JP2008064890A - Photosensitive composition, photosensitive film, permanent pattern forming method and printed circuit board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition having high sensitivity, high resolution and proper storage stability and capable of forming a high-definition permanent pattern having proper various properties required, a photosensitive film, a permanent pattern forming method that uses the photosensitive composition, and a printed circuit board on which a pattern is formed by the permanent pattern forming method. <P>SOLUTION: The photosensitive composition comprises a binder, a polymerizable compound, a photopolymerization initiation compound and a thermal crosslinking agent, wherein the photopolymerization initiation compound comprises a merocyanine compound and an oxime derivative. The photosensitive film has a photosensitive layer, comprising the photosensitive composition on a support, the permanent pattern forming method includes exposing of a photosensitive layer formed from the photosensitive composition, and the printed circuit board is formed by the permanent pattern forming method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive composition, a photosensitive film, a method for forming a permanent pattern, and a printed board suitable for forming a high-definition permanent pattern.

  In a permanent pattern forming material such as a solder resist, for the purpose of improving exposure sensitivity, the permanent pattern forming material may be used in combination with a sensitizer such as a coumarin compound and a polymerization initiator such as a peroxide compound. There have been proposals such as the combined use of sensitizers such as dyes and imidazole dimeric polymerization initiators (see Patent Document 1). However, these combinations are highly sensitive but have poor storage stability and are problematic in practice.

  On the other hand, in the photoresist for manufacturing printed circuit boards, switching from a liquid resist to a dry film is progressing. This may be because, for example, high sensitivity and high resolution are easily obtained, and handling properties are excellent. On the other hand, with regard to the formation of a permanent pattern such as a solder resist, even today, liquid resist is mostly used, and dry film formation is delayed.

One of the causes is that the solder resist contains a carboxylic acid group-containing resin and an epoxy resin.
More specifically, in the production of the solder resist, an alkali development system is generalized, the carboxylic acid group-containing resin is an essential component for the alkali development treatment, and an epoxy resin is obtained. It is an essential component for realizing heat resistance, hardness, substrate adhesion and the like.

That is, it is necessary that the originally reactive epoxy group and carboxyl group coexist in the solder resist, which limits the storage stability of the solder resist film. In particular, in order to realize a high-sensitivity solder resist when applying an exposure system such as a blue-violet laser (wavelength 405 ± 5 nm) that is excellent in light stability under a yellow safety light and capable of maskless exposure, Improving storage stability is one of the major issues.
Also, the solder resist as a permanent pattern is required to have good properties such as pencil hardness, adhesion, electrical insulation, acid resistance, alkali resistance, electroless gold plating resistance, PCT resistance and the like.

Here, acyl oximes (see Patent Document 2) have been proposed as highly sensitive photopolymerization initiators. Moreover, as a solder resist application, a curable composition using oxime ether and an epoxy acrylate oligomer in combination (see Patent Document 3), a curable composition using oxime ether (see Patent Document 4), acyl oxime and sulfur. A curable composition using a combination of benzophenone having atoms (see Patent Document 5) has been proposed. Furthermore, photolithographic compositions using dithiolidene merocyanine sensitizing dyes (see Patent Document 6) and polymerizable compounds using a combination of dithiolidene merocyanine sensitizing dyes and acylphosphines are proposed as lithographic printing plate precursors. (See Patent Document 7).
However, a photosensitive composition using a combination of a merocyanine compound and an oxime derivative as a high-definition permanent pattern such as a solder resist application has not been proposed yet.

  Therefore, a photosensitive composition, a photosensitive film, and the photosensitive composition, which have high sensitivity and high resolution, have good storage stability, have good required properties, and can form a high-definition permanent pattern. The permanent pattern forming method used and the printed circuit board on which the pattern is formed by the permanent pattern forming method have not yet been provided, and further improvement and development are desired.

Japanese Patent No. 3295012 JP 2000-80068 A JP 2001-302871 A International Publication No. 02/96969 Pamphlet JP 2005-182004 A JP-A-3-296759 JP 2001-133968 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention is a photosensitive composition, photosensitive film, high sensitivity and high resolution, good storage stability, good properties required and capable of forming a high-definition permanent pattern, It is an object of the present invention to provide a permanent pattern forming method using a photosensitive composition, and a printed circuit board on which a pattern is formed by the permanent pattern forming method.

Means for solving the problems are as follows. That is,
<1> A photosensitive composition comprising a binder, a polymerizable compound, a photopolymerization initiating compound, and a thermal crosslinking agent, wherein the photopolymerization initiating compound comprises a merocyanine compound and an oxime derivative.
<2> The photosensitive composition according to <1>, wherein the merocyanine compound is represented by the following general formula (I).
In the general formula (I), X represents an oxygen atom, a sulfur atom, and either NR ^1. Z represents a nonmetallic atomic group that forms a basic nucleus of the dye together with X and an adjacent carbon atom, and R ¹ represents any ^one of a hydrogen atom, an aliphatic group, and an aromatic group. X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and the X ₁ and X ₂ may be bonded to each other to form an acidic nucleus of the dye. W represents either an oxygen atom or a sulfur atom. m represents an integer of 0 or more.
<3> The photosensitive composition according to <2>, wherein the merocyanine compound is further represented by any one of the following general formula (I-1) and general formula (I-2).
In the general formula (I-1) and the general formula (I-2), ^{R 1} represents the same meaning as the general formula (I). R ² and R ³ each independently represents any one of a hydrogen atom, an aliphatic group, an aromatic group, and a heterocyclic group, and R ² and R ³ are bonded to other carbon atoms and substituted. You may form the 5-7 membered ring which may be. X ₁ and X ₂ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and X ₁ and X ₂ may be bonded to each other to form an acidic nucleus of the dye. W represents either an oxygen atom or a sulfur atom. Each Y independently represents a carbon atom or a heteroatom of any one of Groups 15 and 16 in the periodic table.
<4> The skeleton constituted by X ₁ , X ₂ , and W in the general formula (I-1) and the general formula (I-2) is thiobarbituric acid, indanedione, and tetrahydroquinoline-2,4-dione. It is a photosensitive composition as described in said <3> which is either of frame | skeleton.
<5> The photosensitive composition according to any one of <1> to <4>, wherein the oxime derivative has a partial structure represented by any one of the following general formula (II) and the following general formula (III). is there.
In the general formula (II) and the general formula (III), Ar represents either an aromatic group and a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² Represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ represent an aliphatic group, an aromatic group, And a heterocyclic group, and n represents an integer of 1 or more.
<6> The photosensitive composition according to <5>, wherein Ar in the general formulas (II) and (III) has either a phenyl group or a naphthyl group.
<7> The photosensitive composition according to any one of <5> to <6>, wherein Ar in the general formulas (II) and (III) has a naphthyl group.
<8> The photosensitive composition according to any one of <1> to <7>, wherein the oxime derivative is an acyloxime derivative.
<9> The photosensitive composition according to any one of <1> to <8>, wherein the content ratio of the merocyanine compound and the oxime derivative is 0.01: 1 to 10: 1.

<10> From the above <1>, wherein the thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. 9>. The photosensitive composition according to any one of 9>.
<11> The photosensitive composition according to any one of <1> to <10>, including a thermal crosslinking accelerator.
<12> The photosensitive composition according to any one of <1> to <11>, wherein the binder is an alkali-soluble crosslinkable resin.
<13> The photosensitive composition according to any one of <1> to <12>, wherein the polymerizable compound includes a monomer having a (meth) acryl group.
<14> The photosensitive composition according to any one of <1> to <13>, including an inorganic filler.

<15> A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to any one of <1> to <14> on a support.
<16> The photosensitive film according to <15>, wherein the support includes a synthetic resin and is transparent.
<17> The photosensitive film according to any one of <15> to <16>, wherein the support has a long shape.
<18> The photosensitive film according to any one of <15> to <17>, which is long and wound in a roll.
<19> The photosensitive film according to any one of <15> to <18>, which has a protective film on the photosensitive layer.
<20> The photosensitive film according to any one of <15> to <19>, wherein the photosensitive layer has a thickness of 1 to 100 μm.

<21> A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive composition according to any one of <1> to <14>.
<22> The method for forming a permanent pattern according to <21>, wherein the photosensitive layer is formed of the photosensitive film according to any one of <15> to <20>.
<23> The method for forming a permanent pattern according to any one of <21> to <22>, wherein the exposure is performed without using a photomask.
<24> The method for forming a permanent pattern according to <23>, wherein the exposure is performed while relatively moving the exposure light and the photosensitive layer.
<25> Exposure is emitted from the light irradiation unit to the photosensitive layer while moving at least one of the exposure head including at least a light irradiation unit and a light modulation unit, and the photosensitive layer. The permanent pattern forming method according to any one of <23> to <24>, wherein the light is irradiated from the exposure head while modulating light according to pattern information by the light modulation unit.
<26> The light modulation unit according to <25>, wherein the light modulation unit can control any less than n pixel elements arranged continuously from n pixel elements according to pattern information. This is a permanent pattern forming method.
<27> The method for forming a permanent pattern according to any one of <25> to <26>, wherein the light modulator is a spatial light modulator.
<28> The method for forming a permanent pattern according to <27>, wherein the spatial light modulation element is a digital micromirror device (DMD).
<29> The permanent pattern forming method according to any one of <25> to <28>, wherein the exposure is performed through an aperture array.
<30> The method for forming a permanent pattern according to any one of <25> to <29>, wherein the light irradiation unit can synthesize and irradiate two or more lights.
<31> The light irradiation means includes a plurality of lasers, a multimode optical fiber, and a collective optical system that collects and couples the laser beams emitted from the plurality of lasers to the multimode optical fiber. The permanent pattern forming method according to any one of <25> to <30>.
<32> The method for forming a permanent pattern according to any one of <21> to <31>, wherein the exposure is performed using a laser beam having a wavelength of 350 to 420 nm.

<33> The method for forming a permanent pattern according to any one of <21> to <32>, wherein the photosensitive layer is developed after the exposure.
<34> The method for forming a permanent pattern according to <33>, wherein after the development, the photosensitive layer is subjected to a curing treatment.
<35> The method for forming a permanent pattern according to <34>, wherein the curing treatment is at least one of a whole surface exposure treatment and a whole surface heat treatment performed at 120 to 200 ° C.

<36> A permanent pattern formed by the method for forming a permanent pattern according to any one of <21> to <35>.
<37> The pattern according to <36>, which is at least one of a protective film, an interlayer insulating film, and a solder resist pattern.

  <38> A printed circuit board wherein a permanent pattern is formed by the method for forming a permanent pattern according to any one of <21> to <35>.

  The photosensitive composition and photosensitive film of the present invention contain a binder, a polymerizable compound, a photopolymerization initiation compound, and a thermal crosslinking agent, and the photopolymerization initiation compound contains a merocyanine compound and an oxime derivative. As a result, it is possible to form a high-definition permanent pattern having high sensitivity and high resolution, good storage stability, and good required properties.

  Since the permanent pattern of the present invention uses a photosensitive layer formed of the photosensitive composition of the present invention, it has high sensitivity and high resolution, good storage stability, and good properties required. A fine permanent pattern can be formed. In particular, by performing direct patterning without using a photomask, a permanent pattern can be formed with high production.

  According to the present invention, the conventional problems can be solved, the sensitivity and the high resolution, the storage stability is good, the required properties are good, and a high-definition permanent pattern can be formed. A composition, a photosensitive film, a permanent pattern forming method using the photosensitive composition, and a printed board on which a pattern is formed by the permanent pattern forming method can be provided.

(Photosensitive composition)
The photosensitive composition of the present invention contains at least a binder, a polymerizable compound, a photopolymerization initiating compound, and a thermal crosslinking agent, and contains other components appropriately selected as necessary.

<Photopolymerization initiation compound>
The photopolymerization initiating compound includes at least a merocyanine compound and an oxime derivative.
-Merocyanine compounds-
In the present invention, the merocyanine compound means a compound in which a cyanine dye has a basic nucleus in a molecule and an electron-withdrawing group such as a carbonyl group connected directly or with an even number of methine chains. .
There is no restriction | limiting in particular as said merocyanine type compound, Although it can select suitably according to the objective, For example, the compound represented by the following general formula (I) is preferable.
In the general formula (I), X represents an oxygen atom, a sulfur atom, and either NR ^1. Z represents a nonmetallic atomic group that forms a basic nucleus of the dye together with X and an adjacent carbon atom, and R ¹ represents any one of a hydrogen atom, an aliphatic group, and an aromatic group. X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and the X ₁ and X ₂ may be bonded to each other to form an acidic nucleus of the dye. W represents either an oxygen atom or a sulfur atom. m represents an integer of 0 or more.

Examples of the basic nucleus formed by Z in the general formula (I) together with X and an adjacent carbon atom include L.I. G. Brooker et al. , J .; Am. Chem. Soc. 73, 5326-5358 (1951), and any of those known as constituting basic nuclei in merocyanine dyes described in the references can be suitably used.
Specifically, for example, thiazole nucleus such as thiazole nucleus, benzothiazole nucleus and naphthothiazole nucleus; oxazole nucleus such as oxazole nucleus, benzoxazole nucleus and naphthoxazole nucleus; thiazoline nucleus; selenazole nucleus, benzoselenazole nucleus, naphthoselena nucleus Serenazole nucleus such as sol nucleus; Serenazoline nucleus; Tellurazole nucleus such as tellurazole nucleus, benzotelrazole nucleus, naphthotelrazole nucleus; Tellrazol nucleus; 3,3-dialkylindolenin nucleus; Imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, etc. Imidazole nucleus; pyridine nucleus; quinoline nucleus such as quinoline nucleus and isoquinoline nucleus; imidazo [4,5-b] quinoxaline nucleus; oxadiazole nucleus; thiadiazole nucleus; tetrazole nucleus; pyrimidine nucleus.

Examples of the thiazole nucleus include thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, and 4,5-diphenylthiazole.
Examples of the benzothiazole nucleus include benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylthiobenzothiazole, 5- Methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiobenzo Thiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro 6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethylthiobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole Is mentioned.
Examples of the naphthothiazole nucleus include naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, and 5-methoxynaphtho [1,2-d]. Thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole).
Examples of the thiazoline nucleus include thiazoline, 4-methylthiazoline, and 4-nitrothiazoline.

Examples of the oxazole nucleus include oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, and 4-ethyloxazole.
Examples of the benzoxazole nucleus include benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5- Nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6- Examples include hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, and 5-ethoxybenzoxazole.
Examples of the naphthoxazole nucleus include naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, and 5-nitronaphtho [2,1-d] oxazole. ).
Examples of the oxazoline nucleus include 4,4-dimethyloxazoline.

Examples of the selenazole nucleus include 4-methylselenazole, 4-nitroselenazole, and 4-phenylselenazole.
Examples of the benzoselenazole nucleus include benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5 -Chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole.
Examples of the naphthoselenazole nucleus include naphtho [2,1-d] selenazole and naphtho [1,2-d] selenazole).
Examples of the selenazoline nucleus include selenazoline and 4-methylselenazoline.

Examples of the tellurazole nucleus include tellurazole, 4-methyl tellurazole, and 4-phenyl tellurazole.
Examples of the benzotellazole nucleus include benzotellazole, 5-chlorobenzotellazole, 5-methylbenzotellazole, 5,6-dimethylbenzotellazole, and 6-methoxybenzotellazole.
Examples of the naphthotelrazole nucleus include naphtho [2,1-d] tellazole and naphtho [1,2-d] tellazole.

Examples of the tellurazoline nucleus include tellurazoline and 4-methyltellazoline.
Examples of the 3,3-dialkylindolenine nucleus include 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenin, and 3,3-dimethyl-6- Nitroindolenine, 3,3-dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenin, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine Can be mentioned.

