CN101149562A - Photosensitive composition, photosensitive film, permanent pattern forming method and printing circuit board - Google Patents

Abstract

The invention aims to provide a photosensitivity mixture which can be used for forming permanent pattern with better sensitivity, better developobility, better adhesion and high elaboration, a photosensitivity film, a method for forming the permanent pattern using the photosensitivity mixture and a printed circuit board used for forming pattern by using the method for forming the permanent pattern. The invention includes adhesive, polymerization compound, photopolymerization, heat crosslinking agent, and inorganic pigment. The photopolymerization is a photosensitivity mixture containing oxime derivatives by using silane coupler to make surface treatment on the inorganic pigment. The silane coupler preferentially selects at least one functional group from alkoxylsilyl, chloride silyl, acetoxy silyl, and at least one functional group from vinyl, amino, mercapto, epoxy and (methyl) acryloyl.

Description

Photosensitive composite, photosensitive film, permanent pattern formation method and printed circuit board (PCB)

Technical field

The present invention relates to a kind of photosensitive composite, photosensitive film, permanent pattern formation method and printed circuit board (PCB) that can form the meticulous permanent pattern of height effectively.

Background technology

All the time, form that solder resist (solder resist) waits wait permanent pattern the time, use be by the photosensitive film that on supporter, is coated with, the dry sensation photosensitive resin composition forms photographic layer.Manufacture method as described permanent pattern, for example on the base material of the copper plate lamination that forms described permanent pattern etc., thereby stacked described photosensitive film forms duplexer, described photographic layer in this duplexer is exposed, after this exposure, develop described photographic layer and then form pattern forms described permanent pattern by being cured to handle to wait then.

Known at this, in described photosensitive composite, no matter its purposes how, suppress to be low value for the skin hardness that improves permanent pattern or with linear expansion coefficient, perhaps suppress to be low value for specific inductive capacity or dielectric loss tangent with cured film self, usually use inorganic pigment,, can give the low water absorbable and the obdurability of the solidfied material that applies the dispersed of liquid or obtain by this inorganic pigment of surface treatment.

In addition, in the solder resist purposes, for prevent use barium sulphate as the situation of inorganic pigment under development residue residue, thereby the development deterioration has also proposed inorganic pigment is implemented surface treatment (spy opens the 2002-296771 communique).

But, in described proposal, because the sensitivity that the Photoepolymerizationinitiater initiater that utilize to use obtains may not be abundant, so be difficult to high meticulous and obtain permanent pattern effectively.

And then in order to make described permanent pattern height meticulous, making the adhesiveness (fine rule adhesiveness) after the development also is very important well.

Thereby, at present, can form sensitivity, development and good adhesion and photosensitive composite, the photosensitive film of high meticulous permanent pattern effectively, the printed circuit board (PCB) that has used the permanent pattern method of formationing of described photosensitive composite and utilized described permanent pattern formation method to form pattern remains to be developed.

Summary of the invention

The present invention proposes in view of this present situation just, thereby its problem is to provide a kind of solution described each problem in the past to realize following purpose.That is, the object of the present invention is to provide and a kind ofly can form sensitivity, development and good adhesion and photosensitive composite, the photosensitive film of high meticulous permanent pattern, the printed circuit board (PCB) that has used the permanent pattern method of formationing of described photosensitive composite and utilized described permanent pattern formation method formation pattern effectively.

As the means that are used to solve described problem, as described below.That is,

＜1〉a kind of photosensitive composite is characterized in that, contains bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater, thermal cross-linking agent and inorganic pigment, and described Photoepolymerizationinitiater initiater contains 9 oxime derivate, and described inorganic pigment is by the silane coupling agent surface treatment.

＜2〉according to described＜1〉record photosensitive composite; wherein, silane coupling agent has: at least a functional group of selecting from alkoxysilyl, chloromethane silylation and acetoxyl group silicyl and at least a functional group of selecting from vinyl, amino, sulfydryl, epoxy radicals and (methyl) acryloyl group.

＜3〉according to described＜1〉or＜2 the record photosensitive composite, wherein, inorganic pigment is a silicon dioxide.

＜4〉according to described＜1 〉～＜3 in the photosensitive composite of any record, wherein, 9 oxime derivate is for having the compound of aromatic series base at least.

＜5〉according to described＜1 〉～＜4 in the photosensitive composite of any record, wherein, 9 oxime derivate has the part-structure with any one expression of following general formula (I), general formula (II) and general formula (X).

[changing 4]

Ar  C (Y ¹)=N-O-Y ²) _mGeneral formula (I)

[changing 5]

Ar  CO-C (Y ¹)=N-O-Y ²) _mGeneral formula (II)

[changing 6]

General formula (X)

Wherein, during described general formula (I) reached (II), Ar represented any one in aromatic series base and the heterocyclic radical.Y ¹In the substituting group of expression hydrogen atom and monovalence any one.Y ²Expression fatty group, aromatic series base, heterocyclic radical, COY ³, CO ₂Y ³And CONY ⁴Y ⁵In any one.Y ³, Y ⁴And Y ⁵In expression fatty group, aromatic series base and the heterocyclic radical any one.M represents the integer more than 1.

In addition, in the described general formula (X), R ¹⁰⁰In expression acyl group, alkoxy carbonyl and the aryloxycarbonyl any one, these substituting groups also can further have substituting group.α represents the arbitrary integer more than 0.R ²⁰⁰The expression substituting group, under α is situation more than 2, this R ²⁰⁰Can be identical or different.Ar represents any one in aromatic ring and the heteroaromatic ring.A represents any one of 4,5,6 and 7 Yuans rings, and these rings also can contain heteroatoms respectively.

＜6〉according to described＜5〉record photosensitive composite, wherein, the Ar in general formula (I), general formula (II) and the general formula (X) has any one in phenyl and the naphthyl.

＜7〉according to described＜6〉record photosensitive composite, wherein, the Ar in general formula (I), general formula (II) and the general formula (X) has naphthyl.

＜8〉according to described＜5 〉～＜7 in the photosensitive composite of any record, wherein, general formula (I) and then can be with following general formula (III) and general formula (IV) expression.

[changing 7]

General formula (III)

General formula (IV)

Wherein, in described general formula (III) and the general formula (IV), R ₁₀₁Y in expression and general formula (I) and the general formula (II) ¹Identical meaning, Y ¹²Y in expression expression and general formula (I) and the general formula (II) ²Identical meaning.

＜9〉according to described＜1 〉～＜8 in the photosensitive composite of any record, wherein, bonding agent contains the macromolecular compound that has acidic groups and ethene unsaturated link at side chain.

＜10〉according to described＜9〉photosensitive composite of record, wherein, bonding agent contains at side chain and has acidic groups, can contain the aromatic series base of heterocycle and the macromolecular compound of ethene unsaturated link.

＜11〉according to described＜9〉or＜10 the record photosensitive composite, wherein, macromolecular compound contains 0.5～3.0meq/g ethene unsaturated link.

＜12〉according to described＜9 〉～＜11 in the photosensitive composite of any record, wherein, macromolecular compound has carboxyl at side chain, the content of described carboxyl in macromolecular compound is 1.0～4.0meq/g.

＜13〉according to described＜9 〉～＜12 in the photosensitive composite of any record, wherein, the matter average molecular weight of macromolecular compound is more than 10,000, less than 100,000.

＜14〉according to described＜10 〉～＜13 in the photosensitive composite of any record, wherein, macromolecular compound contains the structural unit of above following general formula (A-3) expression of 20mol%.

[changing 8]

General formula (A-3)

Wherein, in described structural formula (A-3), R ₁, R ₂And R ₃The organic group of expression hydrogen atom or 1 valency.L represents organic group, also can not have.Ar represents the aromatic series base.

＜15〉according to described＜1 〉～＜14 in the photosensitive composite of any record, wherein, polymerizable compound contains select at least a from the monomer with (methyl) acrylic.

＜16〉according to described＜1 〉～＜15 in the photosensitive composite of any record, wherein, thermal cross-linking agent is at least a for what select from epoxy compound, oxetane compound, polyisocyanate compounds, the compound that block (block) agent and polyisocyanate compounds reacted obtain and the melamine derivative.

＜17〉according to described＜16〉record photosensitive composite, wherein, thermal cross-linking agent contains epoxy compound, and this epoxy compound is from bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, contains select ester ring type fundamental mode epoxy resin and the slightly solubility epoxy resin at least a.

＜18〉according to described＜1 〉～＜17 in the photosensitive composite of any record, wherein, contain sensitizer.

＜19〉according to described＜18〉photosensitive composite of record, wherein, sensitizer contains the assorted compound ring series that contracts.

＜20〉according to described＜19〉photosensitive composite of record, wherein, the assorted compound ring series that contracts is the thioxanthones compound.

＜21〉a kind of photosensitive film is characterized in that, has described＜1 on supporter 〉～＜20 in the photographic layer that constitutes of the photosensitive composite of any record form.

＜22〉according to described＜21〉record photosensitive film, wherein, the thickness of photographic layer is 1～100 μ m.

＜23〉according to described＜21〉or＜22〉record photosensitive film, wherein, supporter contains synthetic resin and for transparent.

＜24〉according to described＜21 〉～＜23 in the photosensitive film of any record, wherein, supporter is a strip.

＜25〉according to described＜21 〉～＜24 in the photosensitive film of any record, wherein, be strip, and be rolled into the roller shape and form.

＜26〉according to described＜21 〉～＜25 in the photosensitive film of any record, wherein, on photographic layer, have protective film.

＜27〉a kind of permanent pattern formation method is characterized in that, comprises utilizing described＜1 relatively 〉～＜20 in the photographic layer that forms of the photosensitive composite of any record expose.

＜28〉according to described＜27〉the permanent pattern method of formationing of record, wherein, photographic layer utilizes described＜21 〉～＜26 in the photosensitive film formation of any record.

＜29〉according to described＜27〉or＜28 the record permanent pattern formation method, wherein, do not use photomask to expose.

＜30〉according to described＜29〉the permanent pattern method of formationing of record, wherein, exposure is carried out when expose light and photographic layer are relatively moved.

＜31〉according to described＜29〉or＜30 the record permanent pattern formation method, wherein, exposure be make the photohead that possesses light irradiating means and optical modulator body at least and described photographic layer any one moves at least, simultaneously, the light that utilizes the modulation of described optical modulator body corresponding pattern information to penetrate from described light irradiating means, and from described photohead described photographic layer is shone simultaneously and carry out.

＜32〉according to described＜31〉the permanent pattern method of formationing of record, wherein, optical modulator body can corresponding pattern information, to controlling less than the individual described drawing section of n arbitrarily of disposing continuously from n drawing section.

＜33〉according to described＜31〉or＜32 the record permanent pattern formation method, wherein, optical modulator body is a spatial optical modulation element.

＜34〉according to described＜33〉record permanent pattern formation method, wherein, spatial optical modulation element be Digital Micromirror Device (digitalmicromirrordevice) (DMD).

＜35〉according to described＜31 〉～＜34 in the permanent pattern formation method of any record, wherein, exposure is undertaken by array of apertures.

＜36〉according to described＜31 〉～＜35 in the permanent pattern formation method of any record, wherein, light irradiating means can the two or more light of compound irradiation.

＜37〉according to described＜31 〉～＜36 in the permanent pattern formation method of any record, wherein, thus light irradiating means possesses multiple laser instrument, multimode optical fiber and will carry out the light-gathering optics system that optically focused is coupled in described multimode optical fiber from the laser beam that this multiple laser instrument shines respectively.

＜38〉according to described＜27 〉～＜37 in the permanent pattern formation method of any record, wherein, exposure uses the laser of the wavelength of 350～420nm to carry out.

＜39〉according to described＜27 〉～＜38 in the permanent pattern formation method of any record, wherein, after having carried out exposure, carry out the development of photographic layer.

＜40〉according to described＜39〉record the permanent pattern method of formationing, wherein, carried out the development after, carry out the formation of permanent pattern.

＜41〉according to described＜40〉record the permanent pattern method of formationing, wherein, carried out the development after, photographic layer is cured processing.

＜42〉according to described＜41〉the permanent pattern method of formationing of record, wherein, solidify be treated to blanket exposure handle reach comprehensive heat treated of under 120～200 ℃, carrying out at least any one.

＜43〉a kind of permanent pattern is characterized in that, utilizes described＜27 〉～＜42 in the permanent pattern formation method of any record form.

＜44〉according to described＜43〉record pattern, wherein, in diaphragm, interlayer dielectric and the solder resist pattern at least any one.

＜45〉a kind of printed circuit board (PCB) is characterized in that, utilizes described＜27 〉～＜42 in the permanent pattern formation method of any record form permanent pattern.

Photosensitive composite of the present invention contains bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater, thermal cross-linking agent and inorganic pigment, and described Photoepolymerizationinitiater initiater contains 9 oxime derivate, utilizes the described inorganic pigment of silane coupling agent surface treatment.So can form sensitivity, development and good adhesion effectively and be high meticulous permanent pattern.

Utilize the present invention, can solve problem in the past, can provide a kind of and can form sensitivity, development and good adhesion effectively and for the permanent pattern method of formationing of the photosensitive composite of high meticulous permanent pattern, photosensitive film, the described photosensitive composite of use and utilize the printed circuit board (PCB) of described permanent pattern formation method formation pattern.

Embodiment

Photosensitive composite of the present invention contains bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater, thermal cross-linking agent and inorganic pigment, and then contains other compositions as required.

-inorganic pigment-

Described inorganic pigment is to suppress to be low value for the skin hardness that improves permanent pattern or with linear expansion coefficient, perhaps adds for low value for the specific inductive capacity of cured film self or dielectric loss tangent suppressed.

Described inorganic pigment in order to improve the adhesiveness of inorganic pigment and bonding agent, utilizes silane coupling agent to carry out surface treatment after heat curing.As described silane coupling agent, preferably have at least a functional group from alkoxysilyl, chloromethane silylation and acetoxyl group (ア セ ト キ シ) silicyl, selected (below be also referred to as " the 1st functional group ".) and at least a functional group from vinyl, amino, sulfydryl, epoxy radicals and (methyl) acryloyl group, selected (below be also referred to as " the 2nd functional group ".), more preferably the 2nd functional group is (methyl) acrylate-based or epoxy radicals.

In addition, can also equally preferably use at least a at least a mode of putting down in writing in the special fair 7-68256 communique of from alkoxysilyl, chloromethane silylation and acetoxyl group silicyl, selecting of selecting as the 1st functional group with from imidazole radicals, alkyl imidazole base and vinyl imidazole base that has as the 2nd functional group.

As described silane coupling agent, be not particularly limited, for example can preferably enumerate vinyl trichlorosilane, vinyltriethoxysilane, gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, vinyl triacetic acid base silane, α-[[3-(trimethoxysilyl) propoxyl group] methyl]-imidazole radicals-1-ethanol of putting down in writing in the special fair 7-68256 communique, 2-ethyl-4-methyl-α-[[3-(trimethoxysilyl) propoxyl group] methyl]-imidazole radicals-1-ethanol, 4-vinyl-α-[[3-(trimethoxysilyl) propoxyl group] methyl]-imidazole radicals-1-ethanol, 2-ethyl-4-methylimidazole and propyl trimethoxy silicane, and their salt, the intramolecular condensation thing, intermolecular condensation thing etc.

The surface treatment of the described inorganic pigment that utilizes silane coupling agent can only be carried out (being also referred to as " pre-service " below this situation to this inorganic pigment in advance.), also can carry out with part or all of the composition in other photosensitive compositions.

As carrying out described pretreated method, be not particularly limited, for example can enumerate methods such as dry process, aqua-solution method, organic solvent method, gunite.Be not particularly limited preferred normal temperature～200 ℃ to carrying out described pretreated temperature.

When carrying out described pre-service, also preferably add catalyzer.As this catalyzer, be not particularly limited, for example can enumerate acid, alkali, metallic compound, organometallics etc.

The addition of the described silane coupling agent when carrying out described pre-service is not particularly limited, and inorganic pigment 100 mass parts relatively are preferably the scope of 0.01～50 mass parts, more preferably the scope of 0.05～50 mass parts.If described addition is less than 0.01 mass parts, then surface treatment is insufficient, can not obtain the effect of needs sometimes, if surpass 50 mass parts, then inorganic filler becomes and condenses easily, and operability reduces sometimes.

Because described the 1st functional group in the described silane coupling agent and the reaction of the active group of substrate surface, inorganic filler surface and bonding agent, and then the carboxyl of described the 2nd functional group and bonding agent and the reaction of ethene unsaturated group, so have the adhering effect that improves base material and photographic layer.On the other hand, the reactive height of described silane coupling agent, so under the situation of it being added in the photosensitive composite, diffusion can cause in preservation it mainly is that the 2nd functional group reacts or inactivation, the storage life (shelf life) or the term of validity (pot life) may shorten.

But, as long as use with the described inorganic pigment of silane coupling agent pre-service ground as mentioned above,, can improve the problem of the storage life or the term of validity significantly by suppressing diffusion, also can be used as single component.And then, inorganic pigment is being implemented under the pretreated situation, freely select the condition of the use and so on of stirring condition, temperature conditions and catalyzer, so compare with not carrying out the situation that pre-service promptly adds, can improve the 1st functional group of silane coupling agent and the conversion ratio of the active group in the inorganic pigment significantly.Thereby, particularly, can obtain extraordinary result harsh the requirement in the characteristic of non-electrolysis gold plate, non-electrolysis soft solder coating, moisture-proof load test and so on.In addition,, the use amount of silane coupling agent can be reduced, the storage life and the term of validity can be further improved by carrying out pre-service.

As described inorganic pigment, be not particularly limited, can from known inorganic pigment, suitably select, for example can enumerate 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, clay, magnesium carbonate, lime carbonate, aluminium oxide, aluminium hydroxide, mica etc.

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

In the described photosensitive composite, also can add organic fine particles together as required.As described organic fine particles, be not particularly limited, can suitably select according to purpose, for example can enumerate melamine resin, benzene guanamine resin, cross-linked polystyrene resin etc.In addition, can also use mean grain size 0.01～5 μ m, oil absorption 100～200m ²Spherical small porous particle that constitutes by silicon dioxide, cross-linked resin about/g etc.

Described inorganic pigment and organic fine particles are added together addition, and whole compositions of photosensitive composite are preferably 1～60 quality % relatively.If this addition less than 1 quality %, then can not reduce linear expansion coefficient sometimes fully, if surpass 60 quality %; when then forming cured film on the photographic layer surface; sometimes the membranous of this cured film becomes fragile, and be when forming wiring with permanent pattern, destroyed as the function of the diaphragm that connects up sometimes.

-Photoepolymerizationinitiater initiater-

As described Photoepolymerizationinitiater initiater, use 9 oxime derivate.In addition, also can contain other Photoepolymerizationinitiater initiaters as required.

As described 9 oxime derivate, be not particularly limited, can suitably select according to purpose, preferably have the compound of aromatic series base at least, more preferably have the compound of part-structure of any one expression of following general formula (I) and general formula (II).Described 9 oxime derivate also can be also with two or more.

[changing 9]

Ar  C (Y ¹)=N-O-Y ²) _mGeneral formula (I)

[changing 10]

Ar  CO-C (Y ¹)=N-O-Y ²) _mGeneral formula (II)

Wherein, during described general formula (I) reached (II), Ar represented any one in aromatic series base and the heterocyclic radical.Y ¹In expression hydrogen atom and the monovalence substituting group any one.Y ²Expression fatty group, aromatic series base, heterocyclic radical, COY ³, CO ₂Y ³And CONY ⁴Y ⁵In any one.Y ³, Y ⁴And Y ⁵In expression fatty group, aromatic series base and the heterocyclic radical any one.M represents the integer more than 1.

As described Y ¹, be preferably in hydrogen atom, fatty group and the aromatic series base any one.

As described Y ², the preferred aliphat base ,-CO-(fatty group) ,-CO-(aromatic series base) ,-CO-(heterocyclic radical) ,-CO ₂-(fatty group) ,-CO ₂-(aromatic series base) reaches-CO ₂In-(heterocyclic radical) any one.

As described Y ³And Y ⁴, be preferably in fatty group and the aromatic series base any one.

As 9 oxime derivate, also can for the structure of described general formula (I) and general formula (II) expression via concatenating group in conjunction with a plurality of compounds that form.

Wherein, in described general formula (I) and general formula (II), described fatty group represents to have substituent alkyl, alkenyl, alkynyl respectively, described aromatic series basis representation can have substituent aryl, heterocycle (hetero ring) base respectively, as the substituting group of described monovalence, represent halogen atom, can have substituent amino, alkoxy carbonyl, hydroxyl, ether, mercapto, thioether group, silicyl, nitro, cyano group, can have substituent alkyl, alkenyl, alkynyl, aryl, heterocyclic radical respectively.

As described aromatic series base, can enumerate the base of base, phenyl ring and 5 Yuans unsaturated ring formation condensed ring of 1～3 phenyl ring formation condensed ring, as concrete example, can enumerate phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl, wherein, preferably have any one the base in phenyl and the naphthyl, especially preferably have the base of naphthyl.

In addition, these aromatic series bases also can have substituting group, as such substituting group, can enumerate the base that is made of the monovalence nonmetallic atom group except hydrogen atom.The base that for example can enumerate alkyl described later, substituted alkyl or represent as the substituting group in the substituted alkyl etc.

In addition, as described heterocycle (hetero ring) base, can enumerate pyrroles's cyclic group, the furans cyclic group, the thiophene cyclic group, the indoles cyclic group, the coumarone cyclic group, the benzothiophene cyclic group, pyrazoles cyclic group; isoxazole cyclic group, the isothiazole cyclic group, the indazole cyclic group, the benzoisoxazole cyclic group, the benzisothiazole cyclic group, imidazoles cyclic group; oxazole cyclic group, the thiazole cyclic group, benzimidazole cyclic group; benzoxazole cyclic group, the benzothiazole cyclic group, the pyridine cyclic group, the quinoline cyclic group, the isoquinoline cyclic group, the pyridazine cyclic group, the pyrimidine cyclic group, the pyrazine cyclic group, the phthalazines cyclic group, the quinazoline cyclic group, the quinoxaline cyclic group, aziridine (ア ジ リ ジ Application) cyclic group, the phenanthridines cyclic group, the carbazole cyclic group, the purine cyclic group, the pyrans cyclic group, the piperidines cyclic group, the piperazine cyclic group, the morpholine cyclic group, the indoles cyclic group, the indolizine cyclic group, the chromene cyclic group, the cinnoline cyclic group, the acridine cyclic group, the phenothiazine cyclic group, the tetrazolium cyclic group, triazine cyclic group etc., wherein, preferred especially furans cyclic group, the thiophene cyclic group, the imidazoles cyclic group, the thiazole cyclic group, the benzothiazole cyclic group, the pyrimidine cyclic group, the indoles cyclic group, the acridine cyclic group.

