CN101398623A - Photosensitive composition, phososensitive film, photosensitive laminated body, permanent pattern forming method and printed substrate - Google Patents

Abstract

A photosensitive composition according to the invention comprises an adhesive formed by the following modified copolymer, a polymerized compound, a photopolymerization initiating agent, a thermal cross-linking agent and a catalyst. The modified polymer is obtained through adding (methyl) glycidyl acrylate on one part of acid group of copolymer which is obtained from (methyl) acrylate (A) and a compound that contains an unsaturated group and is provided with at least one acid group. The invention is characterized in that the residual quantity of catalyst is below 500ppm (parts per million) by weight.

Description

Photosensitive composite, photosensitive film, photosensitive laminate, permanent pattern formation method and printed base plate

Technical field

The present invention relates to a kind of sensitivity and excellent storage stability, can form expeditiously high meticulous permanent pattern (diaphragm, interlayer dielectric and solder resist pattern etc.) photosensitive composite, photosensitive film, photosensitive laminate, the described photosensitive composite of use permanent pattern formation method and utilize this permanent pattern formation method to be formed with printed base plate (the Japanese original text: プ リ Application ト substrate) of permanent pattern.

Background technology

All the time, when permanent patterns such as formation solder resist (solder resist) pattern, use by on supporter, being coated with photosensitive composite and carrying out the photosensitive film that drying forms photographic layer.Manufacture method as described permanent pattern, for example form duplexer being formed with stacked described photosensitive film on the matrixes such as copper-surfaced plywood of described permanent pattern, described photographic layer in this duplexer is exposed, after this exposure described photographic layer development is made the formation pattern, be cured processing etc. afterwards, thereby form described permanent pattern.

When forming described permanent pattern, as the method that in the side chain of ethene base system macromolecular compound, imports the olefinic unsaturated link, usually adopt following method: use lewis base compound etc. as catalyzer, addition contains the unsaturated compound (for example glycidyl methacrylate) of epoxy radicals and the method (with reference to following reaction equation) that obtains on the carboxyl of the high molecular side chain of described ethene base system.

But, with photographic layer, in being mixed with the system of epoxy compound, if employed modified catalyst when in polymkeric substance, having synthesizing epoxy modified adhesive polymkeric substance, then describedly changing the carboxyl reaction of thing and solidify as solder resist.Therefore, non-image part can't be removed by development, has the problem of storage stability deterioration.In addition, described modified catalyst is to cause adhesive resin and the painted reason of resin solution thereof, because this adhesive resin painted, and has the problem of the color and taste variation of sense material.

Wherein, the someone has proposed to contain the tertiary phosphine (with reference to Japanese kokai publication hei 10-17779 communique) of 0.5～5 weight % or has contained the catalyzer (with reference to TOHKEMY 2000-191737 communique) of 0.4～0.6 weight % and stipulated the kind of catalyzer and the motion of content thereof in adhesive resin in adhesive resin.

In addition, someone discloses the manufacture method of following unsaturated epoxy ester resin: use the trivalent organophosphorus compounds catalyzer, make the synthetic unsaturated epoxy ester resin of epoxy compound and polymerism monocarboxylic acid reaction, afterwards by described trivalent organophosphorus compounds catalyst oxidation is made its inactivation, thereby promote the manufacture method that does not contain the unsaturated epoxy ester resin of catalyzer in fact (No. 2593019 communique of Jap.P.) of the reaction of epoxy radicals and carboxylic acid.

The somebody discloses the manufacture method of following curable resin: by (methyl) acrylate (A) with contain unsaturated group and contain at least on a part of acid group of the multipolymer that the compound (B) of 1 acid group obtains that addition contains the unsaturated compound of epoxy radicals and when obtaining modified copolymer (C), carry out making after the addition reaction manufacture method (TOHKEMY 2000-72814 communique) of the curable resin that is formed by polymer-modified (D) of catalyst deactivation in the presence of catalyzer.

But in these methods, the storage stability of sense material is insufficient, and the problem painted remarkable, that feel the color and taste difference of material of adhesive resin is not resolved yet.

Therefore; present situation is by the kind of abundant minimizing bonding agent and the residual quantity of catalyzer; excellent storage stability can't be provided; and alleviated the painted of adhesive resin and suppressed the color and taste variation (look fault) of sense material; can form high meticulous permanent pattern (diaphragm expeditiously; interlayer dielectric and solder resist pattern etc.) photosensitive composite; photosensitive film; photosensitive laminate; use the permanent pattern formation method of described photosensitive composite; utilize described permanent pattern formation method to form figuratum printed base plate; and the manufacture method of photosensitive composite, people wish further to improve exploitation.

Summary of the invention

The present invention establishes in view of described present situation, and problem of the present invention is to solve existing described variety of issue, reaches following purpose.Promptly; the objective of the invention is to by the kind of regulation bonding agent and the residual quantity of catalyzer, the ageing stability excellence of the exploring degree (circular hole) behind a kind of storage stability and the lamination is provided; and alleviated the painted of adhesive resin and suppressed the color and taste variation (look fault) of sense material; can form high meticulous permanent pattern (diaphragm expeditiously; interlayer dielectric and solder resist pattern etc.) photosensitive composite; photosensitive film; photosensitive laminate; use the permanent pattern formation method of described photosensitive composite and by utilizing described permanent pattern formation method to form figuratum printed base plate.

The method that is used to solve described problem is as follows.That is:

＜1〉a kind of photosensitive composite, it comprises bonding agent, polymerizable compound, photopolymerization initiator, thermal cross-linking agent and the catalyzer that is formed by following modified copolymer, described modified copolymer is by (methyl) acrylate (A) with contain unsaturated group and have the modified copolymer that addition (methyl) glycidyl acrylate forms on a part of acid group of the resulting multipolymer of compound (B) of 1 acid group at least, it is characterized in that, become component with respect to described adhesive solids, the residual quantity of described catalyzer is below the 500 quality ppm.

＜2〉according to described＜1〉photosensitive composite put down in writing, wherein, become component with respect to adhesive solids, the residual quantity of catalyzer is below the 300 quality ppm.

＜3〉according to described＜1 〉～＜2 in each photosensitive composite of putting down in writing, wherein, catalyzer is a triphenyl phasphine.

＜4〉according to described＜1 〉～＜3 in each photosensitive composite of putting down in writing, wherein, the photopolymerization initiator is a 9 oxime derivate.

＜5〉according to described＜1 〉～＜4 in each photosensitive composite of putting down in writing, wherein, thermal cross-linking agent is at least a for what select from epoxy compound, oxetane compound, polyisocyanate compounds, blocked polyisocyanate compound and melamine derivative.

＜6〉according to described＜5〉photosensitive composite put down in writing, wherein, thermal cross-linking agent is an epoxy compound, and this epoxy compound is selected from phenolic varnish type epoxy compound, bisphenol type epoxy compound, the epoxy compound that contains heterocycle and alicyclic epoxy compound.

＜7〉according to described＜5 〉～＜6 in each photosensitive composite of putting down in writing, wherein, it is 150g/eq.～9 that thermal cross-linking agent contains epoxy compound and the epoxide equivalent that epoxide equivalent is 90g/eq.～400g/eq., the epoxy compound of 000g/eq..

＜8〉according to described＜1 〉～＜7 in each photosensitive composite of putting down in writing, wherein, also contain heat curing promoter.

＜9〉according to described＜1 〉～＜8 in each photosensitive composite of putting down in writing, wherein, also contain inorganic filler.

＜10〉according to described＜9〉photosensitive composite put down in writing, wherein, inorganic filler is a silicon dioxide.

＜11〉a kind of photosensitive film is characterized in that, by having on supporter by described＜1 〉～＜10 in the formed photographic layer of each photosensitive composite of putting down in writing form.

＜12〉according to described＜11〉photosensitive film put down in writing, this film is long chi shape, and forms by being rolled into the roller shape.

＜13〉a kind of photosensitive laminate is characterized in that, it has on matrix by described＜1 〉～＜10 in the formed photographic layer of each photosensitive composite of putting down in writing.

＜14〉according to described＜13〉photosensitive laminate put down in writing, wherein, photographic layer is by described＜11 〉～＜12 in each photosensitive film of putting down in writing form.

＜15〉a kind of formation method of permanent pattern is characterized in that, comprises at least by described＜1 〉～＜10 in the formed photographic layer of each photosensitive composite of putting down in writing carry out step of exposing.

＜16〉according to described＜15〉the permanent pattern formation method put down in writing, wherein, use the laser of 350～415nm wavelength to expose.

＜17〉a kind of printed base plate is characterized in that, utilizes described＜15 〉～＜16 in the formation method of each permanent pattern of putting down in writing form permanent pattern.

The invention effect

According to the present invention; can solve existing issue; by the regulation kind of bonding agent and the residual quantity of catalyzer, can provide a kind of ageing stability excellence that can form the exploring degree (circular hole) behind storage stability and the lamination expeditiously; and alleviated the painted of adhesive resin; and suppressed the color and taste variation (look fault) of sense material; high meticulous permanent pattern (diaphragm; interlayer dielectric and solder resist pattern etc.) photosensitive composite; photosensitive film; photosensitive laminate; use the permanent pattern formation method of described photosensitive composite and utilize described permanent pattern formation method to form figuratum printed base plate.

Embodiment

(photosensitive composite)

Photosensitive composite of the present invention is by containing bonding agent, polymerizable compound, photopolymerization initiator, thermal cross-linking agent and catalyzer, and contains other compositions as required and form.

＜bonding agent 〉

As described bonding agent, it is formed by following modified copolymer, and described modified copolymer is by (methyl) acrylate (A) with contain unsaturated group and contain the modified copolymer that addition (methyl) glycidyl acrylate forms on a part of acid group of the resulting multipolymer of compound (B) of 1 acid group at least.

-(methyl) acrylate (A)-

As described (methyl) acrylate (A), can list: (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate; (methyl) esters of acrylic acid of hydroxyls such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxy butyl ester, caprolactone modification (methyl) acrylic acid 2-hydroxyl ethyl ester; (methyl) esters of acrylic acids such as methoxyl diglycol (methyl) acrylate, ethoxydiglycol (methyl) acrylate, different octyloxy diglycol (methyl) acrylate, phenoxy group triethylene glycol (methyl) acrylate, methoxyl triethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate etc.

-contain the compound (B) of unsaturated group-

As the described compound (B) that contains unsaturated group, can list: acrylic acid, methacrylic acid, vinylphenol, chain is extended between unsaturated group and carboxylic acid modification unsaturated monocarboxylic for example β-carboxyethyl (methyl) acrylate, 2-acrylyl oxy-ethyl succinic acid, 2-acrylyl oxy-ethyl phthalic acid, 2-acrylyl oxy-ethyl hexahydro-phthalic acid, the interior unsaturated monocarboxylic that contains ester bond such as ester modified, contain the modification unsaturated monocarboxylic of ehter bond etc.

---modification unsaturated monocarboxylic---

As described modification unsaturated monocarboxylic, particularly, can list: as the ester modified compound that forms in (methyl) acrylic acid is carried out,

CH ₂＝C(-R ₁)CO-[O(CR ₂R ₃) _mCO] _n-OH (1)；

As terminal hydroxyl is carried out the lactone modifier that sour modification forms with acid anhydrides,

CH ₂＝C(-R ₁)COO-CH ₂CH ₂O[CO(CR ₂CR ₃) _mO]nCOR ₄COOH(

" in formula (1), (2), R ₁Expression hydrogen atom or methyl.M R ₂And R ₃Represent hydrogen atom, methyl or ethyl respectively, each other can be different.R ₄The expression carbon number be the saturated or unsaturated alkyl of 1～10 divalence aliphatics, carbon number be the saturated or unsaturated alkyl of 1～6 divalence ester ring type, to xylylene, phenylene etc.M represents 4～8 integer, and n represents 1～10 integer.”。

---the modification unsaturated monocarboxylic that contains ehter bond---

As the described modification unsaturated monocarboxylic that contains ehter bond, can list: epoxy compound such as addition of ethylene oxide and the molecular end hydroxyl of addition product carried out the following general formula that sour modification forms with acid anhydrides on (methyl) acrylic acid:

CH ₂＝C(-R ₁)COO-[(CR ₂R ₃) _mO] _n-COR ₄COOH (3)

" in the formula, R ₁Expression hydrogen atom or methyl.M R ₂And R ₃Represent hydrogen atom, methyl, ethyl, propyl group or butyl respectively, each other can be different.R ₄The expression carbon number be the saturated or unsaturated alkyl of 1～10 divalence aliphatics, carbon number be the saturated or unsaturated alkyl of 1～6 divalence ester ring type, to xylylene, phenylene etc.M and n represent 1～10 integer.”。Perhaps, also can be the material that contains the hydroxy-acid group of plural maleic acid etc. in the molecule.Described material can be used alone, but also also mix together.

---addition (methyl) glycidyl acrylate---

Next, by by described (A) with contain that addition (methyl) glycidyl acrylate obtains modified copolymer on a part of acid group of the resulting multipolymer of compound (B) of unsaturated group.(methyl) glycidyl acrylate gathers in 1 molecule at least one free-radical polymerised unsaturated group and epoxy radicals.

With respect to resulting modified copolymer, the addition amount of being somebody's turn to do (methyl) glycidyl acrylate is preferably the scope of 5～70 weight %.During described addition quantity not sufficient 5 weight %, ultra-violet solidified poor, the physical property of curing overlay film reduces.Described addition amount is 70 weight % when above, the storage stability variation of resin.

