, R 4, R 5} , R 14, R 15 and R ¹⁶ is an unsaturated bond, an ether bond, An ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl moiety of the substituent may have branched side chains and may be cyclic alkyl , The alkyl terminal of the substituent may be an unsaturated bond, and a, b, and d are each independently an integer of 0 to 3.

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom of the alkyl group is preferably a hydrogen atom, And the methylene group of the alkylene moiety of the alkyl group may be substituted one to five times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond , The alkyl moiety may have branched side chains, may be cyclic alkyl, the alkyl terminus may be an unsaturated bond, and R ⁷ and R ⁸ may form a ring together.

Component (B): A photopolymerization initiator comprising at least one oxime ester compound represented by the following general formula (2-1) or (2-2), which has a cycloalkyl structure represented by the following general formula (4)

In the general formula (2-1) or (2-2), R ²¹ and R ²² each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 30 carbon atoms An aryl group, an aryloxy group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or a cyano group, and the alkyl, alkoxy, aryl, aryloxy , The aralkyl group and the hydrogen atom of the heterocyclic group may be further substituted by OR ³¹ , COR ³¹ , SR ³¹ , NR ³² R ³³ , -NCOR ³² -OCOR ³³ , CN, a halogen atom, -CR ³¹ = CR ³² R ^33, CR ³¹ = CR ³² R and ³³ if it is substituted by, R ^31, R ³² and R ³³ each independently represent a hydrogen atom, carbon atom alkyl group having 1 to 20 carbon atoms, 6 to 30 aryl group, a carbon An aralkyl group having 7 to 30 atoms or a heterocyclic group having 2 to 20 carbon atoms and the alkylene moiety of the substituent represented by R ²¹ , R ²² , R ³¹ , R ³² and R ³³ is an unsaturated bond, an ether bond The alkyl moiety of the substituent may have branched side chains, and when the alkyl moiety is cyclic alkyl, the alkyl moiety of the substituent may be branched, , The alkyl terminal of the substituent may be an unsaturated bond, and R < ²² > may form a ring together with the adjacent benzene ring.

R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, An aralkyl group having 7 to 30 atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and the hydrogen atom of the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group and heterocyclic group is ^{oR 34, COR 34, SR 34} , NR 35 R 36, -NCOR 35 -OCOR 36, CN, halogen atom, -CR ³⁴ = CR ³⁵ R ³⁶ or ^{-CO-CR 34 = CR 35 R} 36 when substituted with Each of R ³⁴ , R ³⁵ and R ³⁶ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, It represents a heterocyclic group having 2 to 20, the alkylene portion of the substituent represented by the above ^{R 23, R 24, R 34} , R 35 and R ³⁶ is an unsaturated bond, an ether bond, a thioether The alkyl moiety of the substituent may have a branched side chain, may be cyclic alkyl, may be branched, or may be substituted with 1 to 5 times by a linkage, ester bond, thioester bond, amide bond or urethane bond, The alkyl terminal of the substituent may be an unsaturated bond, and u and v are each independently an integer of 0 to 3.

Ar represents an aryl group or a heterocyclic group selected from the following structures,

L ¹ represents a hydrogen atom or a benzoyl group,

X ¹ represents a direct bond or a carbonyl group,

G ¹ represents a group of the general formula (4), n in the general formula (4) is an integer of 1 to 5, and m is an integer of 1 to 6.

The present invention also provides a photosensitive composition comprising the above-mentioned photopolymerization initiator composition in a polymerizable compound having an ethylenically unsaturated bond.

Further, the present invention provides the above photosensitive composition comprising an inorganic compound.

The present invention also provides an alkali-developable photosensitive resin composition comprising the above-mentioned photopolymerization initiator composition in an alkali developing compound having an ethylenic unsaturated bond and a polymerizable compound having an ethylenic unsaturated bond.

The present invention also provides the above-described alkali-developable photosensitive resin composition comprising an inorganic compound.

The present invention also provides a colored alkali developable photosensitive resin composition comprising the alkali developable photosensitive resin composition further containing a colorant.

The present invention also provides a cured product obtained by irradiating the photosensitive composition, the alkali developable photosensitive composition or the colored alkali developable photosensitive resin composition with an energy ray.

The photopolymerization initiator composition of the present invention will be described.

The oxime ester compound used as the component (A) in the photopolymerization initiator composition of the present invention is characterized by having an ether structure represented by the above general formulas (1-1) to (1-3) and represented by the general formula (3) .

The oxime ester compound used as the component (A) has geometrical isomers due to a double bond of oximes. However, the oxime ester compounds used in the formulas (1-1) to (1-3) Is not limited to the structure showing the isomer.

The component (A) in the present invention contains at least one oxime ester compound represented by any one of the above-mentioned general formulas (1-1) to (1-3), and at least one oxime ester compound .

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 in} the general formulas (1-1) For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl , Octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isonyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formulas (1-1) to (1-3) ≪ / RTI >

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 in} the general formulas (1-1) Examples of the aryl group having 6 to 30 carbon atoms represented by the above formula include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, biphenyl, naphthyl, anthryl, phenanthrenyl, , Biphenyl, naphthyl and anthryl.

Examples of the aryloxy group having 6 to 30 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formulas (1-1) to (1-3) .

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 in} the general formulas (1-1) Examples of the aralkyl group having 7 to 30 carbon atoms include benzyl, chlorobenzyl,? -Methylbenzyl,?,? - dimethylbenzyl, phenylethyl and the like.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 in} the general formulas (1-1) Examples of the heterocyclic group having 2 to 20 carbon atoms represented by the above formula include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, 5- to 7-membered heterocycles such as pyrrolidyl, imidazolyl, pyrazolidid, thiazolidid, isothiazolidid, oxazolidid, isoxazolididyl, piperidyl, piperazyl, .

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁷ , R ⁸ and R ⁹ in the general formula (3) representing A ¹ in the general formulas (1-1) to (1-3) .

Among the oxime ester compounds of the component (A), R ¹ is preferably an alkyl group having 1 to 20 carbon atoms in terms of sensitivity and resolution in the general formulas (1-1) to (1-3) More preferably an alkyl group having 1 to 4 atoms, and still more preferably a methyl group.

In the general formulas (1-1) and (1-2), from the viewpoints of sensitivity and resolution, R ² is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms More preferably an ethyl group, and still more preferably an ethyl group.

In (R ³ ) a of the general formulas (1-1) to (1-3), a is preferably 0 or 1, and more preferably 0, from the viewpoints of sensitivity and resolution. When a is 1 to 3, R ³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

In the (R ⁴ ) b of the general formulas (1-1) to (1-3), b is preferably 0 or 1, and more preferably 0 in view of sensitivity and resolution. When b is 1 to 3, R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

In the (R ⁵ ) d of the general formulas (1-1) to (1-3), d is preferably 0 or 1, and more preferably 1 from the viewpoints of sensitivity and resolution. When d is 1 to 3, R ⁵ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

In the general formulas (1-1) and (1-3), from the viewpoints of sensitivity and resolution, R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms More preferably a methyl group.