In addition, these heterocyclic radicals also can have substituting group, as such substituting group, can enumerate the base that 1 valency nonmetallic atom group except hydrogen atom constitutes.The base that for example can enumerate alkyl described later, show as the substituting group in substituted alkyl or the substituted alkyl.

As described monovalence substituting group, preferred halogen atom, can have substituent amino, alkoxy carbonyl, hydroxyl, ether, mercapto, thioether group, silicyl, nitro, cyano group, can have substituent alkyl, alkenyl, alkynyl, aryl, heterocyclic radical respectively.

In addition, as the described 1 valency substituting group that constitutes by non-metallic atom, preferably can have substituent alkyl, alkenyl, alkynyl, aryl, heterocyclic radical respectively.

Has a substituent alkyl as described, can enumerate carbon number and be the alkyl of 1～20 straight chain shape, branch-like and ring-type, as its concrete example, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norborny.Wherein, more preferably carbon number is that 1～12 straight chain shape, carbon number are that 3～12 branch-like and carbon number are the alkyl of 5～10 ring-type.

As described substituting group with substituent alkyl; can enumerate the substituting group of the monovalence non-metallic atom formation of removing hydrogen atom; as preference; can enumerate halogen atom (F;-Br;-Cl;-I); hydroxyl; alkoxy; aryloxy group; sulfydryl; alkyl thio-base; the aryl thio group; alkyl two thio groups; aryl two thio groups; amino; the N-alkyl amino; N; the N-dialkyl amido; the N-arylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; carbamoyloxy; N-alkyl carbamoyloxy base; N-arylamino formyloxy; N; N-dialkyl amido formyloxy; N; N-ammonia diaryl base formyloxy; N-alkyl-N-arylamino formyloxy; alkyl sulfide oxygen base; aryl sulphur oxygen (sulfoxy) base; the acyl group thio group; amide group; the N-alkylamidoalkyl; the N-aryl amido group; urea groups; N '-alkyl urea groups; N '; N '-dialkyl group urea groups; N '-aryl-ureido; N '; N '-diaryl urea groups; N '-alkyl-N '-aryl-ureido; N-alkyl urea groups; the N-aryl-ureido; N '-alkyl-N-alkyl urea groups; N '-alkyl-N-aryl-ureido; N '; N '-dialkyl group-N-alkyl urea groups; N '; N '-dialkyl group-N-aryl-ureido; N '-aryl-N-alkyl urea groups; N '-aryl-N-aryl-ureido; N '; N '-diaryl-N-alkyl urea groups; N '; N '-diaryl-N-aryl-ureido; N '-alkyl-N '-aryl-N-alkyl urea groups; N '-alkyl-N '-aryl-N-aryl-ureido; alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxycarbonyl amino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxycarbonyl amino; formyl; acyl group; carboxyl; alkoxy carbonyl group; aryloxycarbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; the N-aryl-amino-carbonyl; N, N-ammonia diaryl base formoxyl; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfo group (SO ₃H) and conjugate base (being called sulfonate radical (sulfonato) base), alkoxy sulfonyl, aryloxy sulfonyl, sulfinic acid acyl group (sulfinamoyl; ス Le Off イ Na モ イ Le) base, N-alkyl sulfinic acid acyl group, N; N-dialkyl group sulfinic acid acyl group, N-aryl sulfinic acid acyl group, N; N-diaryl sulfinic acid acyl group, N-alkyl-N-aryl sulfinic acid acyl group, sulfamoyl, N-alkylsulfamoyl group, N; N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N, N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono (PO ₃H ₂) and conjugate base (being called phosphonate radical (phosphonato, ホ ス ホ Na ト) base), dialkyl phosphine acyl group (PO ₃(alkyl) ₂) " alkyl=alkyl, as follows ", diaryl phosphono (PO ₃(aryl) ₂) " aryl=aryl, as follows ", alkylaryl phosphono (PO ₃(alkyl) (aryl)), an alkylphosphines acyl group (PO ₃And conjugate base (being called the alkyl phosphonic acid foundation), an aryl phosphine acyl group (PO (alkyl)) ₃H (aryl)) and conjugate base (being called the arylphosphonic acid foundation), phosphonato (OPO ₃H ₂) and conjugate base (being called phosphonate radical oxygen base), dialkyl phosphine acyloxy (OPO ₃H (alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), alkylaryl phosphonato (OPO ₃(alkyl) (aryl)), an alkylphosphines acyloxy (OPO ₃H (alkyl)) and conjugate base (being called alkylphosphines acid group oxygen base), an aryl phosphine acyloxy (OPO ₃H (aryl)) and conjugate base (being called aryl phosphine acid group oxygen base), cyano group, nitro, aryl, alkenyl, alkynyl, heterocyclic radical, silicyl etc.

Concrete example as the alkyl in these substituting groups, can enumerate above-mentioned alkyl, as the concrete example of the aryl in the described substituting group, can enumerate phenyl, xenyl, naphthyl, tolyl, xylyl, rice (mesityl) base, cumenyl, chlorphenyl, bromophenyl, chloromethyl phenyl, hydroxy phenyl, anisyl, ethoxyphenyl, phenoxy phenyl, the acetate phenyl, the benzoxy phenyl, the methyl mercapto phenyl, the thiophenyl phenyl, the methylamino phenyl, dimethylaminophenyl, the acetamido phenyl, carboxy phenyl, the methoxycarbonyl group phenyl, the ethoxyphenyl carbonyl, the carbobenzoxy phenyl, N-phenylcarbamoyl phenyl, cyano-phenyl, the sulfo group phenyl, the sulfonate radical phenyl, the phosphono phenyl, phosphonate radical phenyl etc.

In addition, example as the alkenyl in the described substituting group, can enumerate vinyl, 1-propenyl, 1-butenyl group, cinnamyl, 2-chloro-1-vinyl etc., as the example of the alkynyl in the described substituting group, can enumerate ethinyl, 1-propinyl, 1-butynyl, trimethyl silyl ethinyl etc.

As the heterocyclic radical in the described substituting group, for example can enumerate pyridine radicals, piperidyl etc.

As the silicyl in the described substituting group, can enumerate trimethyl silyl etc.

In described substituting group, also can contain acyl group (R ⁰¹CO-), as this acyl group, for example can enumerate this R ⁰¹Acyl group for hydrogen atom, abovementioned alkyl, aryl etc.

As acyl group (R ⁰¹CO-) R ⁰¹, can enumerate hydrogen atom and described alkyl, aryl.In these substituting groups; and then preferred halogen atom (F;-Br;-Cl;-I); alkoxy; aryloxy group; alkyl thio-base; the aryl thio group; the N-alkyl amino; N; the N-dialkyl amido; acyloxy; N-alkyl carbamoyloxy base; N-arylamino formyloxy; amide group; formyl; acyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; the N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl; sulfo group; the sulfonic acid foundation; sulfamoyl; the N-alkylsulfamoyl group; N, the N-dialkyl sulfamine; the N-ammonia aryl sulfonyl; N-alkyl-N-ammonia aryl sulfonyl; phosphono; the phosphonic acids foundation; the dialkyl phosphine acyl group; the diaryl phosphono; one alkylphosphines acyl group; the alkyl phosphonic acid foundation; one aryl phosphine acyl group; the arylphosphonic acid foundation; phosphonato; phosphonate radical oxygen base; aryl; alkenyl.

On the other hand, as the alkylidene in the substituted alkyl, can enumerate and remove described carbon number is that any one of hydrogen atom on 1～20 the alkyl becomes the alkylidene of organic residue of divalent, can preferably enumerate carbon number and be 1～12 straight chain shape, carbon number and be 3～12 branch-like and carbon number and be the alkylidene of 5～10 ring-type.Preferred concrete example as the substituted alkyl that obtains by combination substituting group and alkylidene like this; can enumerate chloromethyl; bromomethyl; the 2-chloroethyl; trifluoromethyl; methoxy; the isopropoxy methyl; butoxymethyl; the tert-butoxy butyl; methoxyethoxyethyl; the allyloxy methyl; phenoxymethyl; Phenoxymethyl; methylthiomethyl; the tolyl sulphomethyl; pyridylmethyl; the tetramethyl piperidine ylmethyl; N-acetyl group tetramethyl piperidine ylmethyl; the trimethyl silyl methyl; methoxy ethyl; the ethylamino-ethyl; the diethylin propyl group; the morpholino propyl group; acetoxy-methyl; the benzoxy methyl; N-cyclohexyl carboxyamide oxygen base ethyl; N-phenyl amino formyloxy ethyl; the acetamido ethyl; N-methyl benzoyl aminopropyl; 2-oxygen base ethyl; 2-oxygen base propyl group; the carboxyl propyl group; the methoxycarbonyl group ethyl; the allyloxy carbonyl butyl; chlorobenzene oxygen carbonyl methyl; the carbamyl ylmethyl; N-methylamino formoxyl ethyl; N; N-dipropyl carbamyl ylmethyl; N-(anisyl) carbamyl ethyl; N-methyl-N-(sulfo group phenyl) carbamyl ylmethyl; the sulfo group butyl; phosphono and sulfonic root butyl; the sulfonamide butyl; N-ethyl sulfonamide methyl; N; N-dipropyl sulfonamide propyl group; N-tolyl sulfonamide propyl group; N, N-dipropyl sulfonamide propyl group; N-tolyl sulfonamide propyl group; N-methyl-N-(phosphono phenyl) sulfonamide octyl group; the phosphono butyl; phosphonate radical is base; diethyl phosphono butyl; diphenyl phosphono propyl group; methyl phosphono butyl; methylphosphine acid group butyl; tolyl phosphono hexyl; tolylphosphine acid group hexyl; the phosphonato propyl group; phosphonate radical oxygen Ji Dingji; benzyl; phenethyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenethyl; to methylbenzyl; cinnamyl; allyl; 1-propenyl methyl; the 2-butenyl group; the 2-methylallyl; 2-metering system ylmethyl; 2-propynyl; the 2-butynyl; 3-butynyl etc.

As described aryl, can enumerate 1～3 phenyl ring and form base, phenyl ring and 5 Yuans bases that unsaturated rings formation condensed ring forms that condensed ring forms,, can enumerate phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl as concrete example, wherein, more preferably phenyl, naphthyl.

As described substituted aryl,, can use the substituting group of base with monovalence nonmetallic atom group formation of removing hydrogen atom as the substituting group on the ring formation carbon atom of described aryl.As the example of preferred substituents, the base that can enumerate described alkyl, substituted alkyl and show as the substituting group in the substituted alkyl in front.

Preferred concrete example as described substituted aryl; can enumerate xenyl; tolyl; xylyl; Mi Ji; cumenyl; chlorphenyl; bromophenyl; fluorophenyl; chloromethyl phenyl; trifluoromethyl; hydroxyphenyl; anisyl; the methoxy ethoxy phenyl; the allyloxy phenyl; phenoxy phenyl; the methyl mercapto phenyl; the thiophenyl phenyl; the ethylamino-phenyl; the diethylin phenyl; the morpholino phenyl; the acetoxyl group phenyl; the benzoxy phenyl; N-cyclohexyl carboxyamide oxygen base phenyl; N-phenyl amino formyloxy phenyl; the acetamido phenyl; N-methyl benzoyl aminophenyl; carboxy phenyl; the methoxycarbonyl group phenyl; the allyloxy carbonyl phenyl; chlorobenzene oxygen carbonyl phenyl; the carbamyl phenyl; N-methylamino formoxyl phenyl; N; N-dipropyl carbamyl phenyl; N-(anisyl) carbamyl phenyl; N-methyl-N-(sulfo group phenyl) carbamyl phenyl; the sulfo group phenyl; the sulfonate radical phenyl; sulfamoyl phenyl; N-ethyl sulfamoyl phenyl; N, N-dipropyl sulfamoyl phenyl; N-tolyl sulfamoyl phenyl; N-methyl-N-(phosphono phenyl) sulfamoyl phenyl; the phosphono phenyl; the phosphonate radical phenyl; diethyl phosphono phenyl; diphenyl phosphono phenyl; methyl phosphono phenyl; methylphosphine acid group phenyl; tolyl phosphono phenyl; tolylphosphine acid group phenyl; allyl phenyl; 1-propenyl aminomethyl phenyl; 2-butenyl group phenyl; 2-methacrylic phenyl; 2-methylpropenyl phenyl; the 2-propynyl phenyl; 2-butynyl phenyl; 3-butynyl phenyl etc.

As described alkenyl, described substituted alkenyl base, described alkynyl and described substituted alkynyl (C (R ⁰²)=C (R ⁰³) (R ⁰⁴) and-C ≡ C (R ⁰⁵)), can use R ⁰², R ⁰³, R ⁰⁴, R ⁰⁵The base of the base that constitutes for non-metallic atom by monovalence.

As R ⁰², R ⁰³, R ⁰⁴, R ⁰⁵, preferred hydrogen atom, halogen atom, alkyl, substituted alkyl, aryl and substituted aryl as their concrete example, can be enumerated the base that shows as above-mentioned example.Wherein, more preferably hydrogen atom, halogen atom, carbon number are the alkyl of 1～10 straight chain shape, branch-like, ring-type.

Particularly, can enumerate vinyl, 1-propenyl, 1-butenyl group, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-methyl isophthalic acid-propenyl, 2-methyl isophthalic acid-propenyl, 2-methyl-1-butene thiazolinyl, 2-phenyl-1-vinyl, 2-chloro-1-vinyl, ethinyl, 1-propinyl, 1-butynyl, phenylacetylene base etc.

As heterocyclic radical, can enumerate illustrative pyridine radicals of substituting group as substituted alkyl etc.

As described substituted oxy (R ⁰⁶O-), can use R ⁰⁶The substituting group of the base that constitutes for the non-metallic atom of the monovalence of removing hydrogen atom.As preferred substituted oxy, can enumerate alkoxy, aryloxy group, acyloxy, carbamoyloxy, N-alkyl carbamoyloxy base, N-arylamino formyloxy, N, N-dialkyl amido formyloxy, N, N-ammonia diaryl base formyloxy, N-alkyl-N-arylamino formyloxy, alkyl sulfide oxygen base, aryl sulphur oxygen base, phosphonato, phosphonate radical oxygen base.As alkyl in them and aryl, can enumerate the described base that shows as alkyl, substituted alkyl and aryl, substituted aryl.In addition, as the acyl group (R in the acyloxy ⁰⁷CO-), can enumerate R ⁰⁷Acyl group for alkyl, substituted alkyl, aryl and the substituted aryl enumerated as the example of front.In these substituting groups, more preferably alkoxy, aryloxy group, acyloxy, aryl sulphur oxygen base.As the concrete example of preferred substituted oxy, can enumerate methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, amoxy, own oxygen base, dodecyloxy, benzyloxy, allyloxy, the benzene ethoxy, the carboxyl ethoxy, the methoxycarbonyl group ethoxy, the carbethoxyl group ethoxy, methoxy ethoxy, the phenoxy group ethoxy, the methoxy ethoxy ethoxy, ethoxy ethoxy ethoxy, the morpholino ethoxy, the morpholino propoxyl group, the allyloxy ethoxy ethoxy, phenoxy group, toloxyl, xylyloxy, dish oxygen base, rice oxygen base, isopropyl benzene oxygen base, the methoxyl phenoxy group, ethoxy phenoxy, chlorophenoxy, the bromine phenoxy group, acetoxyl group, benzoxy, naphthoxy, phenylsulfonyloxy, phosphonato, phosphonate radical oxygen base etc.

As the substituted-amino (R that also contains amide group ⁰⁸NH-, (R ⁰⁹) (R ⁰¹⁰) N-), can use R ⁰⁸, R ⁰⁹, R ⁰¹⁰The substituting group of the base that constitutes for the monovalence nonmetallic atom group of removing hydrogen atom.Wherein, R ⁰⁹, R ⁰¹⁰Also can be in conjunction with forming ring.Preference as substituted-amino, can enumerate the N-alkyl amino, N, the N-dialkyl amido, the N-arylamino, N, the N-ammonia diaryl base, N-alkyl-N-arylamino, acid amides (ア シ Le ア ミ ノ) base, the N-alkylamidoalkyl, the N-aryl amido group, urea groups, N '-alkyl urea groups, N ', N '-dialkyl group urea groups, N '-aryl-ureido, N ', N '-diaryl urea groups, N '-alkyl-N '-aryl-ureido, N-alkyl urea groups, the N-aryl-ureido, N '-alkyl-N-alkyl urea groups, N '-alkyl-N-aryl-ureido, N ', N '-dialkyl group-N-alkyl urea groups, N '-alkyl-N '-aryl-ureido, N ', N '-dialkyl group-N-alkyl urea groups, N ', N '-dialkyl group-N '-aryl-ureido, N '-aryl-N-alkyl urea groups, N '-aryl-N-aryl-ureido, N ', N '-diaryl-N-alkyl urea groups, N ', N '-diaryl-N-aryl-ureido, N '-alkyl-N '-aryl-N-alkyl urea groups, N '-alkyl-N '-aryl-N-aryl-ureido, alkoxycarbonyl amido, aryloxy carbonyl amino, N-alkyl-N-alkoxycarbonyl amido, N-alkyl-N-alkoxycarbonyl amido, N-aryl-N-alkoxycarbonyl amido, N-aryl-N-aryloxy carbonyl amino.As the alkyl in them, aryl, can enumerate above-mentioned base, the acyl group (R in amide group, N-alkylamidoalkyl, the N-aryl amido group as alkyl, substituted alkyl and aryl, substituted aryl demonstration ⁰⁷CO-) R ⁰⁷As mentioned above.Wherein, more preferably N-alkyl amino, N, N-dialkyl amido, N-arylamino, amide group.As the preferred concrete example of substituted-amino, can enumerate methylamino, ethylamino-, diethylin, morpholino base, piperidyl, pyrroles for base, anilino-, benzamido, acetamido etc.

As substituted sulphonyl (R ⁰¹¹-SO ₂-), can use R ⁰¹¹Substituting group for the base that constitutes by the monovalence nonmetallic atom group.As preferred example, can enumerate alkyl sulphonyl, aryl sulfonyl.As the alkyl in them, aryl, can enumerate above-mentioned base as alkyl, substituted alkyl and aryl, substituted aryl demonstration.As the concrete example of such substituted sulphonyl, can enumerate butyl sulfonyl, benzenesulfonyl, chlorphenyl sulfonyl etc.

As mentioned above, sulfonate radical (sulfonato, ス Le ホ Na ト) base (SO ₃ ^-) be meant sulfo group (sulpho) base (SO ₃H) conjugate base anion base, preferred usually with kation (to Yang イ オ Application) is used.As such to kation, can enumerate usually known to kation, promptly various types of (ammonium class, sulfonium Lei, Phosphonium class, iodine class, nitrine (ア ジ ニ ウ system) class etc.) and metallic ion class (Na ⁺, K ⁺, Ca ²⁺, Zn ²⁺Deng).

As substituted carbonyl (R ⁰¹³-CO-), can use R ⁰¹³Substituting group for the base that constitutes by the monovalence non-metallic atom.Preference as substituted carbonyl; can enumerate formoxyl, acyl group, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formoxyl, N-aryl-amino-carbonyl, N, N-ammonia diaryl base formoxyl, N-alkyl-N '-aryl-amino-carbonyl.As the alkyl in them, aryl, can enumerate the above-mentioned base that shows as alkyl, substituted alkyl and aryl, substituted aryl.Wherein, as preferred substituted carbonyl; can enumerate formoxyl, acyl group, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formoxyl, N-aryl-amino-carbonyl; as so preferred substituted carbonyl, can enumerate formoxyl, acyl group, alkoxy carbonyl group and aryloxy carbonyl.Concrete example as preferred substituted carbonyl; can enumerate formoxyl, acetyl group, benzoyl, carboxyl, methoxycarbonyl group, carbethoxyl group, allyloxy carbonyl, dimethylaminophenyl vinyl carbonyl, methoxycarbonyl group methoxycarbonyl group, N-methylamino formoxyl, N-phenyl amino formoxyl, N, N-diethylamino formoxyl, morpholino carbonyl etc.

As substituted sulfinyl (R ⁰¹⁴-SO-), can use R ⁰¹⁴Substituting group for the base that constitutes by the monovalence non-metallic atom.As preference, can enumerate alkyl sulphinyl, aryl sulfonyl kia, sulfinyl, N-alkyl sulphinyl, N, N-dialkyl group sulfinyl, N-aryl sulfonyl kia, N, N-diaryl sulfinyl, N-alkyl-N-aryl sulfonyl kia.As the alkyl in them, aryl, can enumerate the described base that shows as alkyl, substituted alkyl and aryl, substituted aryl.Wherein, more preferably alkyl sulphinyl, aryl sulfonyl kia.As the concrete example of such substituted sulfinyl, can enumerate hexyl sulfinyl, benzyl sulfinyl, tolyl sulfinyl etc.

Replace phosphono and be meant that one or two hydroxyl on the phosphono by the base that other organic oxygen bases replace, as preference, can enumerate above-mentioned dialkyl phosphine acyl group, diaryl phosphono, alkylaryl phosphono, an alkylphosphines acyl group, an aryl phosphine acyl group.Wherein, more preferably dialkyl phosphine acyl group and diaryl phosphono.As such concrete example, can enumerate diethyl phosphonyl, dibutyl phosphono, diphenylphosphine acyl group etc.