Examples of the imidazole nucleus include 1-alkylimidazole, 1-alkyl-4-phenylimidazole, and 1-arylimidazole.
Examples of the benzimidazole nucleus include 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl. -5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzoimidazole, 1-alkyl-6 -Chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1 -Aryl-5 6-dichloro-benzimidazole, 1-aryl-5-methoxy-benzimidazole, and 1-aryl-5-cyano-benzimidazole.
Examples of the naphthimidazole nucleus include alkylnaphtho [1,2-d] imidazole and 1-arylnaphtho [1,2-d] imidazole.

Examples of the pyridine nucleus include 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, and 3-methyl-4-pyridine.
Examples of the quinoline nucleus include 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, and 8-fluoro-2- Quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro- 4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4- A quinoline is mentioned.
Examples of the isoquinoline nucleus include 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, and 6-nitro-3-isoquinoline.
Examples of the imidazo [4,5-b] quinoxaline nucleus include 1,3-diethylimidazo [4,5-b] quinoxaline and 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline. Can be mentioned.
Among the basic nuclei exemplified above, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus, and a 4-quinoline nucleus are preferable.

  Examples of the aliphatic group in the exemplified basic nucleus include an alkyl group, an alkenyl group, and an alkynyl group which may have a substituent. In addition, examples of the aromatic group include an aryl group and a heterocyclic (heterocyclic) group, each of which may have a substituent.

Examples of the aromatic group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl Groups, naphthyl groups, anthryl groups, phenanthryl groups, indenyl groups, acenaphthenyl groups, and fluorenyl groups.
In addition, these aromatic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

The heterocyclic (heterocyclic) group includes a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, and an isothiazole ring. Group, indazole ring group, benzisoxazole ring group, benzisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group, pyridine ring group, Quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring group, purine ring group, Pyran ring group, piperidine ring group, piperazine ring group, morpholine ring group, India Ring group, indolizine ring group, chromene ring group, cinnoline ring group, acridine ring group, phenothiazine ring group, tetrazole ring group, triazine ring group, etc., among which furan ring group, thiophene ring group, imidazole ring group , Thiazole ring group, benzothiazole ring group, pyridine ring group, indole ring group, and acridine ring group are particularly preferable.
Moreover, these heterocyclic groups may have a substituent, and examples of such a substituent include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, what was shown as a substituent in the below-mentioned alkyl group, a substituted alkyl group, or a substituted alkyl group can be mentioned.

  In addition, the monovalent substituent composed of the nonmetal atom is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent.

  Examples of the alkyl group that may have a substituent include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group. , Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl A group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group Can do. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

Examples of the substituent of the alkyl group which may have a substituent include a substituent composed of a monovalent nonmetallic atom excluding a hydrogen atom, and preferable examples include a halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkyl Carbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcal Moyloxy group, alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkyl Ureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N -Alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N -Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diary Ru-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl- N-arylcarbamoyl group, al Killsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N— Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group _(-PO 3 _{H 2)} and its conjugated base group (a phosphonato group Referred), a dialkyl phosphono group _(-PO 3 _{(alkyl) 2)} "alkyl = alkyl group, hereinafter the" diarylphosphono group _(-PO 3 _{(aryl) 2)} "aryl = aryl group, hereinafter the" alkyl An arylphosphono group (—PO ₃ (alkyl) (aryl)), a monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as an alkylphosphonato group), a monoarylphosphono group (— PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO) ₃ H _{(alkyl) 2),} diaryl phosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl Suhonookishi group _(-OPO 3 (alkyl) (aryl)), monoalkyl phosphono group _(-OPO 3 H (alkyl)) and (referred to as alkylphosphonato group) a conjugate base group thereof, monoarylphosphono group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. , Cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group , Methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylpheny Group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphate Hona preparative phenyl group.

Examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of the alkynyl group in the substituent Examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group.
Examples of the silyl group in the substituent include a trimethylsilyl group.
The substituent may include an acyl group (R ⁴ CO—), and examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the above alkyl group, or aryl group.

Examples of R ⁴ of the acyl group (R ⁴ CO—) include a hydrogen atom, and the alkyl group and aryl group. Among these substituents, more preferred are a halogen atom (—F, —Br, —Cl, —I), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N-alkylamino group, N, N. -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfur Amoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatooxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group.

Examples of the aryl group include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group , A naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
As the substituted aryl group, those having a group consisting of a monovalent nonmetallic atomic group excluding a hydrogen atom as a substituent on the ring-forming carbon atom of the aryl group described above are used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

The alkenyl group, the substituted alkenyl group, the alkynyl group, and the substituted alkynyl group (—C (R ⁵ ) ═C (R ⁶ ) (R ⁷ ) and —C≡C (R ⁸ )) are R ⁵ , R ⁶ , R ⁷ , R ⁸ can be a group composed of a monovalent nonmetallic atom.
R ⁵ , R ⁶ , R ⁷ , and R ⁸ are preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group, and specific examples thereof are shown in the above examples. Things can be mentioned. Among these, a hydrogen atom, a halogen atom, and a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms are more preferable.
Specifically, vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenylethynyl group and the like.
Examples of the heterocyclic group include the pyridyl group exemplified as the substituent of the substituted alkyl group.

As the substituted oxy group (R ⁹ O—), those in which R ⁹ is a group composed of a monovalent nonmetallic atom excluding a hydrogen atom can be used. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above. Further, examples of the acyl group (R ¹⁰ CO—) in the acyloxy group include those in which R ¹⁰ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned as the previous example. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyl Alkoxy group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy group, and the like.

The substituted amino group (R ¹¹ NH—, (R ¹² ) (R ¹³ ) N—) including an amide group is a group in which R ¹¹ , R ¹² , and R ¹³ are monovalent nonmetallic atomic groups excluding a hydrogen atom. Can be used. R ¹² and R ¹³ may combine to form a ring. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, and an N-aryl-N-aryloxycarbonylamino group. Can be mentioned. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, and aryl groups and substituted aryl groups described above, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. ^{R 10} groups definitive acyl group ^(R 10 CO-) are as described above. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted sulfonyl group (R ¹⁴ —SO ₂ —), those in which R ¹⁴ is a group composed of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, a chlorophenylsulfonyl group, and the like.

As described above, the sulfonate group (—SO ₃ ^— ) means a conjugated base anion group of the sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammonium compounds, sulfonium compounds, phosphonium compounds, iodonium compounds, azinium compounds, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

As the substituted carbonyl group (R ¹⁵ —CO—), a group in which R ¹⁵ is a monovalent nonmetallic atom can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-ary. A rucarbamoyl group can be mentioned, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ¹⁶ —SO—), those in which R ¹⁶ is a group composed of a monovalent nonmetallic atomic group can be used. Preferable examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl. Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups. Preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

As described above, the phosphonate group (—PO ₃ H ₂ ^— , —PO ₃ H ⁻ ) is a conjugate base anion derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). Means group. Usually, it is preferable to use it with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammonium compounds, sulfonium compounds, phosphonium compounds, iodonium compounds, azinium compounds, etc.), and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^{2+ and the} like).

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic oxo group in the above-described substituted phosphono group. As a specific example, the above-described monoalkylphosphono group (—PO ₃ H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

Specific examples of X ₁ and X ₂ in the general formula (I) include halogen atom (—F, —Br, —Cl, —I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group. Group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group , Acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group Alkylsulfoxy group, arylsulfoxy group, acylthio group, acyl Ruamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′- Diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfuric group Nyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group N-alkyl-N-arylsulfamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N- alkyl -N- arylsulfamoyl group, a dialkyl phosphono group -PO ₃ (alkyl) _2), diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group (-PO ₃ (Alkyl) (aryl)), a dialkylphosphonooxy group (—OPO ₃ (alk) yl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), cyano group, nitro group, substituted or unsubstituted aryl Groups, heteroaryl groups, alkenyl groups, and alkynyl groups, and more specific examples thereof include those described above for R ¹ .

In the general formula (I), X ₁ and X ₂ are bonded to each other, G. Brooker et al. , J .; Am. Chem. Soc., 73, 5326-5358 (1951) may constitute an acidic nucleus in merocyanine dyes.
Specific examples of the acidic nucleus include (a) 1 such as 1,3-indandione, 1,3-cyclohexanedione, 5,5-dimethylcyclohexanedione, 1,3-dioxane-4,6-dione and the like. , 3-dicarbonyl nucleus, (b), for example, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazolyl) -3- A pyrazolinone nucleus such as methyl-2-pyrazolin-5-one; (c) isoxazolinones such as 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one Nucleus, (d) an oxindole nucleus such as 1-alkyl-2,3-dihydro-2-oxindole, (e) 2,4 such as barbituric acid or 2-thiobarbituric acid A trioxohexahydropyrimidine nucleus and, for example, 1,3-diethylbarbituric acid, 1,3-diethyl-2-thiobarbituric acid, 1,3-dibutylbarbituric acid, 1,3-dibutyl-2-thiobarbituric Acid, 1,3-diphenylbarbituric acid, 1,3-diphenyl-2-thiobarbituric acid, 1,3-dimethoxycarbonylmethylbarbituric acid, 1,3-dimethoxycarbonylmethyl-2-thiobarbituric acid, etc. , 4, 6-trioxohexahydropyrimidine substituted with a nuclear nitrogen atom, (f) 3-methylrhodanine, 3-ethylrhodanine, 3-phenylrhodanine, 3-allylrhodanine, 3-benzylrhodanine, 3-carboxymethylrhodanine, 3-carboxyethylrhodanine, 3-methoxycarbonylmethyl rho 2-thio-2,4-thiazolidinedione nuclei such as rhodanine and its N-substituted derivatives, such as danin, 3-hydroxyethylrhodanine, 3-morpholinoethylrhodanine, (g) for example 2-ethyl-2- 2-thio-2,4-oxazolidinedione nuclei such as thio-2,4-oxazolidinedione, ie 2-thio-2,4- (3H, 4H) -oxazoledione nuclei, (h) for example 3 (2H) -Thianaphthenone nucleus such as thianaphthenone, 3 (2H) -thianaphthenone-1,1-dioxide, (i) 2-thio-2,5- such as 3-ethyl-2-thio-2,5-thiazolidinedione Thiazolidinedione nucleus, (j) for example 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione (K) a thiazolidinone nucleus such as 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 2-ethylmercapto-4-thizolidinone, 2-methylphenylamino-4-thiazolidinone, l) 4-thiazolinone nuclei such as 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one, (m) 2-imino-2-oxazoline-4- On nuclei, i.e. pseudohydantoin nuclei, (n) 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedione, etc. 4-imidazolidinedione nucleus (ie, hydantoin nucleus), (o), for example, 2-thio-2,4-imidazolidinedione, 3- 2-thio-2,4-imidazolidinedione nuclei such as til-2-thio-2,4-imidazolidinedione, 1,3-diethyl-2-thio-2,4-imidazolidinedione, ie, thiohydantoin nuclei (P) an imidazolin-5-one nucleus such as, for example, 2-propylmercapto-2-imidazolin-5-one; (q) a furan-5-one nucleus such as, for example, furan-5-one; 4, N-methyl-4-hydroxy-2 (1H) -pyridinone, N-methyl-4-hydroxy-2 (1H) -quinolinone, Nn-butyl-4-hydroxy-2 (1H) -quinolinone, etc. -Hydroxy-2 (1H) -pyridinone nucleus or 4-hydroxy-2 (1H) -quinolinone nucleus, (s) substituted or unsubstituted 4-hydroxy-2H- such as, for example, 4-hydroxycoumarin Pyran-2-one nuclei, (t) substituted or unsubstituted thioindoxyl nuclei such as, for example, 5-methylthioindoxyl. These acidic nuclei may further have a substituent.

Further, among the compounds represented by the general formula (I), any of the following general formulas (I-1) and (II) is particularly preferable as a merocyanine dye because it has high sensitivity and storage stability. The compound represented by these is mentioned.
In the general formula (I-1) and the general formula (I-2), ^{R 1} represents the same meaning as the general formula (I). R ² and R ³ each independently represents any one of a hydrogen atom, an aliphatic group, an aromatic group, and a heterocyclic group, and R ² and R ³ are bonded to other carbon atoms and substituted. You may form the 5-7 membered ring which may be. X ₁ and X ₂ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and X ₁ and X ₂ may be bonded to each other to form an acidic nucleus of the dye. W represents either an oxygen atom or a sulfur atom. Each Y independently represents a carbon atom or a heteroatom of any one of Groups 15 and 16 in the periodic table.

Specific examples of X and R ^{1 to} R ^{3 in} the general formula (I-1) and the general formula (I-2) are the same as those described for X and R ¹ in the general formula (I), respectively. Things.
As the 5- to 7-membered ring in which R ² and R ^{3 in} General Formula (I-1) and General Formula (I-2) may be bonded to each other and substituted with each other, specifically, Examples include thiophene ring, benzene ring, naphthalene ring, pyridine ring, quinoline ring, and azulene ring. Among these, a benzene ring and a naphthalene ring are preferable.
In the general formula (I-2), examples of the hetero atom of Group 15 and Group 16 in the periodic table represented by Y include a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, and selenium. An atom, a tellurium atom, etc. are mentioned.

Examples of preferable specific compounds represented by the general formula (I-1) include the following D1 to D28.
D1: benzo-1,3-dithiolidene-dibenzoylmethane D2: benzo-1,3-dithiolidene-cyanoacetophenone D3: benzo-1,3-dithiolidene-1-furylpropylketone D4: 5- (5-tert-butylbenzo -1,3-dithiolidene) -1,3-diethyl-2-thiobarbituric acid D5: 5- (naphtho [2,1-d] -1,3-dithiolidene) -1-butyl-3-phenyl-2-thiobarbitur Acid D6: 5- (5-methylbenzo-1,3-dithiolidene) -3-ethylrhodanine D7: 5- (naphth [1,2-d] -1,3-dithiolidene) -1,3-thiazolidine-4 -On-2-ylidene-benzoylmethane D8: 5-[(5-tert-butyl-benzo-1,3-dithiolidene) -ethylidene] -1,3-diethy 2-thiobarbituric acid D9: 4,5-dimethyl-1,3-dithiolidene-dibenzoylmethane D10: 5- (5-tert-butylbenzo-1,3-dithiolidene) -dithiophenoylmethane D11: 5- (furano [2,3-f] benzo-1,3-dithiolidene) -1,3-diethylthiobarbituric acid D12: 5-tert-butylbenzo-1,3-dithiolidene-acetophenone D13: 5-tert-butyl-benzo- 1,3-dithiolidene-1,3-indandione D14: 4- (5-tert-butyl-benzo-1,3-dithiolidene) -pyrazolidine-3,5-dione D15: 4- (5-tert-butyl- Benzo-1,3-dithiolidene) -2-phenyl-5-methyl-3-pyrazolone D16: 4- (5-tert-butyl Benzo-1,3-dithiolidene) -5-phenyl-3-isoxazolidone D17: 4- (5-tert-butyl-benzo-1,3-dithiolidene) -2-phenyl-5-oxazolidone D18: 3- (5 -Tert-butyl-benzo-1,3-dithiolidene) -1-methyl-tetrahydroquinoline-2,4-dione D19: 5- (4-phenyl-1,3-dithiolidene) -1,3-diethylthiobarbitur Acid D20: 3- (1,3-dithiolidene) -1-methyltetrahydroquinoline-2,4-dione D21: 5- (4,5-ditrifluoromethyl-1,3-dithiolidene) -1,3-diethylthio Barbituric acid D22: 3- (1,3-dithianylidene) -1-methyltetrahydroquinoline-2,4-dione D23: 3- (5-tert- Butyl-benzo-1,3-dithiolidene) -chroman-2,4-dione D24: 2- (5-tert-butyl-benzo-1,3-dithiolidene) -5-methylbenzothiolane-3-one D25: 3- (4-Methoxycarbonyl-1,3-dithiolidene) -1-methyltetrahydroquinoline-2,4-dione D26: 3- (5-tert-butyl-benzo-1,3-dithiolidene) -1-n- Butyltetrahydroquinoline-2,4-dione D27: 5- (4,5-dimethoxycarbonyl-1,3-dithiolidene) -1,3-diethylthiobarbituric acid D28: 3- (4,5-dicyano-1, 3-Dithiolidene) -1-methyltetrahydroquinoline-2,4-dione Among the D1 to D28, thiobarbituric acid, indandione, and tetrahi More preferred is a compound having any of the drokinoline-2,4-dione skeleton, D4: 5- (5-tert-butylbenzo-1,3-dithiolidene) -1,3-diethyl-2-thiobarbituric acid, D13: 5 -Tert-butyl-benzo-1,3-dithiolidene-1,3-indandione, D18: 3- (5-tert-butyl-benzo-1,3-dithiolidene) -1-methyl-tetrahydroquinoline-2,4 -Dione is particularly preferred.