The oxime ester compound of the component (A) is characterized by having an ether structure of A ¹ represented by the above general formula (3). Thus, it has excellent sensitivity and resolution when used in combination with the component (B).

In the general formula (3), from the viewpoints of sensitivity and resolution, R ⁹ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Even more preferred are atoms or methyl groups.

From the viewpoints of sensitivity and resolution, R ⁸ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoints of sensitivity and resolution, R ⁷ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is also preferable that R ⁷ and R ⁸ together form a ring, and it is also preferable that R ⁷ and R ⁸ have an ether bond in the ring. A specific example of the ring formed by R ⁷ and R ⁸ together is dimethyl dioxolane ring.

Specific preferred examples of the oxime ester compound represented by the above general formula (1-1) in the component (A) include the following compounds No. 1 to 4.

Specific preferred examples of the oxime ester compound represented by the above general formula (1-2) in the component (A) include the following compounds No. 5 to No. 8.

Specific preferred examples of the oxime ester compound represented by the above general formula (1-3) as the component (A) include the following Compound Nos. 9 to 12.

Next, the component (B) will be described.

The oxime ester compound used as the component (B) in the photopolymerization initiator composition of the present invention is a compound having a cycloalkyl structure represented by the general formula (2-1) or (2-2) and represented by the general formula (4) .

The oxime ester compound used as the component (B) is present in the form of a geometric isomer due to a double bond of oxime, but does not distinguish them. The above-mentioned general formula (2-1) or (2-2) But is not limited to a structure showing either a mixture of the two, or a isomer (isomer).

The component (B) in the present invention contains at least one oxime ester compound represented by the general formula (2-1) or (2-2), and at least one of the above oxime ester compounds .

The number of carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the general formula (2-1) Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t- amyl, hexyl, heptyl, 2-ethylhexyl, t-octyl, nonyl, isonyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (2-1) or (2-2) include those corresponding to the above alkyl groups.

The number of carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the general formula (2-1) Examples of the aryl group having 1 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, biphenyl, naphthyl, anthryl, phenanthrenyl, T-butyl and anthryl.

Examples of the aryloxy group having 6 to 30 carbon atoms represented by R ²¹ , R ²² , R ²³ and R ²⁴ in the general formula (2-1) or (2-2) include those corresponding to the above aryl groups.

The number of carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the general formula (2-1) Examples of the aralkyl group of -30 include benzyl, chlorobenzyl,? -Methylbenzyl,?,? - dimethylbenzyl, phenylethyl and the like.

The number of carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ in the general formula (2-1) Examples of the heterocyclic group of 1 to 20 include pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazoli And 5- to 7-membered heterocycles such as pyrrolyl, pyrrolyl, pyrrolyl, thiazolyl, thiazolyl, isothiazolyl, oxazolidid, isoxazolididyl, piperidyl, piperazyl and morpholinyl.

(2-1) or (2-2), R ²¹ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 6 to 30 carbon atoms in the oxime ester compound of the component (B) More preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms, and still more preferably a methyl group or a phenyl group.

In the general formula (2-1), R ²² is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms, Is more preferable.

Also, in (R ²³ ) u of the general formula (2-1) or (2-2), u is preferably 0 or 1, and more preferably 0, from the viewpoints of sensitivity and resolution. When u is 1 to 3, R ²³ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

In the (R ²⁴ ) v of the general formula (2-1) or (2-2), v is preferably 0 or 1, and more preferably 0, from the viewpoints of sensitivity and resolution. When v is 1 to 3, R ²⁴ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

In the general formula (2-1), X ¹ is preferably a direct bond in view of sensitivity and resolution.

In the general formula (2-1), Ar is preferably an aryl group or a heterocyclic group selected from the following structures in view of sensitivity and resolution.

The oxime ester compound of component (B) is characterized by having a cycloalkyl structure of G ¹ represented by general formula (4). Thus, it has excellent sensitivity and resolution when used in combination with component (A).

In the general formula (4), n is preferably 1 or 2 from the viewpoints of sensitivity and resolution.

In the general formula (4), m is preferably 3 or 4 in view of sensitivity and resolution. In this case, they have a cyclopentane ring and a cyclohexane ring, respectively.

Specific preferred examples of the oxime ester compound represented by the above general formula (2-1) as the component (B) include the following compounds No. 13 to No. 20.

Specific preferred examples of the oxime ester compound represented by the above general formula (2-2) as the component (B) include the following compounds No. 21 to No. 26.

In the photopolymerization initiator composition of the present invention, the total content of the component (A) and the component (B) is 100 parts by mass, the content of the component (A) is 1 part by mass to 99 parts by mass, Is 1 to 99 parts by mass. The content of the component (A) is preferably 20 to 80 parts by mass, more preferably 40 to 60 parts by mass, and the content of the component (B) is preferably 20 to 80 parts by mass, more preferably 40 to 60 parts by mass More preferable.

The photopolymerization initiator composition of the present invention may further contain other photopolymerization initiators such as Irgacure 369 (manufactured by BASF), Irgacure 907 (manufactured by BASF), diisocyanurate as the optional components in addition to the components (A) and (B) Bis (2-chlorophenyl) propane, N, N'-dicyclohexylcarbodiimide (trade name) manufactured by BASF) -4,5,4 ', 5'-tetraphenyl-2'-biimidazole, and the like. As for the details of these optional components, descriptions of these components in the photosensitive composition of the present invention to be described later can be suitably applied.

Next, the photosensitive composition of the present invention will be described.

The photosensitive composition of the present invention contains a photopolymerization initiator composition of the present invention and a polymerizable compound having an ethylenically unsaturated bond as essential components and contains an optional component such as an inorganic compound, a coloring material, and a solvent.

The polymerizable compound having an ethylenically unsaturated bond is not particularly limited and those conventionally used in the photosensitive composition can be used. Examples of the polymerizable compound include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride , Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (Meth) acrylic acid,? -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, histamic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, Mono (meth) acryloyloxyethyl] phthalate mono [2- (meth) acryloyloxyethyl], omega -carboxypolycaprolactone mono (meth) acrylate and the like having a carboxyl group and a hydroxyl group at both terminals (Meth) acrylate; (Meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate or polyfunctional (meth) acrylate having one carboxyl group and two or more Unsaturated polybasic acids such as methacrylic acid and methacrylic acid; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl Butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl Stearyl acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (Meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (Meth) acrylate, allyl (meth) acrylate, (Meth) acrylate, benzyl (meth) acrylate, ethyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di Acrylate, trimethylolethane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol penta Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as tri [(meth) acryloylethyl] isocyanurate and polyester (meth) acrylate oligomer; Metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -Cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-acid anhydrides of unsaturated polybasic acids such as maleic anhydride moiety, dodecenyl ansuccinic acid, and anhydrous methyl hemiamic acid; (Meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriamintris (meth) acrylamide, xylylene bis (meth) acrylamide,? -Chloroacrylamide, N-2-hydroxyethyl Amides of unsaturated monobasic acids and polyamines such as methacrylamide; Unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth) acrylonitrile,? -Chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Vinylbenzene sulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, and vinylbenzenesulfonic acid. Unsaturated aromatic compounds such as vinylbenzyl methyl ether and vinyl benzyl glycidyl ether; Unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; Vinyl alcohols such as allyl alcohol and cloetyl alcohol; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; Indene such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl Pyridine, a vinyl urethane compound of a hydroxyl group-containing vinyl monomer and a polyisocyanate compound, a vinyl epoxy compound of a hydroxyl group-containing vinyl monomer and a polyepoxy compound.