As mentioned above, phosphonic acids foundation (PO ₃H ₂ ^-,-PO ₃H ^-) be meant phosphono (PO ₃H ₂) derive from acid first the disassociation or acid second the disassociation the conjugate base anion base.Usually preferably with kation is used.As such to kation, can enumerate usually known to kation, promptly various types of (ammonium class, sulfonium Lei, Phosphonium class, iodine class, nitrine (ア ジ ニ ウ system) class etc.) and metallic ion class (Na ⁺, K ⁺, Ca ²⁺, Zn ²⁺Deng).

Replace the phosphonic acids foundation and be meant the conjugate base anion base that in the above-mentioned replacement phosphono hydroxyl is replaced to the base of organic oxygen base,, can enumerate an above-mentioned alkylphosphines acyl group (PO as concrete example ₃H (alkyl)), an aryl phosphine acyl group (PO ₃H (aryl)) conjugate base.

As described 9 oxime derivate, more preferably use the compound of any one expression of following general formula (III) and general formula (IV).

[changing 11]

General formula (III)

General formula (IV)

Wherein, in described general formula (III) and the general formula (IV), R ₁₀₁Y in expression and general formula (I) and the general formula (II) ¹Identical meaning, Y ¹²Y in expression and general formula (I) and the general formula (II) ²Identical meaning.

As described R ₁₀₁, any one in hydrogen atom and the fatty group more preferably is preferably carbon number and is 1～10 fatty group especially.

As described fatty group, for example can enumerate methyl, ethyl, propyl group, octyl group, allyl etc.

As described Y ¹², be preferably-CO-(fatty group) especially.As described Y ¹²In fatty group, preferred carbon number is 1～10 fatty group.

Particularly, for example preferable methyl, ethyl, propyl group, butyl, octyl group, cyclohexyl, benzyl etc.

As other concrete examples of described 9 oxime derivate, for example can enumerate the spy and open compound that disclosed compound in 2001-233842 communique, special table 2004-534797 communique and the special table 2002-519732 communique etc. and following structural formula represent etc.

[changing 12]

[changing 13]

[changing 14]

In the said structure formula, R represents n-C ₃H ₇, n-C ₈H ₁₇, camphor and p-CH ₃C ₆H ₄In any one.

[changing 15]

In the said structure formula, R represents n-C ₃H ₇, and p-CH ₃C ₆H ₄In any one.

[changing 16]

[changing 17]

[changing 18]

As described oxime compound, also can preferably use the oxime compound of following general formula (X) expression.

[changing 19]

General formula (X)

In addition, in the described general formula (X), R ¹⁰⁰In expression acyl group, alkoxy carbonyl group and the aryloxycarbonyl any one, these substituting groups also can further have substituting group.α represents any one integer more than 0.R ²⁰⁰Expression substituting group, α are under the situation more than 2, this R ²⁰⁰Can be identical or different.Ar represents any one of aromatic ring and heteroaromatic ring.A represents any one of 4,5,6 and 7 Yuans rings, and these rings also can contain heteroatoms respectively.

In the oxime compound of described general formula (X) expression, the compound of more preferably following general formula (XI) expression is preferably the compound that following general formula (XII) reaches any one expression (XIII) especially.

[changing 20]

General formula (XI)

Wherein, in the described general formula (XI), R ¹⁰⁰, R ²⁰⁰, α and Ar represent with general formula (X) in identical meaning.X represents any one of O and S.A represents any one of 5 and 6 Yuans rings.

[changing 21]

General formula (XII)

[changing 22]

General formula (XIII)

Wherein, in described general formula (XII) and the general formula (XIII), R ³⁰⁰Also can have substituting group, the expression alkyl.Any one integer of 1 expression 0～6.R ⁴⁰⁰Any one of expression alkyl, alkoxy, aryloxy group, halogen atom, sulfonyl and acyloxy, 1 is under the situation more than 2, this R ⁴⁰⁰Can be identical or different.X and A represent and the identical meaning of general formula (XI).

During described general formula (X) reaches (XI), as using described R ¹⁰⁰The acyl group of expression can be any one of aliphatics, aromatic series and heterocycle, also can and then have substituting group.

As described aliphatic acyl group, for example can enumerate acetyl group, propiono, bytyry, caproyl, capryl, phenoxy group acetyl group, chloracetyl etc.As described aromatic acyl group, for example can enumerate benzoyl, naphthoyl, anisoyl base, nitro benzoyl etc.As the acyl group of described heterocycle, for example can enumerate furans acyl (furanoyl) base, thio phenyl acyl group (thiophenoyl) etc.As described substituting group, for example be preferably any one of alkoxy, aryloxy group and halogen atom.

As described acyl group, preferred total carbon atom number is 2～30 base, and more preferably total carbon atom number is 2～20 base, and preferred especially total carbon atom number is 2～16 base.As such acyl group; for example can enumerate acetyl group, propiono, methylpropionyl, bytyry, pivaloyl group, caproyl, cyclohexane carbonyl, caprylyl, capryl, dodecane acyl group, octadecanoyl, benzyloxycarbonyl group, phenoxy group acetyl group, 2-ethyl hexanoyl base, chloracetyl, benzoyl, to methoxybenzoyl base, 2,5-dibutoxy benzoyl, 1-naphthoyl base, 2-naphthoyl base, pyridine carbonyl, furans acyl group, thio phenyl acyl group, methacryl, acryloyl group etc.

During described general formula (X) reaches (XI), as using described R ¹⁰⁰The alkoxy carbonyl of expression also can have substituting group, is preferably total carbon atom number and is 2～30 alkoxy carbonyl group, and more preferably total carbon atom number is 2～20 alkoxy carbonyl group, is preferably total carbon atom number especially and is 2～6 alkoxy carbonyl group.As such alkoxy carbonyl group, for example can enumerate methoxycarbonyl group, carbethoxyl group, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl, aryloxycarbonyl, carbonyl octyloxy, dodecyloxy carbonyl, ethoxy ethoxy carbonyl etc.

During described general formula (X) reaches (XI), as using described R ¹⁰⁰The aryloxycarbonyl of expression also can have substituting group, is preferably total carbon atom number and is 7～30 alkoxy carbonyl group, and more preferably total carbon atom number is 7～20, and preferred especially total carbon atom number is 7～16.As such aryloxy carbonyl, for example can enumerate phenyloxycarbonyl, 2-naphthoxy carbonyl, to methoxyl phenyloxycarbonyl, 2,5-diethoxy phenyloxycarbonyl, to chlorophenoxy carbonyl, p-nitrophenyl oxygen base carbonyl, to cyano-benzene oxygen carbonyl etc.

During described general formula (X) reaches (XI), as using R ²⁰⁰The substituting group of expression is not particularly limited, and for example can enumerate alkyl, alkoxy, aryloxy group, halogen atom, sulfonyl, acyloxy, nitro, amide group etc.Wherein, be preferably any one of alkyl, alkoxy, aryloxy group, halogen atom, sulfonyl and acyloxy.

At this, as the described concrete example of using the oxime compound of general formula (X) expression, can enumerate the compound of following structural formula (1)～(54) expression, in the present invention, do not limited by these.

[changing 23]

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 formula (20) structural formula (21) structural formula (22)

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

[changing 24]

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)

Structural formula (52) structural formula (53) structural formula (54)

Wherein, in described structural formula (1)～(54), Me represents methyl.Ph represents phenyl.

Ac represents acetyl group.

--other Photoepolymerizationinitiater initiaters--

As described other Photoepolymerizationinitiater initiaters, as long as have the ability of the polymerization that causes described polymerizable compound, then be not particularly limited, can from known Photoepolymerizationinitiater initiater, suitably select, for example preferably the ultraviolet range had photosensitive Photoepolymerizationinitiater initiater to visible light, can for certain effect is taken place by light activated sensitizer, produce the activator of living radical, also can cause the initiating agent of cationic polymerization for the kind of corresponding monomer.

In addition, described Photoepolymerizationinitiater initiater preferably contains a kind of composition that has about 50 molar extinction coefficient in the scope of about 300～800nm at least at least.Described wavelength is 330～500nm more preferably.

As described other Photoepolymerizationinitiater initiaters, for example can enumerate halogenated hydrocarbons derivant (for example having the halogenated hydrocarbon derivant of triazine skeleton, the halogenated hydrocarbon derivant of Ju You oxadiazole skeleton etc.), six aryl bisglyoxalines, organic peroxide, thio-compounds, ketonic compound, acridine compound, aromatic ring alkene metal derivative etc.Particularly, can enumerate and open compound of putting down in writing in the 2005-258431 communique etc. the spy.Wherein, from sensitivity, keeping quality and the photographic layer of photographic layer and the viewpoints such as adhesiveness of substrate, preferred ketonic compound and acridine compound.Described other Photoepolymerizationinitiater initiaters can be used alone or and with two or more.

The solid component content of described Photoepolymerizationinitiater initiater in described photosensitive composite is preferably 0.1～30 quality %, and more preferably 0.5～20 quality % is preferably 0.5～15 quality % especially.

-sensitizer-

As described photosensitive composite, also can contain sensitizer.

Under the situation that described photographic layer is exposed, develops, from improving in this exposure and do not make the viewpoint of the least energy (sensitivity) of the described light that the thickness of the part that this photographic layer need expose changes after developing, preferred especially and use described sensitizer.

As described sensitizer, can suitably select according to described light irradiating means (for example luminous ray or ultraviolet light and visible light laser).

Described sensitizer becomes excited state under the effect of active energy ray, can produce useful bases such as free radical or acid by interact (for example energy moves, electronics moves etc.) with other materials (for example free-radical generating agent, acid producing agent etc.).

As described sensitizer, at least contain a kind of from the compound ring series that contracts, aminophenyl ketone based compound, Ppolynuclear aromatic class, have acyclic acidic compound, have alkalescence ring compound, have select the compound of fluorescer ring at least a, also can contain other sensitizers as required.As sensitizer, from the point of raising sensitivity, and then be preferably assorted contract compound ring series, aminobenzophenone based compound, be preferably the assorted compound ring series that contracts especially.

--compound ring series contracts--

In described exemplary compounds,, be preferably the assorted compound ring series that contracts as the contract compound (compound ring series contracts) of ring of aromatic ring or heterocycle.The described assorted compound ring series that contracts is meant the polycyclic compound that has assorted element in ring, in described ring, preferably contains nitrogen-atoms.As the described assorted compound ring series that contracts, for example can enumerate the assorted ring system ketonic compound that contracts.In the described assorted compound ring series that contracts, more preferably acridone compound and thioxanthones compound, wherein preferred especially thioxanthones compound.

As the described assorted ring system ketonic compound that contracts, particularly, for example can enumerate acridone, chloro-acridine ketone, N-methylacridine ketone, N-butyl acridone, N-butyl-acridone compounds such as chloro-acridine ketone; Thioxanthones, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propoxyl group thioxanthones, QuantacureQTX thioxanthones compounds such as (trade names); 3-(2-coumarone formoxyl)-7-diethyl amino coumarin; 3-(2-coumarone formoxyl)-7-(1-pyrrolidinyl) cumarin; 3-benzoyl-7-diethyl amino coumarin; 3-(2-methoxybenzoyl)-7-diethyl amino coumarin; 3-(4-dimethylamino benzoyl)-7-diethyl amino coumarin; 3; 3 '-carbonyl two (5; 7-two-positive propoxy cumarin); 3; 3 '-carbonyl two (7-diethyl amino coumarin); 3-benzoyl-ayapanin; 3-(2-furoyl)-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; 7-benzotriazole-2-acyl group cumarin; 7-diethylamino-4-methylcoumarin; also have the spy to open in addition flat 5-19475 number; Te Kaiping 7-271028 number; the spy opens 2002-363206 number; the spy opens 2002-363207 number; the spy opens 2002-363208 number; the spy opens the Coumarinses such as coumarin compound of record in the 2002-363209 communique etc. etc.

In addition, can also enumerate known Ppolynuclear aromatic class (for example pyrene, perylene, 9,10-benzophenanthrene), oxa anthracenes (for example fluorescein, tetrabromofluorescein, tetraiodofluorescein, rhodamine B, rose bengal), cyanine glycoside (for example indoles carbocyanine, sulfo-carbocyanine, oxa-carbocyanine), merocyanine class (for example merocyanine, carbonyl merocyanine), thiazide (for example thionine, methylenum careuleum, toluidine blue), anthraquinone class (for example anthraquinone), Si Kualin (ス Network ア リ ウ system) class (for example Si Kualin) etc.

The content of above-mentioned sensitizer, all solids composition of described relatively photosensitive composite is preferably 0.01～4 quality %, and more preferably 0.02～2 quality % is preferably 0.05～1 quality % especially.

If this content is less than 0.01 quality %, sensitivity so sometimes reduces, if surpass 4 quality %, the shape of pattern worsens sometimes so.

The mass ratio of the described sensitizer in the described photosensitive composite and the content of Photoepolymerizationinitiater initiater is preferably [(sensitizer)/(9 oxime derivate)]=1/0.1～1/100, and more preferably 1/1～1/50.

If the mass ratio of the content of the content of described sensitizer and described Photoepolymerizationinitiater initiater is outside above-mentioned scope, then sensitivity may reduce, and sensitivity through the time change and may worsen.

-bonding agent-

As described bonding agent, preferably contain the macromolecular compound of acidic groups and ethene unsaturated link at side chain.As described acidic groups, can enumerate carboxyl, phosphate, sulfonic group etc., and from the point that obtains raw material, preferred carboxyl.

Described bonding agent is preferably insoluble and compound swelling or dissolving under alkaline aqueous solution to water.

In addition, as described bonding agent, in molecule, can use for example acrylic such as (methyl) acrylate-based or (methyl) acrylamido of two keys that at least one can polymerization, two keys such as the various polymerisms of the vinyl acetate of carboxylic acid, vinethene, allyl ether etc.More specifically; as acidic groups; can enumerate to the acryl resin that contains as the carboxyl of acidic groups, the polymerizable compound that addition the contains the ring-type ether for example glycidic ester of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid or compound of ester ring type epoxy radicals (epoxy radicals that for example has cyclohexene oxide etc. in a part) and (methyl) acryloyl group etc. contains compound that the polymerizable compound of epoxy radicals obtains etc.In addition, can also enumerate to acryl resin addition isocyanates (methyl) ethyl acrylate etc. that contains acidic groups and hydroxyl and contain the compound that the polymerizable compound of isocyanate group obtains, contain compound that the polymerizable compound of hydroxyl obtains etc. to acryl resin addition (methyl) acrylic acid hydroxyalkyl acrylate that contains the acid anhydride base etc.In addition, can also enumerate copolymerization glycidyl methacrylate etc. and contain vinyl monomers such as the polymer compound of ring-type ether and (methyl) acryloyl group Arrcostab, the compound that obtains to epoxy radicals addition (methyl) acrylic acid of side chain etc.And then, can also enumerate skeleton with epoxy compound source and the compound that in molecule, contains pair keys and carboxyl.Such compound for example can be with making the multi-functional epoxy compound and contain carboxylic monomer and react, and then the method etc. of multi-anhydride addition is obtained.

These examples can be enumerated patent No. 2763775 communiques, spies and open that flat 3-172301 communique, spy are opened the 2000-232264 communique, the spy opens flat 1-54390 communique etc.

Wherein, the described bonding agent macromolecular compound that more preferably contains macromolecular compound that ring-type ether (for example part-structure has the base of epoxy radicals, oxetanyl) polymerizable compound obtains and to part or all addition of the ring-type ether of macromolecular compound contains any one of macromolecular compound that the carboxyl polymerizable compound obtains, select from a part of addition to the acidic groups of macromolecular compound.At this moment, acidic groups is preferably implemented in the presence of catalyzer with the addition reaction of the compound with ring-type ether, the catalyzer of preferred especially this catalyzer for selecting from acid compound and neutral compound.

Wherein, from photosensitive composite through the time stable developing point, bonding agent is preferably at side chain and contains carboxyl, can contain the aromatic series base of heterocycle and contain the macromolecular compound of ethene unsaturated link at side chain.

--the aromatic series base that can contain heterocycle--

As described aromatic series base (following abbreviate as sometimes " the aromatic series base " that contains heterocycle.), base, phenyl ring and 5 Yuans unsaturated rings of for example can enumerate phenyl ring, forming condensed ring by 2～3 phenyl ring form base of condensed ring etc.

Concrete example as described aromatic series base, can enumerate phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl, the indoles cyclic group, the coumarone cyclic group, the benzothiophene cyclic group, pyrazoles cyclic group; isoxazole cyclic group, the isothiazole cyclic group, the indazole cyclic group, the benzoisoxazole cyclic group, the benzisothiazole cyclic group, imidazoles cyclic group; oxazole cyclic group, the thiazole cyclic group, benzimidazole cyclic group; benzoxazole cyclic group, the benzothiazole cyclic group, the pyridine cyclic group, the quinoline cyclic group, the isoquinoline cyclic group, the pyridazine cyclic group, the pyrimidine cyclic group, the pyrazine cyclic group, the phthalazines cyclic group, the quinazoline cyclic group, the quinoxaline cyclic group, the aziridine cyclic group, the phenanthridines cyclic group, the carbazole cyclic group, the purine cyclic group, the pyrans cyclic group, the piperidines cyclic group, the piperazine cyclic group, the indoles cyclic group, the indolizine cyclic group, the chromene cyclic group, the cinnoline cyclic group, the acridine cyclic group, the phenothiazine cyclic group, the tetrazolium cyclic group, triazine cyclic group etc., wherein, preferably has hydrocarbon aromatic series base, more preferably phenyl, naphthyl.

Described aromatic series base also can have substituting group, as described substituting group, for example can enumerate halogen atom, can have substituent amino, alkoxy carbonyl group, hydroxyl, ether, mercapto, thioether group, silicyl, nitro, cyano group, can have substituent alkyl, alkenyl, alkynyl, aryl, heterocyclic radical etc. respectively.

As described alkyl, for example can enumerate carbon number and be the alkyl of 1～20 straight chain shape, the alkyl of branch-like, alkyl of ring-type etc.

As the concrete example of described alkyl, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norborny etc.Wherein, more preferably carbon number is that alkyl, the carbon number of 1～12 straight chain shape is that the alkyl of 3～12 branch-like and carbon number are the alkyl of 5～10 ring-type.

The substituting group that can have as described alkyl; for example can enumerate the base of the monovalence nonmetallic atom group formation of removing hydrogen atom; as such substituting group; for example can enumerate halogen atom (F;-Br;-Cl;-I); hydroxyl; alkoxy; aryloxy group; sulfydryl; alkyl thio-base; the aryl thio group; alkyl two thio groups; aryl two thio groups; amino; the N-alkyl amino; N; the N-dialkyl amido; the N-arylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; carbamoyloxy; N-alkyl carbamoyloxy base; N-arylamino formyloxy; N; N-dialkyl amido formyloxy; N; N-ammonia diaryl base formyloxy; N-alkyl-N-arylamino formyloxy; alkyl sulfide oxygen base; aryl sulphur oxygen base; the acyl group thio group; amide group; the N-alkylamidoalkyl; the N-aryl amido group; urea groups; N '-alkyl urea groups; N '; N '-dialkyl group urea groups; N '-aryl-ureido; N '; N '-diaryl urea groups; N '-alkyl-N '-aryl-ureido; N-alkyl urea groups; the N-aryl-ureido; N '-alkyl-N-alkyl urea groups; N '-alkyl-N-aryl-ureido; N '; N '-dialkyl group-N-alkyl urea groups; N '; N '-dialkyl group-N-aryl-ureido; N '-aryl-N-alkyl urea groups; N '-aryl-N-aryl-ureido; N '; N '-diaryl-N-alkyl urea groups; N '; N '-diaryl-N-aryl-ureido; N '-alkyl-N '-aryl-N-alkyl urea groups; N '-alkyl-N '-aryl-N-aryl-ureido; alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxycarbonyl amino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxycarbonyl amino; formyl; acyl group; carboxyl; alkoxy carbonyl group; aryloxycarbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; the N-aryl-amino-carbonyl; N, N-ammonia diaryl base formoxyl; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfo group (SO ₃H) and conjugate base (being called the sulfonic acid foundation), alkoxy sulfonyl, aryloxy sulfonyl, sulfinyl, N-alkyl sulphinyl, N; N-dialkyl group sulfinyl, N-aryl sulfonyl kia, N; N-diaryl sulfinyl, N-alkyl-N-aryl sulfonyl kia, sulfamoyl, N-alkylsulfamoyl group, N; N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N, N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono (PO ₃H ₂) and conjugate base (being called the phosphonic acids foundation), dialkyl phosphine acyl group (PO ₃(alkyl) ₂) " following " alkyl " is meant alkyl.", diaryl phosphono (PO ₃(aryl) ₂) " following " aryl " is meant aryl.", alkylaryl phosphono (PO ₃(alkyl) (aryl)), an alkylphosphines acyl group (PO ₃And conjugate base (being called the alkyl phosphonic acid foundation), an aryl phosphine acyl group (PO (alkyl)) ₃H (aryl)) and conjugate base (being called the arylphosphonic acid foundation), phosphonato (OPO ₃H ₂) and conjugate base (being called phosphonate radical oxygen base), dialkyl phosphine acyloxy (OPO ₃H (alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), alkylaryl phosphonato (OPO ₃(alkyl) (aryl)), an alkylphosphines acyloxy (OPO ₃H (alkyl)) and conjugate base (being called alkylphosphines acid group oxygen base), an aryl phosphine acyloxy (OPO ₃H (aryl)) and conjugate base (being called aryl phosphine acid group oxygen base), cyano group, nitro, aryl, alkenyl, alkynyl, heterocyclic radical, silicyl etc.

As the concrete example of the alkyl in these substituting groups, can enumerate above-mentioned alkyl.

As the concrete example of the aryl in the described substituting group, can enumerate phenyl, xenyl, naphthyl, tolyl, xylyl, Mi Ji, cumenyl, chlorphenyl, bromophenyl, chloromethyl phenyl, hydroxy phenyl, anisyl, ethoxyphenyl, phenoxy phenyl, the acetate phenyl, the benzoxy phenyl, the methyl mercapto phenyl, the thiophenyl phenyl, the methylamino phenyl, dimethylaminophenyl, the acetamido phenyl, carboxy phenyl, the methoxycarbonyl group phenyl, the ethoxyphenyl carbonyl, the carbobenzoxy phenyl, N-phenylcarbamoyl phenyl, cyano-phenyl, the sulfo group phenyl, the sulfonate radical phenyl, the phosphono phenyl, phosphonate radical phenyl etc.