Examples of preferred specific compounds represented by the general formula (I-2) include the following D31 to D52.
D31: 2- (1-Methylbenz-1,3-oxazolidene) -1,3-diethylthiobarbituric acid D32: 2- (1-methylbenz-1,3-oxazolidene) -1,3-diphenylthiobarbituric acid D33: 2- (1-methylbenzo-1,3-thiazolidene) -1,3-diethylthiobarbituric acid D34: 2- (1-methylbenzo-1,3-thiazolidene) -1,3-di-n-butyl Thiobarbituric acid D35: 2- (1-methylbenzo-1,3-thiazolidene) -1,3-diphenylthiobarbituric acid D36: 2- (1-ethylbenzo-1,3-thiazolidene) -1-allyl-3 -Ethylthiobarbituric acid D37: 2- (1-methylbenzo-1,3-thiazolidene) -1,3-dimethylbarbituric acid D38: 2- (1-methyl-5-meth) Cibenzo-1,3-thiazolidene) -1,3-diethylthiobarbituric acid D39: 2- (1-methyl-5-ethoxycarbonylbenzo-1,3-thiazolidene) -1,3-diethylthiobarbituric acid D40 : 2- (1-methyl-5,6-dimethoxybenzo-1,3-thiazolidene) thiobarbituric acid D41: 2- (1-methylbenzo-1,3-thiazolidene) -1-phenyl-3-n-butylthiobarbi Turic acid D42: 2- (1-methylbenzo-1,3-thiazolidene) -1-phenyl-3-p-methoxyphenylthiobarbituric acid D43: 2- (1-methyl-α-naphth-1,3-thiazolidene ) -1,3-diethylbarbituric acid D44: 2- (1-methyl-α-naphth-1,3-thiazolidene) -1,3-diethylthiobarbituric acid D4 : 2- (1-methyl-α-naphth-1,3-thiazolidene) -1,3-di-n-butylthiobarbituric acid D46: 2- (1-methyl-α-naphth-1,3-thiazolidene ) -1-phenyl-3-n-butylthiobarbituric acid D47: 2- (1-methyl-α-naphth-1,3-thiazolidene) -1-p-methoxyphenyl-3-phenylthiobarbituric acid D48 : 2- (1-methoxyethyl-α-naphth-1,3-thiazolidene) -1,3-diethylthiobarbituric acid D49: 2- (1-methyl-β-naphth-1,3-thiazolidene) -1 , 3-Di-n-butylthiobarbituric acid D50: 2- (1-methyl-β-naphth-1,3-thiazolidene) -1,3-di-n-butylbarbituric acid D51: 5- (1 -N-octylbenzo-1,3-thiazolyl ) -1,3-diethylthiobarbituric acid D52: 5- [2- (1-ethylbenzo-1,3-thiazolidene) methyl] -methylidene-3-hydroxyethylrhodanine Among the above D-31 to 52, D40: 2- (1-Methyl-5,6-dimethoxybenzo-1,3-thiazolidene) thiobarbituric acid, D48: 2- (1-methoxyethyl-α-naphth-1,3-thiazolidene) -1,3- Diethylthiobarbituric acid, D51: 5- (1-n-octylbenzo-1,3-thiazolidene) -1,3-diethylthiobarbituric acid is preferred.

-Other sensitizers-
Other sensitizers may be used in combination with the merocyanine compound. The other sensitizer is not particularly limited and may be appropriately selected from known sensitizers. Examples thereof include known polynuclear aromatics (eg, pyrene, perylene, triphenylene), and xanthenes. (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, Thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane), anthraquinones (eg, anthraquinone) , Square Riums (for example, squalium), acridones (for example, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone (for example, 2-chloro-10-butylacridone) Etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3 -(2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3, 3'-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxy Coumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5 7-dipropoxycoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, etc. And the like, and thioxanthone compounds (thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, etc.), and the like. , Aromatic ring And a compound in which a heterocyclic ring is condensed (condensed compound), and an amine compound substituted with any of at least two aromatic hydrocarbon rings and aromatic heterocyclic rings.

  Among the condensed ring compounds, hetero-fused ketone compounds (acridone compounds, thioxanthone compounds, coumarin compounds, etc.) and acridine compounds are more preferable. Among the hetero-fused ketone compounds, an acridone compound and a thioxanthone compound are particularly preferable.

  The amine compound substituted with any one of the at least two aromatic hydrocarbon rings and the aromatic heterocyclic ring is preferably a sensitizer having an absorption maximum with respect to light in a wavelength region of 330 to 450 nm, For example, a disubstituted aminobenzophenone compound, a disubstituted amino-benzene compound having a heterocyclic group as a substituent at a carbon atom at the para position relative to an amino group on the benzene ring, Disubstituted amino-benzene compounds having a substituent containing a sulfonylimino group at the carbon atom at the position, disubstituted amino-benzene compounds having a carbostyryl skeleton, and at least two aromatic rings on the nitrogen atom Examples thereof include compounds having a disubstituted amino-benzene as a partial structure, such as a compound having a bonded structure.

  Although there is no restriction | limiting in particular in content in the photosensitive composition solid content which match | combined the said merocyanine type compound and another sensitizer, For example, 0.01-4 mass% is preferable, 0.02-2 mass% Is more preferable, and 0.05-1 mass% is especially preferable.

-Oxime derivatives-
There is no restriction | limiting in particular as said oxime derivative, Although it can select suitably according to the objective, It is preferable that it is a compound which has an aromatic group at least, and the following general formula (I) and the following general formula (II) A compound having a partial structure represented by any of them is more preferable. Two or more oxime derivatives may be used in combination.
In the general formula (II) and the general formula (III), Ar represents either an aromatic group and a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² Represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ represent an aliphatic group, an aromatic group, And a heterocyclic group, and n represents an integer of 1 or more.

As Ar, either a phenyl group or a naphthyl group is preferable, and a naphthyl group is more preferable.
Y ¹ is preferably a hydrogen atom, an aliphatic group, or an aromatic group.
Y ² includes an aliphatic group, —CO— (aliphatic group), —CO— (aromatic group), —CO— (heterocyclic group), —CO ₂ — (aliphatic group), —CO _2. - (aromatic group), and -CO ₂ - is preferably any one of (heterocyclic group).
Y ³ and Y ⁴ are preferably either an aliphatic group or an aromatic group.

  The oxime derivative may be a compound in which a plurality of structures represented by the general formula (I) and the general formula (II) are bonded via a linking group.

  In the general formula (I) and the general formula (II), the aliphatic group represents an alkyl group, an alkenyl group, and an alkynyl group, each of which may have a substituent, and the aromatic group is Each represents an optionally substituted aryl group or heterocyclic (heterocyclic) group, and the monovalent substituent includes a halogen atom, an optionally substituted amino group, an alkoxycarbonyl group, It represents a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, each of which may have a substituent.

  The aliphatic group and the aromatic group are as described in the section “Merocyanine compound”. Examples of the monovalent substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, a thioether group, a silyl group, a nitro group, and a cyano group. An alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group which may have a hydrogen atom is preferred. More specific contents of these groups are also as already described in the section of “Merocyanine compounds”.

  Other specific examples of the oxime derivative include, for example, compounds disclosed in JP-A No. 2001-233842, JP-A No. 2004-534797, JP-A No. 2002-519732, and the following structural formula The compound etc. which are represented by these are mentioned.

In the structural _formulas, R represents _{n-C 3 H 7, n} -C 8 H 17, camphor, and one of the _{p-CH 3 C 6 H 4} .

In the above structural formula, R represents either nC ₃ H ₇ or p-CH ₃ C ₆ H ₄ .

Further, specific examples of the oxime derivative include the following acyloxime derivatives of OE1 to OE37.
OE1: 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-benzoate OE2: 1- (4-methylsulfanylphenyl) -butane-1,2-dione-2- Oxime-O-benzoate OE3: 1- (3,4-dimethoxyphenyl) -butane-1,2-dione-2-oxime-O-acetate OE4: 1- (3,4-dimethoxyphenyl) -butane-1 , 2-Dione-2-oxime-O-benzoate OE5: 1- (4-methylsulfanylphenyl) -3-phenylethane-1,2-dione 2-oxime-O-acetate OE6: 1- (4-methoxy Phenyl) -butane-1,2-dione-2-oxime-O-acetate OE7: 1- (4-methoxyphenyl) -butane-1,2-dione-2- Oxime-O-benzoate OE8: 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-acetate OE9: 1- (4-methylsulfanylphenyl) -butane-1,2 -Dione-2-oxime-O-2,4,6-trimethylbenzoate OE10: 1- (4-methylsulfanylphenyl) -propane-1,2-dione-2-oxime-O-benzoate OE11: 1- (4-Methylsulfanylphenyl) -octane-1,2-dione-2-oxime-O-acetate OE12: 1- (4-methylsulfanylphenyl) -octane-1,2-dione-2-oxime-O-benzo Art OE13: 1- (4-methylsulfanylphenyl) -4,6,6-trimethylhexane-1,2-dione- -Oxime-O-benzoate OE14: 1- (4-methylsulfanylphenyl) -4,6,6-trimethylhexane-1,2-dione 2-oxime-O-acetate OE15: 1- (4-methylsulfanylphenyl) ) -Octane-1,2-dione-2-oxime-Op-methylbenzoate OE16: 1- (4-methylsulfanylphenyl) -octane-1,2-dione-2-oxime-Op-chloro Benzoate OE17: 1- (4-methylsulfanylphenyl) -octane-1,2-dione-2-oxime-Om-methylbenzoate OE18: 1- (4-methylsulfanylphenyl) -butan-1-one oxime -O-acetate OE19: 1- (4-phenylsulfanylphenyl) -butan-1-oneoxy -O-acetate OE20: hydroxyimino- (4-methylsulfanylphenyl) -acetic acid ethyl ester-O-acetate OE21: hydroxyimino- (4-methylsulfanylphenyl) -acetic acid ethyl ester-O-benzoate OE22: hydroxyimino- (3,4-Dimethoxyphenyl) -acetic acid ethyl ester-O-acetate OE23: ethyl 2- (3,4-dimethoxyphenyl) -2-benzoyloxyimino-benzoate OE24: 1- (4-methylsulfanylphenyl)- Butan-1-one oxime-O-benzoate OE25: 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate OE26: 1- (4-phenylsulfanylphenyl) -octane-1-one oxime O-benzoate OE27: 2,2,2-trifluoro-1- (4-methylsulfanylphenyl) -ethanone oxime-O-acetate OE28: 1- (4-phenylsulfanylphenyl) -ethanone oxime-O— Acetate OE29: 1- (4-phenylsulfanylphenyl) -decan-1-one oxime-O-pentafluorobenzoate OE30: 1- (4-methylsulfanylphenyl) -propan-1-one oxime-O-acetate OE31: 1- (4-Methylsulfanylphenyl) -ethanone oxime-O-acetate OE32: 1,9-bis- (4-methylsulfanylphenyl) -nonane-1,2,8,9-tetraone-2,8-dioximedi (O -Acetate)
OE33: 1,9-bis- (4-methylsulfanylphenyl) -nonane-1,9-butanedioxime di (O-acetate)
OE34: 1- {4- [4- (2-acetoxyiminobutyryl) -phenylsulfanyl] -phenyl} -butane-1.2-dione-2-oxime-O-acetate OE35: 1- {4- [4 -(2-Benzoxyiminobutyryl) -phenylsulfanyl] -phenyl} -butane-1.2-dione-2-oxime-O-benzoate OE36: 1- {4- [4- (2-acetoxyiminobutyl) -Phenylsulfanyl] -phenyl} -butan-1-one oxime-O-acetate OE37: 2,4-diethylthioxanthen-9-one oxime-O-benzoate

  Among the specific examples of the oxime derivative, for example, an alkylcarbonyloxyimino group having 2 to 8 carbon atoms such as an acetyloxyimino group, a propionyloxyimino group, a butyryloxyimino group, an octanoyloxyimino group, An oxime derivative containing an acyloxyimino group such as an arylcarbonyloxyimino group having 7 to 12 carbon atoms such as a benzoyloxyimino group or a naphthoyloxyimino group is preferred. Among these, an oxime derivative containing an acetyloxyimino group or a benzoyloxyimino group is particularly preferable.

  The content ratio between the merocyanine compound and the oxime derivative is, for example, preferably 0.01: 1 to 10: 1, more preferably 0.02: 1 to 5: 1, and 0.03: 1 to 1: 1 is more preferable, and 0.05: 1 to 1: 1 is particularly preferable.

-Other photopolymerization initiators-
The oxime derivative may be used in combination with other photopolymerization initiators that are appropriately selected from known photopolymerization initiators. The photopolymerization initiator that may be used in combination is preferably, for example, one having photosensitivity to visible light from the ultraviolet region, and an activator that generates an active radical by generating some action with a photoexcited sensitizer. It may also be an initiator that initiates cationic polymerization depending on the type of monomer.
The photopolymerization initiator that may be used in combination preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 to 800 nm. The wavelength is more preferably 330 to 500 nm.

  Examples of the photopolymerization initiator that may be used in combination include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thios. Compounds, ketone compounds (benzylmethyl ketal compounds, α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, etc.), aromatic onium salts, metallocenes, and the like. Among these, a phosphine oxide compound, a ketone compound, and a hexaarylbiimidazole compound are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the printed wiring board forming substrate.

  Although there is no restriction | limiting in particular in content in the photosensitive composition solid content which match | combined the said oxime derivative and other photoinitiators, For example, 0.1-20 mass% is preferable, 0.3-15 mass% Is more preferable, and 0.5 to 10% by mass is particularly preferable.