So operation and the modified copolymer that obtains, preferred acid number are 10～150KOH-mg/g, further are the scope of 50～150KOH-mg/g.During this acid number deficiency 10KOH-mg/g, be difficult to remove cured films with dilute alkaline aqueous solution; When surpassing 150KOH-mg/g, there are the water tolerance of curing overlay film, the problem of electrical characteristics difference.In addition, modified copolymer (D) preferable weight-average molecular weight is 5,000～100,000 scope.There is (1) not sticking (tack free: in weight-average molecular weight less than 5,000 o'clock _ッNetwork Off リ-) moisture-proof of filming after the exposure of poor performance, (2) is poor, produces film limit youngster, the problem of the non-constant of exploring degree during development.When weight-average molecular weight surpasses at 100,000 o'clock, there are problems such as the obvious variation of (1) development, (2) storage-stable difference.

When making modified copolymer, the solvent as using in the reaction gets final product so long as dissolve raw materials used solvent, is not particularly limited, and for example can use: aromatic hydrocarbons such as benzene,toluene,xylene; Alcohols such as methyl alcohol, ethanol, 2-propyl alcohol; Ketones such as acetone, butanone, methyl isobutyl ketone; Ethers such as diethyl ether, butyl oxide, diox; Ester classes such as ethyl acetate, isobutyl acetate, ethylene glycol acetate, propylene glycol monoacetate, dipropylene glycol monoacetate; The ethylene glycol monoalkyl ether class; The diglycol monotertiary alkyl ether; The propylene-glycol monoalky lether class; Dipropylene glycol monoalkyl ethers; Butylene glycol monoalkyl ethers; The ethylene glycol bisthioglycolate alkyl ether; Diglycol such as diethylene glycol dimethyl ether, diethyl carbitol dialkyl ether; The ethylene glycol monoalkyl ether acetate class; Diglycol monotertiary alkyl ether acetate esters; Amide-type such as dimethyl formamide, dimethyl acetamide; Halogenated hydrocarbons such as phenixin, chloroform etc.Described solvent can use separately, perhaps can mix use.

＜catalyzer 〉

Consider from the angle of reacting rapidly, on the carboxyl of the macromolecular compound that has carboxyl at described side chain, when having (methyl) glycidyl acrylate of at least one free-radical polymerised unsaturated group and epoxy radicals in addition 1 molecule, use catalyzer.

Herein, in the present invention, " catalyzer " is meant the carboxyl that is used to promote to have at described side chain the macromolecular compound of carboxyl, the material of reaction that has (methyl) glycidyl acrylate of at least one free-radical polymerised unsaturated group and epoxy radicals in addition 1 molecule, this material promotes described reaction, and this for example can be by using gas chromatography determination to contain the spending rate of compound of epoxy radicals and olefinic unsaturated link and the mode of the speed when not adding catalyzer is confirmed.

Described catalyzer is not particularly limited, usually employed catalyzer in the time of can suitably being chosen in described (methyl) glycidyl acrylate that contains epoxy radicals and olefinic unsaturated link of addition can be enumerated as the slaine of carboxylic acid, alkyl urea, alkyl guanidine, lewis acid alkalescence compound etc.

As the slaine of described carboxylic acid, can enumerate as lithium salts, chromic salts, zirconates, sylvite or the sodium salt of naphthenic acid, lauric acid, stearic acid, oleic acid, octenoic acid etc.

As described alkyl urea, can enumerate as quaternary ammonium salts such as tetramethyl ammonium chloride, tetraethylammonium bromide, tetrabutyl ammonium bromide, 4-methyl urea etc.

As described alkyl guanidine, can enumerate as tetramethyl guanidine etc.

As described lewis base property compound, can enumerate as phosphine compound, chain-like alkyl tertiary amine compound, aromatic uncle amine compound, heterocycle shape tertiary amine compound etc.

Described phosphine compound can be enumerated as triphenyl phasphine etc.

Described chain-like alkyl tertiary amine compound can be enumerated as dimethyl benzylamine, triethylamine, tetramethylethylenediamine, three n-octylamine etc.

Described aromatic uncle amine compound can be enumerated as pyridine, picoline, lutidines, dimethylamino naphthyridine etc.

Described heterocycle shape tertiary amine compound can be enumerated as N-crassitude, N-methyl piperidine, 1,4-lupetazin, quinuclidine, 1,4-diazabicyclo { 2.2.2} octane (DABCO), N-methylmorpholine, 1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-carbene (DBN), 1,8-diazabicyclo [5.4.0] 11-5-carbene (DBU) etc.

As described catalyzer, consider preferred phosphine compound, wherein preferred especially triphenyl phasphine from the angle of the storage stability of addition reaction facilitation effect, sense material.

The solid constituent residual quantity of described catalyzer in described adhesive solids composition is below the 500 quality ppm, is preferably below the 300 quality ppm, and be more preferably not residual fully.

Herein, the residual quantity of described catalyzer for example can use high performance liquid chromatography, vapor-phase chromatography to measure.

＜polymerizable compound 〉

Described polymerizable compound is not particularly limited, can suitably selects, for example preferably contain the compound of the olefinic unsaturated link more than 1 according to purpose.

As described olefinic unsaturated link, can enumerate as the allyl of vinyl, allyl ether or the allyl ester etc. of (methyl) acryloyl group, (methyl) acrylamido, styryl, vinyl esters or vinyl ether etc. etc.

The described compound that contains the olefinic unsaturated link more than 1 is not particularly limited, can suitably selects according to purpose, can preferably enumerate as: that selects from the monomer with (methyl) acrylic is at least a.

Described monomer with (methyl) acrylic is not particularly limited, can suitably select according to purpose, can enumerate as monofunctional acrylate or simple function methacrylates such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) acrylic acid phenoxy ethyl; Polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexanediol two (methyl) acrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, three (acrylyl oxy-ethyl) chlorinated isocyanurates, three (acrylyl oxy-ethyl) cyanurate, three (methyl) acrylic acid glyceride; Polyfunctional alcohols such as trimethylolpropane or glycerine, bis-phenol are carried out carry out after the addition reaction of oxirane or epoxypropane the product of (methyl) acroleic acid esterification; The urethane acrylate class of putting down in writing in each communique such as Japanese Patent Publication 48-41708 number, Japanese Patent Publication 50-6034 number, Japanese Patent Publication 51-37193 number; The polyester acrylate class of putting down in writing in each communique such as Japanese kokai publication sho 48-64183 number, Japanese Patent Publication 49-43191 number, Japanese Patent Publication 52-30490 number; As polyfunctional acrylic ester such as the epoxy acrylate class of epoxy resin and (methyl) acrylic acid reaction product or methacrylate etc.Wherein, preferred especially trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate.

Preferred 5～50 quality % of the solid constituent residual quantity of described polymerizable compound in described photosensitive composite solid constituent, more preferably 10～40 quality %.If degradation problem under development deterioration, the exposure sensitivity then appears in this solid component content less than 5 quality % sometimes; When described solid component content surpassed 50 quality %, the cohesive of photographic layer became strong sometimes.

＜photopolymerization initiator 〉

As the photopolymerization initiator, as long as have the ability of the polymerization that causes described polymerizable compound, be not particularly limited, can from known photopolymerization initiator, suitably select.For example preferably having photosensitive material from the ultraviolet range to luminous ray, can be with light activated sensitizer certain effect to take place and the activating agent that generates living radical, also can be the initiator that causes cationic polymerization according to monomeric species.

In addition, described photopolymerization initiator preferably contains at least a composition that has at least about 50 molecule absorptivity in the scope of the about 300～800nm of wavelength.Described wavelength is 330～500nm more preferably.

As described photopolymerization initiator, can enumerate as halogenated hydrocarbons derivant (for example having the halogenated hydrocarbons of triazine skeleton, the halogenated hydrocarbons of Ju You oxadiazole skeleton etc.), Hexaarylbiimidazole, 9 oxime derivate, organic peroxide, sulphur compound, ketonic compound, aromatics salt, class of metallocenes etc.Wherein, consider preferably have halogenated hydrocarbons, 9 oxime derivate, ketonic compound, the Hexaarylbiimidazole based compound of triazine skeleton from sensitivity, keeping quality and photographic layer and the printed-wiring board (PWB) formation of photographic layer with the adaptation equal angles of substrate.

As described Hexaarylbiimidazole, can enumerate as 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (3-methoxyphenyl) diimidazole, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-methoxyphenyl) diimidazole, 2,2 '-two (4-methoxyphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-nitrobenzophenones)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, 2,2 '-two (2-trifluoromethyls)-4,4 ', 5,5 '-tetraphenyl diimidazole, the compound of putting down in writing in the WO00/52529 communique etc.

As described diimidazole class, for example can utilize Bull.Chem.Soc.Japan, disclosed methods are easily synthesized in 33,565 (1960) and J.Org.Chem, 36 (16) 2262 (1971).

As halogenated hydrocarbon compound with triazine skeleton, can enumerate as: if Lin Dengzhu, Bull.Chem.Soc.Japan, the J.Org.Chem. of works such as the compound of No. 3337024 instructions records of compound, Deutsche Bundespatent of the compound of No. 1388492 instructions records of compound, the BrP of 42,2924 (1969) records, the record of Japanese kokai publication sho 53-133428 communique, F.C.Schaefer; 29, the compound of putting down in writing in No. 4212976 instructions of compound, United States Patent (USP) of the compound of the compound of compounds, the Japanese kokai publication sho 62-58241 communique record of 1527 (1964) records, the record of Japanese kokai publication hei 5-281728 communique, the record of Japanese kokai publication hei 5-34920 communique etc.

Described if Lin Dengzhu, Bull.Chem.Soc.Japan, the compounds of 42,2924 (1969) records can enumerate as 2-phenyl-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-chlorphenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-tolyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(2, the 4-dichlorophenyl)-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine, 2,4,6-three (trichloromethyl)-1,3, the 5-triazine, 2-methyl-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-n-nonyl-4, two (trichloromethyl)-1 of 6-, 3,5-triazine and 2-(α, α, β-three chloroethyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-etc.

The compound of No. 1388492 instructionss of described BrP record can be enumerated as 2-styryl-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-methyl styrene base)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(4-methoxyl-styrene)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(4-methoxyl-styrene)-4-amino-6-trichloromethyl-1,3,5-triazines etc.

The compound of described Japanese kokai publication sho 53-133428 communique record can be enumerated as 2-(4-methoxyl-naphthalene-1-yl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(4-ethoxy-naphthalene-1-yl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-[4-(2-ethoxyethyl group)-naphthalene-1-yl]-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(4,7-dimethoxy-naphthalene-1-yl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine and 2-(acenaphthene also-5-yl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine etc.

The compound of No. 3337024 instructionss of described Deutsche Bundespatent record can be enumerated as 2-(4-styryl phenyl)-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine, 2-(4-(4-methoxyl-styrene) phenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(1-naphthyl ethenylidene phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-chlorostyrene base phenyl-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-thiophene-2-ethenylidene phenyl)-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine, 2-(4-thiophene-3-ethenylidene phenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-furans-2-ethenylidene phenyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine and 2-(4-coumarone-2-ethenylidene phenyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine etc.

The J.Org.Chem. of work such as described F.C.Schaefer; 29, the compounds of 1527 (1964) records can be enumerated as 2-methyl-4, two (trisbromomethyl)-1,3 of 6-, 5-triazine, 2,4,6-three (trisbromomethyl)-1,3,5-triazine, 2,4,6-three (two bromomethyls)-1,3,5-triazines, 2-amino-4-methyl-6-three (bromomethyl)-1,3,5-triazine and 2-methoxyl-4-methyl-6-trichloromethyl-1,3,5-triazines etc.

The compound of described Japanese kokai publication sho 62-58241 communique record can be enumerated as 2-(4-phenylacetylene base phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-naphthyl-1-ethynyl phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-(4-tolyl ethinyl) phenyl)-4, two (trichloromethyl)-1,3 of 6-, the 5-triazine, 2-(4-(4-methoxyphenyl) ethynyl phenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-(4-isopropyl phenyl ethinyl) phenyl)-4, two (trichloromethyl)-1 of 6-, 3, the 5-triazine, 2-(4-(4-ethylphenyl ethinyl) phenyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine etc.

The compound of described Japanese kokai publication hei 5-281728 communique record can be enumerated as 2-(4-trifluoromethyl)-4, two (trichloromethyl)-1,3 of 6-, 5-triazine, 2-(2, the 6-difluorophenyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(2, the 6-dichlorophenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(2, the 6-dibromo phenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-etc.

The compound of described Japanese kokai publication hei 5-34920 communique record can enumerate as: 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methylamino)-and the 3-bromophenyl]-1,3, trihalomethyl-s-triaizine compounds and 2 of putting down in writing in 5-triazine, No. 4239850 instructions of United States Patent (USP), 4,6-three (trichloromethyl)-s-triazine, 2-(4-chlorphenyl)-4, two (the trisbromomethyl)-s-triazines of 6-etc.

The compound of putting down in writing in No. 4212976 instructions of described United States Patent (USP) can be enumerated compound as: Ju You oxadiazole skeleton (2-trichloromethyl-5-phenyl-1 for example, 3, the 4-oxadiazole, 2-trichloromethyl-5-(4-chlorphenyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3, the 4-oxadiazole, 2-trisbromomethyl-5-phenyl-1,3, the 4-oxadiazole, 2-trisbromomethyl-5-(2-naphthyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-styryl-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(4-chlorostyrene base)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(4-methoxyl-styrene)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxy styryl)-1,3, the 4-oxadiazole, 2-trisbromomethyl-5-styryl-1,3,4-oxadiazole etc.) etc.