Among them, mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals, polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups, unsaturated monobasic acid and polyhydric alcohol Or the ester of a polyhydric phenol is suitable as the photopolymerization initiator composition of the present invention.

These polymerizable compounds may be used alone or as a mixture of two or more of them. When two or more of them are used in combination, they may be copolymerized in advance and used as a copolymer.

As the polymerizable compound having an ethylenically unsaturated bond, an alkali developing compound having an ethylenic unsaturated bond may be used to make the photosensitive composition of the present invention as an alkali developable photosensitive resin composition. Examples of the alkali developing compound having an ethylenically unsaturated bond include a copolymer of an acrylic acid ester, a phenol and / or cresol novolak epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, an epoxy acrylate resin, A resin obtained by allowing an unsaturated monobasic acid to react with an epoxy compound such as an epoxy compound represented by the following general formula (5) and allowing the polybasic acid anhydride to act. Among them, a resin obtained by allowing an unsaturated monobasic acid to react with an epoxy compound such as an epoxy compound represented by the following general formula (5) and further with a polybasic acid anhydride is preferable.

The alkali developing compound having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

(5), X ² represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO ₂ , SS, SO , CO, OCO, or the following general formula (6), equation (7) or represents a substituent group represented by formula (8), there is a case which is substituted with the alkylidene group is a halogen atom, R ^41, R ^42, R ^43, and R ⁴⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the alkyl, alkoxy, The phenyl group may be substituted with a halogen atom, t is an integer of 0 to 10, and an optical isomer present when t is not 0 may be any isomer.

(In the general formula (6), Z ¹ represents a phenyl group which may be substituted by a hydrogen atom, an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, or an alkyl group of 1 to 10 carbon atoms Or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms, Y ¹ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms , An alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and w is an integer of 0 to 5.)

(Y ² and Z ² in the general formula (8) each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom An aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, a carbon atom which may be substituted with a halogen atom An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom an alkylene portion in the alkyl group and the arylalkyl group is, there is a case that is interrupted by an unsaturated bond, -O- or -S-, Z ² is a case that forms the adjacent Z ² together ring P represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, s represents an integer of 0 to 4, and the sum of the numbers of r and s is It is an integer from 2 to 4.)

Examples of the unsaturated monobasic acid acting on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxypropyl methacrylate Maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, maleic anhydride, and maleic anhydride.

Examples of the polybasic acid anhydride to be reacted after the action of the unsaturated monobasic acid may include biphenyltetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic acid anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, hexahydrophthalic anhydride, Acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride moiety, dodecenyl ansuccinic acid, and anhydrous methyl hemiamic acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.

That is, an epoxy adduct having a structure in which the carboxyl group of the unsaturated monobasic acid is added in an amount of 0.1 to 1.0 per one epoxy group of the epoxy compound, wherein the amount of the acid anhydride of the polybasic acid anhydride It is preferable that the ratio be 0.1 to 1.0 in the structure.

The reaction of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.

The alkali-developable photosensitive resin composition of the present invention, which is one of embodiments of the photosensitive composition of the present invention, contains the photopolymerization initiator composition of the present invention as an essential component, the polymerizable compound having an ethylenic unsaturated bond and the ethylenic unsaturated bond An alkaline developing compound which may be present, and optionally contains components such as an inorganic compound, a coloring material and a solvent in combination. Among the alkali-developable photosensitive resin compositions of the present invention, those containing a colorant are also referred to as the colored alkali-developable photosensitive resin composition of the present invention.

The above-mentioned polymerizable compound having an ethylenically unsaturated bond and the above-mentioned alkali-developable compound which may have an ethylenic unsaturated bond may be the same compound or may be different, and when they are used alone Two or more species may also be used in combination.

In order to improve the developability of the (colored) alkali developable photosensitive resin composition of the present invention by adjusting the acid value, an alkali developable compound which may have the ethylenically unsaturated bond and a monofunctional or polyfunctional epoxy Compounds may be used. The compound having alkali developability, which may have the ethylenically unsaturated bond, preferably has an acid value of 5 to 120 mg KOH / g as the solid content, and the amount of the monofunctional or polyfunctional epoxy compound to be used is preferably such that the acid value Is satisfied.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl Ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl Dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, Propyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butyl phenol glycidyl ether, cresyl glycidyl Ether, 2-methylcresol glycidyl ether , 4-nonyl phenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, vinylcyclohexane oxide, vinylcyclohexane monoxide, The following compounds No. E1 and No. E2.

As the polyfunctional epoxy compound, use of at least one compound selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers is preferable because an alkali developing photosensitive resin composition having better characteristics (coloring) can be obtained .

As the bisphenol-type epoxy compound, for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can be used as well as an epoxy compound represented by the general formula (5).

Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1 , 8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, Triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (Glycidyloxymethyl) propane, 1,1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- Cyydoxymethyl) methane and the like can be used.

In addition, novolak type epoxy compounds such as phenol novolak type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds and dicyclopentadiene novolak type epoxy compounds; Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1- Alicyclic epoxy compounds such as epoxyethyl-3,4-epoxycyclohexane; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and dimeric acid glycidyl ester; Glycidyl amines such as tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; A dioxide compound such as dicyclopentadiene dioxide; Naphthalene type epoxy compounds; Triphenylmethane type epoxy compounds; Dicyclopentadiene type epoxy compounds and the like may be used.

In the photosensitive composition of the present invention, the photopolymerization initiator composition of the present invention is prepared by previously preparing a photopolymerization initiator composition from the component (A) and the component (B) and subjecting it to a polymerizable compound having an ethylenically unsaturated bond, The components (A) and (B) may be separately added to the polymerizable compound or other optional components to form a photosensitive composition.

In the photosensitive composition of the present invention, the content of the photopolymerization initiator composition of the present invention is not particularly limited, but 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond (or the alkali developing compound having the ethylenically unsaturated bond) Preferably from 0.1 to 70 parts by mass, more preferably from 0.3 to 50 parts by mass, and most preferably from 0.5 to 30 parts by mass.

In particular, when the photosensitive composition of the present invention is a (colored) alkali developing photosensitive resin composition, the content of the photopolymerization initiator composition of the present invention is preferably such that the solid content of the (colored) alkali developing photosensitive resin composition Is preferably from 0.3 to 20% by mass, more preferably from 0.8 to 12% by mass.