<Hydrogen donor compound>
The photopolymerization initiating compound may further contain a hydrogen donor compound. In some cases, the sensitivity can be further increased by adding the hydrogen donor compound.
The hydrogen donor compound is a compound that can be excited by active energy rays and can donate hydrogen (electrons) by interacting with the merocyanine compound and the oxime derivative. If it is a compound of these, there will be no restriction | limiting in particular, According to the objective, it can select suitably, For example, a mercapto compound, an amino acid, a phosphorus compound, an active hydrogen containing hydrocarbon compound, a borate compound etc. are mentioned.
Examples of the mercapto compound include mercapto compounds represented by the following general formulas (IV-1a) and (IV-1b), thioether compounds represented by the following general formula (IV-2), and the following general formula (IV- 3), a compound represented by the following general formula (IV-4), and the like.
In the general formula (IV-1a) and the general formula (IV-1b), wherein R ²¹ represents any of an alkyl group and an aryl group, R ²² represents a hydrogen atom or an alkyl group.
The alkyl group for R ²¹ and R ²² is preferably an alkyl group having 1 to 4 carbon atoms. In addition, the aryl group of R ²¹ is preferably one having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group, and the substituted aryl group includes a halogen atom such as a chlorine atom, a methyl group as described above, and the like. And those substituted with an alkoxy group such as a methoxy group or an ethoxy group. R ²¹ and R ²² may be an atomic group necessary for bonding to complete a heterocyclic ring which may have a condensed ring together with a carbon atom or a nitrogen atom. Examples of the condensed ring include a benzene ring.
However, the general formula ^{(IV-2), R 23} is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group and an alkenyl ^{group,, R 24} and ^{R 25} are the same meaning as ^{R 23,} Alternatively, it represents a group having a positive Hammett σ _p value.
In the general formula (IV-3), R ²⁶ represents any one of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, and Y ¹ -CS-S-. Y ¹ represents —OR ²⁹ or —NR ³⁰ R ³¹ . R ²⁹ , R ³⁰ , and R ³¹ are each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, an alkanoyl group, an alkenoyl group, or a benzoyl group. R ³⁰ and R ³¹ may combine to form a ring.
In the above (IV-4), Z represents R ³² —SO ₂ —, R ³² —O—SO ₂ —, R ³² represents the same meaning as R ²⁹ , R ³⁰ , and R ³¹ , and R ²⁷ and R ²⁸ represents the same meaning as R ²³ , R ³² , and Z, or represents a hydrogen atom, a group having a positive Hammett σ _p value, —OR ²³ , or —SR ²³ .

  Examples of the compound represented by the general formula (IV-1a) or (IV-1b) include thioformamide, thioacetamide, N-methylthioformamide, N-methylthioacetamide, N-phenylthiopropionic acid amide, N-phenylthiocaproic acid amide, N-o-chloro-phenylthioacetamide, N-o-chlorophenylthiocaproic acid amide, Np-tolylthiocaproic acid amide, Nm-methoxyphenylthioacetamide, Nm -Methoxyphenylthiopropionic acid amide, Np-ethoxyphenylthioacetamide, Np-ethoxyphenylthiopropionic acid amide, No-methoxyphenylthiocaproic acid amide, 2-mercapto-4,5-dihydro- 2-thiazole, 2-mercapto-4-methyl- 4,5-dihydro-2-thiazole, 2-mercapto-5-methyl-4,5-dihydro-2-thiazole, 2-mercapto-4,4-dimethyl-4,5-dihydro-2-thiazole, 2- Mercapto-5,5-dimethyl-4,5-dihydro-2-thiazole, 2-mercapto-4,5-dihydro-2-oxazole, 2-mercapto-4-methyl-4,5-dihydro-2-oxazole, 2-mercapto-4,4-dimethyl-4,5-dihydro-2-oxazole, 1-methyl-2-mercapto-1,3-imidazole, 2-mercapto-4,5-dihydro-1,3-thiazine, 2-mercapto-6-methyl-4,5-dihydro-1,3-thiazine, 2-mercapto-4,5-dihydro-1,3-oxazine, 2-mercapto-tetrahydro 1-pyridine, 1- [p- (n-hexylaminocarbonyl) phenyl} -2-mercaptoimidazole, 1- (p-tolyl) -2-mercapto-4,5,6,7-tetrahydro-1,3- Benzimidazole, 2-mercapto-5-methylthio-1,3,4-oxadiazole, 2-mercapto-3,4,5,6-tetrahydro-1-azepine, 2-mercapto-1,3-benzoxazole, 3-mercapto-5-chloro-1,2-benzisoxazole, 2-mercapto-1,3-benzimidazole, 2-mercapto-6-methoxy-1,3-benzimidazole, 1-methyl-2-mercapto- 1,3-benzimidazole, 2-mercapto-6-methyl-1,3-benzimidazole, 2-mercapto-5,6-dimethyl- , 3-benzimidazole, 2-mercapto-6-methoxy-1,3-benzimidazole, 2-mercapto-5-caproylamino-1,3-benzimidazole, 1- (n-propyl) -2-mercapto- 1,3-benzimidazole, 1-isopropyl-2-mercapto-1,3-benzimidazole, 2-mercapto-6-chloro-1,3-benzimidazole, 1- (n-heptyl) -2-mercapto-1 , 3-benzimidazole, 1- (n-hexyl) -2-mercapto-5-chloro-1,3-benzimidazole, 2-mercapto-6-chloro-1,3-benzimidazole, 1- (n-octyl) ) -2-mercapto-5-methoxy-1,3-benzimidazole, 1- (n-hexyl) -2-mercapto-5-ethoxyca Rubonyl-1,3-benzimidazole, 1- (2-methoxyethyl) -2-mercapto-1,3-benzimidazole, 3-mercapto-6-methyl-1,2-benzothiazole, 1-phenyl-2- Mercapto-1,3-benzimidazole, 1-phenyl-2-mercapto-5-methylsulfonyl-1,3-benzimidazole, 1- (p-sulfonatomethylphenyl) -2-mercapto-1,3-benzimidazole Sodium salt, 3-mercapto-1,2-benzothiazole, 3-mercapto-6-caproylamino-1,2-benzothiazole, 3-mercapto-6-chloro-1,2-benzothiazole, 3-mercapto -6-methyl-1,2-benzothiazole, 2-mercapto-naphtho [2,1] -1,3-imidazole 1- (n-butyl) -2-mercapto-naphtho [2,1] -1,3-imidazole, 1- (n-octyl) -2-mercapto-imidazo [4,5-b] pyridine, 1- ( n-octyl) -2-mercapto-imidazo [4,5-b] pyrazine, 1- (n-butyl) -2-mercapto-1,3-imidazo [4,5-b] quinoxaline, 1- (n- (Hexyl) -2-mercapto-6-chloro-1,3-imidazo [4,5-b] quinoxaline, 1,5-diethyl-3-mercapto-1,2,4-triazole, 4- (n-hexyl) -3-mercapto-1,2,4-triazole, 4-phenyl-3-mercapto-1,2,4-triazole, 4-phenyl-3-mercapto-5-methylthio-1,2,4-triazole, 1 -(N-hexyl)- -Mercaptotetrazole, 1- (n-octyl) -5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole, 2- (n-hexyl) -3-mercapto-1,2,4-oxadiazine, 2-phenyl- Examples include 3-mercapto-5-methyl-1,2,4-thiadiazine, 3-phenyl-4-mercapto-6-phenyl-1,2,3,6-tetrahydro-1,3,5-thiadiazine. Among these, 1-phenyl-2-mercapto-1,3-benzimidazole is preferable.

  Examples of the thioether compound represented by the general formula (IV-2) include di-n-butyl sulfide, di-n-octyl sulfide, triphenylthiomethane, diphenylthiomethane, phenylmethyl sulfide, and p-methylthiobenzoate. Acid, p-methylthiobenzaldehyde, p-methylthiobenzonitrile, 1-phenylthioethylmethyl ketone, 1-phenylthiopropionitrile, 1-chloromethylphenyl sulfide, 1,3,5-trithiane, 2-methyl-4- Examples include methoxyphenyl methyl sulfide, thiochroman, 4-oxothiochroman and the like.

  Examples of the compound represented by the general formula (IV-3) include O-isobutyl S-n-butyl dithiocarbonate, O-isobutyl S-benzyl dithiocarbonate, n-butyl diethyldithiocarbamate, benzyl diethyldithiocarbamate, N, N, N ′, N′-tetraethylthiuram disulfide, N, N-diethyl-N ′, N′-di-n-butylthiuram disulfide, 1,2,3-tri (diethyldithiocarbamoylthio) propane, etc. Is mentioned.

  Examples of the compound represented by the general formula (IV-4) include di-n-butylsulfone, ethyl p-tolylsulfone, p-tolylmethylthiomethylsulfone, acetylmethyl p-tolylsulfone, and bis (p-toluene). Sulfonyl) methane, cyanomethyl p-tolylsulfone, n-butyl p-toluenesulfonate, ethyl methanesulfonate, phenyl acetylmethanesulfonate, diphenylmethanedisulfonate, phenylsulfolane 3-sulfolene cyanomethanesulfonate, and the like.

Examples of the amino acid include N-phenylamino acid derivatives represented by the following general formula (V).
In the general formula (V), X ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, a nitro group, an amino group, a halogen It represents any of an atom, an acyl group, and a carboxyl group, and n is an integer of 1 to 5. R ³³ represents any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group, and an aralkyl group, and R ³⁴ represents a hydrogen atom, hydroxy group Represents a group, a methylthio group, an alkyl group having 1 to 4 carbon atoms that may be substituted with a -COOR ³⁵ group, or a benzyl group, and R ³³ and R ³⁴ together with a nitrogen atom and an adjacent carbon atom A 6-membered ring may be formed. R ³⁵ represents either an alkyl group having 1 to 4 carbon atoms or a benzyl group.

  The N-phenylamino acid derivative represented by the general formula (V) is not particularly limited, and examples thereof include N-phenylglycine, N- (p-acetylphenyl) glycine, and N- (m-trifluoromethylphenyl). ) Glycine, N- (m-acetylphenyl) glycine, N- (p-trifluoromethylphenyl) glycine, N-phenylalanine, N-phenylserine, N-phenylthreonine, N-phenylcysteine, N-phenylproline, N -Phenylglutamic acid and the like. The glycine derivative may be a bipolar ion compound containing an amino cation and a carboxylic acid anion in the structure. Among these, N-phenylglycine is particularly preferable.

Examples of the phosphorus compound include phosphonic acid diesters represented by the following general formula (VI-1), phosphorous acid triesters represented by the following general formula (VI-2), and the like.
However, if in the general formula (VI-1), R ³⁶ represents an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a alkenyl group, R ³⁷ represents the same meaning as R ³⁶ , Represents a group having a positive Hammett σ _p value.
In the general formula (VI-2), R ³⁸ represents any of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and an alkenyl group, and R ³⁹ and R ⁴⁰ have the same meaning as R ^38. Or a group having a positive Hammett σ _p value.

  Examples of the phosphonic acid diester represented by the general formula (VI-1) include dimethyl phosphonate, diethyl phosphonate, di (n-butyl) phosphonate, di (2-ethylhexyl) phosphonate, and ethyl methyl phosphonate. Phosphonate diphenyl, phosphonate ethylphenyl, phosphonate di (p-dimethylaminophenyl), phosphonate di (p-cyanophenyl), phosphonate di (p-acetylphenyl), phosphonate di (p-methoxyphenyl) Phosphonate di (p-tolyl), phosphonate di (o-methoxyphenyl), phosphonate di (o-chlorophenyl), phosphonate di (m-bromophenyl), phosphonate (o-chlorophenyl) (p-methoxy) Phenyl), methylphenyl phosphonate, β-naphthylphenyl phosphonate, ethyl phosphonate Lene, propylene diphosphonate, trimethylene phosphonate, oxydiethylene phosphonate, and the like.

  Examples of the phosphorous acid triester represented by the general formula (VI-2) include diethyl phosphite, di-n-butyl phosphite, di (2-ethylhexyl) phosphite, ethyl methyl phosphite, Triethyl phosphite, triphenyl phosphite, diphenyl phosphite, tri (p-dimethylaminophenyl) phosphite, tri (p-cyanophenyl) phosphite, di (p-cyanophenyl) phosphite, Tri (p-methoxyphenyl) phosphite, di (p-methoxyphenyl) phosphite, tri (o-chlorophenyl) phosphite, di (o-chlorophenyl) phosphite, tri (m-bromophosphite) Phenyl), phenyldimethyl phosphite, diphenylmethyl phosphite, phenylmethyl phosphite, dimethyl phosphite (α-naphthyl), ethylene methyl phosphite, ethylene phosphite Nyl, orthophosphoric acid orthoformate, triethylene phosphite, and the like.

Examples of the active hydrogen-containing hydrocarbon compound include cyclic β-dicarbonyl compounds represented by the following general formula (VII).
In the general formula (VII), R ⁴¹ is a substituted or unsubstituted alkyl group, and represents one of the aralkyl group, G is a divalent organic group, a hetero atom in the chain group It may contain and may have a substituent in at least any one of carbon and a hetero atom.

  Examples of the cyclic β-dicarbonyl compound represented by the general formula (VII) include 2,4-diethyl-1,3-cyclobutanedione, 2-methyl-1,3-cycloheptanedione, 5-methyl- 2-thiobarbituric acid, 3-ethyltetronic acid, 2,4-dimethyl-3-oxo-5-hydroxy-5-methoxypentenoic acid δ-lactone, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl -5-ethylbarbituric acid, 2-methyl-1,3-cyclopentanedione, 5-methylbarbituric acid, 1,5-dimethylbarbituric acid, 2-methyldimedone, 2-methyl-1,3-indandione 1,3-dimethyl-5-benzylbarbituric acid, bis- [5- (1,3-dimethylbarbituryl))-methane, 1,5-diphenyl-3- [2- (pheny Thio) ethyl] -2,4-pyrrolidinedione, 1-phenyl-3,5-diketo -4-n-butyl - tetrahydrophthalic pyrazole, and the like.

Examples of the borate compound include organic boron compounds represented by the following general formula (VIII).
However, R ^<42 > in the said general formula (VIII) represents an aliphatic group. R ⁴³ , R ⁴⁴ , and R ⁴⁵ each independently represents any of an aliphatic group, an aromatic group, a heterocyclic group, and —SiR ⁴⁶ R ⁴⁷ R ⁴⁸ . R ⁴⁶ , R ⁴⁷ , and R ⁴⁸ each independently represent either an aliphatic group or an aromatic group. Y ⁺ represents a group that forms a cation.

  Examples of the organoboron compound represented by the general formula (VIII) include tetra (n-butyl) ammonium-n-butyltriphenylborate, tetraethylammonium diphenylmethylsilyltriphenylborate, tetramethylammonium-diphenylmethyl. Silyltriphenylborate, tetra (n-hexyl) ammonium-n-hexyltriphenylborate, tetra (n-butyl) ammonium-n-butyldi (p-fluorophenyl) phenylborate, tetra (n-butyl) ammonium -N-butyltri (p-fluorophenyl) borate, tetra (n-butyl) ammonium-n-hexyltri (p-chlorophenyl) borate, tetra (n-butyl) ammonium-n-hexyldi (p-chlorophenyl) phenyl , Tetra (n-butyl) ammonium-di (n-hexyl) di (m-fluorophenyl) borate, tetra (n-butyl) ammonium-n-hexyltri (2-methyl-5-fluorophenyl) borate, tetra ( n-butyl) ammonium-methyldimesitylphenylborate and the like.

  Among these hydrogen donors, 1-phenyl-2-mercapto-1,3-benzimidazole, N-phenylglycine, 4,4′-bis (diethylamino) benzophenone, leucocrystal violet, 2-dimethylamino-2- Methyl-1- (4-methoxyphenyl) propan-1-one-O-allyloxime and tetra (n-butyl) ammonium-n-butyltriphenylborate are particularly preferred.

  The blending amount of the hydrogen donor compound in the photopolymerization initiation compound is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, and 0.1 to 5.0% by mass. % Is particularly preferred.

<Thermal crosslinking agent>
There is no restriction | limiting in particular as said heat-crosslinking agent, According to the objective, it can select suitably, For example, an epoxy resin, a polyfunctional oxetane compound, etc. are mentioned suitably.
The epoxy resin and the polyfunctional oxetane compound are not particularly limited and can be appropriately selected according to the purpose. For example, the film strength after curing of the photosensitive layer formed using the photosensitive composition is improved. Therefore, an epoxy resin compound having at least two oxirane groups in one molecule, an oxetane compound having at least two oxetanyl groups in one molecule, and the like can be used within a range that does not adversely affect developability.