As the concrete example of the alkenyl in the described substituting group, can enumerate vinyl, 1-propenyl, 1-butenyl group, cinnamyl, 2-chloro-1-vinyl etc.

As the concrete example of the alkynyl in the described substituting group, can enumerate ethinyl, 1-propinyl, 1-butynyl, trimethyl silyl ethinyl etc.

As the acyl group (R in the described substituting group ⁰¹CO-) R ⁰¹, can enumerate hydrogen atom, described alkyl, aryl etc.

In these substituting groups; preferred halogen atom (F;-Br;-Cl;-I); alkoxy; aryloxy group; alkyl thio-base; the aryl thio group; the N-alkyl amino; N; the N-dialkyl amido; acyloxy; N-alkyl carbamoyloxy base; N-arylamino formyloxy; amide group; formyl; acyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; carbamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formoxyl; the N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl; sulfo group; the sulfonic acid foundation; sulfamoyl; the N-alkylsulfamoyl group; N, the N-dialkyl sulfamine; the N-ammonia aryl sulfonyl; N-alkyl-N-ammonia aryl sulfonyl; phosphono; the phosphonic acids foundation; the dialkyl phosphine acyl group; the diaryl phosphono; one alkylphosphines acyl group; the alkyl phosphonic acid foundation; one aryl phosphine acyl group; the arylphosphonic acid foundation; phosphonato; phosphonate radical oxygen base; aryl; alkenyl etc.

In addition,, for example pyridine radicals, piperidyl etc. can be enumerated,, trimethyl silyl etc. can be enumerated as the silicyl in the described substituting group as the heterocyclic radical in the described substituting group.

On the other hand, as the alkylidene in the substituted alkyl, for example can enumerate and remove described carbon number is that any one of hydrogen atom on 1～20 the alkyl becomes the alkylidene of organic residue of divalent, and alkylidene, the carbon number that can preferably enumerate carbon number and be 1～12 straight chain shape is that the alkylidene of 3～12 branch-like and carbon number are alkylidene of 5～10 ring-type etc.

Preferred concrete example as the substituted alkyl that obtains by combination substituting group and alkylidene like this; can enumerate chloromethyl; bromomethyl; the 2-chloroethyl; trifluoromethyl; methoxy; the isopropoxy methyl; butoxymethyl; the tert-butoxy butyl; methoxyethoxyethyl; the allyloxy methyl; phenoxymethyl; Phenoxymethyl; methylthiomethyl; the tolyl sulphomethyl; pyridylmethyl; the tetramethyl piperidine ylmethyl; N-acetyl group tetramethyl piperidine ylmethyl; the trimethyl silyl methyl; methoxy ethyl; the ethylamino-ethyl; the diethylin propyl group; the morpholino propyl group; acetoxy-methyl; the benzoxy methyl; N-cyclohexyl carboxyamide oxygen base ethyl; N-phenyl amino formyloxy ethyl; the acetamido ethyl; N-methyl benzoyl aminopropyl; 2-oxygen base ethyl; 2-oxygen base propyl group; the carboxyl propyl group; the methoxycarbonyl group ethyl; the allyloxy carbonyl butyl; chlorobenzene oxygen carbonyl methyl; the carbamyl ylmethyl; N-methylamino formoxyl ethyl; N; N-dipropyl carbamyl ylmethyl; N-(anisyl) carbamyl ethyl; N-methyl-N-(sulfo group phenyl) carbamyl ylmethyl; the sulfo group butyl; the sulfonate radical butyl; the sulfonamide butyl; N-ethyl sulfonamide methyl; N; N-dipropyl sulfonamide propyl group; N-tolyl sulfonamide propyl group; N, N-dipropyl sulfonamide propyl group; N-tolyl sulfonamide propyl group; N-methyl-N-(phosphono phenyl) sulfonamide octyl group; the phosphono butyl; the phosphonate radical hexyl; diethyl phosphono butyl; diphenyl phosphono propyl group; methyl phosphono butyl; methylphosphine acid group butyl; tolyl phosphono phosphonate radical hexyl; tolylphosphine acid group hexyl; the phosphonato propyl group; phosphonate radical oxygen Ji Dingji; benzyl; phenethyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenethyl; to methylbenzyl; cinnamyl; allyl; 1-propenyl methyl; the 2-butenyl group; the 2-methacrylic; 2-metering system ylmethyl; 2-propynyl; the 2-butynyl; 3-butynyl etc.

As described aryl, for example can enumerate phenyl ring, 2～3 phenyl ring and form base that base that condensed ring forms, phenyl ring and 5 Yuans unsaturated ring formation condensed ring form etc.

As the concrete example of aryl, for example can enumerate phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl etc.Wherein, more preferably phenyl, naphthyl.

Described alkyl also can have substituting group, as having so substituent aryl (following be also referred to as sometimes " substituted aryl ".), for example as the substituting group on the ring formation carbon atom of described aryl, can enumerate the substituting group of base with monovalence nonmetallic atom group formation of removing hydrogen atom.

As the substituting group that described aryl can have, the base that the substituting group that for example can enumerate described alkyl, substituted alkyl, can have as described alkyl shows.

Preferred concrete example as described substituted aryl; can enumerate xenyl; tolyl; xylyl; Mi Ji; cumenyl; chlorphenyl; bromophenyl; fluorophenyl; chloromethyl phenyl; trifluoromethyl; hydroxyphenyl; anisyl; the methoxy ethoxy phenyl; the allyloxy phenyl; phenoxy phenyl; the methyl mercapto phenyl; the thiophenyl phenyl; the ethylamino-phenyl; the diethylin phenyl; the morpholino phenyl; the acetoxyl group phenyl; the benzoxy phenyl; N-cyclohexyl carboxyamide oxygen base phenyl; N-phenyl amino formyloxy phenyl; the acetamido phenyl; N-methyl benzoyl aminophenyl; carboxy phenyl; the methoxycarbonyl group phenyl; the allyloxy carbonyl phenyl; chlorobenzene oxygen carbonyl phenyl; the carbamyl phenyl; N-methylamino formoxyl phenyl; N; N-dipropyl carbamyl phenyl; N-(anisyl) carbamyl phenyl; N-methyl-N-(sulfo group phenyl) carbamyl phenyl; the sulfo group phenyl; the sulfonate radical phenyl; sulfamoyl phenyl; N-ethyl sulfamoyl phenyl; N, N-dipropyl sulfamoyl phenyl; N-tolyl sulfamoyl phenyl; N-methyl-N-(phosphono phenyl) sulfamoyl phenyl; the phosphono phenyl; the phosphonate radical phenyl; diethyl phosphono phenyl; diphenyl phosphono phenyl; methyl phosphono phenyl; methylphosphine acid group phenyl; tolyl phosphono phenyl; tolylphosphine acid group phenyl; allyl phenyl; 1-propenyl aminomethyl phenyl; 2-butenyl group phenyl; 2-methacrylic phenyl; 2-methylpropenyl phenyl; the 2-propynyl phenyl; 2-butynyl phenyl; 3-butynyl phenyl etc.

As described alkenyl (C (R ⁰²)=C (R ⁰³) (R ⁰⁴)) and alkynyl (C ≡ C (R ⁰⁵)), for example can enumerate R ⁰², R ⁰³, R ⁰⁴And R ⁰⁵Base for the base that constitutes by the monovalence nonmetallic atom group.

As R ⁰², R ⁰³, R ⁰⁴, R ⁰⁵, preferred hydrogen atom, halogen atom, alkyl, substituted alkyl, aryl, substituted aryl etc.As their concrete example, can enumerate the base that shows as above-mentioned example.Wherein, more preferably hydrogen atom, halogen atom, carbon number are the alkyl of 1～10 straight chain shape, the alkyl of branch-like, the alkyl of ring-type.

As the preferred concrete example of described alkenyl and alkynyl, can enumerate vinyl, 1-propenyl, 1-butenyl group, 1-pentenyl, 1-hexenyl, 1-octenyl, 1-methyl isophthalic acid-propenyl, 2-methyl isophthalic acid-propenyl, 2-methyl-1-butene thiazolinyl, 2-phenyl-1-vinyl, 2-chloro-1-vinyl, ethinyl, 1-propinyl, 1-butynyl, phenylacetylene base etc.

As heterocyclic radical, can enumerate illustrative pyridine radicals of substituting group as substituted alkyl etc.

As described oxygen base (R ⁰⁶O-), can use R ⁰⁶The substituting group of the base that constitutes for the nonmetallic atom group of the monovalence of removing hydrogen atom.

As such oxygen base, can enumerate alkoxy, aryloxy group, acyloxy, carbamoyloxy, N-alkyl carbamoyloxy base, N-arylamino formyloxy, N, N-dialkyl amido formyloxy, N, N-ammonia diaryl base formyloxy, N-alkyl-N-arylamino formyloxy, alkyl sulfide oxygen base, aryl sulphur oxygen base, phosphonato, phosphonate radical oxygen base etc.

As alkyl in them and aryl, can enumerate the described base that shows as alkyl, substituted alkyl, aryl, substituted aryl.In addition, as the acyl group (R in the acyloxy ⁰⁷CO-), can enumerate R ⁰⁷Acyl group for alkyl, substituted alkyl, aryl and the substituted aryl enumerated as the example of front.In these substituting groups, more preferably alkoxy, aryloxy group, acyloxy, aryl sulphur oxygen base.

As the concrete example of preferred oxygen base, can enumerate methoxyl, ethoxy, propoxyl group, isopropoxy, butoxy, amoxy, own oxygen base, dodecyloxy, benzyloxy, allyloxy, the benzene ethoxy, the carboxyl ethoxy, the methoxycarbonyl group ethoxy, the carbethoxyl group ethoxy, methoxy ethoxy, the phenoxy group ethoxy, the methoxy ethoxy ethoxy, ethoxy ethoxy ethoxy, the morpholino ethoxy, the morpholino propoxyl group, the allyloxy ethoxy ethoxy, phenoxy group, toloxyl, xylyloxy, dish oxygen base, dish oxygen base, isopropyl benzene oxygen base, the methoxyl phenoxy group, ethoxy phenoxy, chlorophenoxy, the bromine phenoxy group, acetoxyl group, benzoxy, naphthoxy, phenylsulfonyloxy, phosphonato, phosphonate radical oxygen base etc.

As the amino (R that also contains amide group ⁰⁸NH-, (R ⁰⁹) (R ⁰¹⁰) N-), for example can enumerate R ⁰⁵, R ⁰⁹, R ⁰¹⁰The substituting group of the base that constitutes for the monovalence nonmetallic atom group of removing hydrogen atom.Wherein, R ⁰⁹, R ⁰¹⁰Also can be in conjunction with forming ring.

As described amino, for example can enumerate the N-alkyl amino, N, the N-dialkyl amido, the N-arylamino, N, the N-ammonia diaryl base, N-alkyl-N-arylamino, amide group, the N-alkylamidoalkyl, the N-aryl amido group, urea groups, N '-alkyl urea groups, N ', N '-dialkyl group urea groups, N '-aryl-ureido, N ', N '-diaryl urea groups, N '-alkyl-N '-aryl-ureido, N-alkyl urea groups, the N-aryl-ureido, N '-alkyl-N-alkyl urea groups, N '-alkyl-N-aryl-ureido, N ', N '-dialkyl group-N-alkyl urea groups, N '-alkyl-N '-aryl-ureido, N ', N '-dialkyl group-N-alkyl urea groups, N ', N '-dialkyl group-N '-aryl-ureido, N '-aryl-N-alkyl urea groups, N '-aryl-N-aryl-ureido, N ', N '-diaryl-N-alkyl urea groups, N ', N '-diaryl-N-aryl-ureido, N '-alkyl-N '-aryl-N-alkyl urea groups, N '-alkyl-N '-aryl-N-aryl-ureido, alkoxycarbonyl amido, aryloxy carbonyl amino, N-alkyl-N-alkoxycarbonyl amido, N-alkyl-N-alkoxycarbonyl amido, N-aryl-N-alkoxycarbonyl amido, N-aryl-N-aryloxy carbonyl amino etc.As alkyl in them and aryl, can enumerate above-mentioned base as alkyl, substituted alkyl, aryl and substituted aryl demonstration.In addition, the acyl group (R in acid amides (ア シ Le ア ミ ノ) base, N-alkylamidoalkyl, the N-aryl amido group ⁰⁷CO-) R ⁰⁷As mentioned above.Wherein, more preferably N-alkyl amino, N, N-dialkyl amido, N-arylamino, amide group.

As the preferred concrete example of substituted-amino, can enumerate methylamino, ethylamino-, diethylin, morpholino base, piperidyl, pyrroles for base, anilino-, benzamido, acetamido etc.

As sulfonyl (R ⁰¹¹-SO ₂-), for example can enumerate R ⁰¹¹Base for the base that constitutes by the monovalence nonmetallic atom group.

As such sulfonyl, for example preferred alkyl sulfonyl, aryl sulfonyl etc.As the alkyl in them, aryl, can enumerate above-mentioned base as alkyl, substituted alkyl, aryl and substituted aryl demonstration.

As the concrete example of described sulfonyl, can enumerate butyl sulfonyl, benzenesulfonyl, chlorphenyl sulfonyl etc.

As mentioned above, described sulfonic acid foundation (SO ₃ ^-) be meant sulfo group (sulpho) base (SO ₃H) conjugate base anion base is usually preferably with kation is used.

As such to kation, can suitably use usually known to kation, class (for example ammonium class, sulfonium Lei, Phosphonium class, iodine class, nitrine (ア ジ ニ ウ system) class etc.), metallic ion class (Na for example for example ⁺, K ⁺, Ca ²⁺, Zn ²⁺Deng).

As described carbonyl (R ⁰¹³-CO-), for example can use R ⁰¹³Base for the base that constitutes by the monovalence nonmetallic atom group.

As such carbonyl; for example can enumerate formyl, acyl group, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formoxyl, N-aryl-amino-carbonyl, N, N-ammonia diaryl base formoxyl, N-alkyl-N '-aryl-amino-carbonyl etc.As alkyl in them and aryl, can enumerate the above-mentioned base that shows as alkyl, substituted alkyl aryl and substituted aryl.

As described carbonyl; can enumerate formoxyl, acyl group, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, carbamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formoxyl, N-aryl-amino-carbonyl, and then more preferably formyl, acyl group, alkoxy carbonyl group and aryloxy carbonyl.

Concrete example as described carbonyl; can enumerate formoxyl, acetyl group, benzoyl, carboxyl, methoxycarbonyl group, carbethoxyl group, allyloxy carbonyl, dimethylaminophenyl vinyl carbonyl, methoxycarbonyl group methoxycarbonyl group, N-methylamino formoxyl, N-phenyl amino formoxyl, N, N-diethylamino formoxyl, morpholino carbonyl etc.

As described sulfinyl (R ⁰¹⁴-SO-), can use R ⁰¹⁴Base for the base that constitutes by the monovalence nonmetallic atom group.

As such sulfinyl; for example can enumerate alkyl sulphinyl, aryl sulfonyl kia, sulfinic acid acyl group, N-alkyl sulfinic acid acyl group, N; N-dialkyl group sulfinic acid acyl group, N-aryl sulfinic acid acyl group, N, N-diaryl sulfinic acid acyl group, N-alkyl-N-aryl sulfinic acid acyl group etc.As alkyl in them and aryl, can enumerate the described base that shows as alkyl, substituted alkyl, aryl and substituted aryl.Wherein, more preferably alkyl sulphinyl, aryl sulfonyl kia.

As the concrete example of such substituted sulfinyl, can enumerate hexyl sulfinyl, benzyl sulfinyl, tolyl sulfinyl etc.

Described replacement phosphono is meant that one or two hydroxyl on the phosphono by the base that other organic oxygen bases replace, for example can enumerate above-mentioned dialkyl phosphine acyl group, diaryl phosphono, alkylaryl phosphono, an alkylphosphines acyl group, an aryl phosphine acyl group etc.Wherein, more preferably dialkyl phosphine acyl group, diaryl phosphono.

As the preferred concrete example of described phosphono, can enumerate diethyl phosphonyl, dibutyl phosphono, diphenylphosphine acyl group etc.

As mentioned above, described phosphonic acids foundation (PO ₃H ₂ ^-,-PO ₃H ^-) be meant phosphono (PO ₃H ₂) derive from acid first the disassociation or acid second the disassociation the conjugate base anion base.Usually preferably with kation is used.As such to kation, can suitably select usually known to kation, for example various types of (ammonium class, sulfonium Lei, Phosphonium class, iodine class, nitrine (ア ジ ニ ウ system) class etc.) and metallic ion class (Na ⁺, K ⁺, Ca ²⁺, Zn ²⁺Deng).

Described phosphonic acids foundation is meant the conjugate base anion base that in the above-mentioned phosphono hydroxyl is replaced to the base of organic oxygen base, as such concrete example, can enumerate an above-mentioned alkylphosphines acyl group (PO ₃H (alkyl)), an aryl phosphine acyl group (PO ₃H (aryl)) conjugate base.

Described aromatic series base can contain by common radical polymerization utilization the aromatic series base free-radical polymerised compound more than one and as required as more than one manufacturings of other free-radical polymerised compounds of copolymerization composition.

As described radical polymerization, can enumerate for example suspension polymerization or solution polymerization process etc. usually.

As the described free-radical polymerised compound that contains the aromatic series base, the compound of the compound of preferred formula (A-1) expression, general formula (A-2) expression for example.

[changing 25]

General formula (A-1)

Wherein, in the described general formula (A-1), R ₁, R ₂And R ₃The organic group of expression hydrogen atom or 1 valency.L represents organic group, also can not have.Ar represents to contain the aromatic series base of heterocycle.

[changing 26]

General formula (A-2)

Wherein, in the described general formula (A-2), R ₁, R ₂And R ₃And Ar represents and the identical meaning of described general formula (A-1).

As the organic group of described L, for example, can enumerate by 1～60 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～100 hydrogen atom and 0～20 organic group that sulphur atom constitutes for the organic group of the multivalence that constitutes by non-metallic atom.

More specifically, as the organic group of described L, can enumerate the following structural unit of combination and the organic group that constitutes, multivalence naphthalene, multivalence anthracene etc.

[changing 27]

-CH ₂- -O-

-S-

The concatenating group of described L also can have substituting group; as described substituting group, can enumerate described halogen atom, hydroxyl, carboxyl, sulfonate radical, nitro, cyano group, amide group, amino, alkyl, alkenyl, alkynyl, aryl, substituted oxy, substituted sulphonyl, substituted carbonyl, substituted sulfinyl, sulfo group, phosphono, phosphonic acids foundation, silicyl, heterocyclic radical.

In the compound that the compound and the general formula (A-2) of described general formula (A-1) expression are represented, from the aspect of sensitivity, preferred formula (A-1).In addition, in described general formula (A-1), the point from stability preferably has concatenating group, and as the organic group of described L, from the aspect of the removing property (development) of non-image portion, preferred carbon number is 1～4 alkylidene.

The compound of described general formula (A-1) expression becomes the compound of the structural unit that contains following general formula (A-3).In addition, the compound of described general formula (A-2) expression becomes the compound of the structural unit that contains following general formula (A-4).Wherein, from the aspect of bin stability, the structural unit of preferred formula (A-3).

[changing 28]

General formula (A-3)

[changing 29]

General formula (A-4)

Wherein, in described general formula (A-3) and general formula (A-4), R ₁, R ₂And R ₃And Ar represents and described general formula (A-1) and the identical meaning of general formula (A-2).

In described general formula (A-3) and general formula (A-4), from the aspect of the removing property (development) of non-image portion, preferred R ₁And R ₂Be hydrogen atom, R ₃Be methyl.

In addition, from the aspect of the removing property (development) of non-image portion, it is 1～4 alkylidene that the L of described general formula (A-3) is preferably carbon number.

As the compound of described general formula (A-1) expression or the compound of general formula (A-2) expression, be not particularly limited, for example can enumerate following exemplary compounds (1)～(30).

[changing 30]

[changing 31]

In described exemplary compounds (1)～(30), preferred (5), (6), (11), (14) and (28), wherein, from the aspect of bin stability and development, more preferably (5) and (6).

To the described content of aromatic series base in described bonding agent that contains heterocycle, be not particularly limited, be made as under the situation of 100mol% in entire infrastructure unit macromolecular compound, preferably contain the structural unit of the above general formula of 20mol% (A-3) expression, more preferably contain 30～45mol%.If described content is less than 20mol, then bin stability may step-down, if surpass 45mol%, then development property may reduce.

--ethene unsaturated link--

As described ethene unsaturated link, be not particularly limited, can suitably select the ethene unsaturated link of for example preferred following general formula (A-5)～(A-7) expression according to purpose.

[changing 32]

General formula (A-5)

General formula (A-6)

General formula (A-6)

Wherein, in the described general formula (A-5)～(A-7), R ₁～R ₁₁Independently of one another, represent 1 valency organic group.X and Y are independently of one another, expression oxygen atom, sulphur atom or-N-R ₄Z represent oxygen atom, sulphur atom ,-N-R ₅Or phenylene.R ₄The organic group of expression hydrogen atom or 1 valency.

In described general formula (A-5), as R ₁, independently of one another, for example be preferably hydrogen atom, can have substituent alkyl etc., from the high aspect of free radical reaction, more preferably hydrogen atom, methyl.

As described R ₂And R ₃Independently of one another; for example can enumerate hydrogen atom; halogen atom; amino; carboxyl; alkoxy carbonyl group; sulfo group; nitro; cyano group; can have substituent alkyl; can have substituent aryl; can have substituent alkoxy; can have substituent aryloxy group; can have substituent alkyl amino; can have substituent arylamino; can have substituent alkyl sulphonyl; can have substituent aryl sulfonyl etc.; from the high aspect of free radical reaction, more preferably hydrogen atom; carboxyl; alkoxy carbonyl group; can have substituent alkyl; can have substituent aryl.