A solvent may also be added to the photosensitive composition of the present invention. As the solvent, a solvent capable of dissolving or dispersing the respective components (the photopolymerization initiator composition of the present invention and the polymerizable compound having an ethylenically unsaturated bond, etc.), for example, methyl ethyl ketone, methyl Ketones such as amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol; Ether esters such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate Based solvent; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Sekiyu K.K.) and Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol-based solvents; aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; Dimethyl sulfoxide; Water, and the like. These solvents can be used singly or as a mixed solvent of two or more kinds.

Of these, ketones, ether ester solvents and the like, especially propylene glycol-1-monomethyl ether-2-acetate and cyclohexanone, are preferable because they have good compatibility with a photopolymerization initiator in a photosensitive composition.

When a solvent is used in the photosensitive composition of the present invention, the amount of the solvent is preferably such that the concentration of the solid component (component other than the solvent) is 5 to 85% by mass from the viewpoint of handling and the like.

Further, the photosensitive composition (particularly, the alkali developing photosensitive resin composition) of the present invention may further contain a coloring material to make a colored (alkali developable) photosensitive composition. Examples of the colorant include pigments, dyes, and natural pigments. These coloring materials can be used alone or in combination of two or more kinds.

As the pigment, for example, nitroso compounds; Nitro compounds; Azo compounds; Diazo compounds; Xanthene compounds; Quinoline compounds; Anthraquinone compounds; Coumarin compounds; Phthalocyanine compounds; Isoindolinone compounds; Isoindoline compounds; Quinacridone compounds; Anthanthrone compounds; Perinone compounds; Perylene compounds; Diketopyrrolopyrrole compounds; Thioindigo compounds; Dioxazine compounds; Triphenylmethane compounds; Quinophthalone compounds; Naphthalene tetracarboxylic acid; Azo dyes, metal complex compounds of cyanine dyes; Lake pigment; Carbon black obtained by a furnace method, a channel method, or a thermal method; carbon black such as acetylene black, Ketjen black or lamp black; The carbon black is adjusted or coated with an epoxy resin, the carbon black is dispersed in a solvent in advance in a solvent to adsorb a resin of 20 to 200 mg / g, an acidic or alkaline surface-treated carbon black , An average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen amount calculated from CO and CO ₂ in volatile matter at 950 ° C of 9 mg or more per 100 m 2 of the surface area of carbon black; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; Aniline black, pigment black 7, titanium black; Chromium oxide green, milori blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate salt, ultramarine, cerulean blue, viridian, emerald green, lead sulfate, yellow Organic or inorganic pigments such as lead, zinc sulfur, red iron oxide (red iron oxide (III)), cadmium red, synthetic iron black and amber may be used. These pigments can be used singly or in combination.

As the pigment, commercially available pigments may be used. For example, pigments of Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90 , 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220 , 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, , 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

Examples of the dye include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, Dyes such as indanamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These dyes may be used by mixing a plurality of them.

In the photosensitive composition of the present invention, the content of the coloring material is preferably 50 to 350 parts by mass, and more preferably 100 to 250 parts by mass, based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

The photosensitive composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; (In particular, glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides (such as calcium carbonate, magnesium carbonate, cobalt, manganese, , Aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver and copper. Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable.

In the photosensitive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 1000 parts by mass, more preferably 10 to 800 parts by mass, relative to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond . These inorganic compounds may be used alone or in combination of two or more.

These inorganic compounds are used, for example, as fillers, antireflective agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbents, ink repellants and the like.

To the photosensitive composition of the present invention, a dispersing agent for dispersing the coloring material and / or the inorganic compound may be added. The dispersing agent is not limited as long as it can disperse and stabilize the coloring material or the inorganic compound, and a commercially available dispersing agent such as BYK series manufactured by BIGKEMIS can be used. Particularly, a polymer dispersing agent comprising a polyester having a basic functional group, a polyether or a polyurethane, a functional group having a nitrogen atom as a basic functional group and having a nitrogen atom is an amine and / or a quaternary salt thereof and an amine value of 1 to 100 mgKOH / g is suitably used.

In the photosensitive composition of the present invention, other photopolymerization initiators may be used together with the oxime ester compound of component (A) and the oxime ester compound of component (B). As other photopolymerization initiators that can be used in combination, conventionally known compounds can be used. For example, benzophenone, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethylketal, 2-morpholyl-2- (4'-methylmercapto) benzoyl propane, thioxanthone, 1-chloro-4- Benzoyl-4-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy- Butyl benzoyl trichloromethane, 4-phenoxybenzoyl dichloromethane, methyl benzoate, 1,7-bis (9'-acridinyl) benzoyl chloride, (Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) Phenyl-4,6-bis (trichloromethyl) - (trichloromethyl) -s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl N-1717 (product of ADEKA), IRGACURE 369, IRGACURE 907, and N-174 (product of ADEKA) IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF Japan), benzoyl peroxide, and compounds represented by the following general formula (9). When these other photopolymerization initiators are used, Is set to be not more than 1 time by mass of the total amount of the components (A) and (B) of the photopolymerization initiator composition of the present invention. These photopolymerization initiators may be used alone or in combination of two or more.

(In the general formula (9), R ¹ , R ² and R ⁶ are the same as in the general formula (1-2), R ⁵¹ is a halogen atom or an alkyl group, and e is an integer of 0 to 5)

The photosensitive composition of the present invention may optionally contain thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine and the like; Plasticizers; Adhesion promoters; Fillers; Defoamer; Leveling agents; Surface modifiers; Antioxidants; Ultraviolet absorber; Dispersing aids; An anti-aggregation agent; catalyst; Effect promoters; A crosslinking agent; A common additive such as a thickener may be added.

In the photosensitive composition of the present invention, the polymerizable compound having an ethylenically unsaturated bond and an optional component other than the photopolymerization initiator composition of the present invention (except for the above-mentioned other photopolymerization initiator, an alkali developing property which may have an ethylenic unsaturated group (Filler), coloring material and solvent are excluded) is appropriately selected according to the purpose of use and is not particularly limited, but preferably 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond The total amount is not more than 50 parts by mass.

Further, the photosensitive composition of the present invention may improve the properties of the cured product by using another organic polymer together with the polymerizable compound having an ethylenically unsaturated bond. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Acrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, Amide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Of these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer and epoxy resin are preferable Do.