  There is no restriction | limiting in particular as said epoxy resin, According to the objective, it can select suitably, For example, a bixylenol type or a biphenol type epoxy resin ("YX4000; Japan Epoxy Resin Co., Ltd." etc.) or mixtures thereof, isocyania Heterocyclic epoxy resins having a nurate skeleton ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol F type Epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A Borac type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin (“ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, “HP-4032” , EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.), epoxy resins having a dicyclopentadiene skeleton (“HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.”), glycidyl Examples thereof include a methacrylate copolymer epoxy resin (“CP-50S, CP-50M; manufactured by NOF Corporation”), a copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, and the like. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

  The polyfunctional oxetane compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3 -Oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3 -Methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers thereof or In addition to polyfunctional oxetanes such as copolymers, oxetane groups and Novo And ether compounds with hydroxyl groups such as poly (p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, silsesquioxanes, etc., and oxetane A copolymer of an unsaturated monomer having a ring and an alkyl (meth) acrylate is also included.

  There is no restriction | limiting in particular as solid content in solid content of the said photosensitive composition solution of the said epoxy resin or a polyfunctional oxetane compound, According to the objective, it can select suitably, For example, 2-50 mass% Is preferable, and 3-30 mass% is more preferable. If the solid content is less than 2% by mass, the hygroscopicity of the cured film is increased, resulting in deterioration of insulation, or solder heat resistance and electroless plating resistance may be reduced. If it exceeds mass%, the developability may deteriorate and the exposure sensitivity may decrease, which is not preferable.

-Other thermal crosslinking agents-
The other thermal crosslinking agent can be added separately from the epoxy resin and the polyfunctional oxetane compound. The thermal crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. For example, a polyisocyanate compound described in JP-A-5-9407 can be used. As the polyisocyanate compound, It may be derived from an aliphatic, cycloaliphatic or aromatic group-substituted aliphatic compound containing at least two isocyanate groups.
Specifically, a mixture of 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, bis (4 -Isocyanate-phenyl) methane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc .; bifunctional isocyanate; An adduct of the polyfunctional alcohol with an alkylene oxide adduct and the bifunctional isocyanate; hexamethylene diisocyanate, hexamethylene-1,6-diisocyanate Over preparative and cyclic trimer of such derivatives, and the like.

Furthermore, for the purpose of improving the preservability of the photosensitive composition or photosensitive layer (hereinafter also referred to as photosensitive solder resist film), a blocking agent is reacted with the isocyanate group of the polyisocyanate and its derivatives. You may use the compound obtained by this.
The isocyanate group blocking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols such as isopropanol and tert-butanol; lactams such as ε-caprolactam; phenol, cresol, p- phenols such as tert-butylphenol, p-sec-butylphenol, p-sec-amylphenol, p-octylphenol and p-nonylphenol; heterocyclic hydroxyl compounds such as 3-hydroxypyridine and 8-hydroxyquinoline; dialkylmalonate; Active methylene compounds such as methyl ethyl ketoxime, acetylacetone, alkyl acetoacetate oxime, acetoxime, and cyclohexanone oxime; In addition to these, compounds having at least one polymerizable double bond and at least one blocked isocyanate group in the molecule described in JP-A-6-295060 can be used.

  Moreover, an aldehyde condensation product, a resin precursor, etc. can be used. Specifically, N, N′-dimethylolurea, N, N′-dimethylolmalonamide, N, N′-dimethylolsuccinimide, trimethylolmelamine, tetramethylolmelamine, hexamethylolmelamine, 1,3-N, N'-dimethylol terephthalamide, 2,4,6-trimethylolphenol, 2,6-dimethylol-4-methyliloanisole, 1,3-dimethylol-4,6-diisopropylbenzene and the like can be mentioned. Instead of these methylol compounds, the corresponding ethyl or butyl ether, or acetic acid or propionic acid ester may be used. Moreover, you may use the hexamethylated methylol melamine which consists of a formaldehyde condensation product of a melamine and urea, the butyl ether of a melamine and a formaldehyde condensation product, etc.

<Thermal crosslinking accelerator>
The thermal crosslinking accelerator has a function of promoting thermal crosslinking of the epoxy resin compound or the polyfunctional oxetane compound, and is preferably added to the photosensitive resin.
The thermal crosslinking accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy. Amine compounds such as -N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; quaternary ammonium salt compounds such as triethylbenzylammonium chloride; blocked isocyanate compounds such as dimethylamine; imidazole and 2-methyl Imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl Imidazole Any imidazole derivatives bicyclic amidine compounds and salts thereof; phosphorus compounds such as triphenylphosphine; guanamine compounds such as melamine, guanamine, acetoguanamine, benzoguanamine; 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2 -Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives such as adducts, boron trifluoride-amine complex, organic hydrazide cumulative, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) , Benzo Aromatic acid anhydrides such as enone tetracarboxylic acid anhydride, aliphatic acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride, polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac, etc. Etc. can be used. These may be used alone or in combination of two or more. The epoxy resin compound or the polyfunctional oxetane compound is a curing catalyst, or any compound capable of promoting the thermal crosslinking other than the above as long as it can promote the reaction of these with a carboxyl group. May be used.
The solid content in the solid content of the photosensitive composition solution of the epoxy resin, the polyfunctional oxetane compound, and a compound capable of promoting thermal crosslinking between the epoxy resin and the carboxylic acid is usually 0.01 to 20% by mass. It is.

<Binder>
The binder in the photosensitive composition is preferably, for example, swellable in an alkaline aqueous solution, and more preferably soluble in an alkaline aqueous solution. Moreover, it is preferable to have crosslinkability.
The alkali-soluble refers to the property that the photosensitive composition containing it is dissolved by an alkaline developer, and specifically, it should be soluble to the extent that the intended development processing is performed. The alkaline developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal hydroxides such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, hydroxyethylamine, triethylamine Or an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide or a mixture thereof with a miscible organic solvent. pH is 8-14 and 0.01-10 mass% aqueous solution of these alkali agents is preferable. Among these alkaline developers, in the printed wiring board industry, 0.2 to 2% by mass sodium carbonate aqueous solution is generally used, and 1% by mass sodium carbonate aqueous solution is the most common.
An example of the development method is as follows. The surface of the copper-clad laminate is prepared by pressure-bonding the photosensitive layer with a laminator while removing the protective film of the photosensitive film on the surface of the dried copper-clad laminate. A laminate comprising a photosensitive layer and a support film is prepared. The pressure bonding conditions are a laminate temperature of 70 ° C., a pressure roll temperature of 105 ° C., a pressure roll pressure of 3 kg / cm ^2, and a pressure bonding speed of 1.2 m / min.
The support film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed at a pressure of 0.1 MPa over the entire surface of the photosensitive layer on the copper-clad laminate. If the photosensitive layer on the copper clad laminate is removed after spraying for at least 60 seconds, it will be developed.
Such an alkali-soluble resin can be suitably selected from those showing a solubility of 1% by mass or more in a 1% by mass sodium carbonate aqueous solution at 30 ° C., for example.
The crosslinkability refers to the property of changing a linear polymer molecule into a network having a three-dimensional network structure by a photochemical reaction. Specifically, the action of free radicals generated by the photolysis of a photopolymerization initiator. Means a polymer that can be reticulated by polymerization reaction.

The binder (hereinafter also referred to as alkali-soluble crosslinkable resin) is a resin soluble in a 1% aqueous sodium carbonate solution (pH = 10) containing an alkali-soluble group and a crosslinkable group involved in photopolymerization in the molecule. is there.
There is no restriction | limiting in particular as said alkali-soluble crosslinking resin, According to the objective, it can select suitably, For example, a vinyl polymer type alkali-soluble crosslinking resin, an epoxy resin ester type alkali-soluble crosslinking resin, etc. are mentioned.

-Vinyl polymer type alkali-soluble crosslinkable resin-
The vinyl polymer type alkali-soluble crosslinkable resin is classified into the following types (A-1), (A-2) and (A-3), and is selected from at least one of the types.
Type (A-1): produced by reaction of (a) a carboxyl group-containing copolymer resin and (b) an epoxy group-containing unsaturated compound.
Type (A-2): (c) An epoxy group-containing copolymer resin and (d) a carboxyl group-containing unsaturated compound are subjected to an addition reaction, and (e) a polybasic acid anhydride is converted into a hydroxyl group of the resulting product. Produced by addition reaction.
Type (A-3): produced by addition reaction of (f) a copolymer resin containing an acid anhydride group and (g) a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule. The

-Type (A-1)-
The (a) carboxyl group-containing copolymer resin used for the production of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-1) is one unsaturated group and at least one carboxyl group in one molecule. Alternatively, it is obtained by copolymerizing a compound having an acid anhydride group with at least one of (meth) acrylic acid ester and styrenes.

  The compound (a) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule having the carboxyl group-containing copolymer resin as a structural unit is (meth) acrylic acid, Include those containing two or more carboxyl groups in the molecule, such as maleic acid and itaconic acid. Also included are maleic acid, itaconic acid monoesters, or monoamides. Moreover, the half ester compound which is a reaction product of a hydroxyl group containing (meth) acrylate and a saturated or unsaturated dibasic acid anhydride is mentioned. These half ester compounds can be obtained by reacting a hydroxyl group-containing (meth) acrylate with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio.

  Examples of the hydroxyl group-containing acrylate used in the synthesis of the half ester compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and trimethylolpropane. Examples include di (meth) acrylate, pendaerythritol tri (meth) acrylate, diventaerythritol penta (meth) acrylate, and the like.

Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyl nadrahydrophthalic anhydride, ethyl tetrahydro Examples thereof include phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like. Of these, (meth) acrylic acid is preferred.
These compounds having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid ester that constitutes the structural unit of the carboxyl group-containing copolymer resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meta ) Acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate , Β-phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meta ) Acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of the styrenes constituting the structural unit of the carboxyl group-containing copolymer resin (a) include, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, Butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, α-methyl Examples include styrene.
The (a) carboxyl group-containing copolymer resin is composed of a compound having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule, a (meth) acrylic acid ester monomer, and styrene. It is obtained by copolymerization by a usual copolymerization method with at least one of the above classes, for example, a solution polymerization method.
In addition, (a) maleic acid monoester / styrene copolymers, maleic acid monoamide / styrene copolymers, itaconic acid monoester / styrene copolymers, and itacon included in the carboxyl group-containing copolymer resin. In the case of acid monoamide / styrene copolymers, obtain by polymer reaction of maleic anhydride / styrene copolymers or itaconic anhydride / styrene copolymers with alcohols or primary or secondary amines, respectively. Can do.

Examples of the alcohols used for the polymer reaction with the maleic anhydride include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, hexanol, and cyclohexanol. Preferable examples include methoxyethanol, ethoxyethanol, methoxypropanol, and ethoxypropanol.
Examples of the primary amines include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, and 6-phenyl-1-hexylamine. , Α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2- Chlorobenzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- (3-Chlorophenyl) ethyl Amine, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, isopropylamine, n -Propylamine, n-butylamine, tert-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, phenylamine, 1 -Naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3- Preferable examples include isopropoxypropylamine.
Further, examples of the secondary amines preferably include dimethylamine, diethylamine, methylethylamine, methylpropylamine, diethylamine, ethylpropylamine, dipropylamine, dibutylamine, N, N-methylbenzylamine and the like. Can do.

-(B) Epoxy group-containing unsaturated compound-
The (b) epoxy group-containing unsaturated compound used for the production of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-1) is one radical polymerizable unsaturated group and epoxy group in one molecule. And compounds represented by the following general formulas (IX-1) to (IX-14) can be used.

However, in the general formula (IX-1) ~ (IX -14), R 49 is either a hydrogen atom or a methyl ^{group, R 50} is an alkylene group having 1 to 10 carbon ^{atoms, R 51} is 1 to carbon atoms 10 hydrocarbon groups, p represents 0 or the integer of 1-10.
These (b) epoxy group-containing unsaturated compounds may be used alone or in a combination of two or more. Among these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.

-Type (A-2)-
The epoxy group-containing copolymer resin (c) used for the production of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-2) is a non-reactive (meth) epoxy group-containing monomer and other epoxy groups. It can be obtained by copolymerization with acrylic esters and / or styrenes.
As the epoxy group-containing monomer, the compounds described above in the description of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-1) are preferably used.
At least one of the (meth) acrylic acid ester and styrenes that are non-reactive with the epoxy group is a carboxyl group, an alcoholic hydroxyl group, among the above-described alkali-soluble crosslinkable resins of the type (A-1), Those not containing a phenolic hydroxyl group, amino group, etc. are preferably used.
The production method is obtained by copolymerizing an epoxy group-containing monomer, a non-reactive (meth) acrylic acid ester and styrenes with a conventional method such as a solution polymerization method.
Here, the molar ratio of the epoxy group-containing monomer and the other epoxy group and non-reactive (meth) acrylic ester and / or styrenes is preferably 60:40 to 20:80. If the amount of the epoxy group-containing monomer is too small and the molar ratio is larger than 20:80, the amount of addition of the next unsaturated carboxylic acid and polybasic acid anhydride to the copolymer is reduced. If the molar ratio is less than 60:40, the softening point tends to be too low.
In addition, in the description of the vinyl polymer type alkali-soluble crosslinkable resin of type (A-1), the carboxyl group-containing unsaturated compound (d) is one unsaturated group and at least one carboxyl group in one molecule or As the compound having an acid anhydride group, each of the aforementioned compounds can be suitably used.
Further, as the polybasic acid anhydride (e), maleic anhydride, succinic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydrophthalic anhydride, 4-ethylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-ethyltetrahydrophthalic acid Saturated or unsaturated aliphatic, alicyclic or aromatic compounds having one acid anhydride group in the molecule, such as anhydride, 4-ethyltetrahydrophthalic anhydride and phthalic anhydride are preferred. Among these, tetrahydrophthalic anhydride is particularly preferable.
The reaction of the epoxy group-containing copolymer, the carboxyl group-containing unsaturated compound and the subsequent polybasic acid anhydride is preferably carried out as follows. After addition reaction of 0.8 to 1.2 mol of unsaturated carboxylic acid per one epoxy group equivalent of the copolymer to the copolymer of the epoxy group-containing monomer, the resulting hydroxyl group of the resulting product Polybasic acid anhydride is subjected to addition reaction.

-Type (A-3)-
The acid anhydride group-containing resin (f) used for the production of the vinyl polymer type alkali-soluble crosslinkable resin of type (A-3) is a copolymer of maleic anhydride and styrene or itaconic anhydride and styrene. Can be obtained by copolymerization.
As the styrene as the copolymer component, those described above in the description of the alkali-soluble crosslinkable resin of type (A-1) are preferably used. The copolymer composition ratio of maleic anhydride or itaconic anhydride and styrene is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70. When it is 90:10 or more, the development resistance of the cured portion is inferior, and when it is 10:90 or less, the developability is inferior.
A copolymer having a mass average molecular weight of about 1,000 to 5,000 obtained by copolymerizing styrene at a ratio of 1 mol to 3 mol with respect to 1 mol of maleic anhydride is preferable. For example, ARCO Chemical Company Examples thereof include SMA ranges 1000, 2000, and 3000.

  Examples of the compound (g) having one hydroxyl group and at least one (meth) acryloyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polycaprolactone mono (meth) acrylate, pendaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol mono (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) acryloyloxyethyl) ) Acid phosphate, glycerol di (meth) acrylate.