As described R ₄, for example preferably can have substituent alkyl etc., from the high point of free radical reaction, more preferably hydrogen atom, methyl, ethyl, isopropyl.

At this; as the described substituting group that can import, for example can enumerate alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy group, halogen atom, cyano group, alkyl amino, arylamino, carboxyl, alkoxy carbonyl group, sulfo group, nitro, cyano group, amide group, alkyl sulphonyl, aryl sulfonyl etc.

In described general formula (A-6), as R ₄～R ₈For example preferred hydrogen atom, halogen atom, amino, dialkyl amido, carboxyl, alkoxy carbonyl group, sulfo group, nitro, cyano group, can have substituent alkyl, can have substituent aryl, can have substituent alkoxy, can have substituent aryloxy group, can have substituent alkyl amino, can have substituent arylamino, can have substituent alkyl sulphonyl, can have substituent aryl sulfonyl etc., more preferably hydrogen atom, carboxyl, alkoxy carbonyl group, can have substituent alkyl, can have substituent aryl.

As the described substituting group that can import, be illustrated in the substituting group of enumerating in the described general formula (A-5).

In described general formula (A-7), as R ₉, for example preferred hydrogen atom, can have substituent alkyl etc., from the high aspect of free radical reaction, more preferably hydrogen atom, methyl.

As described R ₁₀, R ₁₁Independently of one another; for example preferred hydrogen atom; halogen atom; amino; dialkyl amido; carboxyl; alkoxy carbonyl group; sulfo group; nitro; cyano group; can have substituent alkyl; can have substituent aryl; can have substituent alkoxy; can have substituent aryloxy group; can have substituent alkyl amino; can have substituent arylamino; can have substituent alkyl sulphonyl; can have substituent aryl sulfonyl etc.; from the high aspect of free radical reaction, more preferably hydrogen atom; carboxyl; alkoxy carbonyl group; can have substituent alkyl; can have substituent aryl.

At this,, be illustrated in the substituting group of enumerating in the described general formula (A-5) as the described substituting group that can import.

As Z, expression oxygen atom, sulphur atom ,-NR ₁₃-maybe can have substituent phenylene.R ₁₃Expression can have substituent alkyl etc., from the high aspect of free radical reaction, and preferred hydrogen atom, methyl, ethyl, isopropyl.

In the side chain ethene unsaturated link of described general formula (A-5)～(A-7) expression, from polymerisation reactivity height, highly sensitive aspect, the more preferably compound of (A-5) usually.

To the content of described ethene unsaturated link in described macromolecular compound, be not particularly limited, be preferably 0.5～3.0meq/g, more preferably 1.0～3.0meq/g is preferably 1.5～2.8meq/g especially.If described content is less than 0.5meq/g, then the curing reaction amount is few, thereby may become muting sensitivity, if more than 3.0meq/g, then bin stability may deterioration.

At this, described content (meq/g) for example can utilize the iodine number titration to measure.

Method as the ethene unsaturated link that imports from described general formula (A-5) expression to side chain, be not particularly limited, for example can obtain by making the compound generation addition reaction that contains the macromolecular compound and the ethene unsaturated link of carboxyl and contain epoxy radicals at side chain.

The described macromolecular compound that has carboxyl at side chain, for example can contain by common radical polymerization utilization carboxyl free-radical polymerised compound more than one and as required as more than one manufacturings of other free-radical polymerised compounds of copolymerization composition, as described radical polymerization, for example can enumerate suspension polymerization, solution polymerization process etc.

As described compound,, be not particularly limited the compound of the compound of for example preferred following general formula (A-8) expression and general formula (A-9) expression as long as have them with ethene unsaturated link and epoxy radicals.

[changing 33]

General formula (A-8)

Wherein, in the described general formula (A-8), R ₁Expression hydrogen atom or methyl.L ₁The expression organic group.

[changing 34]

General formula (A-9)

Wherein, in the described general formula (A-9), R ₂Expression hydrogen atom or methyl.L ₂The expression organic group.W represents the aliphatic alkyl of 4～7 Yuans rings.

In the compound that the compound and the general formula (A-9) of described general formula (A-8) expression are represented, the compound of preferred formula (A-8) expression, in described general formula (A-8), more preferably L1 is the alkylidene of carbon number 1～4.

As the compound of described general formula (A-8) expression and the compound of general formula (A-9) expression, be not particularly limited, for example can enumerate following exemplary compounds (31)～(40).

[changing 35]

As the described free-radical polymerised compound that contains carboxyl, for example comprise acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid, to carboxyl styrene etc., preferred especially acrylic acid, methacrylic acid etc.

As described importing reaction to side chain, for example can pass through tertiary amines such as triethylamine, benzyl methylamines, quaternary ammonium salts such as DTAC, tetramethyl ammonium chloride, etamon chloride, pyridine, triphenyl phasphines etc. are as catalyzer, in organic solvent, make it at 50～150 ℃ of following stoichiometric numbers of temperature of reaction hour～carried out in tens of hours.

Have the structural unit of ethene unsaturated link as described at side chain, be not particularly limited, the structure of for example preferred following general formula (A-10) expression, the structure of general formula (A-11) expression and the structure of utilizing their hybrid representation.

[changing 36]

General formula (A-10)

General formula (A-11)

Wherein, in described general formula (A-10) and the general formula (A-11), Ra～Rc represents the organic group of hydrogen atom or 1 valency.R ₁Expression hydrogen atom or methyl.L ₁Expression can have the organic group of concatenating group.

Content in the macromolecular compound of the structure that the structure or the general formula (A-11) of described general formula (A-10) expression are represented is preferably more than the 20mol%, and more preferably 20～50mol% is preferably 25～45mol% especially.If described content is less than 20mol%, then the curing reaction amount is few, thereby may become muting sensitivity, if more than 50mol%, then bin stability may deterioration.

--carboxyl--

In macromolecular compound of the present invention,, also can have carboxyl in order to improve each performance such as removing property of non-image portion.

Described carboxyl can be given to described macromolecular compound by making the free-radical polymerised compound generation copolymerization with acidic group.

As so free-radical polymerised acidic group that has, for example can enumerate carboxylic acid, sulfonic acid, phosphate etc., special optimization acid.

As described free-radical polymerised compound with carboxyl, be not particularly limited, can suitably select according to purpose, for example can enumerate acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid, to carboxyl styrene etc., wherein, preferred acrylic acid, methacrylic acid, to carboxyl styrene.They can be used alone, also can be also with two or more.

The content of described carboxyl in bonding agent is 1.0～4.0meq/g, is preferably 1.5～3.0meq/g.Described content is during less than 1.0meq/g, and it is insufficient that development becomes sometimes, if surpass 4.0meq/g, then may becoming, it is impaired to be subjected to the image intensity that liquid alkali developing causes easily.

In order to improve each performance such as image intensity, macromolecular compound of the present invention also preferably makes other free-radical polymerised compound copolymerizations except described free-radical polymerised compound.

As described other free-radical polymerised compounds, for example can enumerate the free-radical polymerised compound of selection from esters of acrylic acid, methyl acrylic ester, phenylethylene etc. etc.

Particularly, can enumerate esters of acrylic acids such as alkyl acrylate, the acrylic acid aryl ester, methyl acrylic esters such as alkyl methacrylate, aryl methacrylate, phenylethylenes such as styrene, ring-alkylated styrenes, alkoxystyrene, halogenated styrenes etc.

As described esters of acrylic acid, the carbon number of alkyl is preferably 1～20, for example can enumerate methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, the acrylic acid pentyl ester, the acrylic acid ethylhexyl, 2-ethyl hexyl acrylate, acrylic acid uncle monooctyl ester, the acrylic acid chloro-ethyl ester, acrylic acid 2,2-dimethyl hydroxyl propyl diester, acrylic acid 5-hydroxyalkyl acrylate, trimethylolpropane one acrylate, pentaerythrite one acrylate, epihydric alcohol acrylic ester, the acrylic acid benzyl ester, acrylic acid methoxy-benzyl ester, acrylic acid chaff ester, tetrahydrofurfuryl acrylate etc.

As described acrylic acid aryl ester, for example can enumerate phenyl acrylate etc.

As described methyl acrylic ester, the carbon number of alkyl is preferably 1～20, for example can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, isopropyl methacrylate, methacrylic acid amyl group ester, hexyl methacrylate, cyclohexyl methacrylate, the methacrylic acid benzyl ester, methacrylic acid chlorine benzyl ester, methacrylic acid octyl group ester, methacrylic acid 4-hydroxybutyl ester, methacrylic acid 5-hydroxyl amyl group ester, methacrylic acid 2,2-dimethyl-3-hydroxy-propyl ester, trimethylolpropane monomethyl acrylate, pentaerythrite monomethyl acrylate, glycidyl methacrylate, methacrylic acid chaff ester, tetrahydrofurfuryl methacrylate etc.

As described aryl methacrylate, for example can enumerate methacrylic acid phenylester, methyl methacrylate phenylester, naphthyl etc.

As described phenylethylene, for example can enumerate methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, diethylbenzene ethene, cumene ethene, butylstyrene, hexyl benzene ethene, cyclohexyl benzene ethene, decyl styrene, benzyl styrene, 1-chloro-4-methyl-benzene, trifluoromethyl styrene, ethoxyl methyl styrene, acetate methyl styrene etc.

As described alkoxystyrene, for example can enumerate methoxy styrene, 4-methoxyl-3-methyl styrene, dimethoxy styrene etc.

As described halogenated styrenes, for example can enumerate chlorostyrene, dichlorostyrene, trichloro-benzenes ethene, tetrachlorobenzene ethene, pentachlorobenzene ethene, bromstyrol, Dowspray 9, iodobenzene ethene, fluorobenzene ethene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.

These free-radical polymerised compounds can be used alone, also can be also with two or more.

As the solvent that when synthesizing macromolecular compound of the present invention, uses, be not particularly limited, can suitably select according to purpose, for example can enumerate ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, propyl alcohol, butanols, glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy ethyl acetic acid esters, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl-acetic acid ester, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, ethyl lactate etc.They can be used alone, and it is two or more also can to mix use.

The molecular weight of macromolecular compound of the present invention is preferably more than 10,000 with the matter average molecular weight, and more preferably 10,000～50,000.If described matter average molecular weight is lower than 10,000, then cured film intensity may be not enough, if surpass 50,000, and the trend that reduces of development property existence then.

In addition, in macromolecular compound of the present invention, also can contain unreacted monomer.In this case, the content of described monomer in described macromolecular compound is preferably below the 15 quality %.

Macromolecular compound among the present invention can be used alone, and it is two or more also can to mix use.In addition, also can mix other macromolecular compounds of use.In this case, the content of described other macromolecular compounds in described macromolecular compound of the present invention is preferably below the 50 quality %, more preferably below the 30 quality %.

The solid component content of described bonding agent in described photosensitive composite is preferably 5～80 quality %, more preferably 10～70 quality %.If this solid component content is less than 5 quality %, then the film strength of photographic layer dies down easily, and the viscosity on the surface of this photographic layer (tack) worsens sometimes, if surpass 80 quality %, then exposure sensitivity may reduce.

-polymerizable compound-

As described polymerizable compound, be not particularly limited, can suitably select according to purpose, at least have in the preferred molecule one can addition polymerization base, boiling point be the compound more than 100 ℃ under normal pressure, for example can preferably enumerate from monomer, select at least a with (methyl) acrylic.Wherein, in the present invention, " polymerizable compound " do not comprise the polymerizable compound that can contain in the bonding agent.

As described monomer with (methyl) acrylic, be not particularly limited, can suitably select according to purpose, for example can enumerate monofunctional acrylate or simple function methacrylates such as polyglycol one (methyl) acrylate, polypropylene glycol one (methyl) acrylate, (methyl) acrylic acid phenoxy group ethyl ester; 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 (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate, trimethylolpropane or glycerine, bis-phenols etc. carry out the product of (methyl) acroleic acid esterification after polyfunctional alcohol's addition reaction oxirane or epoxypropane; Special public clear 48-41708 number, special public clear 50-6034 number, spy such as open clear 51-37193 number at the urethanes esters of acrylic acid of putting down in writing in each communique; The spy such as opens clear 48-64183 number, special public clear 49-43191 number, special public clear 52-30490 number at the polyester acrylate class of putting down in writing in each communique; 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.

The solid component content of described polymerizable compound in described photosensitive composite solid constituent is preferably 5～50 quality %, more preferably 10～40 quality %.If this solid component content less than 5 quality %, then can produce the deterioration of development, the problems such as reduction of exposure sensitivity, if surpass 50 quality %, then the cohesive of photographic layer became strong sometimes, and was not preferred.

-thermal cross-linking agent-

As described thermal cross-linking agent, be not particularly limited, can suitably select according to purpose, in order to improve the film strength of photographic layer after curing that forms with described photosensitive film, bringing in the dysgenic scope for development etc., for example can use the epoxy compound that in 1 molecule, has 2 Oxyranyles at least, oxetanes (oxetane) compound that in 1 molecule, has 2 oxetanyls at least.

As the described epoxy compound that in 1 molecule, has 2 Oxyranyles at least, for example can enumerate di-cresols type or connection phenol-type epoxy resin (" YX4000 japan epoxy resin (JapanEpoxy Resin) corporate system " etc.) or their potpourri, have hetero ring type the epoxy resin (" TEIPIC of isocyanuric acid ester skeleton etc.; Daily output chemical industrial company system ", " ア ラ Le ダ イ ト PT810; The west different chemicals of Bart (CIBA SPECIALTY CHEMICALS) corporate 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, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, halogen epoxy resin (for example low brominated epoxy resin, high halogen epoxy resin, bromination phenol novolak type epoxy resin etc.), contain the propenyl 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 industrial company system " etc.); glycidyl amine type epoxy resin (diaminodiphenyl-methane type epoxy resin; diglycidylaniline; triglycidyl group amino-phenol etc.); glycidyl ester type epoxy resin (phthalic acid diglycidyl ester; hexane diacid diglycidyl ester, hexahydro-phthalic acid diglycidyl ester, dimer acid diglycidyl 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 bicyclopentadiene diepoxide, " GT-300; GT-400; ZEHPE3150; ダ イ セ Le chemical industry system " etc.), imide-type alicyclic epoxy resin, trihydroxy benzene methylmethane type epoxy resin, bisphenol A-type phenolic resin varnish type epoxy resin, four phenylol ethane type epoxy resin, phthalic acid glycidyl esters resin, four glycidyl group dimethylbenzene acyl group ethane resin, contain naphthyl epoxy resin (naphthols aralkyl-type epoxy resin, naphthol novolac varnish type epoxy resin, 4 officials can naphthalene type epoxy resin, as " ESN-190, the ESN-360 of commercially available product; Chemical company of Nippon Steel system ", " HP-4032, EXA-4750, EXA-4700; Big Japanese ink chemical industrial company system " etc.); the polyphenyl phenolic compounds that the addition reaction of diolefin compounds such as oxybenzene compound and divinylbenzene or bicyclopentadiene obtains and the reactant of chloropropylene oxide utilized; the product that obtains with the ring-opening polymerization polymer of epoxidations such as peracetic acid 4 vinyl cyclohexene-1-oxide; have the epoxy resin of wire phosphor-containing structure; have the epoxy resin of cyclic phosphorus-containing structure; Alpha-Methyl stilbene type epoxy resin by using liquid crystal, dibenzoyl Oxybenzene type epoxy resin by using liquid crystal, benzeneazo fundamental mode epoxy resin by using liquid crystal, azo methylbenzene fundamental mode epoxy resin by using liquid crystal, dinaphthalene type epoxy resin by using liquid crystal, azine type epoxy resin, epihydric alcohol methylpropenoic acid ester copolymerization system epoxy resin (" CP-50S; CP-50M; Nof Corp.'s system " etc.), cyclohexyl maleimide and the copolymerization epoxy resin of epihydric alcohol methylpropenoic acid ester, two (glycidoxypropyl phenyl) diamantane type epoxy resin etc., but do not limited by these.These epoxy resin can be used alone or and with two or more.

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

Describedly containing at least that have the epoxy radicals more than 2 that the epoxy compound of the epoxy radicals of alkyl contains in can be for 1 molecule in the β position all be that β-alkyl replaces glycidyl, can be that β-alkyl replaces glycidyl at least 1 epoxy radicals also.

Viewpoint from room temperature bin stability, the described epoxy compound that has the epoxy radicals of alkyl in the β position that contains, β in total epoxy radicals in the described epoxy compound total amount that contains in the described photosensitive composite-alkyl replaces the ratio of glycidyl, be preferably more than 30%, more preferably more than 40%, be preferably more than 50% especially.

Replace glycidyl as described β-alkyl, be not particularly limited, can suitably select according to purpose, for example can enumerate Beta-methyl glycidyl, β-ethyl glycidyl, β-propyl group glycidyl, β-butyl glycidyl base etc., wherein, from the viewpoint of the viewpoint of the bin stability that improves described photosensitive composite and synthetic easiness, preferred Beta-methyl glycidyl.

As the epoxy compound that the described β of containing position has the epoxy radicals of alkyl, for example preferred polyphenol compound and the epoxy compound that β-the alkyl epihalohydrins is derived and formed.

As described β-alkyl epihalohydrins, be not particularly limited, can suitably select according to purpose, for example can enumerate Beta-methyl epihalohydrins such as Beta-methyl chloropropylene oxide, Beta-methyl epoxy bromopropane, Beta-methyl epichlorhydrin; β-ethyl chloropropylene oxide, β-ethyl epoxy bromopropane, β-β-ethyl epihalohydrins such as ethyl epichlorhydrin; β-propyl group chloropropylene oxide, β-propyl group epoxy bromopropane, β-β-propyl group epihalohydrins such as propyl group epichlorhydrin; β such as β-butyl chloropropylene oxide, β-butyl epoxy bromopropane, β-butyl epichlorhydrin-butyl epihalohydrins etc.Wherein, from the reactive and mobile viewpoint of described polyhydric phenol, preferred Beta-methyl epihalohydrins.

As described polyphenol compound, get final product so long as in 1 molecule, contain the compound of the fragrant family hydroxyl more than 2, be not particularly limited, can suitably select according to purpose, for example can enumerate bisphenol-A, Bisphenol F, bisphenol compounds such as bisphenol S, connection phenol, connection phenolic compounds such as tetramethyl connection phenol, dihydroxy naphthalene, naphthol compounds such as dinaphthol, phenol novolac resins such as P-F condensed polymer, carbon numbers such as cresols-formaldehyde condensation products are one alkyl substituted phenol-formaldehyde condensation products of 1～10, carbon numbers such as xylenols-formaldehyde condensation products are dialkyl substituted phenol-formaldehyde condensation products of 1～10, bisphenol compound-formaldehyde condensation products such as bisphenol-A-formaldehyde condensation products, phenol and carbon number are 1～10 the alkyl substituted phenol and the copolymerization condensation product of formaldehyde, the addition polymer of oxybenzene compound and divinylbenzene etc.Wherein, for example under situation about selecting in order to improve flowability and bin stability, preferred described bisphenol compound.

As the described epoxy compound that has the epoxy radicals of alkyl in the β position that contains, for example can enumerate the two-β-alkyl glycidyl ether of two-β-bisphenol compounds such as alkyl glycidyl ether of two-β-alkyl glycidyl ether, the bisphenol S of two-β-alkyl glycidyl ether, the Bisphenol F of bisphenol-A; Two-β-the alkyl glycidyl ether of the connection phenolic compounds such as two-β-glycidol ether of the two-β-alkyl glycidyl ether of connection phenol, tetramethyl connection phenol; β-the alkyl glycidyl ether of two-β of two-β of dihydroxy naphthalene-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 one alkyl substituted phenol-formaldehyde condensation products of 1～10; Poly--carbon numbers such as β-alkyl glycidyl ether of xylenols-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, the oxybenzene compound-formaldehyde condensation products of the β-alkyl glycidyl ether of the bisphenol compound of preferred following general formula (D-1) expression and the polymer-derived that obtains from itself and chloropropylene oxide etc. and following general formula (D-2) expression gathers-β-alkyl glycidyl ether.

[changing 37]

General formula (D-1)

[changing 38]

General formula (D-2)

Wherein, in the described general formula (D-1), R represents that hydrogen atom and carbon number are any one of 1～6 alkyl, and n represents 0～20 integer.

Wherein, in the described general formula (D-2), R represents that hydrogen atom and carbon number are any one of 1～6 alkyl, R " expression hydrogen atom and CH ₃Any one, n represents 0～20 integer.

These contain the epoxy compound that has the epoxy radicals of alkyl in the β position and can be used alone, also can and with two or more.In addition, can also and be used in and have the epoxy compound of 2 oxirane rings in 1 molecule at least and contain the epoxy compound that has the epoxy radicals of alkyl in the β position.

As the skeleton of described epoxy compound, preferably from bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, contain select ester ring type fundamental mode epoxy resin and the slightly solubility epoxy resin at least a.

As described oxetane compound, for example can enumerate two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, 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 ester, acrylic acid (3-ethyl-3-oxetanyl) methyl ester, methacrylic acid (3-methyl-3-oxetanyl) methyl ester, methacrylic acid (3-ethyl-3-oxetanyl) methyl ester or multifunctional oxetanes classes such as their oligomer or multipolymer, in addition, can also enumerate compound and novolac resin with oxetanyl, poly-(para hydroxybenzene ethene), Ka Er many (カ Le De) type bisphenols, cup (Calix, カ リ Star Network ス) aromatic hydrocarbons, cup (Calix, カ リ Star Network ス) resorcinol aromatic hydrocarbons, silsesquioxane (Silsesquioxane, シ Le セ ス キ オ キ サ Application) etc. has the ether compound between the resin etc. of hydroxyl, in addition, can also enumerate unsaturated monomer with oxetanes ring and the multipolymer between (methyl) alkyl acrylate etc.