When other organic polymers are used, the amount thereof is preferably 10 to 500 parts by mass based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

A chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound and the like may be used in combination in the photosensitive composition of the present invention.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. 3-mercaptopropionic acid, N- (2-mercaptopropionyl) glycine, 2-mercapto nicotinic acid, 3-mercaptopropionic acid, 3-mercaptopropionic acid and the like are exemplified by thioglycolic acid, thioferric acid, thiosalicylic acid, 2- mercaptopropionic acid, - [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanol Mercaptoethanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2- (2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) Mercapto compounds, disulfide compounds obtained by oxidizing the mercapto compounds, alkyl iodides such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid and 3-iodopropanesulfonic acid, trimethylolpropane tris (3 -Mercaptoisobutyrate), butanediol bis (3-mercaptoisobutylate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bis-thiouropionate, butanediol bis- Propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether glycolate, ethylene glycol bistioglycolate, trimethylolpropane tristhioglycolate, butanediol bis-thiophosphate, trimethylolpropane tris thiopropionate, trimethylolpropane tris thioglycolate, pentaerythritol tetrakisthiopropionate , Pentaerythritol tetrakisthioglycolate, trishydroxyetilide Aliphatic polyfunctional thiol compounds such as stearoyl phonate, diethyl thioxanthone, diisopropyl thioxanthone, the following compound No. C1 and trimercapto propionic acid tris (2-hydroxyethyl) isocyanurate, And car lenses MT BD1, PE1, and NR1 manufactured by Denko Corporation.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphoric acid esters and perfluoroalkyl carboxylates; Anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonic acid salts and alkylsulfuric acid salts; Cationic surfactants such as higher amine halides and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides; Amphoteric surfactants; A surfactant such as a silicone surfactant may be used, and these surfactants may be used in combination.

Examples of the silane coupling agent include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, vinyl Methyldimethoxysilane, octenyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane and the like. As the silane coupling agent having an acryl group, 3-acryloxypropyltrimethoxysilane, Acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, and the like. As the silane coupling agent having an epoxy group, 2- (3,4-epoxycyclohexyl ) Ethyl trimme Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, (Aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl) -3-aminopropyltriethoxysilane. Examples of the silane coupling agent having an amino group include N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- -Aminopropyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N- (vinylbenzyl) -2-aminoethyl- As the silane coupling agent having an isocyanurate group, tris- (trimethoxysilylpropyl) isocyanurate may be used as the silane coupling agent having an isocyanurate group. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like. Examples of the silane coupling agent include 3-ureide propyl trimethoxysilane and 3-ureide propyl triethoxysilane. As the silane coupling agent having a sulfide group, bis (triethoxysilylpropyl) tetrasulfide 3-octanoylthio-1-propyltriethoxysilane can be exemplified as the silane coupling agent having a thioester group, and as the silane coupling agent having an isocyanate group, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, and the like.

As the silane-capping agent, a commercially available product can be used. Examples of the vinyltrimethoxysilane include KBM-1003 manufactured by Shinetsu Kagaku Kogyo Co., Ltd., A-171 manufactured by Momentive Performance Materiaruzu Japan Kogyo Co., Z-6300 manufactured by Toray Dow Corning Co., Ltd., GENIOSIL XL10 manufactured by Asahi Kasei Wakasa Silicones Co., Ltd., and Silia Ace S210 manufactured by Nichibe Shoji Co., Ltd. As vinyltriethoxysilane, KBE-1003 manufactured by Shinetsu Kagaku Kogyo Co., Ltd., A-151 manufactured by Momentive Performance Materiaruzu Japan Co., Ltd., Z-6519 manufactured by Toray Dow Corning Co., Ltd., Asahi Kasei Wakasa Silicone Co., GENIOSIL GF56 manufactured by Nichibishi Chemical Co., Ltd., and SILA ACE S220 manufactured by Nichibo Shoji Co., Ltd., and GENIOSIL GF62 manufactured by Asahi Kasei Wakasa Silicone Co., Ltd. may be mentioned as the vinyltriacetoxysilane. As the tris (2-methoxyethoxy) silane, A-172 manufactured by Momentive Performance Materiaruzu Japan Co., Ltd. may be mentioned, and vinyl methyl dimethoxysilane may be exemplified by Momentive Performance Motheriaruzu Japan Co., A-2171 of Asahi Chemical Industry Co., Ltd., GENIOSIL XL12 of Asahi Chemical Industry Co., Ltd., and KBM-1083 manufactured by Shin-Etsu Chemical Co., Ltd. as an octenyltrimethoxysilane. Z-6825 available from Toray Dow Corning Co., Ltd. may be mentioned. As p-styryltrimethoxysilane, KBM-1403 available from Shin-Etsu Chemical Co., Ltd., and 3- Examples of the acryloxypropyltrimethoxysilane include KBM-5103. Examples of the 3-methacryloxypropylmethyldimethoxysilane include KBM-502 manufactured by Shin-Etsu Chemical Co., Ltd., Tokyo Dow Corning Co., Ltd. Z-6033 of the formula KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., A-174 manufactured by Momentive Performance Materiaruzu Japan Co., Ltd., and Z-100 manufactured by Toray Dow Corning Co., 6030, GENIOSIL GF31 available from Asahi Kasei Wakasa Silicone Co., Ltd., and Syllace S710 available from Nichibishi Co., Ltd. As the 3-methacryloxypropylmethyldiethoxysilane, Shin-Etsu Chemical Co., KBE-502 manufactured by Shin-Etsu Chemical Co., Ltd., KBE-503 manufactured by Shinetsu Kagaku Kogyo Co., Ltd., and Y-503 manufactured by Momentive Performance Materiaruzu Japan Co., Ltd. as the 3-methacryloxypropyltriethoxysilane. 9936 can be given. As the methacryloxypropyltrimethoxysilane, KBM-5803 available from Shin-Etsu Chemical Co., Ltd. can be mentioned. As 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, , Shin-Etsu Chemical Co., Ltd. A-186 of Momentive Performance Japan Co., Ltd., Z-6043 of Toray Dow Corning Co., Ltd., and Syllace S530 of Nichibishi Co., Ltd. As the 3-glycidoxypropylmethyldimethoxysilane, KBM-402 manufactured by Shinetsu Kagaku Kogyo Co., Ltd., Z-6044 manufactured by Toray Dow Corning Co., Ltd., Silla of Nichibo Shoji Co., Ltd., Ace S520 and the like. Examples of the 3-glycidoxypropyltrimethoxysilane include KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd., A-187 produced by Momentive Performance Corporation Materieluzu Japan Co., Z-6040 manufactured by ODA Dow Corning Co., Ltd., GENIOSIL GF80 manufactured by Asahi Kasei Wakasa Silicone Co., Ltd., and Silia Ace S510 manufactured by Nichibishi Co., Ltd. and 3-glycidoxypropylmethyl di As the toxic silane, KBE-402 manufactured by Kagaku Kogyo Co., Ltd., and 3-glycidoxypropyltriethoxysilane include KBE-403 manufactured by Shinetsu Kagaku Kogyo Co., Ltd., Momentive Perfumeries Materieluzu Japan Co., Ltd. A-1871 of Asahi Chemical Industry Co., Ltd., GENIOSIL GF82 of Asahi Chemical Industry Co., Ltd., and KBM-4803 of Shin-Etsu Chemical Co., Ltd. as N-glycidoxypropyltrimethoxysilane. N Examples of the 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane include KBM-602 manufactured by Shinetsu Kagaku Kogyo Co., Ltd., A-2120 produced by Momentive Performance Materiaruzu Japan Kogyo Co., GENIOSIL GF-95, a product of Silicone Co., Ltd., and SILAACE S310, a product of Nichibishi Kogyo Co., Ltd., and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, KBM-603 manufactured by Kugo Kogyo Co., Ltd., Momentive Perfumes A-1120 of Mitsubishi Chemical Industries, Ltd., A-1120 of Mitsubishi Chemical Industries Co., Ltd., Z-6020 of Toray Dow Corning Co., Ltd., Z of Toray Dow Corning Co., -6094, GENIOSIL GF-91 of Asahi Kasei Wakasa Silicone Co., Ltd., and Sylar Ace S320 of Nichibishi Co., Ltd. As the 3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., KBM-903 manufactured by Momentive Performance Corporation, A-1110 manufactured by Momentive Performance Japan Co., Ltd., Z-6610 manufactured by Toray Dow Corning Co., Ltd., Syllace S360 manufactured by Nichibishi Corporation, etc. KBE-903, A-1100 manufactured by Momentive Performance Corporation Materiaruzu Japan Co., Ltd., Z-6011 manufactured by Toray Dow Corning Co., Ltd., Nichibu Co., Ltd., Shiraishi Co., Ltd. A3S303, and the like. Examples of the 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine include KBE-9103, SILA ACE S340 manufactured by Nichibishi Kogyo Co., Examples of the N-phenyl-3-aminopropyltrimethoxysilane include KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd., Y-9669 produced by Momentive Performance Materiaruzu Japan Chemical Co., Z-6883 manufactured by Corning Incorporated. Examples of the N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine include SILA ACE XS1003 manufactured by Nichibo Co., As the hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, KBM-575 manufactured by Shin-Etsu Chemical Co., Ltd., Z -6032, SILA ACE S350 available from Nichibo Shoji Co., Ltd., and tris- (trimethoxy) KBM-9659, manufactured by Shin-Etsu Chemical Co., Ltd., and 3-mercaptopropylmethyldimethoxysilane, KBM-802 manufactured by Shin-Etsu Chemical Co., As Z-6852 and 3-mercaptopropyltrimethoxysilane available from Toray Industries, Inc., KBM-803 manufactured by Shinetsu Kagaku Kogyo Co., Ltd., A (trade name) manufactured by Momentive Performance Materiaruzu Japan Kogyo Co., -189, Z-6062 manufactured by Toray Dow Corning Co., Ltd., Syllace S810 manufactured by Nichibishi Co., Ltd., and 3-mercaptopropyltriethoxysilane, A-1891 available from Materia Rouge Japan Kogyo Co., Ltd. and Z-6911 available from Toray Dow Corning Co., Ltd. As the 3-ureide propyl triethoxysilane, Momentive Perfumance Materiaruzu Japan Co., Ltd. Of A-1160, and 3 -Ureido propyl trialkoxysilane can be KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd. As the bis (triethoxysilylpropyl) tetrasulfide, KBE-585 available from Shinetsu Kagaku Kogyo Co., 846. Examples of the 3-octanoylthio-1-propyltriethoxysilane include A-LINK599 manufactured by Momentive Performance Materiaruzu Japan Co., Ltd. As the 3-isocyanate propyltriethoxysilane, , KBE-9007 (product of Shin-Etsu Chemical Co., Ltd.), A-1310 (product of Momentive Performance Materieluzu Japan Co., Ltd.), and 3-isocyanate propyl trimethoxysilane Y-5187 available from Materia Rouge Japan Kogyo Co., and GENIOSIL GF40 available from Asahi Kasei Wakasa Silicone Co., Ltd., and the like.