The ring-opening addition reaction of the acid anhydride copolymer and a monomer having one hydroxyl group and at least one (meth) acryloyl group in the molecule is performed in an organic solvent not containing active hydrogen. It can manufacture by the method of. Preferred solvents are ethyl acetate, methoxypropyl acetate, methyl ethyl ketone and the like. In this case, the molar ratio of hydroxyl group in the monomer / acid anhydride group in the copolymer is preferably 0.8 to 1.2.
The above ring-opening addition reaction is usually carried out at 50 to 200 ° C., but is preferably about 80 to 150 ° C. in order to prevent formation of diester and gelation. As reaction accelerators, tertiary amines such as triethylamine, triethanolamine, morpholine, and pentamethyldiethylenetriamine, or quaternary ammonium salts can be used. On the other hand, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone, t-butylcatechol, benzoquinone, phenothiazine and the like can be added and used to prevent the formation of a polymer during the reaction.

As described above, the obtained vinyl polymer type alkali-soluble crosslinkable resin composed of at least one of the types (A-1), (A-2) and (A-3) has an acid value of 50 to 50. It is preferably in the range of 250 mg KOH / g.
The acid value is more preferably from 70 to 200 mgKOH / g, particularly preferably from 90 to 180 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed portion with a developing solution that is a weak alkaline aqueous solution. On the other hand, when the acid value exceeds 250 mgKOH / g, the water resistance and electrical properties of the cured film are inferior. There are harmful effects. The vinyl polymer type alkali-soluble crosslinkable polymer (A) preferably has a mass average molecular weight in the range of 5,000 to 200,000. The mass average molecular weight is more preferably 10,000 to 100,000, and particularly preferably 30,000 to 80,000. When the mass average molecular weight is less than 5,000, the dryness to touch is remarkably inferior and the peelability from the support is inferior. On the other hand, if the mass average molecular weight exceeds 200,000, problems such as removability of unexposed areas with an alkaline developer and storage stability become undesirably deteriorated.
The solid content of the alkali-soluble crosslinkable resin in the total solid content of the photosensitive composition is preferably 15 to 70% by mass. If it is less than 15% by mass, the toughness of the cured film may be inferior, and if it exceeds 70% by mass, the performance balance such as a decrease in reliability may be deteriorated.

-Epoxy resin ester type alkali-soluble crosslinkable resin-
The epoxy resin ester type alkali-soluble crosslinkable resin is not particularly limited and may be appropriately selected depending on the purpose. For example, (h) epoxy resin and (i) one unsaturated group in one molecule It is produced by further reacting (j) a polybasic acid anhydride with an esterification reaction product of a compound having at least one carboxyl group or acid anhydride group.
Examples of the epoxy resin (h) include YDCN-701, YDCN-704 manufactured by Toto Kasei Co., Ltd .; N-665, N-680, N-695 manufactured by Dainippon Ink & Chemicals, Inc .; Nippon Kayaku Co., Ltd. EOCN-102, EOCN-104 manufactured by Asahi Kasei Kogyo Co., Ltd. ECN-265, ECN-293, ECN-285, ECN-299 and other cresol novolac type epoxy resins, and Toto Kasei K.K. -602; DEN-431, DEN-438, DEN-439 manufactured by Dow Chemical Japan Co., Ltd .; EPN-1138, EPN-1235, EPN-1299 manufactured by Ciba Specialty Chemicals Co., Ltd .; Phenol novolac type epoxy resins such as N-730 and N-770 manufactured by the same company may be mentioned. In addition, a part of the novolac type epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, bixylenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetra Epoxy resins such as a phenylethane type epoxy resin, an alicyclic epoxy resin, and a salicylaldehyde type epoxy resin can also be used advantageously.

Next, the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule is a vinyl polymer type alkali-soluble crosslinkable resin of the type (A-1). Each compound already described in the description can be preferably used.
Similarly, the polybasic acid anhydride (j) may use the above-mentioned compounds as the component (e) in the description of the vinyl polymer type alkali-soluble crosslinkable resin of the type (A-2).

--Method for producing epoxy resin ester type alkali-soluble crosslinkable resin--
There is no restriction | limiting in particular as a manufacturing method of the said epoxy resin ester type alkali soluble crosslinkable resin, According to the objective, it can select suitably, For example, the epoxy resin (h) in the case of manufacture, and one piece in 1 molecule In the reaction of the compound (i) having at least one carboxyl group or acid anhydride group with one unsaturated group in one molecule per one equivalent of the epoxy group of the epoxy resin (h) It is preferable that the compound (i) having a group and at least one carboxyl group or acid anhydride group is reacted at a ratio of 0.8 to 1.05 equivalent, more preferably 0.9 to 1.0 equivalent.
The epoxy resin (h) and the compound (i) having one unsaturated group and at least one carboxyl group or acid anhydride group in one molecule are dissolved and reacted in an organic solvent. For example, ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl Glycol ethers such as ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, fats such as octane and decane Hydrocarbons, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha.

Furthermore, it is preferable to use a catalyst to accelerate the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chlorite, benzyltrimethylammonium chlorite, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, triphenylphosphine, and the like. The amount of the catalyst used is preferably 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the epoxy resin and the vinyl group-containing monocarboxylic acid (b).
Further, it is preferable to use a polymerization inhibitor because it prevents the polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the amount used is 100 parts by mass in total of the epoxy resin (a) and the vinyl group-containing monocarboxylic acid (b). The amount is preferably 0.01 to 1 part by mass. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  The epoxy resin ester type alkali-soluble crosslinkable resin is obtained by reacting the reaction product thus obtained with a polybasic acid anhydride (j). The reaction temperature between the reaction product and the polybasic acid anhydride (c) is preferably 60 to 120 ° C.

By reacting 0.1 to 1.0 equivalent of polybasic acid anhydride (j) with respect to 1 equivalent of hydroxyl group in the reaction product, the acid value of the epoxy resin ester type alkali-soluble crosslinkable resin is reduced. Can be adjusted. The acid value of the epoxy resin ester type alkali-soluble crosslinkable resin is preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the photocurable resin composition in a dilute alkali solution decreases, and when it exceeds 150 mgKOH / g, the electric characteristics of the cured film tend to decrease.
The epoxy resin ester type alkali-soluble crosslinkable resin preferably has a mass average molecular weight of 500 to 5,000, more preferably 1,000 to 4,000, and particularly preferably 1,500 to 3,500. If it is 500 or less, the adhesiveness is too high, and it may be difficult to peel off the protective film, and if it exceeds 5,000, it may be difficult to produce the resin.

-Polymerizable compound-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. The compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. For example, at least one selected from monomers having a (meth) acryl group is preferable.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Polyfunctional alcohols such as glycerin tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, and the like, and (meth) acrylated after addition reaction of ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication Urethane acrylates described in publications such as JP 50-6034 and JP 51-37193; JP 48-64183, JP 49-4319 Polyester acrylates described in various publications such as JP, JP 30-30490, and polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. It is done. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

  5-75 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration in developability and reduction in exposure sensitivity may occur, and if it exceeds 75% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include inorganic fillers, colorants, solvents, surfactants, adhesion promoters, thermal polymerization inhibitors, plasticizers, and the like. Other additives, etc., and adhesion promoters to the substrate surface and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants) Agents, fragrances, surface tension adjusting agents, chain transfer agents, etc.) may be used in combination. By appropriately containing these components, it is possible to adjust properties such as the stability, photographic properties, and film properties of the intended photosensitive composition or photosensitive film.

-Inorganic filler-
The inorganic filler can improve the surface hardness of the permanent pattern, can keep the coefficient of linear expansion low, and can keep the dielectric constant and dielectric loss tangent of the cured layer itself low. It can use suitably for a composition.
The inorganic filler is not particularly limited and can be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, none Examples include regular silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.

The average particle size of the inorganic filler is preferably less than 3 μm, more preferably 0.1 to 2 μm. If the average particle size is 3 μm or more, resolution may be deteriorated due to light scattering.
5-75 mass% is preferable, as for the addition amount of the said inorganic filler, 8-70 mass% is more preferable, and 10-65 mass% is especially preferable. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 90% by mass, when the cured film is formed on the surface of the photosensitive layer, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

Further, organic fine particles can be added as necessary. Suitable organic fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine resin, benzoguanamine resin, and crosslinked polystyrene resin. Further, silica having an average particle size of 0.1 to ² μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  Since the inorganic filler contains particles having an average particle diameter of 0.1 to 2 μm, even if the permanent pattern is thinned to a thickness of 5 to 20 μm along with the thinning of the printed wiring board, The inorganic filler particles do not cross-link the front and back surfaces of the permanent pattern, and as a result, no ion migration occurs even in the high acceleration test (HAST), and a permanent pattern excellent in heat resistance and moisture resistance can be obtained. .

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, dyes, such as a coloring pigment suitably selected from well-known dyes, can be used.

  There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat black HB (C I.26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 185, Permanent Carmine FBB (C.I. Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanentorby FBH (C.I. Pigment Red 11) Fastel Pink B Supra (C Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite First Black B (CI Pigment Black 1), Carbon, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Blue 64. These may be used alone or in combination of two or more.

  The solid content in the solid content of the photosensitive composition solution of the color pigment can be determined in consideration of the exposure sensitivity, resolution, etc. of the photosensitive layer during permanent pattern formation. Although it varies depending on the type, generally 0.1 to 10% by mass is preferable, and 0.5 to 8% by mass is more preferable.

-Solvent-
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.
-Surfactant-
A known surfactant can be added to the photosensitive composition in order to improve the surface unevenness generated when the pattern forming material of the present invention is produced.
The surfactant can be appropriately selected from, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a fluorine-containing surfactant.

As for content of the said surfactant, 0.001-10 mass% is preferable with respect to solid content of the photosensitive composition for pattern formation materials.
When the content is less than 0.001% by mass, the effect of improving the surface shape may not be obtained, and when it exceeds 10% by mass, the adhesion may be deteriorated.

  As the surfactant, in addition to the above-mentioned surfactant, as a fluorine-based surfactant, it contains 40% by mass or more of fluorine atoms in a carbon chain of 3 to 20, and at least 3 counted from the non-bonding terminal A polymer surfactant having, as a copolymerization component, an acrylate or methacrylate having a fluoroaliphatic group in which a hydrogen atom bonded to a carbon atom is fluorine-substituted is also preferred.

-Adhesion promoter-
The adhesion promoter has a function of improving adhesion between layers, adhesion between the photosensitive layer and the substrate, and electrolytic corrosion.
The adhesion promoter is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include melamine, acetoguanamine, benzoguatemine, melamine-phenol formalin resin, ethyldiamino-S-triazine, 2,4-diamino. And triazine compounds such as -S-triazine and 2,4-diamino-6-xylyl-S-triazine. Commercially available triazine compounds include Shikoku Kasei Kogyo Co., Ltd. shown in the following structural formulas (E) to (G); 2MZ-AZINE (structural formula (E)), 2E4MZ-AZINE (structural formula (F)), CllZ -AZINE (Structural Formula (G)) and the like can be given.
These compounds increase the adhesion to the copper circuit, improve the PCT resistance, and have an effect on electrolytic corrosion. These can be used alone or in combination of two or more. 0.1-40 mass% is preferable with respect to photosensitive composition solid content, and, as for content of an adhesion promoter, 0.1-20 mass% is more preferable.

-Thermal polymerization inhibitor-
The thermal polymerization inhibitor is preferably added to prevent thermal polymerization or temporal polymerization of the polymerizable compound and improve storage stability.
The thermal polymerization inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 4-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound Such as chelates with Al and the like.

  The content of the thermal polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and particularly preferably 0.01 to 1% by mass with respect to the polymerizable compound. When the content is less than 0.001% by mass, stability during storage may be lowered, and when it exceeds 5% by mass, sensitivity to active energy rays may be lowered.

(Photosensitive film)
The photosensitive film has at least a support and a photosensitive layer made of the photosensitive composition of the present invention on the support, and other layers appropriately selected such as a cushion layer according to the purpose. Laminated.

<Support>
The support is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the photosensitive layer can be peeled off and has good light transmittance, and further has a smooth surface. It is more preferable that it is good.

The material of the support is preferably made of a synthetic resin and transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester , Poly (meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, Various plastic films such as polytrifluoroethylene, cellulose-based film, nylon film and the like can be mentioned, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.
As the support, for example, the support described in JP-A-4-208940, JP-A-5-80503, JP-A-5-173320, JP-A-5-72724, or the like is used. You can also.

  There is no restriction | limiting in particular in the thickness of the said support body, According to the objective, it can select suitably, For example, 4-300 micrometers is preferable and 5-175 micrometers is more preferable.

  The shape of the support is not particularly limited and can be appropriately selected according to the purpose. For example, the support is wound around a cylindrical core, wound into a long roll, and stored. preferable. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator on the end face, and it is also preferable to use a material with low moisture permeability for packaging. As the separator, those having moisture resistance and those containing a desiccant are particularly preferable.

<Photosensitive layer>
The photosensitive layer is formed using the photosensitive composition of the present invention. There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, According to the objective, it can select suitably, Usually, it laminates | stacks on the said support body.
The photosensitive layer may be a single layer or a plurality of layers.

  There is no restriction | limiting in particular in the thickness of the said photosensitive layer, According to the objective, it can select suitably, For example, 1-100 micrometers is preferable and 5-70 micrometers is more preferable.

<Other layers>
The other layers in the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. You may have layers, such as a surface protective layer. These layers may be used alone or in combination of two or more. Moreover, you may have a protective film on the said photosensitive layer.

−Cushion layer−
There is no restriction | limiting in particular as said cushion layer, According to the objective, it can select suitably, Swelling thru | or soluble with respect to alkaline liquid may be sufficient, and it may be insoluble.

  When the cushion layer is swellable or soluble in an alkaline liquid, examples of the thermoplastic resin include a saponified product of ethylene and an acrylate ester copolymer, a copolymer of styrene and a (meth) acrylate ester Saponification of coalescence, saponification of vinyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer such as (meth) acrylic acid butyl and vinyl acetate And a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, a copolymer of styrene, (meth) acrylic acid ester and (meth) acrylic acid, and the like.

The softening point (Vicat) of the thermoplastic resin in this case is not particularly limited and can be appropriately selected according to the purpose. For example, 80 ° C. or lower is preferable.
As the thermoplastic resin having a softening point of 80 ° C. or lower, in addition to the above-mentioned thermoplastic resin, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, October 1968) Among those organic polymers having a softening point of about 80 ° C. or less, which are soluble in an alkaline solution. In addition, even in an organic polymer material having a softening point of 80 ° C. or higher, various plasticizers compatible with the organic polymer material are added to the organic polymer material so that the substantial softening point is 80 ° C. or lower. It is also possible to lower it.

  Further, when the cushion layer is swellable or soluble in an alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and can be appropriately selected according to the purpose. Of the interlayer adhesive strength of each layer, it is preferable that the interlayer adhesive strength between the support and the cushion layer is the smallest. By setting such an interlayer adhesive force, only the support is peeled off from the photosensitive film, the photosensitive layer is exposed through the cushion layer, and then the photosensitive layer is developed using an alkaline developer. can do. In addition, after exposing the photosensitive layer while leaving the support, only the support is peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer.

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected according to the purpose. For example, a known polymer, supercooling substance, adhesion improver, surfactant in the thermoplastic resin, The method of adding a mold release agent etc. is mentioned.

  The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl Examples thereof include alcohols and esters such as phosphate and biphenyldiphenyl phosphate; amides such as toluenesulfonamide.

When the cushion layer is insoluble in an alkaline liquid, examples of the thermoplastic resin include a copolymer whose main component is ethylene as an essential copolymer component.
The copolymer having ethylene as an essential copolymer component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate. A copolymer (EEA) etc. are mentioned.