In addition, in order to promote the heat curing of described epoxy compound or described oxetane compound, for example can use amines (for example two cyanogen diamides, benzyl dimethylamine, 4-(dimethylamino)-N, N-diformazan benzylamine, 4-methoxyl-N, N-diformazan benzylamine, 4-methyl-N, N-diformazan benzylamine etc.), quarternary ammonium salt compound (for example triethyl benzyl ammonia chloride etc.), block isocyanate compound (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-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole etc.), phosphorus compound (for example triphenyl phasphine etc.), guanamine compound (melamine for example, guanamine, the methyl guanamines, benzene guanamine etc.), S-pyrrolotriazine derivatives (for example 2,4-diamido-6-methacryloxyethyl)-the S-triazine, 2-vinyl-2,4-diamido-S-triazine, 2-vinyl-4,6-diamido-S-triazine cyamelide addition product, 2,4-diamido-6-methacryloxyethyl-S-triazine cyamelide addition product etc.) etc.They can be used alone or and with two or more.In addition,, be not particularly limited, also can use the compound that can promote heat curing beyond above-mentioned so long as the curing catalysts of described epoxy compound or described oxetane compound or the material that can promote carboxyl and them to react get final product.

Described epoxy resin, described oxetane compound and can promote carboxylic acid and they carry out the compound of heat curing, the solid component content in described photosensitive composite solid constituent is generally 0.01～15 quality %.

In addition, as described thermal cross-linking agent, can use the spy to open the polyisocyanate compounds of putting down in writing in the flat 5-9407 communique, this polyisocyanate compounds also can replace fatty compound and derive from aliphatics, ring type aliphatics or the aryl that contains two isocyanate group at least.Particularly, can enumerate two functional isocyanate (for example 1,3-phenylene vulcabond and 1, the potpourri of 4-phenylene vulcabond, 2,4-and 2,6-toluene diisocyanate, 1,3-and 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 between this two functional isocyanate and trimethylolpropane, pentaerythrite, glycerine etc.; Addition product between this polyfunctional alcohol's alkylene oxide adducts and described two functional isocyanate; Hexamethylene diisocyanate, hexa-methylene-1, the ring type tripolymer of 6-diisocyanate and derivant thereof etc. etc.

And then, in order to improve the keeping quality of photosensitive film of the present invention, the compound that also can use the isocyanates radical reaction of block agent and described polyisocyanate and derivant thereof to obtain.

As the agent of described isocyanate group block, can enumerate alcohols (for example isopropyl alcohol, the tert-butyl alcohol etc.), lactams (for example epsilon-caprolactams etc.), phenol (for example phenol, cresols, p-t-butyl phenol, to sec-butyl phenol, to sec-amyl phenol, paraoctyl phenol, to nonyl phenol etc.), hetero ring type hydroxyl compound (for example 3-pyridone, oxine etc.), activity methene compound (for example dialkyl malonate, methyl ethyl ketoxime, diacetone, alkyl acetoacetate oxime, acetoxime, cyclohexanone-oxime etc.) etc.Compound of any one party of in molecule, having of in addition, can also using the spy to open to put down in writing in the flat 6-295060 communique two keys that at least one can polymerization and at least one blocked isocyanate base etc.

In addition, as described thermal cross-linking agent, can use melamine derivative.As this melamine derivative, for example can enumerate methylol melamine, alkylated methylol melamine (compound that obtains with etherificate methylols such as methyl, ethyl, butyl) etc.They can be used alone or and with two or more.Wherein, good from bin stability, be effective point in the raising of the film strength of the skin hardness of photographic layer or cured film itself, preferred alkyl methylol melamine, especially preferably hexamethyl methylol melamine.

The solid component content of described thermal cross-linking agent in described photosensitive composite solid constituent is preferably 1～50 quality %, more preferably 3～30 quality %.If this solid component content does not then have the raising of the film strength of cured film less than 1 quality %, if surpass 50 quality %, the deterioration of development or the reduction of exposure sensitivity take place sometimes then.

-other compositions-

As described other compositions, for example can enumerate thermal polymerization inhibitor, plastifier, colorant (coloring pigment or dyestuff) etc., and then also can and use the adhesion promoter of substrate surface and other assistant classes (for example conductive particle, filling agent, defoamer, fire retardant, levelling agent, peel off promoter, antioxidant, spices, surface tension modifier, chain move agent etc.).By suitably containing these compositions, can regulate the character such as stability, photograph, film physical property of the photosensitive film that needs.

-thermal polymerization inhibitor-

Described thermal polymerization inhibitor can prevent the thermal polymerization of the described polymerizable compound in the described photographic layer or through the polymerization of time ground, so also can add.

As described thermal polymerization inhibitor, for example can enumerate the 4-metoxyphenol, quinhydrones, alkyl or aryl replaces quinhydrones, tert-butyl catechol, pyrogaelol, the 2-Viosorb 110,4-methoxyl-2-Viosorb 110, stannous chloride, phenothiazine, the tetrahydrochysene quinone, 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, methylenum careuleum, copper and organic sequestering agent reactant, gaultherolin and phenothiazine, nitroso compound, the chelate of nitroso compound and Al etc.

As the content of described thermal polymerization inhibitor, described relatively polymerizable compound, preferred 0.001～5 quality %, more preferably 0.005～2 quality %, preferred especially 0.01～1 quality %.

If this content is less than 0.001 quality %, the stability when then preserving sometimes can reduce, if surpass 5 quality %, then the sensitivity meeting of relative activity energy line reduces.

-plastifier-

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

As described plastifier, for example can enumerate phthalates such as phthalic acid dimethyl ester, dibutyl phthalate, diisobutyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, dicyclohexyl phthalate, phthalic acid tricosyl ester, butyl benzyl phthalate, diisooctyl phthalate, phthalic acid diphenyl, diallyl phthalate, phthalic acid octyl group capryl ester; Diol-lipids such as triethylene-glycol diacetate, tetraethylene glycol diacetate esters, phthalic acid dimethyl glucose ester, ethyl phthalyl ethyl hexanol acid esters, methyl phthalyl ethyl hexanol acid esters, butyl phthalyl butyl alcohol acid esters, triethylene glycol dieaprylate; Phosphoric acid ester such as phosphoric acid trimethylbenzene phenolic ester, triphenyl phosphate; Amide-types such as 4-toluenesulfonamide, benzsulfamide, N-n-butylbenzene sulfonamide, N-normal-butyl acetamide; Fatty acid dibasic acid ester classes such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, dioctyl azelate, dibutyl maleate; Triethyl citrate, tributyl citrate, glycerol triacetate, butyl laurate, 4,5-diethoxy cyclohexane-1, glycols such as polyglycol, polypropylene glycol such as 2-dicarboxylic acid dioctyl ester.

The content of described plastifier, whole compositions of described relatively photosensitive composite, preferred 0.1～50 quality %, more preferably 0.5～40 quality %, preferred especially 1～30 quality %.

-coloring pigment-

As described coloring pigment, be not particularly limited, can suitably select according to purpose, for example can enumerate Victoria's pure blue B O (C.I.42595), (alkalescence) Chinese scholartree Huang (C.I.41000), liposoluble (fat) HB (C.I.26150), the Monot relies special yellow GT (C.I. pigment Yellow 12), permanent yellow GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), permanent carmine FBB (C.I. pigment red 146), advertisement poster paratonere ESB (C.I. pigment violet 1 9), permanent red jewel FBH (C.I. paratonere 11), the pink B of Fa Siteer Soviet Union pula (C.I. pigment red 81), sodium Si Telaer fast blue (C.I. pigment blue 15) not, the Monot rely special Jian Lao B (C.I. Yan Liao 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.They can be used alone or and with two or more.In addition, as required, also can use the dyestuff of from known dyestuff, suitably selecting.

The solid component content of described coloring pigment in described photosensitive composite, decisions such as the exposure sensitivity of the photographic layer in the time of can considering permanent pattern formation, exploring degree, kind according to described coloring pigment is different and different, usually be preferably 0.01～10 quality %, more preferably 0.05～5 quality %.

-adhesion promoter-

For the adhesiveness that improves each interlayer or the adhesiveness between photographic layer and the base material, can in each layer, use known so-called adhesion promoter.

As described adhesion promoter, for example can preferably enumerate the spy and open flat 5-11439 communique, spy and open flat 5-341532 communique and the special adhesion promoter of opening record in the flat 6-43638 communique etc.Particularly, can enumerate benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholino methyl isophthalic acid-phenyl-triazole-2-thioketones, 3-morpholino methyl-5-phenyl-oxadiazole-2-thioketones, 5-amino-3-morpholino methyl-thiadiazoles-2-thioketones, and 2-sulfydryl-5-methyl sulfo--thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, contain amino benzotriazole, silane coupling agent etc.

As the content of described adhesion promoter, whole compositions of described relatively photographic layer are preferably 0.001 quality %～20 quality %, and more preferably 0.01～10 quality % is preferably 0.1 quality %～5 quality % especially.

-photographic layer-

Under the situation that the photographic layer that is formed by described photosensitive composite is exposed, develops, in this exposure and the least energy of the front and back light that do not change, that in described exposure, use after developing, be preferably 0.1～200mJ/cm as the thickness of the exposed portion of this photographic layer ², 0.2～100mJ/cm more preferably ², be preferably 0.5～50mJ/cm especially ²

If described least energy is less than 0.1mJ/cm ², photographic fog then takes place in treatment process sometimes, if surpass 200mJ/cm ², the required time that then exposes sometimes is elongated, and processing speed is slack-off.

At this, described " least energy of the thickness of exposed portion that makes this photographic layer light that do not change, that in described exposure, use " (following abbreviate as sometimes " least energy of light " in this exposure and after developing.) being meant so-called development sensitivity, the energy (exposure) of the light that uses for example can the described exposure when expression exposes to described photographic layer utilizes the curve map (sensitivity curve) of the relation between the thickness of described cured layer of described development treatment generation to try to achieve with following described exposure.

The thickness of described cured layer increases and increases along with described exposure, become then with described exposure before the roughly the same and constant of thickness of described photographic layer.Described development sensitivity is the value that the minimum exposure amount when becoming constant by the thickness that reads described cured layer is tried to achieve.

At this, the difference between the thickness of the described photographic layer before the thickness of described cured layer and the described exposure is in ± 1 μ m time, thinks that the thickness of described cured layer is not exposed and the change of developing.

Determination of thickness method as the described photographic layer before described cured layer and the described exposure, be not particularly limited, can suitably select according to purpose, for example can enumerate and use determining film thickness device, surface roughness measurement machine (for example サ one Off コ system 1400D (Tokyo Micronics Inc. system)) etc. to carry out method for measuring etc.

In addition, the rate of change (%) of the least energy of the described light under the light of wavelength 400～410nm (followingly is also referred to as " skew of sensitivity " sometimes.) be preferably in 20%.If the described rate of change surpasses 20%, then the pattern form in the face may produce skew.

At this, the described rate of change for example can be passed through after the least energy of the described light under the light of measuring wavelength 400nm, whenever the 1nm wavelength staggers, measure once least energy until the described light of the light of wavelength 410nm, utilize following formula, try to achieve from the maximal value (Emax) of the least energy of these light and the difference of minimum value (Emin).

[formula]

(Emax-Emin)/Emax

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

(photosensitive film)

As the photosensitive film among the present invention, the photographic layer that is made of described photosensitive composite of the present invention that preferably has supporter at least and form on this supporter suitably has other layers such as thermoplastic resin as required.In addition, for photographic layer, as mentioned above.

＜supporter 〉

As described supporter, be not particularly limited, can suitably select according to purpose, preferably can peel off the permeability good supporting body of described photographic layer and light, and then more preferably surperficial flatness is good.

Described supporter is preferably synthetic resin system and transparent supporter, for example can enumerate polyethylene terephthalate, PEN, polypropylene, tygon, cellulose triacetate, cellulose diacetate, poly-(methyl) alkyl acrylate, poly-(methyl) acrylate copolymer, Polyvinylchloride, polyvinyl alcohol (PVA), polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, the vinyl chloride acetate ethylene copolymer, teflon, poly-triclene, cellulose-based film, various plastic sheetings such as nylon film, wherein, preferred especially polyethylene terephthalate.They can use separately a kind or and with more than 2 kinds.

Thickness as 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.Described supporter can be individual layer, also can have multilayer.

Shape as described supporter is not particularly limited, can suitably select according to purpose, but preferred strip.Length as the supporter of described strip is not particularly limited, and for example can enumerate 10～20, the length of 000m.

＜protective film 〉

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

As described protective film, for example can enumerate the protective film that in described supporter, uses, paper is laminated with tygon, polyacrylic paper etc., wherein, preferably polyethylene film, polypropylene film.

Thickness as 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, for example can enumerate polyethylene terephthalate/polypropylene, polyethylene terephthalate/tygon, Polyvinylchloride/cellophane, polyimide/polypropylene, polyethylene terephthalate/polyethylene terephthalate etc.In addition, by at least one of surface treatment supporter and protective film, can regulating course between bonding force.The surface treatment of described supporter also can be used to improve with the bonding force of described photographic layer implement, and for example can enumerate being coated with of undercoat, Corona discharge Treatment, flame treatment, ultraviolet treatment with irradiation, high frequency treatment with irradiation, glow discharge treatment with irradiation, active plasma treatment with irradiation, laser light irradiation processing etc.

In addition, the coefficient of static friction as between described supporter and the described protective film is preferably 0.3～1.4, and more preferably 0.5～1.2.

If described coefficient of static friction less than 0.3, then owing to sliding excessively, under the situation that becomes the roller shape, volume may take place depart from,, may be difficult to be rolled into good roller shape if surpass 1.4.

Described photosensitive film for example preferably is wound on the volume core cylindraceous, is rolled into the keeping of roller shape with strip.Length as the photosensitive film of described strip 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, also can cut off processing, make 100～1, the strip of 000m scope becomes the roller shape.In addition, in this case, preferred described supporter is wound into and is outermost.In addition, also the photosensitive film of described roller shape can be thinly sliced shape.When keeping from the protection end face, prevent the viewpoint of edge fusion, preferably is provided with separator (separator) (particularly the separator of moisture resistance, put the separator of drying agent) at end face, goes back preferred packaging in addition and also uses the low material of moisture-penetrability.

Described protective film also can carry out surface treatment in order to regulate the cementability between described protective film and the described photographic layer.Described surface treatment for example forms the undercoat that is made of polymkeric substance such as polysiloxane, fluorinated polyolefin, polyvinyl fluoride, polyvinyl alcohol (PVA) on the surface of described protective film.The formation of this undercoat can be passed through after the coating liquid of the described polymkeric substance of surface applied of described protective film, and it was formed down at 30～150 ℃ in dry 1～30 minute.Described temperature when making it dry is preferably 50～120 ℃ especially.

＜other layers 〉

Other layers as in the described photosensitive film are not particularly limited, and can suitably select according to purpose, for example can enumerate layers such as cushion, oxidation prevention layer (PC layer), peel ply, adhesive linkage, light absorbing zone, sealer.Can have 1 layer in these layers separately, also can have more than 2 layers.In addition, also can on described photographic layer, have protective film.

-cushion-

As described cushion, be not particularly limited, can suitably select according to purpose, can be swellability or solubility to alkalies, also can be for insoluble.

The relative alkalies of described cushion is under the situation of swellability or solubility, as described thermoplastic resin, for example can enumerate the saponified of ethene and acrylate copolymer, styrene is saponified with (methyl) acrylate copolymer, vinyltoluene is saponified with (methyl) acrylate copolymer, poly-(methyl) acrylate, (methyl) acrylate copolymer of (methyl) butyl acrylate and vinyl acetate etc. etc. saponified, the multipolymer of (methyl) acrylate and (methyl) acrylate, styrene and (methyl) acrylate and (methyl) acrylic acid multipolymer etc.

Softening point (Vicat) as in this case thermoplastic resin is not particularly limited, and can suitably select according to purpose, for example is preferably below 80 ℃.

As described softening point is thermoplastic resin below 80 ℃, except above-mentioned thermoplastic resin, can also enumerate that (Japanese plastics industry connects alliance in " plastics performance brief guide ", all Japan plastics forming industry Colaesce meeting is write, the census of manufacturing can be issued, October 25 nineteen sixty-eight distribution) softening point to be about in the organic polymer below 80 ℃ alkalies be the soluble thermoplastic resin.In addition, in softening point is organic polymer material more than 80 ℃, also can actual softening point be dropped to below 80 ℃ in this organic polymer material, adding the various plastifier that have mutual solubility with this organic polymer material.

In addition, the relative alkalies of described cushion is under the situation of swellability or solubility, interlayer bonding force as described photosensitive film, be not particularly limited, can suitably select according to purpose, for example in the interlayer bonding force of each layer, the interlayer bonding force between preferred described supporter and the described cushion is minimum.By becoming such interlayer bonding force, can be after only peeling off described supporter from described photosensitive film and described photographic layer being exposed via described cushion, with the developer solution of alkalescence this photographic layer is developed.In addition, can also stay described supporter, after described photographic layer is exposed, only peel off described supporter, this photographic layer be developed with alkaline developer solution from described photosensitive film.

Control method as described interlayer bonding force, be not particularly limited, can suitably select according to purpose, for example can enumerate the method for in described thermoplastic resin, adding known polymkeric substance, supercooling material, adhering to modifying agent, surfactant, release agent etc.

As described plastifier, be not particularly limited, can suitably select according to purpose, for example can enumerate alcohols or ester classes such as polypropylene glycol, polyglycol, dioctyl phthalate, dibutyl phthalate (DHP), dioctyl phthalate, dibutyl phthalate, phosphoric acid trimethylbenzene phenolic ester, tricresyl phosphate diphenyl, phosphoric acid xenyl diphenyl; Amide-types such as toluenesulfonamide etc.

The relative alkalies of described cushion is under the insoluble situation, and as described thermoplastic resin, for example can enumerate principal ingredient is with the multipolymer of ethene as necessary copolymerization composition.

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

The relative alkalies of described cushion is under the insoluble situation, interlayer bonding force as described photosensitive film is not particularly limited, and can suitably select according to purpose, for example in the interlayer bonding force of each layer, the bonding force between preferred described photographic layer and the described cushion is minimum.By becoming such interlayer bonding force, can after only peeling off described supporter and cushion from described photosensitive film, described photographic layer is exposed, this photographic layer be developed with alkaline developer solution.In addition, can also stay described supporter, after described photographic layer is exposed, peel off described supporter and described cushion, this photographic layer be developed with alkaline developer solution from described photosensitive film.

Control method as described interlayer bonding force, be not particularly limited, can suitably select according to purpose, for example can enumerate in described thermoplastic resin the method for adding various polymkeric substance, supercooling material, adhering to modifying agent, surfactant, release agent etc., below the method for Shuo Ming adjusting ethylene copolymer composition and division in a proportion etc.

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

The copolymerization of described ethene such as the fruit less than 60 quality %, interlayer bonding force between then described cushion and the described photographic layer uprises, peel off at the interface that is difficult to sometimes between this cushion and this photographic layer, if surpass 90 quality %, then because the interlayer bonding force between described cushion and the described photographic layer becomes too small, so be very easy to peel off between this cushion and this photographic layer, be 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 is less than 5 μ m, then concavo-convex in the surface of matrix or the concavo-convex tracing ability of bubble etc. reduced can not form high meticulous permanent pattern sometimes, if surpass 50 μ m, then produces the unfavorable conditions such as drying load increase on making sometimes.

-oxidation prevention layer (PC layer)-

Described oxidation prevention layer preferably is that principal ingredient forms usually with the polyvinyl alcohol (PVA), is preferably the tunicle of thickness about 0.5～5 μ m.

[manufacture method of photosensitive film]

Described photosensitive film for example can as described belowly be made.

At first, with the material dissolves, the emulsification that contain in the described photosensitive composite be scattered in water or solvent in, the photosensitive composite solution that the preparation photosensitive film is used.

As described solvent, be not particularly limited, can suitably select according to purpose, for example can enumerate alcohols such as methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol, sec-butyl alcohol, n-hexyl alcohol; Ketones such as acetone, methyl ethyl ketone, hexone, cyclohexanone, isobutyrone; Ester classes such as ethyl acetate, butyl acetate, n-amyl acetate, dimethyl suflfate, ethyl propionate, dimethyl phthalate, ethyl benzoate and methoxy propyl yl acetate; Toluene, dimethylbenzene, benzene, ethylbenzene etc. are aromatic hydrocarbon based; Phenixin, triclene, chloroform, 1,1, halogenated hydrocarbons such as 1-trichloroethanes, methylene chloride, monochloro-benzene; Tetrahydrofuran, diethyl ether, glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxyl-ethers such as 2-propyl alcohol; Dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, sulfolane etc.They can use separately a kind or and with more than 2 kinds.In addition, also can add known surfactant.

Then, can on described supporter, apply described photosensitive composite solution, make its drying, form photographic layer, make photosensitive film.

Coating method as described photosensitive composite solution, be not particularly limited, can suitably select according to purpose, for example can enumerate that gunite, rolling method, spin-coating method, gap coating method, extrusion coated method, curtain are coated with method, mould is coated with known coating methods such as method, intaglio rubbing method, wire bar rubbing method, air knife Tu Fa.

As the condition of described drying, according to the kind of each composition, solvent, usage ratio etc. and different, but be about 30 seconds～15 minutes under 60～110 ℃ the temperature usually.

Described photosensitive film for example preference is rolled into the keeping of roller shape as preferably being wound on the volume core cylindraceous with strip.

Length as the photosensitive film of described strip 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, also can cut off processing, make 100～1, the strip of 000m scope becomes the roller shape.In addition, in this case, preferred described supporter is wound into and is outermost.In addition, also the photosensitive film of described roller shape can be thinly sliced shape.When keeping from the protection end face, prevent the viewpoint of edge fusion, preferably is provided with separator (separator) (particularly the separator of moisture resistance, put the separator of drying agent) at end face, goes back preferred packaging in addition and also uses the low material of moisture-penetrability.

(photosensitive laminate)

Described photosensitive laminate be on matrix, have described photographic layer at least, stacked other layers of suitably selecting according to purpose form.

-matrix-

Described matrix should become the transfer printing body of the photographic layer at least that the processed matrix that is formed with photographic layer or transfer printing have 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 surface that convex-concave is arranged.Preferred tabular matrix can use so-called substrate.Particularly, can enumerate known printed-wiring board (PWB) manufacturing with substrate (printed circuit board (PCB)), glass plate (for example soda-lime glass plate etc.), synthetic resin film, paper, sheet metal etc.