Of these silane coupling agents, a silane coupling agent having a methacryloyl group, an epoxy group or an isocyanate group is suitably used. For example, KBM-502, KBE-403, KBE-9007 and the like manufactured by Shin-Etsu Chemical Co., .

Examples of the melamine compound include compounds having an active methylol group (CH ₂ OH group) in a nitrogen compound such as (poly) methylol melamine, (poly) methylol glycoluryl, (poly) methylolbenzoguanamine, And compounds in which all or a part (at least two) are alkyl-etherified.

Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, and they may be the same or different in some cases. In addition, the methylol group which is not alkyl-etherified may self-condense in one molecule, and may condense between two molecules, resulting in the formation of an oligomer component.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.

Of these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

The photosensitive composition of the present invention may be applied to a support such as a soda glass, a quartz glass, a semiconductor substrate, a metal, a paper, a plastic or the like by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, . ≪ / RTI > Further, after being once applied onto a support such as a film, it may be transferred onto another support, and the application method thereof is not limited.

Examples of the light source of the energy ray used for curing the photosensitive composition of the present invention include ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, Electromagnetic energy having a wavelength of 2000 angstroms to 7000 angstroms obtained from a light source such as a metal halide lamp, a fluorescent lamp, a tungsten lamp, an excimer lamp, a sterilizing lamp, a light emitting diode, or a CRT light source or a high energy line such as an electron beam, an X- , An ultrahigh pressure mercury lamp which emits light with a wavelength of 300 to 450 nm, a mercury vapor arc, a carbon arc lamp, a xenon arc lamp, and the like.

In addition, since the laser direct writing method for forming an image directly from digital information such as a computer without using a mask by using laser light for the exposure light source can improve not only productivity but also resolution and positional accuracy A nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, a variety of semiconductor lasers, and a YAG laser are used as the laser light. It is also used to emit light in the infrared region from visible light. In the case of using these lasers, a sensitizing dye which absorbs the corresponding infrared region is added from visible.

The photosensitive composition of the present invention can also be used for the production of other steps or height patterns using a halftone mask.

The photosensitive composition of the present invention is a photocurable paint or varnish; Photocurable adhesive; A printed board; A color filter in a liquid crystal display element of color display such as a color television, a PC monitor, a portable information terminal, and a digital camera; A color filter of a CCD image sensor; An electrode material for a plasma display panel; Powder coating; Printing ink; Printing plates; glue; Dental compositions; Gelcoat; Photoresists for electronics; Electroplating resist; Etching resist; Dry film; Solder resist; A resist for forming a color filter for various display applications or for forming a structure in a plasma display panel, an electroluminescence display, and a manufacturing process of an LCD; A composition for enclosing electrical and electronic components; Solder resist; Magnetic recording material; Micro machine parts; Waveguides; Optical switch; A plating mask; An etching mask; Color test system; Glass fiber cable coating; A stencil for screen printing; A material for producing a three-dimensional object by stereolithography; A material for holography recording; Image recording material; Microelectronic circuits; Decolorizing material; A decolorizing material for an image recording material; A decolorizing material for an image recording material using a microcapsule; Photoresist materials for printed wiring boards; Photoresist materials for UV and visible laser direct imaging systems; And can be used for various uses such as a photoresist material or a protective film used for forming a dielectric layer in successive lamination of a printed circuit board, and there is no particular limitation on its use.