As the 9 oxime derivate that is fit among the present invention use, for example represent with following general formula (1).

General formula (1)

Wherein, in the described general formula (1), R ¹The expression hydrogen atom, can have in substituent acyl group, alkoxy carbonyl, aryloxycarbonyl, alkyl sulphonyl and the aryl sulfonyl any; R ²Independent respectively expression substituting group.M represents 0～4 integer, when m is 2 when above, can link mutually to form ring.A represents any in 4,5,6,7 yuan of rings.A is preferably any in 5 and 6 yuan of rings.

As the 9 oxime derivate that uses among the present invention (oxime compound), the compound of more preferably following general formula (2) expression.

General formula (2)

Wherein, in the described general formula (2), R ¹The expression hydrogen atom, can have in substituent acyl group, alkoxy carbonyl, aryloxycarbonyl, alkyl sulphonyl and the aryl sulfonyl any; R ²Represent substituting group respectively independently.M represents 0～4 integer, when m is 2 when above, can link mutually to form ring.X represents CH ₂, among O and the S any; A represents any in 5 and 6 yuan of rings.

In described general formula (1) and (2), R ¹The acyl group of expression can be any in aliphatics, aromatics and the heterocycle, can further have substituting group.

As aliphatic group, can list: acetyl group, propiono, bytyry, caproyl, capryl, phenoxy group acetyl group, chloracetyl etc.As aromatic group, can list: benzoyl, naphthoyl, methoxybenzoyl base, nitro benzoyl etc.As heterocyclic radical, can list: furyl (Off ラ ノ イ Le base), sulfydryl phenyl (チ オ Off _ェノ イ Le) etc.

As substituting group, any in preferred alkoxy, aryloxy group and the halogen atom.As acyl group, preferred total carbon atom number is 2～30 acyl group, and more preferably total carbon atom number is 2～20 acyl group, and preferred especially total carbon atom number is 2～16 acyl group.As described acyl group; can enumerate as: acetyl group, propiono, methylpropionyl, bytyry, valeryl, caproyl, cyclohexane carbonyl, caprylyl, capryl, lauryl, octadecanoyl, benzyloxycarbonyl group, phenoxy group acetyl group, 2-ethyl hexanoyl base, chloracetyl, benzoyl, to methoxybenzoyl base, 2 5-dibutoxy benzoyl, 1-naphthoyl, 2-naphthoyl, pyridine radicals carbonyl, methacryl, acryloyl group etc.

As alkoxy carbonyl, can have substituting group, preferred total carbon atom number is 2～30 alkoxy carbonyl, and more preferably total carbon atom number is 2～20 alkoxy carbonyl, and preferred especially total carbon atom number is 2～16 alkoxy carbonyl.As described alkoxy carbonyl, can enumerate as methoxycarbonyl, ethoxy carbonyl, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl, allyloxy carbonyl, carbonyl octyloxy, dodecyloxy carbonyl, ethoxy ethoxy carbonyl.

As aryloxycarbonyl, can have substituting group, preferred total carbon atom number is 7～30 aryloxycarbonyl, and more preferably total carbon atom number is 7～20 aryloxycarbonyl, and preferred especially total carbon atom number is 7～16 aryloxycarbonyl.As described aryloxycarbonyl, can enumerate as: phenyloxycarbonyl, 2-naphthoxy carbonyl, to methoxyl phenyloxycarbonyl, 2 5-diethoxy phenyloxycarbonyl, to chlorophenoxy carbonyl, p-nitrophenyl oxygen base carbonyl, to the cyano-benzene oxygen carbonyl.

As alkyl sulphonyl, can further have substituting group.As this substituting group, can preferably enumerate as phenyl, halogen atom, alkoxy, aryloxy group, alkoxy carbonyl, acyloxy, acyl amino, carbamyl, cyano group, carboxylic acid group, sulfonic group, heterocyclic radical.As alkyl sulphonyl, especially preferably enumerate: methyl sulphonyl, butyl sulfonyl, octyl group sulfonyl, decyl sulfonyl, dodecyl sulfonyl, benzyl sulfonyl, trifluoromethyl sulfonyl.

As aryl sulfonyl, can further have substituting group.As this substituting group, can preferably enumerate as phenyl, halogen atom, alkoxy, aryloxy group, alkoxy carbonyl, acyloxy, acyl amino, carbamyl, cyano group, carboxylic acid group, sulfonic group, heterocyclic radical.As aryl sulfonyl, especially preferably enumerate: benzenesulfonyl, tosyl, chlorobenzene sulfonyl, butyl phenyl ether sulfonyl, 2,5-dibutoxy benzenesulfonyl, p-nitrophenyl sulfonyl, the fluorobenzene sulfonyl.

In described general formula (1) and (2), R ²The substituting group of expression can list: aliphatics, aromatics and heteroaromatic, halogen atom ,-OR ³,-SR ³,-NR ³R ⁴R ³And R ⁴Can be connected to each other and form ring.In addition, R ₃And R ₄In independent separately expression hydrogen atom or aliphatic group, aromatic group, the heteroaromatic group any.When m is more than 2, during formation ring connected to each other, R independently separately ²Between can form ring, can also be via R ³And R ⁴In at least any and form ring.

When via described substituent R ²And form when encircling, can list following structure:

In the described structural formula, Y and Z represent CH ₂,-O-,-S-and-among the NR-any.

R ², R ³And R ⁴The object lesson of aliphatic group, aromatic group and heteroaromatic group can list and described R ¹Identical example.

As the object lesson of the oxime compound of described general formula (1) expression, can list the compound of following structural formula (1)～(5) expression, but the present invention is not limited to these.

Structural formula (1) structural formula (2) structural formula (3) structural formula (4) structural formula (5) structural formula (6)

Structural formula (7) structural formula (8) structural formula (9) structural formula: (10) structural formula: (11) structural formula (12)

Structural formula (15) structural formula (16) structural formula (17) structural formula (18)

Structural formula (19 structural formulas (20) structural formulas (21) structural formulas (22)

Structural formula (23) structural formula (24) structural formula (25) structural formula (26) structural formula (27) structural formula: (28)

Structural formula (29) structural formula (30) structural formula (31) structural formula (32) structural formula (33) structural formula (34)

Structural formula (35) structural formula (36) structural formula (37) structural formula (38) structural formula (39)

Structural formula (40) structural formula (41) structural formula (42) structural formula (43) structural formula (44)

Structural formula (45) structural formula (46) structural formula (47) structural formula (48) structural formula (49) structural formula (50) structural formula (51)

Need to prove that the oxime compound that uses among the present invention can be measured ¹H-NMR collection of illustrative plates, UV-vis absorb collection of illustrative plates and judge.

(manufacture method of oxime compound)

As the manufacture method of described oxime compound of the present invention, can be easily synthetic by corresponding oxime compound and acyl group salt or anhydride are reacted in the presence of alkali (for example triethylamine, pyridine), in inert solvents such as THF, DMF, acetonitrile or in the basic solvent such as pyridine.Preferred-10～60 ℃ of described temperature of reaction.

In addition, by using chloro-carbonate, alkyl sulfonyl chloride, aryl sulfonyl chloride, can synthesize corresponding various oxime ester compounds as described acyl group salt.

Be used as the synthetic method of the oxime compound of initiation material during as the described oxime compound of manufacturing, utilize standard chemical textbook (J.March for example, Advanced Organic Chemisrey, 4th Edition, Wiley Interscience, 1992) or special single chapter, for example S.R.Sandler ﹠amp; W.Karo, Organic functional group preparations, Vol.3, the whole bag of tricks of putting down in writing among the Academic Press can obtain.

As the particularly preferred synthetic method of described oxime compound, can enumerate as method that aldehydes or ketones and azanol or its salt are reacted in ethanol or ethanol water isopolarity solvent.Under this situation, add the pH that alkali such as sodium acetate or pyridine are controlled reaction mixture.As everyone knows, reaction velocity depends on pH, can add alkali continuously when the reaction beginning or between the reaction period.

Can use basic solvents such as pyridine as alkali and/or solvent or cosolvent.

Described temperature of reaction is preferably the reflux temperature of potpourri, promptly about 60～120 ℃ usually.

Other different preferred synthetic methods as described oxime compound can list: the method that " activity " methylene that utilizes nitrous acid or alkyl nitrite to produce carries out nitrosylation.For example, Organic Syntheses coll.Vol.VI (J.Wiley﹠amp; Sons, New York, 1988), the alkali condition and for example Organic Syntheses coll.Vol.V of record among the pp.199 and 840, pp.32 and 373, coll.Vol.III.pp.191 and 513, coll.Vol.II, these two kinds of conditions of acid condition of record all are suitable for being used as among synthetic the present invention the oxime compound of initiation material among the pp.202,204 and 363.

Described nitrous acid is generated by sodium nitrite usually.

As described alkyl nitrite, can enumerate as methyl nitrite, nitrous ether (ethyl nitrite), Isopropyl Nitrite, butyl nitrite or isoamyl nitrite.

As the group of described oxime ester, can be with two kinds of spatial configurations (Z) or the group that (E) exists.Can pass through customary way separating isomerism body, also can be directly with the kind of isomer mixture as the initial usefulness of light.Therefore, oxime compound of the present invention can be the mixture of isomers on the spatial configuration of compound of described structural formula (1)～(51).

The excellent storage stability of oxime compound, highly sensitive, therefore by oxime compound is added in the polymerizable composition, polymerizable composition, the irradiation that polymerization, excellent storage stability do not take place in the time of can obtaining a kind of the preservation, utilizes energy line, particularly light produces living radical and initiated polymerization, this polymerizable compound highly sensitive polymerizable composition, polymerizable composition that can carry out polymerization at short notice efficiently efficiently.

As the photopolymerization initiator beyond above-mentioned, can list: acridine derivatives (9-phenylacridine for example, 1,7-two (9,9 '-acridinyl) heptane etc.), N-phenylglycine etc., polydentate compound (carbon tetrabromide for example, phenyl trisbromomethyl sulfone, phenyl trichloromethyl ketone etc.), Coumarins (3-(2-coumarone formoxyl)-7-diethyl amino coumarin for example, 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin, 3-benzoyl-7-diethyl amino coumarin, 3-(2-methoxybenzoyl base)-7-diethyl amino coumarin, 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin, 3,3 '-carbonyl two (5,7-two positive propoxy cumarins), 3,3 '-carbonyl two (7-diethyl amino coumarin), 3-benzoyl-ayapanin, 3-(2-furanylcarbonyl)-7-diethyl amino coumarin, 3-(4-diethylamino cinnamyl)-7-diethyl amino coumarin, 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin, 3-benzoyl-5,7-dipropoxy cumarin, 7-benzotriazole-2-basic note legumin, and Japanese kokai publication hei 5-19475 number, Japanese kokai publication hei 7-271028 number, TOHKEMY 2002-363206 number, TOHKEMY 2002-363207 number, TOHKEMY 2002-363208 number, the coumarin compound of record such as TOHKEMY 2002-363209 communique etc.), amine (4-dimethyl ethyl aminobenzoate for example, the positive butyl ester of 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid phenethyl ester, 4-dimethylaminobenzoic acid 2-phthalimide ethyl ester, 4-dimethylaminobenzoic acid 2-methacryl 2-ethoxyethyl acetate, pentamethylene two (4-dimethylaminobenzoic acid ester), the phenethyl ester of 3-dimethylaminobenzoic acid, the pentamethylene ester; The 4-dimethylaminobenzaldehyde; 2-chloro-4-dimethylaminobenzaldehyde; 4-dimethylamino phenmethylol; ethyl (4-dimethylamino benzoyl) acetic acid esters; 4-piperidyl acetophenone; 4-dimethylamino benzoin; N; N-dimethyl-4-toluidine; N; N-diethyl-3-phenetidine; tribenzyl amine; the dibenzyl phenyl amine; N-methyl-N-phenylbenzyl amine; 4-bromo-N; accelerine; Alamine 304; amino Material of Fluoran (ODB; ODBII etc.); the gentian violet lactone; colourless gentian violet etc.); acylphosphine oxide class (for example two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide; two (2; 6-dimethoxy benzoyl)-2; 4,6-tri-methyl-amyl phenyl phosphine oxide; LucirinTPO etc.) etc.

Can further list: the VicinalPolyketal Donyl that puts down in writing in No. 2367660 instructions of United States Patent (USP) (PVC シ Na Le Port リ ケ Le De ニ Le) compound, the acyloin ether compound of putting down in writing in No. 2448828 instructions of United States Patent (USP), the aromatic series acyloin compound of putting down in writing in No. 2722512 instructions of United States Patent (USP) that is replaced by α-hydrocarbon, the multinuclear naphtoquinone compounds of putting down in writing in No. 3046127 instructions of United States Patent (USP) and No. 2951758 instructions of United States Patent (USP), the organoboron compound of putting down in writing in the TOHKEMY 2002-229194 communique, free-radical generating agent, the triarylsulfonium salt salt of hexafluoro antimony or hexafluorophosphoric acid ester (for example with), microcosmic salt compound (for example phenyl thio-phenyl) diphenyl sulfonium salt etc.) (effective) as the cationic polymerization initiator, the salt compound of WO01/71428 communique record etc.

Described photopolymerization initiator can be used alone, and also can be used in combination two or more.As two or more combinations, can enumerate as the Hexaarylbiimidazole of putting down in writing in No. 3549367 instructions of United States Patent (USP) and the combination of 4-aminoketones; The combination of benzothiazole compound of putting down in writing in the Japanese Patent Publication 51-48516 communique and trihalomethyl-s-triaizine compounds; And aromatic ketone compound (for example thioxanthones etc.) and hydrogen are for giving the body combination of (for example containing the compound, phenolic compound of dialkyl amido etc.); The combination of Hexaarylbiimidazole and two luxuriant titaniums; The combination of Coumarins and two luxuriant titaniums and phenylglycine class etc.