  When the cushion layer is insoluble in the alkaline liquid, the interlayer adhesive force of the photosensitive film is not particularly limited and may be appropriately selected depending on the intended purpose. Of the adhesive strength, it is preferable that the adhesive force between the photosensitive layer and the cushion layer is the smallest. With such an interlayer adhesive strength, the support and the cushion layer are peeled off from the photosensitive film, and after the photosensitive layer is exposed, the photosensitive layer can be developed using an alkaline developer. . Further, after exposing the photosensitive layer while leaving the support, the support and the cushion layer are peeled off from the photosensitive film, and the photosensitive layer can be developed using an alkaline developer. .

  The method for adjusting the interlayer adhesion is not particularly limited and can be appropriately selected depending on the purpose. For example, various polymers, supercooling substances, adhesion improvers, surfactants in the thermoplastic resin, Examples thereof include a method of adding a release agent and the like, and a method of adjusting an ethylene copolymerization ratio described below.

The ethylene copolymerization ratio in the copolymer containing ethylene as an essential copolymerization component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 to 90% by mass is preferable, and 60 to 80 % By mass is more preferable, and 65 to 80% by mass is particularly preferable.
When the ethylene copolymerization ratio is less than 60% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer increases, and it becomes difficult to peel off at the interface between the cushion layer and the photosensitive layer. When the amount exceeds 90% by mass, the interlayer adhesive force between the cushion layer and the photosensitive layer becomes too small, so that the cushion layer and the photosensitive layer are easily peeled off, and includes the cushion layer. Production of the photosensitive film may be difficult.

There is no restriction | limiting in particular in the thickness of the said cushion layer, Although it can select suitably according to the objective, For example, 5-50 micrometers is preferable, 10-50 micrometers is more preferable, and 15-40 micrometers is especially preferable.
If the thickness is less than 5 μm, unevenness on the surface of the substrate and unevenness followability to bubbles and the like may be reduced, and a high-definition permanent pattern may not be formed. Such a problem may occur.

-Oxygen barrier layer (PC layer)-
The oxygen barrier layer is preferably formed usually with polyvinyl alcohol as a main component, and is preferably a film having a thickness of about 0.5 to 5 μm.

-Protective film-
The protective film has a function of preventing and protecting the photosensitive layer from being stained and damaged.
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said protective film, According to the objective, it can select suitably, Usually, it provides on the said photosensitive layer.
Examples of the protective film include those used for the support, silicone paper, polyethylene, paper laminated with polypropylene, polyolefin or polytetrafluoroethylene sheet, and among these, polyethylene film, Polypropylene film is preferred.
There is no restriction | limiting in particular in the thickness of the said protective film, According to the objective, it can select suitably, For example, 5-100 micrometers is preferable and 8-30 micrometers is more preferable.
When the protective film is used, it is preferable that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B.
Examples of the combination of the support and the protective film (support / protective film) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, the relationship of the above adhesive forces can be satisfy | filled by surface-treating at least any one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include a discharge irradiation process, an active plasma irradiation process, and a laser beam irradiation process.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

  The protective film may be surface-treated in order to adjust the adhesion between the protective film and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective film. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective film and then drying at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 to 120 ° C.

[Method for producing photosensitive film]
The said photosensitive film can be manufactured as follows, for example.
First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive resin composition solution for a photosensitive film.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, and ethylbenzene; halogenated carbonization such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene Motorui; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive resin composition solution is applied on the support and dried to form a photosensitive layer, whereby a photosensitive film can be produced.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer on the substrate and other layers appropriately selected according to the purpose.

<Substrate>
The substrate is a substrate to be processed on which a photosensitive layer is formed or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and may be appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having a rough surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a known printed wiring board (printed board), a glass plate (soda glass plate, etc.), a synthetic resin film, paper, and a metal plate.

[Method for producing photosensitive laminate]
Examples of the method for producing the photosensitive laminate include, as the first aspect, a method of applying the photosensitive composition to the surface of the substrate and drying, and as the second aspect, at least in the photosensitive film of the present invention. Examples of the method include transferring and laminating the photosensitive layer while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate of the first aspect, a photosensitive layer is formed by applying and drying the photosensitive composition on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent on the surface of the substrate. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, The same solvent as what was used for the said photosensitive film is mentioned. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective film, it is preferable to peel this protective film and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

  The photosensitive composition, the pattern forming material, and the photosensitive laminate of the present invention have a high sensitivity and high resolution, good storage stability, and various required properties and a high definition permanent pattern. Since it can be formed, it forms various permanent patterns such as protective films, interlayer insulating films, solder resists, manufactures liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, manufactures holograms, micromachines, and proofs. In particular, it can be suitably used for forming a permanent pattern on a printed circuit board.

(Pattern forming apparatus and permanent pattern forming method)
The pattern forming apparatus of the present invention includes the photosensitive layer and includes at least light irradiation means and light modulation means.

The permanent pattern forming method of the present invention includes at least an exposure step, and includes other steps such as an appropriately selected development step.
In addition, the said pattern formation apparatus of this invention is clarified through description of the said permanent pattern formation method of this invention.

[Exposure process]
The said exposure process is a process of exposing with respect to the photosensitive layer of this invention. The photosensitive layer and substrate material of the present invention are as described above.

  The subject of the exposure is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. For example, as described above, the photosensitive composition is heated and pressurized on the substrate. It is preferable to carry out with respect to the photosensitive layer in the photosensitive laminate formed by laminating at least one of the above.

  There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.

  The analog exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, exposure with a (super) high pressure mercury lamp, xenon lamp, halogen lamp, etc. through a photomask having a predetermined pattern. The method of performing is mentioned.

  The digital exposure is not particularly limited as long as it is performed without using the photomask, and can be appropriately selected according to the purpose. For example, an exposure head including at least a light irradiation unit and a light modulation unit; The exposure head irradiates the photosensitive layer with light emitted from the light irradiation means while modulating at least one of the photosensitive layers according to pattern information by the light modulation means. It is preferable.

  The light source used in the digital exposure is not particularly limited as long as it is a light source that emits ultraviolet to near infrared rays, and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp , Fluorescent lamps for use in halogen lamps and copying machines, or known light sources such as laser light are used. Among these, (ultra) high pressure mercury lamps and laser light are preferable, and laser light is more preferable.

  The (super) high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube or the like, and has a higher vapor pressure to increase luminous efficiency. Among the emission line spectra, an emission line spectrum of only one wavelength may be used using an ND filter or the like, or a light beam having a plurality of emission line spectra may be used.

The “laser” of the laser light is an acronym for Light Amplification by Stimulated Emission of Radiation. As an apparatus for emitting the laser light, an oscillator and an amplifier that generate monochromatic light having a higher coherence and directivity by amplification and oscillation of light waves using a phenomenon of stimulated emission that occurs in a material having an inversion distribution is preferably used. Can be mentioned.
Examples of the laser light excitation medium include crystals, glass, liquid, pigment, gas, and the like, and known lasers such as a solid laser, a liquid laser, a gas laser, and a semiconductor laser can be used.
Specifically, examples of the gas laser include an Ar ion laser (364 nm, 351 nm), a Kr ion laser (356 nm, 351 nm), and a He—Cd laser (325 nm), and examples of the solid laser include a YAG laser and a YVO ₄ laser (1, 064 nm), YAG laser or YVO ₄ laser, 2nd harmonic (532 nm), 3rd harmonic (355 nm), 4th harmonic (266 nm), a combination of a waveguide wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 nm to 400 nm) ), A combination of a waveguide wavelength conversion element and an AlGaInP or AlGaAs semiconductor t (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like. Among these, suitable laser light includes an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm) in terms of cost, and a 355 nm laser having high output in terms of productivity.

  The wavelength of the laser beam is, for example, preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 350 to 420 nm.

-Light modulation means-
As the light modulation means, a typical method is a method having n pixel parts and controlling the pixel parts according to the pattern information. Specifically, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect. And liquid crystal light shutter (FLC). Among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. In this state, the light spot is not exposed between the light spots. However, if the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction, the light spots in the first row are used. The light spot in the rear row exposes between the light spot and the light spot, so that the entire surface of the photosensitive layer can be exposed. The DMD can form an image pattern by controlling the angle of each mirror and controlling the light spot on and off. By aligning and using such exposure heads having the DMD, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed using a mirror gradation type spatial modulation element.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

  On the other hand, another typical method of the light modulation means is a method using a polygon mirror. Here, the polygon mirror is a rotating member having a series of plane reflecting surfaces around it. The polygon mirror reflects and irradiates light from the light source onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. Then, an image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. At this time, the scanning time can be shortened by using a plurality of lights from the light source.

  As the light modulation means of the present invention, in addition, an example of drawing using a polygon mirror described in JP-A-5-150175, as described in JP-T-2004-523101 (International Publication No. 2002/039793 pamphlet). An example in which a part of the image of the lower layer is visually acquired, and exposure is performed by aligning the position of the upper layer with the position of the lower layer with an apparatus using a polygon mirror, and exposure with the DMD described in JP-A-2004-56080 For example, an exposure apparatus provided with a polygon mirror described in JP-T-2002-523905, an exposure apparatus provided with a polygon mirror described in JP-A-2001-255661, DMD, LD, and multiple exposure described in JP-A-2003-50469 An example of a combination of an exposure method in which the exposure amount is changed depending on the part of the substrate described in Japanese Patent Application Laid-Open No. 2003-156853 , Etc. Examples of an exposure method for performing a positional deviation adjustment described in JP 2005-43576 Publication and the like.

-Light irradiation means-
There is no restriction | limiting in particular as said light irradiation means, ie, the light irradiation method, Although the above-mentioned exposure light source can be suitably selected according to the objective, Two or more light from these light sources is synthesize | combined and irradiated. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by combining two or more lights.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of composing and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber is preferable.

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the dark color separation partition wall, the Gaussian beam 1 / e ² value is preferably 5 to 30 μm, 7-20 micrometers is more preferable.
In the present invention, it is preferable to spatially modulate laser light according to image data. Therefore, it is preferable to use the DMD which is a spatial light modulator for this purpose.

  Examples of the exposure apparatus having the light modulating unit and the light irradiating unit are described in JP-A-2005-222039, JP-A-2005-258431, JP-A-2006-30966, and the like. However, the exposure apparatus in the present invention is not limited to this.

[Other processes]
There is no restriction | limiting in particular as said other process, Although selecting suitably from the process in well-known pattern formation is mentioned, For example, a image development process, a hardening process process, etc. are mentioned.

-Development process-
The developing step is a step of forming a pattern by exposing the photosensitive layer in the exposing step, curing the exposed region of the photosensitive layer, and then developing the uncured region by removing the uncured region.
The developing step can be preferably performed by, for example, developing means.
The developing means is not particularly limited as long as it can be developed using a developer, and can be appropriately selected according to the purpose. For example, means for spraying the developer, means for applying the developer And means for immersing in the developer. These may be used alone or in combination of two or more.
In addition, the developing unit may include a developer replacing unit that replaces the developer, a developer supplying unit that supplies the developer, and the like.

  There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, an alkaline solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline liquid include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

The pH of the weak alkaline aqueous solution is, for example, preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

-Curing process-
The curing treatment step is a step of performing a curing treatment on the formed pattern after the developing step is performed on the photosensitive layer.

  There is no restriction | limiting in particular as said hardening process, According to the objective, it can select suitably, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the photosensitive laminate on which the permanent pattern is formed after the developing step. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, According to the objective, it can select suitably, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the photosensitive laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.
The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention can be formed on the printed wiring board, and soldering can be performed as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  The permanent pattern forming method of the present invention uses a photosensitive layer formed of the photosensitive composition of the present invention, so that various permanent patterns such as a protective film, an interlayer insulating film, and a solder resist pattern are formed, a color filter, It can be suitably used for the production of liquid crystal structural members such as pillars, ribs, spacers, partition walls, holograms, micromachines, proofs, etc., and in particular, it can be suitably used for forming a permanent pattern on a printed circuit board. .

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
(Example 1)
-Preparation of pigment dispersion-
The following components were prepared by dispersing for 3 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 1.0 mm with a mill type disperser (manufactured by Eiger, Motor Mill M-200).
Inorganic filler (barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30) dispersion) 30.0 parts by mass Dicyandiamide 0.92 parts by mass Coloring pigment 1 (chromophthal yellow 2RF (Ciba Specialty) CI Pigment Yellow 139, manufactured by Chemicals Co., Ltd. 0.09 parts by mass Coloring Pigment 2 (HELIOGEN BLUE D707PB (CISF Blue 15: 3, manufactured by BASF)) 0.20 Mass parts / PR300P-CP (trade name: Showa High Polymer Co., Ltd .: 67.3% of the resin obtained by adding a ring opening addition of acrylic acid to a cresol novolac epoxy resin and adding tetrahydrophthalic anhydride to the resulting hydroxy group Propylene glycol monomethyl ether acetate solution) ... 10.0 parts by mass / propyl acetate ... 36.6 parts by mass

-Preparation of photosensitive composition coating solution-
The following components were mixed to prepare a photosensitive composition solution.
[Composition of photosensitive composition coating solution]
-Pigment dispersion-82.9 parts by mass-Cyclomer P-ACA200 (manufactured by Daicel Corporation, methyl methacrylate / methacrylic acid / 2-hydroxy-4-acryloyloxymethylcyclohexyl methacrylate copolymer, molar composition ratio = 30) / 35/35 bromine number _{= 36gBr} 2 / 100g, acid value = 118mgKOH / g, solid content concentration = 45 wt% propylene glycol monomethyl ether solution of weight-average molecular weight = 15,000) ... 53.9 parts by mass Epotohto YD-127 (manufactured by Tohto Kasei, bisphenol A type epoxy resin, hereinafter referred to as “CL1”) ... 14.3 parts by mass / DPHA (Nippon Kayaku, dipentaerythritol hexaacrylate) ... 13.0 masses Part 5- (5-tert-butylbenzo-1,3-dithiolidene) -1 3-diethyl-2-thiobarbituric acid, hereinafter referred to as "D4". ): Merocyanine-based compound: 0.10 parts by mass CGI325 (Ciba Specialty Chemicals, (2-acetyloxyiminomethyl) -thioxanthen-9-one): Oxime derivative: 0.95 parts by mass F780F (manufactured by DIC, fluorine-type surfactant, 30% by mass methyl ethyl ketone solution: 0.57 parts by mass, hydroquinone monomethyl ether: 0.04 parts by mass, methyl ethyl ketone: 20 parts by mass

-Production of photosensitive film-
A polyethylene terephthalate film having a thickness of 16 μm (Lumirror 16QS52, manufactured by Toray Industries, Inc.) is used as a support, and the photosensitive composition coating liquid is dried on the support with a bar coater, so that the thickness of the photosensitive layer after drying becomes about 30 μm. And then dried in a hot air circulating dryer for 30 minutes at 80 ° C., and then a 12 μm thick polypropylene film was laminated as a protective film on the photosensitive layer to produce a photosensitive film. .

-Solder resist pattern formation-
--- Preparation of photosensitive laminate--
As the substrate, a surface of a copper-clad laminate (printed wiring board having no through hole and a copper thickness of 12 μm) on which wiring was formed as a printed board was prepared by subjecting it to chemical polishing. A vacuum laminator (V130, manufactured by Nichigo Morton Co., Ltd.) was used on the copper clad laminate while peeling off the protective film from the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. Lamination was performed to prepare a photosensitive laminate in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

[Evaluation]
The photosensitive film and the photosensitive laminate were evaluated for the shortest development time, sensitivity, resolution, and storage stability under the following conditions. The results other than the shortest development time are shown in Table 2.
The solder resist pattern was evaluated for pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, and gold plating resistance under the following conditions. The results are shown in Tables 2 and 3.

<Minimum development time>
The polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper clad laminate was dissolved and removed was measured, and this was taken as the shortest development time. The shortest development time was 15 seconds (the same applies to the following examples).