The photosensitive composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a projection for a vertical alignment type liquid crystal display element. And is particularly useful as a photosensitive composition for simultaneously forming projections and spacers for vertically aligned liquid crystal display elements.

(2) a step of irradiating the coating film with radiation through a mask having a predetermined pattern shape, (3) a step of irradiating the coating film with radiation through a mask having a predetermined pattern shape, (3) (4) a step of developing the coating film after exposure, and (5) a step of heating the coating film after development.

The (colored) photosensitive composition of the present invention to which an ink repellent agent is added is useful as a barrier rib forming resin composition for an inkjet system. The composition is used for a color filter, and particularly, . As the ink repellent, a composition comprising a fluorine-based surfactant and a fluorine-based surfactant is suitably used.

By a method in which a partition formed from the photosensitive composition of the present invention defines a transferred image and a droplet is applied to the concave portion on the partitioned transferred body by an inkjet method to form an image region An optical element is manufactured. At this time, it is preferable that the droplet contains a coloring agent, the image region is colored, and the substrate has at least a pixel group composed of a plurality of coloring regions and a partition wall isolating each coloring region of the pixel group, An optical element manufactured by a manufacturing method of an optical element of the present invention is preferably used.

The photosensitive composition of the present invention is also used as a protective film or composition for an insulating film, and is useful as an ultraviolet absorber, an alkylated modified melamine and / or an acrylic modified melamine, a monofunctional (meth) acrylate monomer containing an alcoholic hydroxyl group in the molecule, and / Or silica sol.

As the photosensitive composition for the protective film and insulating film, for example,

(I) a carboxyl group-containing resin having a weight average molecular weight of 2,000 to 40,000 and an acid value of 50 to 200 mgKOH / g, obtained by reacting a diol compound with a polycarboxylic acid,

(II) an unsaturated compound containing at least one photopolymerizable ethylenically unsaturated bond in one molecule,

(III) an epoxy compound, and

(IV) a photopolymerization initiator component as a main component,

(III) is contained in an amount of 10 to 40 parts by weight and the component (IV) is contained in an amount of 0.01 to 2.0 parts by weight based on 100 parts by weight of the total of the components (I) and (II) A resin composition using the photopolymerization initiator composition of the present invention is used as the component.

Wherein the insulating film is used for the insulating resin layer in a laminated body provided with an insulating resin layer on a peelable supporting substrate and the laminate is capable of developing with an aqueous alkali solution and the insulating resin layer has a thickness of 10 To 100 mu m.

The photosensitive composition of the present invention can be used as a photosensitive paste composition by containing an inorganic material (inorganic compound). The photosensitive paste composition is used to form a fired pattern such as a barrier rib pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and the like. In the following Examples and Comparative Examples, the% is based on the mass unless otherwise specified.

[Example 1]

Photopolymerization initiator composition No. 1 was prepared at the compounding ratios shown in Table 1. As the component (A) and the component (B), those shown below were used.

Further, 55.46 parts by mass of SPC-1000 (acrylic resin; manufactured by Showa Denko K.K.), 12.91 parts by mass of ARONIX M-450 (multifunctional acrylate, manufactured by Toagosei Co., Ltd.), KBE-403 (silane coupling agent; ), 3.23 parts by mass of a 1% cyclohexanone solution of FZ-2122 (surfactant; manufactured by Nippon Unicar Co., Ltd.) and 27.48 parts by mass of propylene glycol-1-monomethyl ether-2-acetate were mixed to obtain a photopolymerization initiator composition And 0.34 parts by mass of No. 1 were added so that the total amount was 100 parts by mass, and this mixed solution was well stirred to obtain an alkali developable photosensitive resin composition No. 1 as a photosensitive composition of the present invention.

The sensitivity of the obtained alkali-developable photosensitive resin composition No. 1 was evaluated by the following sensitivity evaluation method, and the resolution was evaluated by the following resolution evaluation method. The results are shown in Table 1.

[Examples 2 to 13]

Photopolymerization initiator compositions No. 2 to No. 13 were prepared at the compounding ratios shown in Table 1. As the component (A) and the component (B), those shown below were used. Further, the alkali developable photosensitive resin compositions Nos. 2 to 13 were obtained in the same manner as in Example 1, except that these photopolymerization initiator compositions were used in place of the photopolymerization initiator composition No. 1 used in Example 1. The sensitivity of the obtained alkali-developable photosensitive resin composition was evaluated by the following sensitivity evaluation method, and the resolution was evaluated by the following resolution evaluation method. The results are shown in Table 1.

[Comparative Examples 1 to 15]

Comparative Photopolymerization Initiator Composition Nos. 1 to 15 were prepared at blending ratios shown in Table 2. As the comparative photopolymerization initiators-1 and -2, those shown below were used.

Further, comparative alkali developable photosensitive resin compositions No. 1 to No. 15 were obtained in the same manner as in Example 1, except that these comparative photopolymerization initiator compositions were used in place of the photopolymerization initiator composition No. 1 used in Example 1. The sensitivity of the obtained alkali-developable photosensitive resin composition was evaluated by the following sensitivity evaluation method, and the resolution was evaluated by the following resolution evaluation method. The results are shown in Table 2.

[Component (A)] [

As the component (A), the following Compound No. 1, Compound No. 6 and Compound No. 11 were used.

[Component (B)] [

As the component (B), the following compound No. 13, compound No. 15 and compound No. 21 were used.

[Comparative photopolymerization initiator]

The following comparative photopolymerization initiator-1 and comparative photopolymerization initiator-2 were used in the comparative examples.

<Sensitivity Evaluation Method>

The sensitivities of the obtained alkali-developable photosensitive resin compositions and comparative alkali-developable photosensitive resin compositions were evaluated as follows.

That is, the alkali developable photosensitive resin composition was spin-coated on a glass substrate, pre-baked at 90 占 폚 for 90 seconds using a hot plate, and exposed through a mask using a high-pressure mercury lamp as a light source. After development using a 2.5 mass% sodium carbonate aqueous solution as a developing solution, it was washed well and post-baked at 230 캜 for 30 minutes using an oven to fix the pattern. The pattern for the exposure dose of 40 mJ was observed with an electron microscope to measure the line width of the mask opening of 20 m. The line width was 21 μm or more for A, 20 to 21 μm for B, 19 to 20 μm for C, and 19 μm or less. A is the most sensitive, followed by B and C, and D is the least sensitive.

<Resolution Evaluation Method>

The resolution of the obtained alkali-developable photosensitive resin composition and the comparative alkali-developable photosensitive resin composition was evaluated as follows.