As the more preferred example of described photopolymerization initiator, can list: complex light initiator, Hexaarylbiimidazole compound or two luxuriant titaniums etc. that will be in aftermentioned exposure can response wave length to be the described phosphinoxides of the laser of 405nm, described alpha-aminoalkyl ketone, described halogenated hydrocarbon compound with triazine skeleton make up as the amines of sensitizer with aftermentioned.

Preferred 0.1～30 quality % of the content of described photopolymerization initiator in described photosensitive composite, more preferably 0.5～20 quality %, preferred especially 0.5～15 quality %.

＜thermal cross-linking agent 〉

Thermal cross-linking agent is not particularly limited, can suitably select according to purpose, for the film strength after the curing that improves the photographic layer that uses described photosensitive film formation, can in can not be, use the compound (for example 1 molecule contains the epoxy compound of at least 2 Oxyranyles) that for example comprises epoxy compound to the dysgenic scope of generations such as development, the oxetane compound that has at least 2 oxetanyls in 1 molecule can list: the epoxy compound of putting down in writing in the TOHKEMY 2007-47729 communique with Oxyranyle, the β position has the epoxy compound of alkyl, oxetane compound with oxetanyl, polyisocyanate compounds, the compound that makes the isocyanates radical reaction of end-capping reagent and polyisocyanate and derivant thereof and obtain etc.

As described thermal cross-linking agent, can also use melamine derivative.This melamine derivative can be enumerated as: methylol melamine, alkylated methylol melamine (with the compound with the methylol etherificate such as methyl, ethyl, butyl) etc.Described thermal cross-linking agent can be used alone, and also can be used in combination two or more.Wherein, good from storage stability, to the film strength itself of the skin hardness that improves photographic layer or cured film effectively angle consider preferred alkyl methylol melamine, especially preferably hexamethyl methylol melamine.

The preferred 1 quality % of the solid component content of described thermal cross-linking agent in described photosensitive composite solid constituent～50 quality %, more preferably 3 quality %～30 quality %.If this solid component content less than 1 quality %, then the film strength of cured film can not be improved; When described solid component content surpassed 50 quality %, the decline of development or the decline of exposure sensitivity took place sometimes.

As described epoxy compound, can enumerate as: have epoxy compound that contains 2 epoxy radicals that have alkyl in the β position in the epoxy compound, 1 molecule of 2 Oxyranyles at least etc. in 1 molecule at least.

At least the epoxy compound that has 2 Oxyranyles in described 1 molecule can enumerate as: two xylenol types or bisphenol-type epoxy resin (" YX4000 japan epoxy resin (Japan Epoxy Resin) society's system " etc.) or their potpourri, have hetero ring type the epoxy resin (" TEPIC of chlorinated isocyanurates skeleton etc.; The daily output chemical industry (strain) system ", " ア ラ Le ダ イ ト PT810; The different chemicals of vapour Bart (Ciba Specialty Chemicals) society's system " etc.), bisphenol A type epoxy resin, phenolic resin varnish type epoxy resin, bisphenol f type epoxy resin; Bisphenol-A epoxy resin, bisphenol-s epoxy resin, novalac type epoxy resin; Cresol-novolak varnish type epoxy resin, halogenated epoxy resin (for example low brominated epoxy resin, high halogenated epoxy resin, bromination phenolic resin varnish type epoxy resin etc.), contain allylic bisphenol A type epoxy resin, tris-phenol type epoxy resin, diphenyl dimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene-type epoxy resin (" HP-7200, HP-7200H; Big Japanese ink chemical industry (strain) system " etc.); glycidyl amine type epoxy resin (diaminodiphenyl-methane type epoxy resin; diglycidylaniline; triglycidyl group amino-phenol etc.); glycidyl ester type epoxy resin (o-phthalic acid diglycidyl ester; hexane diacid 2-glycidyl ester, the hexahydro-phthalic acid 2-glycidyl ester, dimer acid 2-glycidyl ester etc.), hydantoins type epoxy resin, alicyclic epoxy resin (3,4-epoxy radicals cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylate, two (3,4-epoxy radicals cyclohexyl methyl) adipate, the dicyclopentadiene diepoxide, " GT-300; GT-400; ZEHPE3150; Daicel chemical industry system " etc.), imide-type alicyclic epoxy resin, trihydroxy benzene methylmethane type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, four phenolic group ethane type epoxy resin, O-phthalic acid glycidyl ester resin, four glycidyl group diformazan phenolic group ethane resin, contain naphthyl epoxy resin (naphthols aralkyl-type epoxy resin, naphthol novolak varnish type epoxy resin, four sense naphthalene type epoxy resin, as " ESN-190, the ESN-360 of commercially available product; Nippon Steel's chemistry (strain) system ", " HP-4032, EXA-4750, EXA-4700; Big Japanese ink chemical industry (strain) system " etc.); the polyphenolic substance that obtains by the addition reaction of diolefin compounds such as oxybenzene compound and divinylbenzene or bicyclopentadiene and the reactant of epichlorokydrin; the ring-opening polymerization polymer of 4 vinyl cyclohexene-1-oxide is carried out epoxidised product with peracetic acid etc.; have the epoxy resin of wire phosphor-containing structure; have the epoxy resin of cyclic phosphorus-containing structure; Alpha-Methyl talan type epoxy resin by using liquid crystal, dibenzoyl oxygen base benzene type epoxy resin by using liquid crystal, benzeneazo fundamental mode epoxy resin by using liquid crystal, azomethine phenyl type epoxy resin by using liquid crystal, dinaphthalene type epoxy resin by using liquid crystal, azine type epoxy resin, the glycidyl methacrylate copolymerization be epoxy resin (" CP-50S, CP-50M; Japan's grease (strain) system " etc.), cyclohexyl maleimide and the copolymerization epoxy resin of glycidyl methacrylate, two (glycidoxypropyl phenyl) fluorenes type epoxy resin, two (glycidoxypropyl phenyl) diamantane type epoxy resin etc., but be not limited to described resin.Described epoxy resin can be used alone, and also can be used in combination two or more.

In 1 molecule, have at least the described epoxy compound of 2 Oxyranyles, can also use and contain 2 epoxy compounds that have the epoxy radicals of alkyl in the β position in 1 molecule at least, especially preferably contain the epoxy radicals that the β position replaced by the alkyl compound of (more specifically for replace glycidyl etc. with β-alkyl).

Have with regard to the epoxy compound of epoxy radicals of alkyl with regard to described containing at least in the β position, the epoxy radicals more than 2 that is contained in 1 molecule can all be the glycidyl that replaces with β-alkyl, also can be that at least 1 epoxy radicals is the glycidyl that replaces with β-alkyl.

Have with regard to the epoxy compound of epoxy radicals of alkyl with regard to described containing at least in the β position, the angle of the storage stability under the room temperature is considered, in total epoxy radicals in described photosensitive composite in the contained described epoxy compound total amount, the ratio that β-alkyl replaces glycidyl is preferably more than 30%, more preferably more than 40%, be preferably more than 50% especially.

Described β-alkyl is replaced glycidyl to be not particularly limited, can suitably select according to purpose, can enumerate as Beta-methyl glycidyl, β-ethyl glycidyl, β-propyl group glycidyl, β-butyl glycidyl base etc., wherein, consider preferred Beta-methyl glycidyl from the angle of the angle of the storage stability that improves described photosensitive polymer combination and synthetic easiness.

As the described epoxy compound that has the epoxy radicals of alkyl in the β position that contains, for example preferably derive and next epoxy compound by polyphenol compound and β-alkyl epoxy halopropane.

Described β-alkyl epoxy halopropane is not particularly limited, can suitably selects, can enumerate as Beta-methyl epoxyhalopropane such as β-Jia Jihuanyanglvbingwan, Beta-methyl epoxy bromopropane, Beta-methyl epoxy fluoro-propanes according to purpose; β-ethyl epichlorokydrin, β-ethyl epoxy bromopropane, β-β-ethyl epoxyhalopropane such as ethyl epoxy fluoro-propane; β-propyl group epichlorokydrin, β-propyl group epoxy bromopropane, β-β-propyl group epoxyhalopropane such as propyl group epoxy fluoro-propane; β-butyl epichlorokydrin, β-butyl epoxy bromopropane, β-β such as butyl epoxy fluoro-propane-butyl epoxyhalopropane etc.Wherein, from considering preferred Beta-methyl epoxyhalopropane with the reactivity of described polyhydric phenol and mobile angle.

As described polyphenol compound, get final product so long as have the compound of the aromaticity hydroxyl more than 2 in 1 molecule, be not particularly limited, can suitably select according to purpose, can enumerate as bisphenol compounds such as bisphenol-A, Bisphenol F, bisphenol Ss; Diphenol compounds such as xenol, tetramethyl biphenyl phenol; Naphthol compound such as dihydroxy naphthlene, dinaphthol; Novolac resins such as P-F condensed polymer; Carbon numbers such as cresols-formaldehyde condensation products are that carbon numbers such as monoalkyl fortified phenol-formaldehyde condensation products of 1～10, xylenol-formaldehyde condensation products are that bisphenol compound-formaldehyde condensation products, phenol and carbon numbers such as dialkyl substituted phenol-formaldehyde condensation products of 1～10, bisphenol-A-formaldehyde condensation products are the addition polymer etc. of co-condensation polymer, oxybenzene compound and the divinylbenzene of 1～10 monoalkyl fortified phenol and formaldehyde.Wherein, when for example selecting in order to improve flowability and storage stability, preferred described bisphenol compound.

The described epoxy compound that has the epoxy radicals of alkyl in the β position of containing can be enumerated as the two-β-alkyl glycidyl ether of two-β of two-β of two-β of bisphenol-A-alkyl glycidyl ether, Bisphenol F-alkyl glycidyl ether, bisphenol S-bisphenol compounds such as alkyl glycidyl ether; Two-β-the alkyl glycidyl ether of two-β of two-β of xenol-alkyl glycidyl ether, tetramethyl biphenyl phenol-diphenol compounds such as alkyl glycidyl ether; β-the alkyl glycidyl ether of two-β of two-β of dihydroxy naphthlene-alkyl glycidyl ether, dinaphthol-naphthol compounds such as alkyl glycidyl ether; Poly--β-the alkyl glycidyl ether of P-F condensed polymer; Poly--carbon numbers such as β-alkyl glycidyl ether of cresols-formaldehyde condensation products are poly--β-alkyl glycidyl ether of monoalkyl fortified phenol-formaldehyde condensation products of 1～10; Poly--carbon numbers such as β-alkyl glycidyl ether of xylenol-formaldehyde condensation products are poly--β-alkyl glycidyl ether of dialkyl substituted phenol-formaldehyde condensation products of 1～10; Poly--β-the alkyl glycidyl ether of the poly--bisphenol compound-formaldehyde condensation products such as β-alkyl glycidyl ether of bisphenol-A-formaldehyde condensation products; Poly--β-the alkyl glycidyl ether of the addition polymer of oxybenzene compound and divinylbenzene etc.

Wherein preferred: the polymer-derived that obtains by the bisphenol compound of following structural formula (i) expression with by itself and epichlorokydrin etc. and β-alkyl glycidyl ether; And poly--β-alkyl glycidyl ether of oxybenzene compound-formaldehyde condensation products of (ii) representing of following structural formula.

Structural formula (i)

Structural formula (ii)

Wherein, in the described structural formula (i), R represents that hydrogen atom and carbon number are any in 1～6 the alkyl, and n represents 0～20 integer.

Wherein, described structural formula (ii) in, R represents that hydrogen atom and carbon number are any in 1～6 the alkyl; R " expression hydrogen atom and CH ₃In any; N represents 0～20 integer.

The described epoxy compound that has the epoxy radicals of alkyl in the β position that contains can be used alone, and also can be used in combination two or more.Can also be used in combination having the epoxy compound of 2 Oxyranyles in 1 molecule at least and containing the epoxy compound that has the epoxy radicals of alkyl in the β position.

And,, can also suitably use commercially available product of record in the TOHKEMY 2005-182004 communique [0037] and composition thereof as described epoxy compound.

As described oxetane compound, can enumerate as the oxetane compound that has 2 oxetanyls in 1 molecule at least.

Specifically can enumerate as two [(3-methyl-3-oxetanes ylmethoxy) methyl] ether, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters or multifunctional oxetanes classes such as their oligomer or multipolymer; Comprise in addition: have the compound of oxetanyl and novolac resin, poly-(para hydroxybenzene ethene), Ka Er many (カ Le De) type bisphenols, cup (calix: カ リ _ッNetwork ス) aromatic hydrocarbons, cup (calix: カ リ _ッNetwork ス) resorcinol aromatic hydrocarbons, silsesquioxane (Silsesquioxane, シ Le セ ス キ オ キ サ Application) etc. have the ether compound of the resin etc. of hydroxyl.In addition, can also list: have the unsaturated monomer of oxetanes ring and the multipolymer of (methyl) alkyl acrylate etc.