[manufacture method of photosensitive laminate]

Manufacture method as described photosensitive laminate, as first mode, can enumerate in the surface applied of described matrix and the method for dry described photosensitive composite, as second mode, can enumerate to the photographic layer at least in the photosensitive film of the present invention heat and pressurize at least a, and transfer printing simultaneously and then stacked method.

It is coating and dry described photosensitive composite on described matrix that described first mode is divided the manufacture method of photosensitive laminate, thereby forms photographic layer.

As described coating and dry method, be not particularly limited, can suitably select according to purpose, for example preferred on the surface of described matrix, make described photosensitive composite dissolving, emulsification or be scattered in water or solvent, preparation photosensitive composite solution, thus directly apply and the stacked method of dry this solution.

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

As described coating method and drying condition, be not particularly limited, can suitably select according to purpose, and carry out under identical method of in described photosensitive film, using and the condition.

The manufacture method of the photosensitive laminate of described second mode is the folded photosensitive film of the present invention of at least one side's boundary layer that the Surface Edge at described matrix heats and pressurizes.Wherein, described photosensitive film has under the situation of described protective film, preferably peels off this protective film, thereby overlapping described photographic layer carries out stacked on described matrix.

As described heating-up temperature, be not particularly limited, can suitably select according to purpose, but for example preferred 15～180 ℃, more preferably 60～140 ℃.

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

As any one the device at least that carries out described heating and pressurization, be not particularly limited, can suitably select, for example can preferably enumerate laminating machine (great achievement laminating machine corporate system for example according to purpose, VP-II, ニ チ go one モ one ト Application (strain) system VP130) etc.

Described photosensitive film of the present invention and described photosensitive laminate are owing to use described photosensitive composite of the present invention; so can form sensitivity effectively; the exploring degree; and good adhesion and high meticulous permanent pattern; so can be preferred for diaphragm; the formation of various patterns such as permanent pattern such as interlayer dielectric and solder resist pattern; color filter; the post material; timber; distance piece; the manufacturing of liquid crystal structure members such as next door; holographic photography; micromachine; patterns such as pull form to be used etc., can be preferred for permanent pattern such as printed circuit board (PCB) especially and form and use.

Particularly because the thickness homogeneous of this film of photosensitive film of the present invention; so when forming permanent pattern; even thin layer permanent pattern (diaphragm, interlayer dielectric and solder resist etc.); ion migration (ion migration) can not take place in high acceleration test (HAST) yet; can obtain the outstanding high meticulous permanent pattern of moisture-proof, so can high carry out stacked to base material subtly.

(pattern forms device and permanent pattern formation method)

Pattern of the present invention forms device and possesses described photographic layer, has light irradiating means and optical modulator body at least.

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

In addition, described pattern of the present invention forms that device communicates with the explanation of described permanent pattern formation method of the present invention and is in addition clear and definite.

[exposure process]

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

Object as described exposure, so long as described photographic layer gets final product, be not particularly limited, can suitably select according to purpose, for example, as mentioned above, thus the photographic layer in the photosensitive laminate that preferably the folded photosensitive composite of at least one side's boundary layer of heating in the matrix top and pressurizeing is formed carries out.

As described exposure, be not particularly limited, can suitably select according to purpose, can enumerate digit explosure, analogue exposure etc., wherein, the digit preference exposure.

As described analogue exposure, be not particularly limited, can suitably select according to purpose, for example can enumerate photomask, the method for using (surpassing) high-pressure sodium lamp, xenon lamp, Halogen lamp LED etc. to expose by pattern with regulation.

As described digit explosure, so long as the exposure of need not described photomask carrying out gets final product, be not particularly limited, can suitably select according to purpose, for example preferably make the photohead that possesses light irradiating means and optical modulator body at least and described photographic layer any one moves at least, simultaneously, thus utilize the light that the modulation of described optical modulator body corresponding pattern information penetrates from described light irradiating means and from described photohead described photographic layer shone simultaneously and expose.

As the light source that uses in the described digit explosure, get final product near infrared light source so long as send from ultraviolet, be not particularly limited, can suitably select according to purpose, for example can use known light sources such as the fluorescent tube of (surpassing) high-pressure sodium lamp, xenon lamp, carbon arc lamp, Halogen lamp LED and used in copy machines etc. or laser, wherein preferred (surpassing) high-pressure sodium lamp, more preferably laser.

(surpassing) high-pressure sodium lamp is the discharge lamp of sealing mercury in silica glass tube etc., and the vapor pressure of mercury is set in the device that high value improves luminescence efficiency.In the bright line spectrum, can use with ND filtrator etc. and have only the bright line spectrum of a kind of wavelength, also can use light with multiple bright line spectrum.

" laser " of described laser is that the initial of Light Amplification by Stimulated Emission ofRadiation (utilizing the amplification of the light of being excited to penetrate of light) is called for short.As the device that sends described laser, be to utilize the phenomenon of inducing ejaculation that in material, takes place with rotation distribution, utilize amplification, the vibration of light wave, creation coherence, monochromatic oscillator and amplifier that directivity is stronger.

As the exciting media of described laser, crystallization, glass, liquid, pigment, gas etc. are arranged, can from these media, use known laser such as Solid State Laser, liquid laser, gas laser, semiconductor laser.

Particularly,, Ar ion laser (364nm, 351nm), Kr ion laser (356nm, 351nm), He-Cd laser (325nm) can be enumerated,, YAG laser, YV0 can be enumerated as Solid State Laser as gas laser ₄Laser (1,064nm), YAG laser or YVO ₄2 times of ripples (532nm) of laser, 3 times of ripples (355nm), 4 times of ripples (266nm), waveguide type wavelength conversion element and the semi-conductive combination of AlGaAs, InGaAs (380～400nm), the combination of waveguide type wavelength conversion element and AlGaInP or AlGaAs semiconductor t (300～350nm), AlGaInN (350～470nm) etc.As preferred laser wherein,, can enumerate AlGaInN semiconductor laser (commercially available InGaN based semiconductor laser 375nm or 405nm) 355nm laser for high output aspect throughput rate from the cost aspect.

Described Wavelength of Laser for example is preferably 200～1,500nm, and 300～800nm more preferably, and then be preferably 330～500nm, be preferably 350～420nm especially.

-optical modulator body-

As described optical modulator body, representative method can be enumerated preferably has n drawing section, and corresponding described pattern-information is controlled the method for described drawing section.Particularly, can enumerate the spatial optical modulation element (SLM of Digital Micromirror Device (DMD), MEMS (microelectromechanical systems (Micro Electro MechanicalSystems)) type; Spatial light modulator (Special LightModulator)), utilize the electrooptics effects modulation to see through the optical element (PLZT element), liquid crystal light shutter (FLC) etc. of light, wherein, can preferably enumerate DMD.

Use under the situation of described DMD, be radiated on the described DMD by suitable optical system, come comfortable DMD to go up the reflected light of each mirror of two-dimensional arrangements,, on photographic layer, form the picture of the luminous point that is arranged in two dimension through other optical system etc. from the light of light source.Can be with form as described below, to exposing of photographic layer comprehensively, if that is: directly between luminous point and luminous point, do not expose, and make the picture of the luminous point of above-mentioned two-dimensional arrangements, the direction of Er Wei orientation slight inclination is shaken relatively, and the luminous point of rear row exposes between initial luminous point that is listed as and luminous point.Described DMD is by each mirror angle of control, and the above-mentioned luminous point of connection-shutoff (ON-OFF) can form picture pattern.By arrange using photohead with so described DMD, substrate that can corresponding various width.

In above-mentioned DMD, the brightness of above-mentioned luminous point only turns on and off 2 grades, if but use mirror grade type spatial modulation element, then can carry out the exposure of 256 grades.

In addition, described optical modulator body preferably has the pattern signal generation mechanism that generates control signal based on the pattern-information that will form.In this case, the corresponding described pattern signal generation of the described optical modulator body control signal that mechanism generated is come light modulated.

As described control signal, be not particularly limited, can suitably select according to purpose, for example can preferably enumerate digital signal.

On the other hand, other exemplary process of described optical modulator body can be enumerated the method for using polygon mirror (polygon mirror).At this, polygon mirror is meant the rotating member of the plane reflection face that has row around.Reflected illumination is from the light of light source on photographic layer for described polygon mirror, and catoptrical luminous point is by the rotation sweep of this level crossing.By substrate is moved relative to this direction of scanning with meeting at right angles, can comprehensively exposing to the photographic layer on the substrate.Then, can form picture pattern by connection-shutoff from the light intensity of light source or control it as medium tone.At this moment, can become multi beam, shorten sweep time by making light from light source.

As optical modulator body of the present invention, except above-mentioned, can also enumerate the spy and open the example that the use polygon mirror put down in writing in the flat 5-150175 communique is described; Obtain to the vision of record the part of the image of lower layer in the special table 2004-523101 communique (international the 2002/039793rd trumpeter's volume that discloses), utilize the device that uses polygon mirror, make the position of upper layer and the position consistency of lower layer, the example of exposure; The spy opens the example of putting down in writing in the 2004-56080 communique with DMD exposure; The exposure device that possesses polygon mirror, the spy that put down in writing in the special table 2002-523905 communique open the exposure device that possesses polygon mirror, the spy that put down in writing in the 2001-255661 communique and open combination DMD, the LD that puts down in writing in the 2003-50469 communique, the example of multiple-exposure; The spy opens the example that the position of putting down in writing in the 2003-156853 communique that utilizes substrate changes the exposure method of exposure; The spy opens the example of the exposure method that the dislocation put down in writing in the 2005-43576 communique adjusts etc.

-light irradiating means-

As described light irradiating means is the illuminating method of light, be not particularly limited, can suitably select described exposure light source according to purpose, preferably enumerate compound and then shine light more than 2 kinds, especially preferably enumerate the laser (closing ripple laser) of the compound light more than 2 kinds of irradiation from these light sources.

As the described illuminating method that closes ripple laser, be not particularly limited, can suitably select according to purpose, for example can preferably enumerate utilize have multiple LASER Light Source, multimode optical fiber and carry out optically focused and make its mechanism in the compound light-gathering optics system of described multimode optical fiber from the laser of this multiple LASER Light Source irradiation, constitute the method that ripple laser is closed in also irradiation.

Beam diameter to described laser is not particularly limited, and can suitably select according to purpose, from the viewpoint of the exploring degree of dark dividing wall, at the 1/e of Gauss (Gaussian) light beam ²Be preferably 5～30 μ m under the value, more preferably 7～20 μ m.

In the present invention, preferred correspondence image data are carried out spatial light modulation to laser.Thereby, the preferred for this reason described DMD that uses as spatial optical modulation element.

As exposure device with described optical modulator body and described light irradiating means, for example can use the spy to open 2005-222039 communique, spy and open the device that 2005-258431 communique, spy are opened record in the 2006-30966 communique etc., but the exposure device among the present invention is not limited by it.

[developing procedure]

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

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

As described developer solution, be not particularly limited, can suitably select according to purpose, for example can enumerate alkaline aqueous solution, water system developer solution, organic solvent etc., wherein, preferred weakly alkaline aqueous solution.As the alkali composition of this weak base aqueous solution, for example can enumerate 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.

As the pH of described weakly alkaline aqueous solution, for example preferably be about 8～12, be more preferably 9～11.As described weakly alkaline aqueous solution, for example can enumerate the aqueous sodium carbonate of 0.1～5 quality % or wet chemical etc.

As the temperature of described developer solution, can suitably select according to the development of described photographic layer, for example preferably be about 25～40 ℃.

Described developer solution also 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 the organic solvent (for example alcohols, ketone, ester class, ethers, amide-type, lactone etc.) that develops etc. and uses.In addition, described developer solution can be the water system developer solution of mixed water or aqueous alkali and organic solvent, can be separately organic solvent also.

In the formation of described pattern, also can comprise and for example solidify treatment process, etching work procedure, plating operation etc.They can be used alone, also can be also with two or more.

[curing treatment process]

The formation method of described pattern is under the situation for the permanent pattern formation method that forms permanent pattern such as diaphragm, interlayer dielectric, solder resist pattern or color filter; preferably possess after carrying out described developing procedure, photographic layer is cured the curing treatment process of processing.

Handle as described curing, be not particularly limited, can suitably select, for example can preferably enumerate blanket exposure processing, comprehensive heat treated etc. according to purpose.

As the method that described blanket exposure is handled, for example can enumerate after described development, the method for exposing on the described duplexer that is formed with described permanent pattern comprehensively.Utilize this blanket exposure, can promote to form the curing of the resin in the photosensitive composite of described photographic layer, can make the surface cure of described permanent pattern.

Device as carrying out described blanket exposure is not particularly limited, and can suitably select according to purpose, for example can enumerate exposure machine that UV exposure machine such as ultrahigh pressure mercury lamp, xenon lamp use, laser explosure machine etc.Exposure is generally 10～2,000mJ/cm ²

As described comprehensive methods of heating treatment, can enumerate after described development, the method that heats on the described duplexer of established described permanent pattern comprehensively.Utilize heating comprehensively, can improve the film strength on the surface of described permanent pattern.

As the described heating-up temperature of pining for that adds comprehensively, be preferably 120～250 ℃, more preferably 120～200 ℃.If this heating-up temperature less than 120 ℃, then can not obtain utilizing the raising of the film strength of heat treated sometimes, if surpass 250 ℃, the decomposition of the resin in the described photosensitive composite then takes place sometimes, membranously slightly become fragile.

As the heat time heating time of described comprehensive heating, be preferably 10～120 minutes, more preferably 15～60 minutes.

Device as carrying out described comprehensive heating is not particularly limited, and can suitably select according to purpose from known device, for example can enumerate hot air drying oven (dry oven), hot plate, IR well heater etc.

The formation method of described pattern can be used for can being preferred for taking into account the formation of densification and large-duty pattern in the formation of the various patterns of directly describing to prevent that the sensitivity of the photographic layer that block causes reduces of the laser explosure that utilizes 405nm etc.

In described permanent pattern formation method; if the permanent pattern that utilizes described permanent pattern formation method to form is described diaphragm, described interlayer dielectric and solder resist pattern; then can protect wiring not to be subjected to impact or bending from the outside; particularly under the situation that is described interlayer dielectric, for example can be used for semiconductor or member to real dress such as the high density of multi-layer wire substrate or interior dress circuit board etc.

Described permanent pattern formation method of the present invention is owing to use described photosensitive composite of the present invention; so can be preferred for manufacturing, holographic photography, the micromachine of the liquid crystal structure member such as formation usefulness, color filter, post material, timber, distance piece, next door of various patterns such as permanent pattern such as diaphragm, interlayer dielectric and solder resist pattern; the manufacturing of pull etc. can be preferred for permanent pattern formation such as printed circuit board (PCB) especially.

Embodiment

Below utilize embodiment that the present invention is described in more detail, but the present invention is not limited by these embodiment.

(surface treatment example 1)

-carried out the preparation of surface-treated inorganic pigment 1-

Contain in 1,000 mass parts in the methylene chloride of 5 mass parts water and 5 mass parts hydrochloric acid (hydrolysis catalyzer), dissolve 15 mass parts γ-Qiu Jibingjisanjiayangjiguiwans, and the slow adding in vigorous stirring limit, limit 100 mass parts barium sulphate (Sakai chemical company system, B30).After fully stirring, filtration, drying have been carried out surface-treated inorganic pigment 1.

(surface treatment example 2)

-carried out the preparation of surface-treated inorganic pigment 2-

In surface treatment example 1, do not add barium sulphate and add 100 mass parts silicon dioxide (utilizing sol-gal process to make) (Japanese ア エ ロ ジ Le (strain) system " ア エ ロ ジ Le 130 "), in addition, similarly carried out surface-treated inorganic pigment 2.

(surface treatment example 3)

-carried out the preparation of surface-treated inorganic pigment 3-

In surface treatment example 1, do not add barium sulphate and add 98 mass parts talcums (Fuji's talcum ( Le Network) industry (strain) system " LMS#200 "), in addition, similarly carried out surface-treated inorganic pigment 3.

(surface treatment example 4)

-carried out the preparation of surface-treated inorganic pigment 4-

In surface treatment example 1, replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 15 mass parts γ-glycidoxypropyltrime,hoxysilane, in addition, similarly carried out surface-treated inorganic pigment 4.

(surface treatment example 5)

-carried out the preparation of surface-treated inorganic pigment 5-

In surface treatment example 1, replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 30 mass parts gamma-aminopropyl-triethoxy-silanes, in addition, similarly carried out surface-treated inorganic pigment 5.

(surface treatment example 6)

-carried out the preparation of surface-treated inorganic pigment 6-

In surface treatment example 1, replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 30 mass parts γ-methacryloxypropyl trimethoxy silane, in addition, similarly carried out surface-treated inorganic pigment 6.

(surface treatment example 7)

-carried out the preparation of surface-treated inorganic pigment 7-

In surface treatment example 1, replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 20 mass parts α-[[3-(trimethoxysilyl) propoxyl group] methyl]-imidazole radicals-1-ethanol ((strain) Japanese energy (ジ ヤ パ Application エ Na ジ one) system " IS-1000 "), in addition, similarly carried out surface-treated inorganic pigment 7.

(surface treatment example 8)

-carried out the preparation of surface-treated inorganic pigment 8-

In surface treatment example 1, replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 20 mass parts 2-ethyl-4-methylimidazoles and propyl trimethoxy silicane hydrochloride (Japanese Wei Nika (ュ ニ power one) (strain) makes " AZ-6160 "), in addition, similarly carried out surface-treated inorganic pigment 8.

(surface treatment example 9)

-carried out the preparation of surface-treated inorganic pigment 9-

In surface treatment example 1, replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 15 mass parts vinyl triacetic acid base silanes, in addition, similarly carried out surface-treated inorganic pigment 9.

(surface treatment example 10)

-carried out the preparation of surface-treated inorganic pigment 10-

In surface treatment example 1, replace barium sulphate and add 50 mass parts spherical silicon dioxides (utilizing firing method to make) ((strain) A De malleable iron restrains this (ア De マ テ Star Network ス) system " A Demafa offspring (ア De マ Off ア イ Application) SO-C1 ", mean grain size 0.25 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 "), in addition, similarly carried out surface-treated inorganic pigment 10.

(surface treatment example 11)

-carried out the preparation of surface-treated inorganic pigment 11-

In surface treatment example 1, replace barium sulphate and add 50 mass parts spherical silicon dioxides (utilizing firing method to make) ((strain) A De malleable iron restrains this system " A Demafa offspring SO-C1 ", mean grain size 0.25 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-methacryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM503 "), in addition, similarly carried out surface-treated inorganic pigment 11.

(surface treatment example 12)

-carried out the preparation of surface-treated inorganic pigment 12-

In surface treatment example 1, replace barium sulphate and add 50 mass parts spherical silicon dioxides (utilizing firing method to make) ((strain) A De malleable iron restrains this system " A Demafa offspring SO-C2 ", mean grain size 0.5 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 "), in addition, similarly carried out surface-treated inorganic pigment 12.

(surface treatment example 13)

-carried out the preparation of surface-treated inorganic pigment 13-

In surface treatment example 1, replace barium sulphate and add 25 mass parts spherical silicon dioxides (utilizing firing method to make) ((strain) A De malleable iron restrains this system " A Demafa offspring SO-C2 ", mean grain size 0.5 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-methacryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM503 "), in addition, similarly carried out surface-treated inorganic pigment 13.

(surface treatment example 14)

-carried out the preparation of surface-treated inorganic pigment 14-

In surface treatment example 1, replace barium sulphate and add 50 mass parts spherical silicon dioxides (utilizing firing method to make) (electrochemical industry (strain) system " SFP-30M ", mean grain size 0.7 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 "), in addition, similarly carried out surface-treated inorganic pigment 14.

(surface treatment example 15)

-carried out the preparation of surface-treated inorganic pigment 15-

In surface treatment example 1, replace barium sulphate and add 50 mass parts spherical silicon dioxides (utilizing firing method to make) (electrochemical industry (strain) system " SFP-30M ", mean grain size 0.7 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-methacryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM503 "), in addition, similarly carried out surface-treated inorganic pigment 15.

(surface treatment example 16)

-carried out the preparation of surface-treated inorganic pigment 16-

In surface treatment example 1, replace barium sulphate and add 50 mass parts spherical silicon dioxides (utilizing firing method to make) (electrochemical industry (strain) system " SFP-20M ", mean grain size 0.3 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-glycidoxypropyltrime,hoxysilane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM403 "), in addition, similarly carried out surface-treated inorganic pigment 16.

(surface treatment example 17)

-carried out the preparation of surface-treated inorganic pigment 17-

In surface treatment example 1, replace barium sulphate and add 50 mass parts spherical silicon dioxides (utilizing firing method to make) (electrochemical industry (strain) system " SFP-20M ", mean grain size 0.3 μ m), replace γ-Qiu Jibingjisanjiayangjiguiwan and dissolve 2.5 mass parts γ-methacryloxypropyl trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system " KBM503 "), in addition, similarly carried out surface-treated inorganic pigment 17.

(synthesis example 1)

-bonding agent 1 synthetic-

To 1, add 1-methoxyl-2-propyl alcohol 159g in the 000mL there-necked flask, flow down at nitrogen, be heated to 85 ℃.With 2 hours to the 1-methoxyl-2-propyl alcohol 159g solution that wherein drips methacrylic acid benzyl ester 63.4g, methacrylic acid 72.3g, V-601 (with the pure medicine system of light) 4.15g.Drippage further heated 5 hours after finishing, and made its reaction.Then, stop heating, obtain the multipolymer of methacrylic acid benzyl ester/methacrylic acid (30/70mol% ratio).

Then, the 120.0g in the described copolymer solution is moved in the 300mL there-necked flask, add epihydric alcohol methylpropenoic acid ester 16.6g, p methoxy phenol 0.16g, stir and make its dissolving.After the dissolving, add triphenylphosphine 3.0g, be heated to 100 ℃, carry out addition reaction.After the disappearance of vapor-phase chromatography (gaschromatography) affirmation epihydric alcohol methylpropenoic acid ester, stop heating.Add 1-methoxyl-2-propyl alcohol, the preparation solid constituent is the solution of the bonding agent 1 represented of the following structural formula of 30 quality %.