That is, the alkali developable photosensitive resin composition was spin-coated on a glass substrate, pre-baked at 90 占 폚 for 90 seconds using a hot plate, and exposed through a mask using a high-pressure mercury lamp as a light source. After development using a 2.5 mass% sodium carbonate aqueous solution as a developing solution, it was washed well and subjected to post-baking at 230 캜 for 30 minutes using an oven to fix the pattern. The pattern when the residual film sensitivity (residual film ratio 75%) was combined was observed with an electron microscope to measure the line width of the mask opening of 20 m. The difference between the mask opening and the line width was 0.5 μm or less, the difference was 0.5 to 1.0 μm was B, the difference between 1.0 and 2.0 μm was C, and the difference was 2.0 μm or more. A has the highest resolution, followed by B and C, and D has the lowest resolution.

According to the present invention, it is possible to provide a photopolymerization initiator composition capable of imparting excellent sensitivity and resolution to a photosensitive composition. Further, according to the present invention, a photosensitive composition excellent in sensitivity and resolution can be provided.

Claims (7)

1 to 99 parts by mass of the following component (A) and 1 to 99 parts by mass of the following component (B) (the sum total of the components (A) and (B) is 100 parts by mass).
Component (A): A photopolymerization initiator comprising at least one oxime ester compound represented by the following general formulas (1-1) to (1-3), which has an ether structure represented by the following general formula (3)

In the general formulas (1-1) to (1-3), R ¹ , R ² and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or a cyano group, and the alkyl, alkoxy, aryl, the hydrogen atoms of the aryloxy group, aralkyl group and heterocyclic group, and ^{oR 11, COR 11, SR 11} , NR 12 R 13, -NCOR 12 -OCOR 13, CN, halogen atom, -CR ¹¹ = CR ¹² R ¹³ or -CO-CR ¹¹ = CR ¹² R ¹³ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms An aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms and the alkylene moiety of the substituent represented by R ¹ , R ² , R ⁶ , R ¹¹ , R ¹² and R ¹³ is , Unsaturated bond, The alkyl moiety of the substituent may have a branched side chain, and the cyclic moiety (ring (s)) may be present in the alkyl moiety of the substituent, And the alkyl terminal (terminal) of the substituent may be an unsaturated bond, and R ² may form a ring together with the adjacent benzene ring in some cases.
R ³ , R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms An aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and the hydrogen atom of the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group and heterocyclic group It is further substituted by ^{oR 14, COR 14, SR 14} , NR 15 R 16, -NCOR 15 -OCOR 16, CN, halogen atom, -CR ¹⁴ = CR ¹⁵ R ¹⁶ or ^{-CO-CR 14 = CR 15 R} 16 R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, represents a heterocyclic group of 2 to 20 carbon atoms, the alkylene portion of the substituent represented by the above ^{R 3, R 4, R 5} , R 14, R 15 and R ¹⁶ is an unsaturated bond, an ether bond, An ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl moiety of the substituent may have branched side chains and may be cyclic alkyl , The alkyl terminal of the substituent may be an unsaturated bond, and a, b, and d are each independently an integer of 0 to 3.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the hydrogen atom of the alkyl group is preferably a hydrogen atom, And the methylene group of the alkylene moiety of the alkyl group may be substituted one to five times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond , The alkyl moiety may have branched side chains, may be cyclic alkyl, the alkyl terminus may be an unsaturated bond, and R ⁷ and R ⁸ may form a ring together.
Component (B): A photopolymerization initiator comprising at least one oxime ester compound represented by the following general formula (2-1) or (2-2), which has a cycloalkyl structure represented by the following general formula (4)

In the general formula (2-1) or (2-2), R ²¹ and R ²² each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 6 to 30 carbon atoms An aryl group, an aryloxy group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms or a cyano group, and the alkyl, alkoxy, aryl, aryloxy , The aralkyl group and the hydrogen atom of the heterocyclic group may be further substituted by OR ³¹ , COR ³¹ , SR ³¹ , NR ³² R ³³ , -NCOR ³² -OCOR ³³ , CN, a halogen atom, -CR ³¹ = CR ³² R ^33, CR ³¹ = CR ³² R and ³³ if it is substituted by, R ^31, R ³² and R ³³ each independently represent a hydrogen atom, carbon atom alkyl group having 1 to 20 carbon atoms, 6 to 30 aryl group, a carbon An aralkyl group having 7 to 30 atoms or a heterocyclic group having 2 to 20 carbon atoms and the alkylene moiety of the substituent represented by R ²¹ , R ²² , R ³¹ , R ³² and R ³³ is an unsaturated bond, an ether bond The alkyl moiety of the substituent may have branched side chains, and when the alkyl moiety is cyclic alkyl, the alkyl moiety of the substituent may be branched, , The alkyl terminal of the substituent may be an unsaturated bond, and R &lt; ²² &gt; may form a ring together with the adjacent benzene ring.
R ²³ and R ²⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, An aralkyl group having 7 to 30 atoms, a heterocyclic group having 2 to 20 carbon atoms, a cyano group or a halogen atom, and the hydrogen atom of the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group and heterocyclic group is ^{oR 34, COR 34, SR 34} , NR 35 R 36, -NCOR 35 -OCOR 36, CN, halogen atom, -CR ³⁴ = CR ³⁵ R ³⁶ or ^{-CO-CR 34 = CR 35 R} 36 when substituted with Each of R ³⁴ , R ³⁵ and R ³⁶ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, It represents a heterocyclic group having 2 to 20, the alkylene portion of the substituent represented by the above ^{R 23, R 24, R 34} , R 35 and R ³⁶ is an unsaturated bond, an ether bond, a thioether The alkyl moiety of the substituent may have a branched side chain, may be cyclic alkyl, may be branched, or may be substituted with 1 to 5 times by a linkage, ester bond, thioester bond, amide bond or urethane bond, The alkyl terminal of the substituent may be an unsaturated bond, and u and v are each independently an integer of 0 to 3.
Ar represents an aryl group or a heterocyclic group selected from the following structures,

L ¹ represents a hydrogen atom or a benzoyl group,
X ¹ represents a direct bond or a carbonyl group,
G ¹ represents a group of the general formula (4), n in the general formula (4) is an integer of 1 to 5, and m is an integer of 1 to 6. A photosensitive composition comprising the photopolymerization initiator composition according to Claim 1 in a polymerizable compound having an ethylenically unsaturated bond. 3. The method of claim 2,
Wherein the photosensitive composition further contains an inorganic compound. An alkaline developing photosensitive resin composition comprising the photopolymerization initiator composition according to claim 1 in an alkali developing compound which may have an ethylenic unsaturated bond and a polymerizable compound having an ethylenic unsaturated bond. 5. The method of claim 4,
Wherein the photosensitive resin composition further contains an inorganic compound. A colored alkali developable photosensitive resin composition comprising the alkali developable photosensitive resin composition according to claim 4 or 5, further comprising a colorant. A photosensitive composition according to claim 2 or 3, an alkali developable photosensitive composition according to claim 4 or 5, or a colored alkali developable photosensitive resin composition according to claim 6, Cured goods.