As described polyisocyanate compounds, can use the polyisocyanate compounds of Japanese kokai publication hei 5-9407 communique record.This polyisocyanate compounds can be derived by the fatty compound that the aliphatics that contains 2 isocyanate group at least, ring type aliphatics or aromatic group replace.Specifically can list: two functional isocyanate (for example 1,3-phenylene vulcabond and 1, the potpourri of 4-phenylene vulcabond, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-Xylene Diisocyanate, 1,4-Xylene Diisocyanate, two (4-isocyanates-phenyl) methane, two (4-isocyanates cyclohexyl) methane, isophorone diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc.); The polyfunctional alcohol of this two functional isocyanate and trimethylolpropane, pentaerythrite, glycerine etc.; The addition product of this polyfunctional alcohol's alkylene oxide adducts and described two functional isocyanate; Hexamethylene diisocyanate, hexa-methylene-1, the ring type trimer of 6-diisocyanate and derivant thereof etc. etc.

The compound that obtains as making the reaction of end-capping reagent and described polyisocyanate compounds, promptly, in the compound that makes the isocyanates radical reaction of end-capping reagent and polyisocyanate and derivant thereof and obtain isocyanate-terminated dose can list: alcohols (isopropyl alcohol for example, the tert-butyl alcohol etc.), lactams (for example epsilon-caprolactams etc.), phenols (phenol for example, cresols, p-t-butyl phenol, to sec-butyl phenol, to sec-amyl phenol, paraoctyl phenol, to nonyl phenol etc.), hetero ring type hydroxyl compound (3-pyridone for example, oxine etc.), activity methene compound (dialkyl malonate for example, methyl ethyl ketone oxime, diacetone, the Acetacetic acid alkyl ester oxime, acetoxime, cyclohexanone-oxime etc.) etc.In addition, can also use any the compound etc. that has in the molecule of Japanese kokai publication hei 6-295060 communique record at least one polymerisable double bonds and at least one blocked isocyanate base.

As described melamine derivative, can enumerate as methylol melamine, alkylated methylol melamine (methylol being carried out the compound of etherificate with methyl, ethyl, butyl etc.) etc.Described melamine derivative can be used alone, and also can be used in combination two or more.Wherein, good from storage stability, to the film strength itself of the skin hardness that improves photographic layer or cured film effectively angle consider preferred alkyl methylol melamine, especially preferably hexamethyl methylol melamine.

Described thermal cross-linking agent also can be used as two or more potpourris and uses.As described combination, combination of compounds, monofunctional compound and polyfunctional compound's that combination, difunctional's compound and the trifunctional between for example preferred difunctional's compound is above combination.In the described combination, the above combination of compounds of combination, difunctional's compound and trifunctional between preferred especially difunctional's compound.

As described difunctional's compound, the bisphenol type epoxy compound in the preferred epoxy compound, concrete two kinds the combination of preferably from bisphenol A-type, Bisphenol F type, bisphenol S type and xenol type, selecting.In addition, the combination of also preferred bisphenol type epoxy compound and phenolic varnish type epoxy compound, bisphenol type epoxy compound and contain the epoxy compound of heterocycle combination, bisphenol type epoxy compound and alicyclic epoxy compound combination, phenolic varnish type epoxy compound and contain the combination of combination, heterocyclic ring oxygen compound and the alicyclic epoxy compound of the epoxy compound of heterocycle.

Epoxy compound and epoxide equivalent that for example preferred epoxide equivalent of the combination of described thermal cross-linking agent is 90～400g/eq. are 150～9,000g/eq. the combination of epoxy compound, more preferably epoxide equivalent is that compound and the epoxide equivalent of 90～300g/eq. are 150～8, the combination of compounds of 000g/eq..That is, when described thermal cross-linking agent be that the epoxide equivalent of this potpourri is preferably 150～400g/eq., more preferably 150～300g/eq. when containing the potpourri of two or more compounds.Need to prove that epoxide equivalent can be measured according to JIS K 7236.

With regard to the content ratio of described resin, when with the little resin of epoxide equivalent value as Resin A, with the high resin of epoxide equivalent value during as resin B, for example by quality ratio, preferred A:B=1:100～100:1, more preferably 1:20～20:1, preferred especially 1:10～10:1.

Preferred 1～50 quality % of the solid component content of described thermal cross-linking agent in described photosensitive composite, more preferably 3～30 quality %.If this solid component content less than 1 quality % then confirms the raising less than the film strength of cured film; If described solid component content surpasses 50 quality %, the decline of development or the decline of exposure sensitivity then take place sometimes.

＜heat curing promoter 〉

In order to promote heat curing as the epoxy compound or the described oxetane compound of described thermal cross-linking agent, as heat curing promoter, for example can use: amines (dicyandiamide for example, benzyl dimethylamine, 4-(dimethylamino)-N, the N-dimethyl benzyl amine, 4-methoxyl-N, the N-dimethyl benzyl amine, 4-methyl-N, N-dimethyl benzyl amine etc.), quarternary ammonium salt compound (for example triethyl benzyl ammonia chloride etc.), blocked isocyanate compounds (for example dimethylamine etc.), imdazole derivatives two ring type amidine compounds and salt thereof (imidazoles for example, glyoxal ethyline, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, the 2-phenylimidazole, the 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole etc.), phosphorus compound (for example triphenyl phasphine etc.), guanamines compound (melamine for example, guanamines, acetylguanamine, benzoguanamine etc.), S-pyrrolotriazine derivatives (for example 2,4-diamido-6-methylacryoyloxyethyl-S-triazine, 2-vinyl-2,4-diamido-S-triazine, 2-vinyl-4,6-diamido-S-triazine isocyanuric acid addition product, 2,4-diamido-6-methylacryoyloxyethyl-S-triazine isocyanuric acid addition product etc.) etc.Described heat curing promoter can be used alone, and also can be used in combination two or more.Need to prove, so long as the curing catalysts of described epoxy resin compound or described oxetane compound or can promote the material of the reaction of described material and carboxyl to get final product, be not particularly limited, can use the above-mentioned substance compound that can promote heat curing in addition.

Described epoxy compound, described oxetane compound and can promote the solid component content of heat curing promoter in described photosensitive composite solid constituent of the heat curing of these materials and carboxylic acid to be generally 0.01～15 quality %.

In addition, in order to promote heat curing as the thermal cross-linking agent except that epoxy compound or described oxetane compound of described thermal cross-linking agent, as heat curing promoter, for example can use: amines (dicyandiamide for example, benzyl dimethylamine, 4-(dimethylamino)-N, the N-dimethyl benzyl amine, 4-methoxyl-N, the N-dimethyl benzyl amine, 4-methyl-N, N-dimethyl benzyl amine etc.), quarternary ammonium salt compound (for example triethyl benzyl ammonia chloride etc.), blocked isocyanate compounds (for example dimethylamine etc.), imdazole derivatives two ring type amidine compounds and salt thereof (imidazoles for example, glyoxal ethyline, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, the 2-phenylimidazole, the 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole etc.), phosphorus compound (for example triphenyl phasphine etc.), guanamines compound (melamine for example, guanamines, acetylguanamine, benzoguanamine etc.), S-pyrrolotriazine derivatives (for example 2,4-diamido-6-methylacryoyloxyethyl-S-triazine, 2-vinyl-2,4-diamido-S-triazine, 2-vinyl-4,6-diamido-S-triazine isocyanuric acid addition product, 2,4-diamido-6-methylacryoyloxyethyl-S-triazine isocyanuric acid addition product etc.) etc.Described heat curing promoter can be used alone, and also can be used in combination two or more.Need to prove,, can use the compound that can promote heat curing beyond the described material so long as the curing catalysts of described thermal cross-linking agent or can promote the material of the reaction of described material and carboxyl to get final product is not particularly limited.

Described thermal cross-linking agent and preferred 0.01～15 quality % of the solid component content of heat curing promoter in described photosensitive composite that can promote the heat curing of these materials and carboxylic acid.

＜other compositions 〉

As described other compositions, can enumerate as sensitizer, thermal polymerization inhibitor, plastifier, colorant (coloring pigment or dyestuff), filler pigment etc., can promote and the driving fit promoter of the adaptation of substrate surface and other auxiliary agent class (for example electrically conductive microparticle, filling agent, defoamer, fire retardant, levelling agent, peel off promoter, antioxidant, spices, surface tension modifier, chain-transferring agent etc.) further combined with using.

By suitably containing described composition, can regulate the character such as stability, photograph, film physical property of target photosensitive film.

-sensitizer-

Described sensitizer is not particularly limited; can from known sensitizer, suitably select; can enumerate as: known Ppolynuclear aromatic class (pyrene perylene for example; benzophenanthrene); xanthene class (fluorescein for example; eosin; erythrosine; rhodamine B; rose-red); cyanine glycoside (indoles carbon cyanines (indocarbocyanine) for example; thiophene carbon cyanines (thiacarbocyanine); oxa-carbocyanine oxacarbocyanine); merocyanine class (merocyanine for example; carbonyl merocyanine (carbomerocyanine)); thiazide (thionine for example; methylene blue; toluidine blue); acridine (acridine orange for example; chloroflavin; acridine yellow; the 9-phenylacridine; 1; 7-two (9; 9 '-acridinyl) heptane); anthraquinone class (for example anthraquinone); suquarium class (for example suquarium); acridine ketone (acridone for example; chloro-acridine ketone; N-methylacridine ketone; N-butyl acridone; N-butyl chloride acridone; 2-chloro-10-butyl acridone etc.); Coumarins (3-(2-coumarone formoxyl)-7-diethyl amino coumarin for example; 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-diethyl amino coumarin; 3-(2-methoxybenzoyl base)-7-diethyl amino coumarin; 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin; 3; 3 '-carbonyl two (5; 7-two positive propoxy cumarins); 3; 3 '-carbonyl two (7-diethyl amino coumarin); 3-benzoyl-ayapanin; 3-(2-furanylcarbonyl)-7-diethyl amino coumarin; 3-(4-diethylamino cinnamoyl)-7-diethyl amino coumarin; 7-methoxyl-3-(3-pyridine radicals carbonyl) cumarin; 3-benzoyl-5; 7-dipropoxy cumarin etc.) and thioxanthones compound (thioxanthones; isopropyl thioxanthone; 2; the 4-diethyl thioxanthone; 1-chloro-4-propoxyl group thioxanthones; QuantacureQTX etc.) etc., can list in addition: Japanese kokai publication hei 5-19475 number; Japanese kokai publication hei 7-271028 number; TOHKEMY 2002-363206 number; TOHKEMY 2002-363207 number; TOHKEMY 2002-363208 number; the coumarin compound that waits to put down in writing in each communique for TOHKEMY 2002-363209 number etc.Wherein, the compound (compound ring series contracts) that preferred aromatic ring or heterocycle contract and encircle, more preferably assorted contract ring system ketonic compound and acridine.In the described assorted ring system ketonic compound that contracts, preferred especially acridone compound and thioxanthones compound.

As the combination of described photopolymerization initiator and described sensitizer, can enumerate combination as: the electron transfer type initiator of putting down in writing in the TOHKEMY 2001-305734 communique [(1) power supply subtype initiator and sensitizing coloring matter, (2) electronics are subjected to appearance type initiator and sensitizing coloring matter, (3) power supply subtype initiator, sensitizing coloring matter and electronics to be subjected to appearance type initiator (ternary initiator)] etc.

With respect to photosensitive film with total composition of photosensitive polymer combination, preferred 0.01～4 quality % of the content of described sensitizer, more preferably 0.02～2 quality %, preferred especially 0.05～1 quality %.

If the described quantity not sufficient 0.01 quality % that contains, then sensitivity descends sometimes; If surpass 4 quality %, then pattern form worsens sometimes.

-thermal polymerization inhibitor-

For thermal polymerization or the time dependent polymerization that prevents the described polymerizable compound in the described photographic layer, can add described thermal polymerization inhibitor.

As described thermal polymerization inhibitor, can enumerate as the 4-metoxyphenol, quinhydrones, the quinhydrones that alkyl or aryl replaces, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, the 2-dihydroxy benaophenonel, 4-methoxyl-2-dihydroxy benaophenonel, stannous chloride, phenothiazine, chloranil, naphthylamines, betanaphthol, 2,6-di-t-butyl-4-cresols, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), pyridine, nitrobenzene, dinitro benzene, picric acid, the 4-toluidine, methylene blue, copper and organic sequestering agent reactant, gaultherolin and phenothiazine, nitroso compound, the chelate of nitroso compound and Al etc.

With respect to the described polymerizable compound of described photographic layer, preferred 0.001～5 quality % of the content of described thermal polymerization inhibitor, more preferably 0.005～2 quality %, preferred especially 0.01～1 quality %.

If the described quantity not sufficient 0.001 quality % that contains, the stability when then preserving descends sometimes; If surpass 5 quality %, then the sensitivity with respect to active energy ray reduces sometimes.

-plastifier-

In order to control the film physical property (pliability) of described photographic layer, can add described plastifier.

As described plastifier, can enumerate as phthalates such as repefral, dibutyl phthalate, diisobutyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, dicyclohexyl phthalate, phthalic acid two (tridecyl) ester, butyl benzyl phthalate, diisooctyl phthalate, diphenyl phthalate, diallyl phthalate, phthalic acid octyl group capryl esters; Diol-lipids such as triethylene-glycol diacetate, tetraethylene glycol diacetate esters, dimethyl glucose phthalic ester, gluconic acid ethyl phthalyl ethyl ester, gluconic acid methyl phthalyl ethyl ester, gluconic acid butyl phthalyl butyl ester, triethylene glycol dieaprylate; Phosphoric acid ester such as tricresyl alkaliine, triphenyl phosphate; Amide-types such as 4-toluenesulfonamide, benzsulfamide, N-n-butylbenzene sulfonamide, N-normal-butyl acetamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, dioctyl azelate, dibutyl maleate; Triethyl citrate, tributyl citrate, glycerine triacetyl ester, butyl laurate, 4,5-bicyclic oxygen cyclohexane-1,2-dicarboxylic acid dioctyl ester etc.; Glycols such as polyglycol, polypropylene glycol.