<Sensitivity>
Using a pattern forming apparatus described in JP-A-2006-30966 having a 405 nm laser light source as the light irradiation unit from the polyethylene terephthalate film (support) side to the photosensitive layer in the photosensitive laminate. It was exposed by irradiating light energy different light from 0.1 mJ / cm ² to 100 mJ / cm ² at ^{2 1/2} times the interval, to cure the part of the area of the photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the photosensitive laminate, and an aqueous sodium carbonate solution (30 ° C., 1% by mass) is formed on the entire surface of the photosensitive layer on the copper clad laminate. Was sprayed at a spray pressure of 0.15 MPa for twice the minimum development time to dissolve and remove the uncured region, and the thickness of the remaining cured region was measured. Subsequently, the relationship between the light irradiation amount and the thickness of the cured layer was plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy when the thickness of the cured region was the same as that before exposure was defined as the amount of light energy (sensitivity) necessary for curing the photosensitive layer.
The pattern forming apparatus has a light modulation unit made of the DMD.

<Resolution>
The photosensitive laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). From the obtained polyethylene terephthalate film (support) of the photosensitive laminate, each line width was exposed in steps of 1 μm from a line width of 20 μm to 50 μm using the pattern forming apparatus. The exposure amount at this time is the amount of light energy required to cure the photosensitive layer determined by the sensitivity measurement. After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. Spray the entire surface of the photosensitive layer on the copper-clad laminate with a sodium carbonate aqueous solution (30 ° C., 1% by mass) as the developer at a spray pressure of 0.15 MPa for twice the shortest development time determined by the above method. Then, the uncured region was dissolved and removed. Observe the surface of the copper-clad laminate with a solder resist pattern as a permanent pattern obtained in this way with an optical microscope, and measure the minimum line width without any abnormalities such as tsumari and twist on the solder resist pattern line, This was the resolution. The smaller the numerical value, the better the resolution.

<Storage stability>
The obtained sheet of photosensitive film was put in a light-proof moisture-proof bag (BF3X manufactured by Tokai Aluminum Foil Co., Ltd.) made of black vinyl and an aluminum foil laminated structure, and stored in a dry oven at 40 ° C. for 3 days. Then removed the film sheet performs shortest development time test described above after laminated on a substrate, and measured the shortest developing time (t _3).
The time required for development was compared with the shortest development time (t ₀ ) on the photosensitive film production day. Specifically, the t ₃ / t ₀ ratio value obtained was evaluated according to the following criteria.
-Evaluation criteria-
○: 1.0 to 1.3
Δ: 1.3-1.8
X: 1.8 or more

<Pencil hardness>
The above-mentioned photosensitive film was vacuum laminated on a copper-clad laminate without a circuit pattern after peeling off the protective film. After cooling this to room temperature, exposure is performed under conditions of an exposure amount of 500 mJ / cm ² , curing is performed at 150 ° C. for 60 minutes in a hot-air circulating drying furnace, and then cooled to room temperature to obtain a solder resist evaluation sample after curing. It was.

  In accordance with the test method of JIS K-5400, a pencil hardness tester was used to determine the highest hardness at which the film was not damaged when a load of 1 kg was applied to the evaluation sample.

<Adhesion>
According to JIS K5400, 100 1 mm grids were prepared in the permanent pattern after curing, and a peel test was performed using a cellophane tape. The peeled state of the grid was observed and evaluated according to the following criteria.
-Evaluation criteria-
○: No peeling at 90/100 or more Δ: No peeling at 50/100 or more to less than 90/100 ×: No peeling at 0/100 to less than 50/100

<Solvent resistance>
A cured solder resist evaluation sample similar to that prepared for the pencil hardness evaluation was immersed in isopropyl alcohol at room temperature for 30 minutes, and after confirming that there was no abnormality in appearance, a peel test was performed using a cellophane tape.
-Evaluation criteria-
○: No abnormality in the appearance of the coating film and no peeling.
X: The appearance of the coating film is abnormal or peels off.

<Acid resistance>
A cured solder resist evaluation sample similar to that prepared for the pencil hardness evaluation is immersed in a 10% by mass hydrochloric acid aqueous solution at room temperature for 30 minutes, and after confirming that there is no abnormality in the appearance, a peel test is performed with a cellophane tape. It was.
-Evaluation criteria-
○: No abnormality in the appearance of the coating film and no peeling.
X: The appearance of the coating film is abnormal or peels off.

<Alkali resistance>
A cured solder resist evaluation sample similar to that prepared for the pencil hardness evaluation was immersed in a 5% by weight aqueous sodium hydroxide solution at room temperature for 30 minutes, and was checked for abnormal appearance and then peeled off using a cellophane tape. Went.
-Evaluation criteria-
○: No abnormality in the appearance of the coating film and no peeling.
X: The appearance of the coating film is abnormal or peels off.

<Solder heat resistance>
A rosin-based flux or a water-soluble flux was applied to a cured solder resist evaluation sample similar to that prepared for the pencil hardness evaluation, and immersed in a solder bath at 260 ° C. for 10 seconds. This was defined as one cycle, and after repeating 6 cycles, the appearance of the coating film was visually observed.
-Evaluation criteria-
○: There is no abnormality (peeling or swelling) in the appearance of the coating film, and there is no solder dent.
X: The appearance of the coating film is abnormal (peeling or swelling) or has a solder dent.

<Insulation resistance>
Necessary for curing the photosensitive layer obtained by measuring the sensitivity as an exposure amount with the laser device, using the IPC-B-25 comb-shaped test pattern B, applying a photomask for pattern B The entire surface is exposed with the amount of light energy, developed at 30 ° C. for 60 seconds, washed with 1% by weight aqueous sodium carbonate solution, washed with water, dried, exposed at 100 mJ / cm ² with an ultra-high pressure mercury lamp (post-exposure), and 150 A test substrate was prepared by post-heating treatment (post-baking treatment) at 1 ° C. for 1 hour. According to the test method of IPC-SM-840B, the insulation resistance in the normal state was measured and evaluated according to the following criteria.
-Evaluation criteria-
○: Insulation resistance value is 10 ¹⁰ Ω or more ×: Insulation resistance value is less than 10 ¹⁰ Ω

<Gold resistance>
A cured solder resist evaluation sample similar to that prepared for the pencil hardness evaluation was dipped in an acidic degreasing solution (manufactured by Nihon McDermitt, 20 vol% aqueous solution of Metex L-5B) for 3 minutes, and then washed with water. did.
Next, the substrate was immersed in a 14.4% by volume aqueous ammonium persulfate solution at room temperature for 3 minutes, then washed with water, and further immersed in a 10% by volume sulfuric acid aqueous solution at room temperature for 1 minute, followed by washing with water.
Next, this test substrate is immersed in a 30 ° C. catalyst solution (Meltex, 10 volume% aqueous solution of Melplate Activator 350) for 7 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex, Melplate). Ni-865M 10 volume% sulfuric acid aqueous solution) was immersed for 1 minute at room temperature and then washed with water.
Next, the test substrate was immersed for 10 minutes in a gold plating solution at 95 ° C. (Meltex, 15% by volume of Aurolectroles UP and 3% by volume of potassium cyanide cyanide, pH 6), followed by electroless gold plating. This was washed with water, further immersed in warm water at 60 ° C. for 3 minutes, washed with water and dried. The obtained electroless gold plating evaluation board was observed and evaluated according to the following criteria.
-Evaluation criteria-
○: No abnormality at all.
X: Bad plating adhesion or dent due to plating was observed.

(Examples 2-9)
In Example 1, except that the kind of merocyanine compound and its content were changed as shown in Table 1, in the same manner as in Example 1, sensitivity, resolution, storage stability, pencil hardness, adhesion, resistance Solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, and gold plating resistance were evaluated. The results are shown in Tables 2 and 3.

(Examples 10 to 13)
In Example 1, the sensitivity, resolution, storage stability, pencil hardness, adhesion, and solvent resistance were the same as in Example 1 except that the types of oxime derivatives and their contents were changed as shown in Table 1. Evaluation of acidity, acid resistance, alkali resistance, solder heat resistance, insulation resistance, and gold plating resistance. The results are shown in Tables 2 and 3.

(Examples 14 to 19)
In Example 1, the sensitivity, resolution, storage stability, pencil hardness, adhesion, resistance, and resistance were the same as in Example 1 except that the type and content of the thermal crosslinking agent were changed as shown in Table 1. Solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, and gold plating resistance were evaluated. The results are shown in Tables 2 and 3.

(Example 20 and Example 21)
In Example 1, except that the content of the merocyanine compound was changed as shown in Table 1, in the same manner as in Example 1, sensitivity, resolution, storage stability, pencil hardness, adhesion, solvent resistance, The acid resistance, alkali resistance, solder heat resistance, insulation resistance, and gold plating resistance were evaluated. The results are shown in Tables 2 and 3.

(Comparative Examples 1-4)
In Example 1, the sensitivity, resolution, storage stability, pencil hardness, adhesion were the same as in Example 1 except that any kind of sensitizing dye and radical generator was changed as shown in Table 1. Evaluation was made on the property, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, and gold plating resistance. The results are shown in Tables 2 and 3.

(Comparative Examples 5-7)
In Example 1, except that any of the merocyanine compound, the oxime derivative, and the thermal crosslinking agent was not added as shown in Table 1, the sensitivity, resolution, storage stability, The pencil hardness, adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, insulation resistance, and gold plating resistance were evaluated. The results are shown in Tables 2 and 3.

The formal names of the components indicated by abbreviations in Table 1 are as follows.
D4: 5- (5-tert-butylbenzo-1,3-dithiolidene) -1,3-diethyl-2-thiobarbituric acid D13: 5-tert-butyl-benzo-1,3-dithiolidene-1,3-indandione D18: 3- (5-tert-butyl-benzo-1,3-dithiolidene) -1-methyl-tetrahydroquinoline-2,4-dione D23: 3- (5-tert-butyl-benzo-1,3-dithiolidene ) -Chroman-2,4-dione D31: 2- (1-methylbenz-1,3-oxazolidene) -1,3-diethylthiobarbituric acid D40: 2- (1-methyl-5,6-dimethoxybenzo-) 1,3-thiazolidene) thiobarbituric acid D48: 2- (1-methoxyethyl-α-naphth-1,3-thiazolidene) -1,3-diethylthiobar Turic acid D51: 5- (1-n-octylbenzo-1,3-thiazolidene) -1,3-diethylthiobarbituric acid D52: 5- [2- (1-ethylbenzo-1,3-thiazolidene) methyl] -Methylidene-3-hydroxyethylrhodanine DETX-S: Diethylthioxanthone OE1: 1- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate OE3: 1- (3,4 -Dimethoxyphenyl) -butane-1,2-dione-2-oxime-O-acetate CGI325: (2-acetyloxyiminomethyl) -thioxanthen-9-one OEN1: a compound represented by the following structural formula
OEP1: Compound represented by the following structural formula
EAB: 4,4′-bis (N, N-diethylamino) benzophenone Irgacure 819: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Irgacure 369: 1- (4-morpholinophenyl) -2-benzyl-2-dimethyl Aminobutan-1-one CL1: Epototo YD-127 (manufactured by Toto Kasei)
CL2: Epototo ZX-1059 (manufactured by Toto Kasei)
CL3: Epototo YSLV-80XY (manufactured by Toto Kasei)
CL4: Epiklon 4050 (Dainippon Ink Chemical Co., Ltd.) and EOCN-103S (Nippon Kayaku Co., Ltd.) in a mass ratio of 1: 1 CL5: Epicoat 1004 (Japan Epoxy Resin Co., Ltd.) and EPPN-501H (Nipponization) 2) Mixture CL6: XD-1000 (manufactured by Nippon Kayaku Co., Ltd.)
CL7: Mixture of Epiklone TSR-960 and Epiklone 4050 (both manufactured by Dainippon Ink & Chemicals) in a mass ratio of 1: 2.

  From the results of Tables 2 and 3, Examples 1 to 21 using the photosensitive composition in which the photopolymerization initiating compound includes a merocyanine compound and an oxy derivative and includes a thermal crosslinking agent are high sensitivity and high resolution. In addition, it was found that the storage stability is good, and various properties required for the solder resist are good and a high-definition permanent pattern can be formed.

The photosensitive composition and photosensitive film of the present invention have high sensitivity and high resolution, good storage stability, and have good properties required to form a high-definition permanent pattern. For this reason, it can be particularly suitably used for forming a permanent pattern such as a solder resist on a printed circuit board.
Since the permanent pattern formation method of the present invention uses a photosensitive layer formed of the photosensitive composition of the present invention, it can be suitably used particularly for forming a high-definition solder resist pattern on a printed circuit board.

Claims (13)

  A photosensitive composition comprising a binder, a polymerizable compound, a photopolymerization initiating compound, and a thermal crosslinking agent, wherein the photopolymerization initiating compound comprises a merocyanine compound and an oxime derivative. The photosensitive composition according to claim 1, wherein the merocyanine compound is represented by the following general formula (I).
In the general formula (I), X represents an oxygen atom, a sulfur atom, and either NR ^1. Z represents a nonmetallic atomic group that forms a basic nucleus of the dye together with X and an adjacent carbon atom, and R ¹ represents any ^one of a hydrogen atom, an aliphatic group, and an aromatic group. X ₁ and X ₂ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and the X ₁ and X ₂ may be bonded to each other to form an acidic nucleus of the dye. W represents either an oxygen atom or a sulfur atom. m represents an integer of 0 or more. The photosensitive composition according to claim 2, wherein the merocyanine compound is further represented by any of the following general formula (I-1) and general formula (I-2).
In the general formula (I-1) and the general formula (I-2), ^{R 1} represents the same meaning as the general formula (I). R ² and R ³ each independently represents any one of a hydrogen atom, an aliphatic group, an aromatic group, and a heterocyclic group, and R ² and R ³ are bonded to other carbon atoms and substituted. You may form the 5-7 membered ring which may be. X ₁ and X ₂ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and X ₁ and X ₂ may be bonded to each other to form an acidic nucleus of the dye. W represents either an oxygen atom or a sulfur atom. Each Y independently represents a carbon atom or a heteroatom of any one of Groups 15 and 16 in the periodic table. In the general formula (I-1) and the general formula (I-2), the skeleton constituted by X ₁ , X ₂ , and W is any of thiobarbituric acid, indandione, and tetrahydroquinoline-2,4-dione skeleton The photosensitive composition according to claim 3. The photosensitive composition according to any one of claims 1 to 4, wherein the oxime derivative has a partial structure represented by any one of the following general formula (II) and the following general formula (III).
In the general formula (II) and the general formula (III), Ar represents either an aromatic group and a heterocyclic group, Y ¹ represents any substituent of a hydrogen atom and monovalent, Y ² Represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ , and Y ³ , Y ⁴ , and Y ⁵ represent an aliphatic group, an aromatic group, And a heterocyclic group, and n represents an integer of 1 or more.   The photosensitive composition of Claim 5 in which Ar in general formula (II) and (III) has either a phenyl group or a naphthyl group.   The photosensitive composition according to any one of claims 5 to 6, wherein Ar in the general formulas (II) and (III) has a naphthyl group.   The photosensitive composition according to claim 1, wherein the oxime derivative is an acyl oxime derivative.   The photosensitive composition according to claim 1, wherein the content ratio of the merocyanine compound and the oxime derivative is 0.01: 1 to 10: 1.   The thermal crosslinking agent is at least one selected from an epoxy compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a polyisocyanate compound with a blocking agent, and a melamine derivative. The photosensitive composition as described.   A photosensitive film comprising a photosensitive layer made of the photosensitive composition according to claim 1 on a support.   A method for forming a permanent pattern, comprising exposing a photosensitive layer formed of the photosensitive composition according to claim 1. A printed circuit board, wherein a permanent pattern is formed by the permanent pattern forming method according to claim 12.