Utilization is measured the matter average molecular weight (Mw) of the bonding agent that obtains with polystyrene as the gel permeation chromatography (GPC) of standard substance, and the result is 15,000.

In addition, use NaOH to carry out titration, the result, the acid number of solid constituent is about 2.2meq/g.

And then, utilize the content (C=C value) of the ethene unsaturated link of the solid constituent that the iodine number titration tries to achieve to be about 2.1meq/g.

Bonding agent 1

[changing 39]

Wherein, in the described macromolecular compound 1, the structure of * 1 expression following structural formula (a) expression and (b) mixing of the structure of expression (mixing ratio is not clear).

[changing 40]

Structural formula (a)

Structural formula (b)

(synthesis example 2)

-bonding agent 2 synthetic-

To 1, add 1-methoxyl-2-propyl alcohol 159g in the 000mL there-necked flask, flow down at nitrogen, be heated to 85 ℃.With 2 hours to the 1-methoxyl-2-propyl alcohol 159g solution that wherein drips methacrylic acid benzyl ester 36g, methacrylic acid 72.3g, V-601 (with the pure medicine system of light) 4.15g.Drippage further heated 5 hours after finishing, and made its reaction.Then, stop heating, obtain the multipolymer of methyl methacrylate/methacrylic acid (30/70mol% ratio).

Then, the 120.0g in the described copolymer solution is moved in the 300mL there-necked flask, add epihydric alcohol methylpropenoic acid ester 16.6g, p methoxy phenol 0.16g, stir and make its dissolving.After the dissolving, add triphenylphosphine 2.4g, be heated to 100 ℃, carry out addition reaction.After the disappearance of vapor-phase chromatography affirmation epihydric alcohol methylpropenoic acid ester, stop heating.Add 1-methoxyl-2-propyl alcohol, the preparation solid constituent is the solution of the bonding agent-2 represented of the following structural formula of 30 quality %.

Utilization is measured the matter average molecular weight (Mw) of the bonding agent that obtains with polystyrene as the gel permeation chromatography (GPC) of standard substance, and the result is 15,000.

In addition, use NaOH to carry out titration, the result, the acid number of solid constituent is about 2.3meq/g.

And then, utilize the content (C=C value) of the ethene unsaturated link of the solid constituent that the iodine number titration tries to achieve to be about 2.6meq/g.

Bonding agent 2

[changing 41]

Wherein, in the described macromolecular compound 1, the meaning that * 1 expression and described macromolecular compound 1 are identical.

(synthesis example 3)

-bonding agent 3 synthetic-

The limit heating edge is dissolved 110 mass parts phenol novolak type epoxy resin (Dongdu is changed into corporate system in 150 mass parts propylene glycol monomethyl ether acetic acid esters, YDPN-702), then add 34 mass parts acrylic acid and 0.8 mass parts benzyl dimethylamine, after 100～120 ℃ are continued down to react 8 hours, add tetrahydrobenzene dicarboxylic acid anhydride 35 mass parts, under 100 ℃, make its reaction 8 hours, obtain the epoxy acrylic ester compounds (bonding agent 3) of acid number 70mgKOH/g.

(embodiment 1)

The preparation of-photosensitive composite-

Cooperate each composition with following amount, preparation photosensitive composite solution.

[photosensitive composite solution respectively become component]

Described bonding agent 1 (solid constituent quality 30 quality % in described 1-methoxyl-2-propanol solution) ... 87.4 mass parts

Dipentaerythritol acrylate (polymerizable compound) ... 13 mass parts

The Photoepolymerizationinitiater initiater that following formula I-1 represents ... 2.6 mass parts

The sensitizer that following formula S-1 represents ... 0.5 mass parts

エ Port ト one ト YD-8125 (epoxide equivalent 170g/eq. Dongdu changes into corporate system, and bisphenol-A is an epoxy resin) ... 8 mass parts

Thermal curing agents (cdicynanmide) ... 0.77 mass parts

Fluorine is surfactant (メ ガ Off ア Star Network F-176, big Japanese ink chemical industry (strain) system, 30 quality %2-butanone solutions) ... 0.2 mass parts

Carried out surface-treated inorganic pigment 1 ... 21.98 mass parts

Methyl ethyl ketone ... 15 mass parts

[changing 42]

The manufacturing of-photosensitive film-

Be coated with machine with rod, the photosensitive composite solution that obtains is coated on (eastern レ corporate system on PET (polyethylene terephthalate) film of thick 16 μ m as described supporter, wide 300mm, long 200m, 16FB50), and in 80 ℃ heated air circulation type dryer, make its drying, form the photographic layer of thick 30 μ m.Then, on this photographic layer, the usefulness laminate is stacked, and (the Oji Paper corporate system E-200), is made photosensitive film as the thick 20 μ m of described protective film, the polypropylene film of wide 310mm, long 210m.

The preparation of-photosensitive laminate-

Then,, handle to implementing chemical grinding as the surface of two copper-clad laminates that form wiring (do not have reach through hole, copper is thick to be 12 μ m) of printed circuit board (PCB) as described base material, thus preparation.On this copper-clad laminates; peel off the protective film in the described photosensitive film; so that the photographic layer of described photosensitive film contacts with described copper-clad laminates; use vacuum laminator (ニ チ go one モ one ト Application (strain) society system simultaneously; VP130) make it stacked, stack gradually the photosensitive laminate that described copper-clad laminates, described photographic layer and described pet film (supporter) form thereby be mixed with.

Press stick spare to be 70 ℃ of the sticking temperature of 40 seconds vacuum attraction time, pressure, to press sticking pressure 0.2MPa, 10 seconds pressing times.

To photosensitive laminate, development property, sensitivity, exploring degree and adhering evaluation.The result is as shown in table 2.

The evaluation of＜development 〉

Prepare after the described photosensitive laminate, peel off polyethylene terephthalate (supporter) from described photosensitive laminate immediately, 1 quality % aqueous sodium carbonate with 30 ℃ of comprehensive injections of the described photographic layer of pressure on copper-clad laminates of 0.15MPa, mensuration is removed needed time of photographic layer on the copper-clad laminates from beginning to spray aqueous sodium carbonate to dissolving, it as the shortest development time, is estimated development.This shortest development time is short more, and then development property runs off look.In addition, after the described photosensitive laminate of preparation, under 3 days situation of preservation under 40 ℃, estimate development similarly.

The evaluation of＜sensitivity 〉

To the photographic layer of the photosensitive film in the described photosensitive laminate of having prepared, from supporting the side, use is opened the pattern formation device of putting down in writing in the 2006-30966 communique as the spy of the LASER Light Source with 405nm of described light irradiating means, and irradiation is with 2 ^1/2Doubly at interval, from 0.1mJ/cm ²To 100mJ/cm ²The different light of luminous energy, carry out 2 heavily exposures, a part of zone of described photographic layer is solidified.At room temperature left standstill 10 minutes, peel off described supporter from described photosensitive laminate then, 1 quality % aqueous sodium carbonate with 30 ℃ of comprehensive injections of spraying the photographic layer of pressure 0.15MPa on copper-clad laminates, injecting time is 2 times of described the shortest development time, uncured zone is removed in dissolving, measures the thickness of residual consolidation zone.Then, the curve map of the relation between the exposure of drafting light and the thickness of cured layer obtains sensitivity curve.So as can be known from the sensitivity curve that obtains, consolidation zone thick become with exposure before the luminous energy of photographic layer when being similarly 30 μ m, solidify necessary luminous energy for making photographic layer.

The evaluation of＜exploring degree 〉

At room temperature (23 ℃ 55%RH) left standstill described photosensitive laminate 10 minutes.From the pet film (supporter) of the described photosensitive laminate that obtains, use described pattern to form device, with line (line)/space (space)=1/1, from the wide 10 μ m of line (line)～100 μ m, with per 1 μ m, carry out the exposure of each live width.

The exposure of this moment is the necessary luminous energy of photographic layer that is solidificated in the described photosensitive film in the evaluation of described sensitivity.After at room temperature leaving standstill 10 minutes, peel off pet film (supporter) from described photosensitive laminate.

With 30 ℃ the 1 quality % aqueous sodium carbonate of comprehensive injection of spray pressing the photographic layer of 0.15MPa on copper-clad laminates as described developer solution, injecting time is 2 times of described the shortest development time, and uncured zone is removed in dissolving.

The surface of the copper-clad laminates of the band solidified resin pattern that obtains like this with observation by light microscope, in the line of solidified resin pattern, measure not have to stop up, wrinkle crust etc. unusually and can form the minimum feature in space, with it as the exploring degree.The numerical value of this exploring degree is more little to be good more.

＜adhering evaluation 〉

At room temperature (23 ℃ 55%RH) left standstill described photosensitive laminate 10 minutes.From the pet film (supporter) of the described photosensitive laminate that obtains, use described pattern to form device, with line/space=1/5, to live width 10 μ m～50 μ m, carry out the exposure of each live width with per 5 μ m, carry out with the exposure identical with the evaluation of exploring degree.

Dissolve in the same manner with the evaluation of exploring degree and to remove uncured zone, the surface of the copper-clad laminates of the band solidified resin pattern that obtains with observation by light microscope then, mensuration can confirm that solidified resin pattern do not peel off, do not enter from the solidified resin pattern periphery live width of the minimum of developer solution from Copper Foil, with it as adhering evaluation result.

(embodiment 2)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 2, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 3)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 3, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 4)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 4, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 5)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 5, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 6)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 6, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 7)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 8)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 8, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 9)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 21.98 mass parts of carrying out surface-treated inorganic pigment 9, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 10)

In embodiment 1, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of following formula I-2, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

[changing 43]

(embodiment 11)

In embodiment 1, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of following formula I-3, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

[changing 44]

(embodiment 12)

In embodiment 1, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of following formula I-4, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

[changing 45]

(embodiment 13)

In embodiment 1, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of following formula I-5, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

[changing 46]

(embodiment 14)

In embodiment 1, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of following formula I-6, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

[changing 47]

(embodiment 15)

In embodiment 1, as shown in table 1, compound 1.3 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-1, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 16)

In embodiment 1, as shown in table 1, with 87.4 mass parts of bonding agent 1 instead of bonding agent 2, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 17)

In embodiment 1, as shown in table 1, with 48.2 mass parts of bonding agent 1 instead of bonding agent 3, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 18)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 10, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of following formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

[changing 48]

(embodiment 19)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 11, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 20)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 12, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 21)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 13, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 22)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 12, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 23)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 14, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 24)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 15, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 25)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 16, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(embodiment 26)

In embodiment 1, as shown in table 1, to carry out surface-treated inorganic pigment 1 instead of 11.0 mass parts of carrying out surface-treated inorganic pigment 17, and then, as shown in table 1, compound 2.6 mass parts that the compound that described formula I-1 is represented is represented instead of described formula I-7, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(comparative example 1)

In embodiment 1, as shown in table 1, will carry out surface-treated inorganic pigment 1 instead of not carrying out surface-treated barium sulphate (Sakai chemical company system, 21.98 mass parts B30), in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(comparative example 2)

In embodiment 1, as shown in table 1, the compound that formula I-1 is represented is instead of comfort and pleasure coffee Cole (Irgacure) 369 (Photoepolymerizationinitiater initiaters of alkaline type, the west different chemicals of Bart (CIBASPECIALTY CHEMICALS) corporate system) 6.1 mass parts, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

(comparative example 3)

In embodiment 1, as shown in table 1, the compound that formula I-1 is represented is instead of the comfort and pleasure coffee Cole 907 (Photoepolymerizationinitiater initiaters of alkaline type, the west different chemicals of Bart (CIBASPECIALTY CHEMICALS) corporate system) 6.1 mass parts, in addition, development property, sensitivity, exploring degree and adhering evaluation similarly.The result is as shown in table 2.

[table 1]

	Inorganic pigment	Photoepolymerizationinitiater initiater	Bonding agent	Exposure
					Embodiment 1	Carried out the inorganic face material 1 of surface treatment	I-1	Bonding agent 1	Digit explosure
Embodiment 2	Carried out the inorganic face material 2 of surface treatment	I-1	Bonding agent 1	Digit explosure
					Embodiment 3	Carried out the inorganic face material 3 of surface treatment	I-1	Bonding agent 1	Digit explosure
Embodiment 4	Carried out the inorganic face material 4 of surface treatment	I-1	Bonding agent 1	Digit explosure
					Embodiment 5	Carried out the inorganic face material 5 of surface treatment	I-1	Bonding agent 1	Digit explosure
Embodiment 6	Carried out the inorganic face material 6 of surface treatment	I-1	Bonding agent 1	Digit explosure
					Embodiment 7	Carried out the inorganic face material 7 of surface treatment	I-1	Bonding agent 1	Digit explosure
Embodiment 8	Carried out the inorganic face material 8 of surface treatment	I-1	Bonding agent 1	Digit explosure
					Embodiment 9	Carried out the inorganic face material 9 of surface treatment	I-1	Bonding agent 1	Digit explosure
Embodiment 10	Carried out the inorganic face material 1 of surface treatment	I-2	Bonding agent 1	Digit explosure
					Embodiment 11	Carried out the inorganic face material 1 of surface treatment	I-3	Bonding agent 1	Digit explosure

Embodiment 12	Carried out the inorganic face material 1 of surface treatment	I-4	Bonding agent 1	Digit explosure
					Embodiment 13	Carried out the inorganic face material 1 of surface treatment	I-5	Bonding agent 1	Digit explosure
Embodiment 14	Carried out the inorganic face material 1 of surface treatment	I-6	Bonding agent 1	Digit explosure
					Embodiment 15	Carried out the inorganic face material 1 of surface treatment	I-1 I-2	Bonding agent 1	Digit explosure
Embodiment 16	Carried out the inorganic face material 1 of surface treatment	I-1	Bonding agent 2	Digit explosure
					Embodiment 17	Carried out the inorganic face material 1 of surface treatment	I-1	Bonding agent 3	Digit explosure
Embodiment 18	Carried out the inorganic face material 10 of surface treatment	I-7	Bonding agent 1	Digit explosure
					Embodiment 19	Carried out the inorganic face material 11 of surface treatment	I-7	Bonding agent 1	Digit explosure
Embodiment 20	Carried out the inorganic face material 12 of surface treatment	I-7	Bonding agent 1	Digit explosure
					Embodiment 21	Carried out the inorganic face material 13 of surface treatment	I-7	Bonding agent 1	Digit explosure
Embodiment 22	Carried out the inorganic face material 12 of surface treatment	I-1	Bonding agent 1	Digit explosure
					Embodiment 23	Carried out the inorganic face material 14 of surface treatment	I-7	Bonding agent 1	Digit explosure
Embodiment 24	Carried out the inorganic face material 15 of surface treatment	I-7	Bonding agent 1	Digit explosure
					Embodiment 25	Carried out the inorganic face material 16 of surface treatment	I-7	Bonding agent 1	Digit explosure
Embodiment 26	Carried out the inorganic face material 17 of surface treatment	I-7	Bonding agent 1	Digit explosure
					Comparative example 1	B-30	I-1	Bonding agent 1	Digit explosure
Comparative example 2	Carried out the inorganic face material 1 of surface treatment	Comfort and pleasure coffee Cole 369	Bonding agent 1	Digit explosure
					Comparative example 3	Carried out the inorganic face material 1 of surface treatment	Comfort and pleasure coffee Cole 907	Bonding agent 1	Digit explosure

[table 2]

	Development (second)		Sensitivity (mJ/cm 2)	Exploring degree (μ m)	Adhesiveness (μ m)	TCT patience
							After finishing immediately	Preserve after 3 days for 40 ℃
	Embodiment 1	15							17	20	45	15	16/27
Embodiment 2			16	17	20	45	15	8/27
	Embodiment 3	15							17	20	40	15	12/27
Embodiment 4			15	17	20	45	15	13/27
	Embodiment 5	16							18	20	45	15	11/27
Embodiment 6			15	17	20	40	15	11/27
	Embodiment 7	15							17	20	45	15	13/27
Embodiment 8			15	17	20	45	15	14/27
	Embodiment 9	15							17	20	45	15	10/27
Embodiment 10			15	17	25	40	15	11/27

Embodiment 11	15	17	25	40	15	12/27
							Embodiment 12	15	17	20	45	15	10/27
Embodiment 13	15	17	25	45	15	15/27
							Embodiment 14	15	17	25	45	20	13/27
Embodiment 15	15	17	25	45	15	12/27
							Embodiment 16	15	17	20	45	15	13/27
Embodiment 17	10	60	20	40	20	11/27
							Embodiment 18	15	18	20	40	15	3/27
Embodiment 19	15	18	20	40	15	2/27
							Embodiment 20	15	18	20	45	15	4/27
Embodiment 21	15	18	20	45	15	0/27
							Embodiment 22	15	18	20	45	15	3/27
Embodiment 23	15	18	20	45	15	1/27
							Embodiment 24	15	18	20	45	15	2/27
Embodiment 25	15	18	20	40	15	1/27
							Embodiment 26	15	18	20	40	15	2/27
Comparative example 1	15	17	20	50	20	24/27
							Comparative example 2	15	＞60	350	60	30	27/27
Comparative example 3	15	＞60	400	60	30	25/27

Can judge from the result of table 2, use Photoepolymerizationinitiater initiater contain 9 oxime derivate, inorganic pigment by the embodiment 1～26 of silane coupling agent surface-treated photosensitive composite in, can form development and good adhesion and high meticulous permanent pattern after sensitivity, the photosensitive laminate preparation effectively.Can judge especially, contain at side chain at bonding agent and have among the embodiment 1～16 and 18～26 of macromolecular compound of acidic groups and ethene unsaturated link, also outstanding 40 ℃ of developments after preserving 3 days down.

In addition, implement thermal cycle to permanent pattern and handle (add under will-65 ℃ cold 30 minutes, 125 ℃ heating carried out 500 round-robin as 1 round-robin heat treated in 30 minutes and handle) down, observe the thermal cycling test (thermal cycle test) (in 27 clathrate patterns, several patterns have crack (TCT patience)) of the mode of entrance in the crack in the square sectional hole patterns of 2mm (clathrate).The result is, in comparative example 1～3, enters the crack easily from the angle of sectional hole patterns, and is relative therewith, in embodiment 1～26, is difficult to take place the crack.Particularly under the situation of using silicon dioxide as inorganic filler (embodiment 2 and 18～26), the crack incidence is low.

Photosensitive composite of the present invention and photosensitive film are owing to can form sensitivity, development and good adhesion effectively and high meticulous permanent pattern; so can be preferred for manufacturing, holographic photography, the micromachine of the liquid crystal structure member such as formation, color filter, post material, timber, distance piece, next door of various patterns such as permanent pattern such as diaphragm, interlayer dielectric and solder resist pattern; the manufacturings of pull etc. etc. can be preferred for permanent pattern formation usefulness such as printed circuit board (PCB) especially.

Described permanent pattern formation method of the present invention is owing to use described photosensitive composite of the present invention; so can be preferred for manufacturing, holographic photography, the micromachine of the liquid crystal structure member such as formation, color filter, post material, timber, distance piece, next door of various patterns such as permanent pattern such as diaphragm, interlayer dielectric and solder resist pattern; the manufacturings of pull etc. etc. can be preferred for permanent pattern formation such as printed circuit board (PCB) especially.

Claims (10)

1. a photosensitive composite is characterized in that,

Contain bonding agent, polymerizable compound, Photoepolymerizationinitiater initiater, thermal cross-linking agent and inorganic pigment, described Photoepolymerizationinitiater initiater contains 9 oxime derivate, and described inorganic pigment is by the silane coupling agent surface treatment.

2. photosensitive composite according to claim 1, wherein,

Silane coupling agent has: be selected from least a functional group in alkoxysilyl, chloromethane silylation and the acetoxyl group silicyl and be selected from vinyl, amino, sulfydryl, epoxy radicals and (methyl) acryloyl group at least a functional group.

3. photosensitive composite according to claim 1, wherein,

Inorganic pigment is a silicon dioxide.

4. photosensitive composite according to claim 1, wherein,

9 oxime derivate is for having the compound of aromatic series base at least.

5. photosensitive composite according to claim 1, wherein,

9 oxime derivate has the part-structure with any one expression in following general formula (I), general formula (II) and the general formula (X),

[changing 1]

Ar  C (Y ¹)=N-O-Y ²) _mGeneral formula (I)

[changing 2]

Ar  CO-C (Y ¹)=N-O-Y ²) _mGeneral formula (II)

[changing 3]

General formula (X)

Wherein, during described general formula (I) reached (II), Ar represented any one in aromatic series base and the heterocyclic radical, Y ¹In expression hydrogen atom and the monovalence substituting group any one, Y ²Expression fatty group, aromatic series base, heterocyclic radical, COY ³, CO ₂Y ³And CONY ⁴Y ⁵In any one, Y ³, Y ⁴And Y ⁵In expression fatty group, aromatic series base and the heterocyclic radical any one, m represents the integer more than 1,

In addition, in the described general formula (X), R ¹⁰⁰In expression acyl group, alkoxy carbonyl and the aryloxycarbonyl any one, these substituting groups also can further have substituting group, and α represents the arbitrary integer more than 0, R ²⁰⁰The expression substituting group, under α is situation more than 2, this R ²⁰⁰Can be identical or different, Ar represents any one in aromatic ring and the heteroaromatic ring, and A represents any one in 4,5,6 and 7 Yuans rings, and these rings also can contain heteroatoms respectively.

6. photosensitive composite according to claim 1, wherein,

Bonding agent contains: the macromolecular compound that has acidic groups and ethene unsaturated link at side chain.

7. photosensitive composite according to claim 6, wherein,

Bonding agent contains: have acidic groups at side chain, can contain the aromatic series base of heterocycle and the macromolecular compound of ethene unsaturated link.

8. a photosensitive film is characterized in that,

Having the photographic layer that is made of the described photosensitive composite of claim 1 on supporter forms.

9. a permanent pattern formation method is characterized in that,

Comprise: the photographic layer that utilizes the described photosensitive composite of claim 1 to form is carried out step of exposing.

10. a printed circuit board (PCB) is characterized in that,

Utilize the described permanent pattern formation of claim 9 method to form permanent pattern.