With respect to total composition of described photographic layer, preferred 0.1～50 quality % of the content of described plastifier, more preferably 0.5～40 quality %, preferred especially 1～30 quality %.

-coloring pigment-

Described coloring pigment is not particularly limited, can suitably select according to purpose, can enumerate as: the gorgeous blue BO of Victoria (C.I.42595), auramine (C.I.41000), solvent black HB (C.I.26150), Monot and rely special yellow (Monolite Yellow) GT (C.I. pigment Yellow 12), permanent yellow GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), permanent fuchsin (Permanent Carmine) FBB (C.I. pigment red 146), advertisement poster paratonere (ホ ス -バ-system レ _ット) ESB (C.I. pigment violet 1 9), the pink B of permanent red jewel (Permanent.Ruby) FBH (C.I. paratonere 11), Fa Siteer Soviet Union pula (Off _ァス テ Le ピ Application Network B ス プ ラ) (C.I. pigment red 81), sodium Si Telaer fast blue (モ Na ス ト ラ Le Off ァ-ス ト Block Le-) (C.I. pigment blue 15) not, the Monot relies special fast black B (Monolite Fast Black B) (C.I. pigment black 1), carbon, C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 168, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. pigment red 21 5, C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment blue 15: 1, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 64 etc.Described pigment can use separately, also can be used in combination two or more.In addition, as required, can use the pigment of from known pigment, suitably selecting.

Exposure sensitivity, the resolution of the photographic layer the when solid component content of described coloring pigment in described photosensitive composite solid constituent can be considered to form permanent pattern waits to determine, kind according to described coloring pigment is different and different, common preferred 0.01～10 quality %, more preferably 0.05～5 quality %.

-filler pigment-

In described photosensitive composite, for skin hardness or reduction linear expansion coefficient that improves permanent pattern or specific inductive capacity or the dielectric loss tangent that reduces cured film itself, can add inorganic pigment (inorganic filler) or organic fine particles as required.

Described inorganic pigment (inorganic filler) is not particularly limited, can be from known material suitably select, can enumerate as porcelain earth, barium sulphate, barium titanate, silica powder, micro mist shape monox, fumed silica, amorphous silica, crystallinity silicon dioxide, fused silica, spherical silicon dioxide, talcum powder, clay, magnesium carbonate, lime carbonate, aluminium oxide, aluminium hydroxide, mica etc.Wherein, consider preferred silicon dioxide from the angle of cold shock testing patience.

The preferred less than 10 μ m of the mean grain size of described inorganic pigment (inorganic filler) are more preferably below the 3 μ m.If this mean grain size is more than the 10 μ m, then because light dispersion causes exploring degree variation sometimes.

Described organic fine particles is not particularly limited, can be according to purpose and suitably select, can enumerate as melamine resin, benzoguanamine resin, cross-linked polystyrene resin etc.In addition, can use mean grain size is that 1～5 μ m, oil absorption are 100～200m ²Spherical small porous particle that forms by silicon dioxide, cross-linked resin about/g etc.

Preferred 5～60 quality % of the addition of described filler pigment.If this addition less than 5 quality % then can't fully reduce linear expansion coefficient sometimes; If surpass 60 quality %, when then forming cured film on the photographic layer surface sometimes the membranous of this cured film become fragile, when using permanent pattern to form wiring, undermine function sometimes as the diaphragm of wiring.

---driving fit promoter---

For the adaptation that improves each interlayer or the adaptation of photosensitive film and matrix, can in each layer, use known so-called driving fit promoter.

As described driving fit promoter, can preferably enumerate as the driving fit promoter of record in Japanese kokai publication hei 5-11439 communique, Japanese kokai publication hei 5-341532 communique and the Japanese kokai publication hei 6-43638 communique etc.Specifically can list: benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, morpholinyl methyl isophthalic acid-Phenyltriazole-2-thioketones, 3-morpholino methyl-5-Ben oxadiazole-2-thioketones, 5-amino-3-morpholino methyl thiazolium diazole-2-thioketones and 2-sulfydryl-5-methyl sulfo-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, the benzotriazole that contains amino, silane coupling agent etc.

With respect to total composition of described photographic layer, the preferred 0.001 quality % of the content of described driving fit promoter～20 quality %, more preferably 0.01～10 quality %, preferred especially 0.1 quality %～5 quality %.

According to photosensitive composite of the present invention, owing to stipulated the residual quantity of catalyzer, so excellent storage stability, can obtain high meticulous permanent pattern (diaphragm, interlayer dielectric and solder resist pattern etc.) expeditiously.

(manufacture method of photosensitive composite)

The manufacture method of described photosensitive composite comprises addition operation and catalyst deactivation operation, also comprises other operation as required.Described addition operation and described catalyst deactivation operation are carried out simultaneously.

＜addition operation 〉

Described addition operation is by (methyl) acrylate (A) with contain unsaturated group and contain the operation of addition (methyl) glycidyl acrylate on a part of acid group of the multipolymer that the compound (B) of 1 acid group obtains at least.

＜catalyst deactivation operation 〉

Described catalyst deactivation operation makes described catalyst deactivation.For example for making the operation of oxygen foaming.

(photosensitive film)

Photosensitive film of the present invention has the photographic layer that is formed by photosensitive composite of the present invention on supporter and this supporter, and other layer of suitably selecting according to the stacked thermoplastic resin of purpose etc. forms.

＜supporter 〉

Described supporter is not particularly limited, can suitably selects according to purpose, but preferably can peel off the permeability good supporting body of described photographic layer and light, further the flatness of preferred surface is good.

Preferred synthetic resin system of described supporter and transparent supporter, can enumerate as polyethylene terephthalate, PEN, polypropylene, tygon, cellulose triacetate, cellulose diacetate, poly-(methyl) alkyl acrylate, poly-(methyl) acrylate copolymer, Polyvinylchloride, polyvinyl alcohol (PVA), polycarbonate, polystyrene, viscose paper, polyvinylidene chloride copolymer, polyamide, polyimide, the trichloroactic acid vinyl ester copolymers, teflon, poly-trifluoro-ethylene, cellulose-based film, various plastic sheetings such as nylon film, wherein preferred especially polyethylene terephthalate.Described supporter can be used alone, and also can be used in combination two or more.

Thickness to described supporter is not particularly limited, and can suitably select according to purpose, for example preferred 2～150 μ m, more preferably 5～100 μ m, preferred especially 8～50 μ m.

Shape to described supporter is not particularly limited, can suitably select according to purpose, but preferably long chi shape.Length to described long chi shape supporter is not particularly limited, and can enumerate as 10～20 the supporter that 000m is long.

＜photographic layer 〉

As mentioned above, described photographic layer uses photosensitive composite of the present invention to form.

Described photographic layer, when its exposure is developed, the thickness of exposed portion that does not make this photographic layer in this exposure and the least energy of the light that uses in the described exposure that changes after developing be preferably 0.1～50mJ/cm ², 0.2～40mJ/cm more preferably ², be preferably 0.5～30mJ/cm especially ²

If the not enough 0.1mJ/cm of described least energy ², then in treatment process, produce veil sometimes; If surpass 50mJ/cm ², the required time of then exposing sometimes is elongated, processing speed is slack-off.

Herein, " thickness of exposed portion that makes this photographic layer in this exposure and do not change after developing, in described exposure the least energy of employed light " be meant so-called development sensitivity, for example can be by expression the energy (exposure) of the light that is used for described exposure during with described photographic layer exposure try to achieve with the curve map (sensitivity curve) of following the relation between the thickness of described cured layer that described exposure utilizes described development treatment generation.

The thickness of described cured layer increases with the increase of described exposure, become afterwards with described exposure before the roughly the same and constant of thickness of described photographic layer.Described development sensitivity is meant the value that the minimum exposure amount when reading the thickness constant when described cured layer is tried to achieve.

Herein, when the thickness of described cured layer and the thickness of the described photographic layer before the described exposure be ± 1

In the time of in the μ m, the thickness of described cured layer is considered as not because of exposure and develops changing.

Determination of thickness method to the described photographic layer before described cured layer and the described exposure is not particularly limited, can suitably select according to purpose, can list: use determining film thickness device, roughness tester (for example サ-Off コ system 1400D (the accurate society in Tokyo system)) etc. to carry out method for measuring.

Thickness to described photographic layer is not particularly limited, and can suitably select according to purpose, for example preferred 1～100 μ m, more preferably 2～50 μ m, preferred especially 4～30 μ m.

＜protective film 〉

Described photosensitive film can form protective film on described photographic layer.

As described protective film, can enumerate as: as described in the film, the lamination that use in the supporter paper, tygon, polyacrylic paper etc., wherein preferably polyethylene film, polypropylene film are arranged.

Thickness to described protective film is not particularly limited, and can suitably select according to purpose, for example preferred 5～100 μ m, more preferably 8～50 μ m, preferred especially 10～30 μ m.

As the combination (supporter/protective film) of described supporter and protective film, can enumerate as polyethylene terephthalate/polypropylene, polyethylene terephthalate/tygon, Polyvinylchloride/viscose paper, polyimide/polypropylene, polyethylene terephthalate/polyethylene terephthalate etc.In addition, by in supporter and the protective film any one carries out surface treatment at least, can adjust interlayer adhesion.In order to improve the bounding force with described photographic layer, can implement surface treatment to described supporter, can enumerate as being coated with of: undercoat, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, high frequency treatment with irradiation, glow discharge treatment with irradiation, plasma active treatment with irradiation, laser light irradiation processing etc.

The coefficient of static friction of described supporter and described protective film is preferred 0.3～1.4, and more preferably 0.5～1.2.

If described coefficient of static friction less than 0.3 then owing to too smooth, is rolled up unevenly when forming the roller shape sometimes; If surpass 1.4, then be difficult to be rolled into good roller shape sometimes.

Described photosensitive film for example preferably is wound on the round-shaped volume core, is rolled into the roller shape with long chi shape and comes keeping.Length to the photosensitive film of described long chi shape is not particularly limited, for example can be from 10～20, and the scope of 000m is suitably selected.In addition, use for the ease of the user, can carry out division processing, make 100～1, the long chi body of 000m scope makes the roller shape.Need to prove that preferred described supporter is wound into and is outermost under this situation.In addition, the photosensitive film of described roller shape can be divided into laminar.When keeping from the protection of end face, prevent that the angle that merges at the edge from considering, preferably is provided with separator (separator) (particularly moisture resistance separator, be placed with the separator of drying agent) on end face, the low material of moisture-penetrability is also preferably used in packing in addition.

In order to adjust the cohesive of described protective film and described photographic layer, can carry out surface treatment to described protective film.Described surface treatment for example is to form the undercoat that is formed by polymkeric substance such as polysiloxane, fluorinated polyolefin, polyvinyl fluoride, polyvinyl alcohol (PVA) on the surface of described protective film.This undercoat can pass through the coating fluid at the described polymkeric substance of surface coated of described protective film, forms 30～150 ℃ of following dryings 1～30 minute afterwards.Preferred especially 50～120 ℃ of described temperature when dry.

＜other layers 〉

To described other the layer be not particularly limited, can suitably select according to purpose, can enumerate as: thermoplastic resin, restraining barrier, peel ply, bonding coat, light absorbing zone, sealer etc. the layer.Described photosensitive film can have a kind of these layers separately, also can have these two or more layers.

＜＜thermoplastic resin〉〉

Described thermoplastic resin (following also be called sometimes " cushion ") is not particularly limited, can suitably selects according to purpose, it can swelling and even solvable in alkalies, also can be insoluble.

,, can enumerate in alkalies under swelling and even the soluble situation at described cushion as ethene and acrylate copolymer saponified as described thermoplastic resin; Styrene is saponified with (methyl) acrylate copolymer; Vinyltoluene is saponified with (methyl) acrylate copolymer; (methyl) acrylate copolymer of poly-(methyl) acrylate, (methyl) butyl acrylate and vinyl acetate etc. saponified; (methyl) acrylate and (methyl) acrylic acid multipolymer; Styrene and (methyl) acrylate and (methyl) acrylic acid multipolymer etc.

Softening point (Vicat) to thermoplastic resin at this moment is not particularly limited, and can suitably select according to purpose, and is for example preferred below 80 ℃.

As described softening point is thermoplastic resin below 80 ℃, except that described thermoplastic resin, can list: the softening point of " plastics performance brief guide " (Japan Plastics Industry Federation, all Japan plastics forming industry Colaesce meeting is write, the census of manufacturing can be issued, distribution on October 25 nineteen sixty-eight) is the thermoplastic resin that dissolves in alkaline liquid in about organic polymer below 80 ℃.In addition,, also can in this organic polymer material, add the various plastifier with this organic polymer material tool intermiscibility, the softening point of essence is reduced to below 80 ℃ even in softening point is organic polymer material more than 80 ℃.

At described cushion in alkalies under swelling and even the soluble situation, interlayer adhesion to described photosensitive film is not particularly limited, can suitably select according to purpose, for example preferred in the interlayer adhesion of each layer, the interlayer adhesion minimum between described supporter and the described cushion.By forming described interlayer adhesion, can on described duplexer, only peel off described supporter, via described cushion described photographic layer is exposed, use alkaline-based developer that this photographic layer is developed afterwards.In addition, all right residual described supporter directly with described photographic layer exposure, is only peeled off described supporter afterwards on described duplexer, use alkaline-based developer that this photographic layer is developed.

Method of adjustment to described interlayer adhesion is not particularly limited, and can suitably select according to purpose, can enumerate as: to as described in add known polymkeric substance, supercooling material, driving fit modifying agent, surfactant, release agent etc. in the thermoplastic resin.

At described cushion in alkalies under the insoluble situation, as described thermoplastic resin, can enumerate as: major component is with the multipolymer of ethene as necessary copolymer composition.

Be not particularly limited with the multipolymer of described ethene described, can suitably select, can enumerate as vinyl-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA) etc. according to purpose as necessary copolymer composition.

At described cushion in alkalies under the insoluble situation, interlayer adhesion to described photosensitive film is not particularly limited, can suitably select according to purpose, for example preferred in the interlayer adhesion of each layer, the interlayer adhesion minimum between described supporter and the described cushion.By forming described interlayer adhesion, can on described duplexer, peel off described supporter and cushion, with described photographic layer exposure, use alkaline-based developer that this photographic layer is developed afterwards.All right residual described supporter directly with described photographic layer exposure, is peeled off described supporter and cushion afterwards on described duplexer, use alkaline-based developer that this photographic layer is developed.

Method of adjustment to described interlayer adhesion is not particularly limited, can suitably select according to purpose, can enumerate as: to as described in add the adjustment ethylene copolymer ratio of the method for various polymkeric substance, supercooling material, driving fit modifying agent, surfactant, release agent etc. and following explanation in the thermoplastic resin method etc.

Be not particularly limited as the ratio of the ethylene copolymer in the multipolymer of necessary copolymer composition with ethene described, can suitably select, for example preferred 60～90 quality %, more preferably 60～80 quality %, preferred especially 65～80 quality % according to purpose.

If the copolymerization ratio less than 60 quality % of described ethene, the interlayer adhesion of then described cushion and described photographic layer uprises, and is difficult to sometimes peel off at the interface of this cushion and this photographic layer; If surpass 90 quality %, the interlayer adhesion of then described cushion and described photographic layer becomes too small, therefore is very easy to peel off between this cushion and this photographic layer, is difficult to make the photosensitive film that contains described cushion sometimes.

Thickness to described cushion is not particularly limited, and can suitably select according to purpose, for example preferred 5～50 μ m, more preferably 10～50 μ m, preferred especially 15～40 μ m.

If described thickness less than 5 μ m, then, can't form high meticulous permanent pattern sometimes to the concavo-convex tracking decline of the concavo-convex or bubble of matrix surface etc.; If surpass 50 μ m, bad situations such as the drying load increase of then making sometimes.

(manufacture method of photosensitive film)

Described photosensitive film for example can followingly be made.

At first, with material dissolves contained in the described photosensitive composite, emulsification be scattered in water or organic solvent in, the photosensitive composite solution used of preparation photosensitive film.Can also add known surfactant.

Next, be coated with described photosensitive composite solution on the described matrix or on the described supporter, making it the dry photographic layer that forms, can make photosensitive film.

Coating process to described photosensitive composite solution is not particularly limited, can suitably select according to purpose, can enumerate as various coating processes such as: spraying process, rolling method, method of spin coating, slot coated method, extrusion coated method, curtain formula rubbing method, mould rubbing method, intaglio plate rubbing method, wire bar rubbing method, knife coatings.

The condition of described drying is also different because of each composition, solvent types, usage ratio etc., usually drying under 60～110 ℃ the temperature about 30 seconds～15 minutes.

(photosensitive laminate)

Described photosensitive laminate is by having described photographic layer at least on substrate, and stacked other layer of suitably selecting according to purpose forms.

＜matrix 〉

Described matrix, the transfer printing body that photographic layer is arranged as the transfer printing at least of handled object that is formed with photographic layer or photosensitive film of the present invention, be not particularly limited, can suitably select according to purpose, for example can to matrix, select arbitrarily from the high matrix of surface smoothing with the concavo-convex surface of tool.Preferred panel-shaped base body uses so-called substrate.Specifically can list: the film of the substrate (printed base plate) of known printed-wiring board (PWB) manufacturing usefulness, glass substrate (soda-lime glass plate etc.), synthetic resin, paper, sheet metal etc.

(manufacture method of photosensitive laminate)

As the manufacture method of described photosensitive laminate,, can list: at the described photosensitive composite of the surface coated of described matrix and carry out dry method as first scheme; As alternative plan, can list: on one side the photographic layer at least in the photosensitive film of the present invention is heated and pressurize at least any, the stacked method Yi Bian carry out transfer printing.

The manufacture method of the photosensitive laminate of described first scheme is: coating and dry described photosensitive composite form photographic layer on described matrix.

Described coating and dry method are not particularly limited, can suitably select according to purpose, can enumerate as: with as described in photosensitive composite dissolving, emulsification be scattered in water or solvent in preparation photosensitive composite solution, this solution directly is coated on the surface of described matrix and makes it dry, thereby carry out stacked method.

Solvent to described photosensitive composite solution is not particularly limited, and can suitably select according to purpose, can enumerate as with as described in the identical solvent of solvent that uses in the photosensitive film.Described solvent can be used alone, and also can be used in combination two or more.Can also add known surfactant.

Described coating process and drying condition are not particularly limited, can suitably select, according to carrying out with employed identical method of described photosensitive film and condition according to purpose.

The manufacture method of the photosensitive laminate of described alternative plan is: in described matrix surface heats photosensitive film of the present invention on one side and pressurizes at least any, Yi Bian carry out stacked.Need to prove, when described photosensitive film has described protective film, preferably this protective film is peeled off, and on described matrix, carry out stacked mode and make described photographic layer overlapping.

Described heating-up temperature is not particularly limited, can suitably selects according to purpose, for example preferred 15～180 ℃, more preferably 60～140 ℃.

Pressure to described pressurization is not particularly limited, and can suitably select according to purpose, for example preferred 0.1～1.0MPa, more preferably 0.2～0.8MPa.

Be not particularly limited carrying out described any the device at least pined for that adds, can suitably select according to purpose, preferably enumerate as: laminating machine (great achievement laminating machine (the society's system VP-11 of ラ ミ ネ-), day close Morton Co., Ltd.: Nichigo-morton co.Ltd makes VP130) etc. for example.

Photosensitive film of the present invention uses described photosensitive composite of the present invention, so excellent storage stability, can obtain high meticulous permanent pattern (diaphragm, interlayer dielectric and solder resist pattern etc.) expeditiously.

Photosensitive film of the present invention and described photosensitive laminate are by the kind of regulation bonding agent and the residual quantity of catalyzer; can form excellent storage stability expeditiously; and alleviated the painted of adhesive resin; the color and taste variation (look fault) that has suppressed the sense material; high meticulous permanent pattern (diaphragm, interlayer dielectric and solder resist pattern etc.); therefore can be widely used in the formation of the high meticulous permanent pattern (interlayer dielectric, diaphragm, solder resist pattern etc.) in the semiconductor applications, the permanent pattern that particularly goes for printed base plate forms.

Pattern of the present invention forms device and has described photosensitive laminate of the present invention, and has light irradiating means and light governor motion at least.

Permanent pattern formation method of the present invention comprises exposure process at least, also comprises other other operations such as developing procedure of suitable selection.

Need to prove that described pattern of the present invention forms that device communicates by the explanation that described permanent pattern formation method of the present invention is described and be in addition clear and definite.

＜exposure process 〉

Described exposure process is the operation that the photographic layer in the photosensitive film of the present invention is exposed.The material of described photosensitive film of the present invention and base material as mentioned above.

Object as described exposure, so long as the photographic layer in the described photosensitive film, be not particularly limited, can suitably select according to purpose, for example preferably on base material, on one side photosensitive film is heated as mentioned above and pressurize in any is stacked on one side and the duplexer of formation exposed at least.

Described exposure is not particularly limited, can suitably selects, can enumerate, wherein digit preference exposure as digit explosure, analogue exposure etc. according to purpose.

[developing procedure]

As described development, undertaken by the unexposed portion of removing described photographic layer.

The method of removing to described uncured zone is not particularly limited, and can suitably select according to purpose, can enumerate as: use method that developer solution removes etc.

Described developer solution is not particularly limited, can suitably selects, can enumerate, wherein preferred weak alkaline aqueous solution as alkaline aqueous solution, water system developer solution, organic solvent etc. according to purpose.As the alkali composition of this weak base aqueous solution, can enumerate as lithium hydroxide, NaOH, potassium hydroxide, lithium carbonate, sodium carbonate, sal tartari, lithium bicarbonate, sodium bicarbonate, saleratus, sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, borax etc.

The pH value of described weak alkaline aqueous solution is for example preferred about 8～12, and more preferably from about 9～11.As described weak alkaline aqueous solution, can enumerate as the aqueous sodium carbonate of 0.1～5 quality % or wet chemical etc.

The temperature of described developer solution can suitably be selected according to the development of described photographic layer, for example preferred about 25～40 ℃.

Described developer solution can be with surfactant, defoamer, organic base (for example ethylenediamine, monoethanolamine, Tetramethylammonium hydroxide, diethylene triamine, triethylene five amine, morpholine, triethanolamine etc.) or is used to promote organic solvent (for example alcohols, ketone, ester class, ethers, amide-type, lactone etc.) of developing etc. to be used in combination.Described developer solution can be the water system developer solution with water or aqueous alkali and organic solvent mixing, also can be independent organic solvent.

[curing treatment process]

Described curing treatment process is after carrying out described developing procedure, the photographic layer in the formed pattern is cured the operation of processing.

Described curing treatment process is not particularly limited, can suitably selects, can preferably enumerate as whole exposure-processed, whole heat treated etc. according to purpose.

As the method for described whole exposure-processed, can enumerate as: as described in after the development with as described in be formed with permanent pattern as described in the method etc. of whole exposure on the duplexer.By this whole exposure, the curing of the resin in the photosensitive composite of the described photographic layer of formation can be obtained promoting that the surface of described permanent pattern is cured.

The device that carries out described whole exposure is not particularly limited, can suitably selects, can preferably enumerate as UV exposure machines such as extra-high-pressure mercury vapour lamps according to purpose.

As described whole methods of heating treatment, can list: after the described development with the method for whole heating on the described described duplexer that is formed with permanent pattern etc.By this whole heating, the film strength on the surface of described permanent pattern is improved.

Preferred 120～250 ℃ of the heating-up temperature of described whole heating, more preferably 120～200 ℃.If this heating-up temperature less than 120 ℃, then can't obtain the raising of the caused film strength of heat treated sometimes; If surpass 250 ℃, the resin in the then described sometimes photosensitive composite decomposes, and membranously dies down, becomes fragile.

Preferred 10～120 minutes of the heat time heating time of described whole heating, more preferably 15～60 minutes.

The device that carries out described whole heating is not particularly limited, can from known device, suitably selects, can enumerate as dry type baking oven, hot plate, IR well heater etc. according to purpose.

-diaphragm, interlayer dielectric, solder resist pattern formation method-

When the formation method of described pattern when forming any the permanent pattern formation method at least in diaphragm, interlayer dielectric and the solder resist pattern; can utilize described permanent pattern formation method on printed-wiring board (PWB), to form permanent pattern, carry out soldering as follows.

That is, utilize the cured layer of described development formation, make metal level expose the surface of described printed-wiring board (PWB) as described permanent pattern.Gold-plated to the metal level position of exposing this print circuit board surface, carry out soldering afterwards.At the position of carrying out soldering semiconductor or part etc. are installed then.At this moment, the function of permanent pattern performance diaphragm that is formed by described cured layer or dielectric film (interlayer dielectric), solder resist prevents from the impact of outside or the conducting of adjacent electrode.

Form in device and the permanent pattern formation method at described pattern,, can protect wiring to avoid impact or bending from the outside when the permanent pattern that utilizes described permanent pattern formation method to form during as described diaphragm or described interlayer dielectric.During particularly as described interlayer dielectric, for example subtend multi-layer wire substrate or composite wiring substrate etc. are gone up the high-density installation semiconductor or part is useful.

Embodiment

Below, utilize embodiment further to specify the present invention, but the present invention is not limited to this.

(synthesis example 1 of bonding agent)

-bonding agent 1 synthetic-

To 1,1-methoxyl-2-propyl alcohol of the 159g that packs in the three-neck flask of 000mL flows down at nitrogen and to be heated to 85 ℃.Spend 2 hours to the 159g 1-methoxyl-2-propanol solution that wherein drips 63.4g benzyl methacrylate, 72.3g methacrylic acid, 3.0g V-601 (with the pure medicine system of light).After drip finishing, heat again and made it reaction in 5 hours.Stop heating then, obtain the multipolymer of benzyl methacrylate/methacrylic acid (30/70mol% ratio).

Next, the 120.0g in the described copolymer solution is moved in the three-neck flask of 300mL, add 16.6g glycidyl methacrylate, 0.16g p methoxy phenol, stirring and dissolving.After the dissolving, froth,, be heated to 100 ℃, after 20 minutes, add glycidyl methacrylate and carry out addition reaction Yi Bian add the 3.0g triphenyl phasphine Yi Bian carry out air.Confirm that by vapor-phase chromatography glycidyl methacrylate disappears, and stops heating.Add 1-methoxyl-2-propyl alcohol, the preparation solid constituent is the solution of the represented bonding agent 1 of the following structural formula of 45 quality %.

Utilization is with the weight-average molecular weight (Mm) of polystyrene as gel permeation chromatography (GPC) the mensuration gained bonding agent of standard substance, and the result is 30,000.In addition, carry out titration with NaOH, the acid number of trying to achieve every solid constituent is 2.2meq/g.And utilizing the content (C=C valency) of the olefinic unsaturated link of every solid constituent that the iodine number titration tries to achieve is 2.1meq/g.And with respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 711ppm.

Wherein, in the described bonding agent 1, ^*The mixing (mixing ratio is indeterminate) of the structure of the structure of 1 expression following structural formula (a) expression and following structural formula (b) expression.

Structural formula (a)

Structural formula (b)

The residual quantity of＜catalyzer 〉

With the macromolecular compound solution dilution to 10 of above-mentioned preparation times, utilize GC-Mass (SIM:m/z=262) to measure, TPP is carried out quantitatively.

＜＜condition determination〉〉

Post: DB-5 (1:30m, Φ: 0.53mm, d:1.5 μ m)

Injection temperature: 270 ℃

Detected temperatures: 300 ℃

Intensification condition: 270 ℃, kept 2 minutes; Kept 5 minutes after being warming up to 300 ℃ with 10 ℃/minute programming rate afterwards

(synthesis example 2 of bonding agent)

-bonding agent 2 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 25 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 600ppm.

(synthesis example 3 of bonding agent)

-bonding agent 3 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 27 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 500ppm.

(synthesis example 4 of bonding agent)

-bonding agent 4 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 30 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 470ppm.

(synthesis example 5 of bonding agent)

-bonding agent 5 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 35 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 450ppm.

(synthesis example 6 of bonding agent)

-bonding agent 6 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 40 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 350ppm.

(synthesis example 7 of bonding agent)

-bonding agent 7 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 45 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 300ppm.

(synthesis example 8 of bonding agent)

-bonding agent 8 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 50 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 220ppm.

(synthesis example 9 of bonding agent)

-bonding agent 9 synthetic-

Except making the elapsed time that adds behind the triphenyl phasphine is 60 minutes, synthesizes according to the method identical with synthesis example 1.With respect to the solid constituent amount of bonding agent, the value of residual TPP amount converts with solid constituent and counts 100ppm.

(embodiment 1)

The preparation of-photosensitive composite-

Each composition is mixed preparation photosensitive composite solution by following amount.

[photosensitive composite solution respectively become component]

Described bonding agent 3 (the solid constituent quality is 45 quality % in described 1-methoxyl-2-propanol solution) ... 49.64 mass parts

Tetramethylol methane tetraacrylate (polymerizable compound) ... 9.15 mass parts

The photopolymerization initiator of following formula 1 expression ... 0.55 mass parts

Sensitizer (diethyl thioxanthone) ... 0.40 mass parts

EPOTOHTO (the ZX-1059 (epoxide equivalent is that bisphenol A type epoxy resin and the epoxide equivalent of 180g/eq. is the potpourri of 170g/eq. bisphenol f type epoxy resin) of エ Port ト-ト) ... 4.99 mass parts

Thermal curing agents (dicyandiamide) ... 0.12 mass parts

Fluorine is a surfactant (メ ガ Off _{ァ ッ}Network F-176, big Japanese ink chemical industry (strain) system, the 2-butanone solution of 30 quality %) ... 0.13 mass parts

Silicon dioxide SO-C2 ... 7.75 mass parts

Coloring pigment ... 0.13 mass parts

Butanone ... 11.88 mass parts

N-propyl acetate ... 15.23 mass parts

Formula (1)

The manufacturing of-photosensitive film-

Be on PET (polyethylene terephthalate) film of 16 μ m with gained photosensitive composite solution coat and make it dry that forming thickness is the photographic layer of 30 μ m at thickness as described supporter.Then, use the laminating machine different propylene film that stacked 20 μ m are thick on this photographic layer, make described photosensitive film as described protective film.

The formation of-permanent pattern-

---preparation of photosensitive laminate---

Next, as described base material, handle and be prepared implement chemical grinding as the surface of the copper-surfaced plywood that forms wiring (no through hole, the thick 12 μ m of copper) of printed base plate.At the enterprising line operate of this copper-surfaced plywood the photographic layer of described photosensitive film is bonded on the described copper-surfaced plywood; peel off the protective film in the described photosensitive film on one side; it is stacked to use vacuum laminator (day is closed Morton Co., Ltd.: Nichigo-morton co.Ltd makes VP130) to carry out on one side, prepares described copper-surfaced plywood, described photographic layer, the stacked in this order photosensitive laminate of described pet film (supporter).

The pressing condition is as follows: the time that vacuumizes is that 40 seconds, pressing-in temp are that 70 ℃, pressing pressure are that 0.2MPa, pressing time are 10 seconds.

＜the evaluation of short development time 〉

Strip pet film (supporter) from described photosensitive laminate, whole aqueous sodium carbonate that sprays 30 ℃ 1 quality % with the described photographic layer of pressure on the copper-surfaced plywood of 0.15MPa, mensuration is removed the required time to the photographic layer on the copper-surfaced plywood is dissolved from beginning to spray aqueous sodium carbonate, with it as the shortest development time.

The evaluation of＜sensitivity 〉

Use the pattern of following explanation to form device, the photographic layer from described support side to the photosensitive film of the photosensitive laminate of above-mentioned preparation shines from 0.1mJ/cm ²Rise by 2 ^1/2Doubly be incremented to 50mJ/cm at interval ²The different light of luminous energy carry out double exposure, a part of zone of described photographic layer is solidified.At room temperature left standstill 10 minutes, on described duplexer, strip described supporter afterwards, spray 30 ℃ the 1 quality % aqueous sodium carbonate of the twice time of described the shortest development time with whole of the photographic layer of atomisation pressure on the copper-surfaced plywood of 0.15MPa, uncured zone is removed in dissolving, measures the thickness of residual consolidation zone.Then, the exposure of light and the relation of cured layer thickness are made figure, obtain sensitivity curve.According to this sensitivity curve, the luminous energy when reaching 30 μ ms identical with photographic layer before the exposure with the thickness of consolidation zone makes photographic layer solidify necessary luminous energy (sensitivity) as being used to.The results are shown in Table 1.

The evaluation of＜exploring degree 〉

Utilize method and the condition identical to make described photosensitive laminate, under room temperature (23 ℃, 55%RH), left standstill 10 minutes with the evaluation method of described the shortest development time.Using described pattern to form device, begin to carry out the exposure of each live width with 5 μ m rags from the pet film (supporter) of gained duplexer, is 10～50 μ m until line/at interval=1/1, live width.The exposure of this moment is to be used to make the photographic layer of described photosensitive film to solidify necessary luminous energy (sensitivity).At room temperature left standstill 10 minutes, and on described photosensitive laminate, stripped pet film (supporter) afterwards.Spray 30 ℃ the 1 quality % aqueous sodium carbonate of the twice time of described the shortest development time with whole of the photographic layer of atomisation pressure on the copper-surfaced plywood of 0.15MPa, uncured zone is removed in dissolving.With observation by light microscope so operation and the surface of the copper-surfaced plywood that has solidified resin pattern that obtains, on the line of solidified resin pattern, do not see obstructions, curl etc. unusually, and mensuration can form the minimum feature at interval, with it as the exploring degree.More little this exploring degree of numerical value is good more.The results are shown in Table 1.

The evaluation of＜storage stability 〉

With the keeping 3 days under 40 ℃, dry promotion condition of described photosensitive laminate.Measure the shortest development time of this photosensitive laminate, measure from the prolongation of the shortest development time of Fresh.The results are shown in Table 1.

[metewand]

◎: the shortest development time is extended for below 1.5 times

Zero: the prolongation deficiency of short development time is 2.0 times

△: the shortest development time be extended for more than 2.0 times, 4.0 times of less thaies

*: can not develop

The evaluation of＜thermal shock patience 〉

To permanent pattern implement thermal cycle handle (with-65 ℃ of coolings 30 minutes down, 125 ℃ down heating 30 minutes as 1 circulation, carry out described round-robin heat treated 500 times), mode appears in the crackle of observing the length of side and being in the sectional hole patterns (clathrate) of 2mm, carries out thermal cycling test (having what patterns crackle to occur in 27 clathrate patterns).The results are shown in Table 1.

The evaluation of exploring degree (circular hole) ageing stability the behind＜lamination 〉

Described photosensitive laminate was placed 1 day, and the circular hole exploring is measured in the back of developing.But table 1 shows the smallest circle aperture of exploring.

(embodiment 2)

Except bonding agent 3 being replaced to bonding agent 4, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

(comparative example 1)

Except bonding agent 3 being replaced to bonding agent 1, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

(comparative example 2)

Except bonding agent 3 being replaced to bonding agent 2, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

(embodiment 3)

Except bonding agent 3 being replaced to bonding agent 5, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

(embodiment 4)

Except bonding agent 3 being replaced to bonding agent 6, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

(embodiment 5)

Except bonding agent 3 being replaced to bonding agent 7, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

(embodiment 6)

Except bonding agent 3 being replaced to bonding agent 8, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, carry out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination at described photosensitive laminate with embodiment.The results are shown in Table 1.

(embodiment 7)

Except bonding agent 3 being replaced to bonding agent 9, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

(embodiment 8)

Except bonding agent 3 being changed to bonding agent 9 and silicon dioxide being replaced to the barium sulphate of 15.85 mass parts, carry out 1 identical operations with embodiment, make photosensitive laminate and permanent pattern.Carry out 1 identical operations, described photosensitive laminate is carried out the evaluation of the evaluation of sensitivity, exploring degree, storage stability, cold shock testing patience and exploring degree (circular hole) ageing stability behind the lamination with embodiment.The results are shown in Table 1.

[table 1]

	Residual TPP amount (ppm)	Sensitivity (mJ/cm 2)	Exploring degree (μ m)	Storage stability	Cold shock testing patience	Exploring degree behind the lamination, (circular hole) ageing stability
							Embodiment 1	500	34	30	○	3/27	80μm
Embodiment 2	470	34	35	○	1/27	80μm
							Embodiment 3	450	34	35	○	4/27	80μm
Embodiment 4	350	34	30	○	6/27	75μm
							Embodiment 5	300	34	30	◎	2/27	80μm
Embodiment 6	220	34	35	◎	3/27	70μm
							Embodiment 7	100	34	35	◎	2/27	75μm
Embodiment 8	100	34	30	◎	16/27	70μm
							Comparative example 1	711	34	30	×	4/27	Can't exploring
Comparative example 2	600	34	35	△	2/27	300μm

When particularly using silicon dioxide as inorganic filler, cracking frequency is low.

Industrial applicability

Photosensitive composite of the present invention and photosensitive film are by the residual quantity of regulation catalyst; exploring degree (circular hole) ageing stability that can form expeditiously behind storage stability and the lamination is excellent; and the permanent pattern of fine (diaphragm, interlayer dielectric and solder resist pattern etc.); therefore can be widely used in the formation of the permanent pattern (interlayer dielectric, diaphragm, solder resist pattern etc.) of the fine in the semiconductor applications, particularly the permanent pattern applicable to printed base plate forms.

Permanent pattern forming method of the present invention, owing to use described photosensitive film of the present invention, therefore applicable to the formation of the various patterns of the exposure of essential fine etc., particularly the permanent pattern applicable to printed base plate forms.

Claims (17)

1. photosensitive composite, it comprises bonding agent, polymerizable compound, photopolymerization initiator, thermal cross-linking agent and the catalyzer that is formed by following modified copolymer, described modified copolymer is by (methyl) acrylate (A) with contain unsaturated group and have the modified copolymer that addition (methyl) glycidyl acrylate forms on a part of acid group of the resulting multipolymer of compound (B) of 1 acid group at least, it is characterized in that, become component with respect to described adhesive solids, the residual quantity of described catalyzer is below the 500 quality ppm.

2. photosensitive composite according to claim 1 wherein, becomes component with respect to adhesive solids, and the residual quantity of catalyzer is below the 300 quality ppm.

3. photosensitive composite according to claim 1, wherein, catalyzer is a triphenyl phasphine.

4. photosensitive composite according to claim 1, wherein, the photopolymerization initiator is a 9 oxime derivate.

5. photosensitive composite according to claim 1, wherein, thermal cross-linking agent is at least a for what select from epoxy compound, oxetane compound, polyisocyanate compounds, blocked polyisocyanate compound and melamine derivative.

6. photosensitive composite according to claim 5, wherein, thermal cross-linking agent is an epoxy compound, this epoxy compound is selected from phenolic varnish type epoxy compound, bisphenol type epoxy compound, the epoxy compound that contains heterocycle and alicyclic epoxy compound.

7. photosensitive composite according to claim 5, wherein, it is 150g/eq.～9 that thermal cross-linking agent contains epoxy compound and the epoxide equivalent that epoxide equivalent is 90g/eq.～400g/eq., the epoxy compound of 000g/eq..

8. photosensitive composite according to claim 1 wherein, also contains heat curing promoter.

9. photosensitive composite according to claim 1 wherein, also contains inorganic filler.

10. photosensitive composite according to claim 9, wherein, inorganic filler is a silicon dioxide.

11. a photosensitive film is characterized in that, forms by having on supporter by the formed photographic layer of the described photosensitive composite of claim 1.

12. photosensitive film according to claim 11, it is long chi shape, and forms by being rolled into the roller shape.

13. a photosensitive laminate is characterized in that, has on matrix by the formed photographic layer of the described photosensitive composite of claim 1.

14. photosensitive laminate according to claim 13, wherein, photographic layer is formed by the described photosensitive film of claim 11.

15. the formation method of a permanent pattern is characterized in that, comprises at least carrying out step of exposing by the formed photographic layer of the described photosensitive composite of claim 1.

16. the formation method of permanent pattern according to claim 15 wherein, uses the laser of 350～415nm wavelength to expose.

17. a printed base plate is characterized in that, utilizes the formation method of the described permanent pattern of claim 15 to form permanent pattern.