CN1270215C - Photopolymerible composition and photosensitive composition for explosure by short wavelength semiconductor laser, and method therefor - Google Patents

Abstract

The present invention discloses a photopolymerisable composition which comprises (i), sensitizing dye represented by the following formula (I-1); (ii), a titanium cyclopentadienyl compound; (iii), an addition polymerization compound which at least has one kind of alkene unsaturated double bonds, wherein A and B respectively stand for-S-and NR3 or NR4; R3 and R4 respectively stand for substituted alkyl or unsubstituted alkyl or substituted aryl or unsubstituted aryl; Y1 and Y2 respectively stand for adjacent A or B and form a nonmetallic atomic base group of a dye alkaline core together with an adjacent carbon atom; R1 and R2 respectively stand for a monovalent nonmetallic atomic base group, or the R1 and the R2 can be mutually bonded for forming a ring of fat or aryl.

Description

Photosensitive composition and the method that is used for the polymerization light sensitive composition

The present invention relates to a kind of photosensitive composition that contains novel Photoepolymerizationinitiater initiater, particularly have the Photoepolymerizationinitiater initiater of high photosensitivity and good stability.The present invention relates more specifically to a kind of conduct can be by the good photopolymerisable compositions or the photosensitive composition that are used for the planographic printing plate precursor raw material of making a plate based on the scan exposure of digital signal.Except that being used as planographic printing plate precursor, this photopolymerisable compositions or photosensitive composition can be used for following field, for example form optical image, holograph, and color photocopying (colorhard copy), the production of electronic material such as photoresist and be used for printing ink, the photo curable resin material of coating and bonding agent.

As plate printing plate, the oleophylic photosensitive resin layer that provides on the hydrophilic support is provided the PS plate that is widely used so far, and obtains required printed panel by the hard contrast film with mask exposure (face exposure), dissolves then and removes the part that does not have image.

In recent years, people have popularized with electronic device and have processed, and use the digitizing technique of robot calculator storage and output image data, and are actually used corresponding to the various images output systems of these digital technologies.Therefore, comprise computing machine making sheet (computer-to-plate) that the scanning digital view data of not using the hard contrast film and high converging light such as laser beam directly make printed panel (CTP) technology be desired.Be accompanied by this trend, obtain the good printed panel precursor that is adapted to this purpose and become an important techniques problem.

A kind of method as the plate printing plate that obtains to carry out this kind scan exposure, people have proposed to use in its structure the high speed photopolymerisable compositions as the photosensitive resin layer (being called " photosensitive layer " hereinafter) that receives printing ink on hydrophilic support so far, and this kind printed panel is to take the lead trend in market.Printed panel precursor with this structure is easy to finish the processing of developing, and in addition, it has desirable performance and printing performance as printed panel, for example, good resolving power, ink adhesion, pressrun (Presslife) and anti-embrocating property (being anti fouling performance).

Photopolymerisable compositions consists essentially of alefinically unsaturated compounds, light polymerization initiator, and adhesive resin.The light polymerization initiator absorbing light produces living radical, causes the polyaddition reaction of alefinically unsaturated compounds, and photosensitive layer is undissolved, forms image thus.For example, people such as Bruce M.Monro, Chemical Revue, 93,435 (1993) and R.S.Davidson, Journal of Photochemistry and biology A:Chemistry, in 73.81 (1993), disclose the most important part of the conventional scheme that uses relevant photopolymerisable compositions that can scan exposure, and also disclose many such compositions with high photosensitivity Photoepolymerizationinitiater initiater.

Comprise that with regard to using these Photoepolymerizationinitiater initiaters and wavelength visible source such as Ar laser (488nm) and FD-YAG laser (532nm) are as with regard to the common used CTP system of the photopolymerisable compositions of light source, people wish in order to increase the efficient of making sheet process, write with higher speed, but because light source output is not high enough, not high enough with the photonasty of photochromics, this technology does not also realize so far.

On the other hand, for example in recent years, use InGaN series material and semiconductor laser that can continuous oscillation in the 350nm-450nm scope near reaching the practical stage.Consider from configuration aspects, in the time cheaply producing, use the scan exposure system of short wavelength light source, be of value to the foundation of economic system as the light source with enough output of semiconductor laser.In addition, compare with the system of Ar laser with using common FD-YAG, the photochromics of the manageable short wavelength's of having sensitive volume can be used for the system of this semiconductor laser under bright safety lamp.

In addition, for example at J.P.Faussier, Photoinitiated Polymerization-Theory and Application, Rapra Review, Vol.9, Report, people's such as Repra Technology (1998) and M.Tsunooka, Prog.Polym.Sci., described in 21,1 (1996), obtaining the high-speed light polymerization initiator is that people really wish to be widely used in the technology in the imaging field.

Except the CTP industry, obtain photopolymerisable compositions that short wavelength's semiconductor laser to the 350nm-450nm scope has high light sensation luminosity and be a kind of in industrial circle the important technology of increasingly extensive demand, for example, laser imaging such as optics moulding, holograph, and color photocopying, the production of electronic material such as photoresist, with be used for printing ink, the light-curable resin material of coating and bonding agent.

But,, the scan exposure in the short wavelength range of 350nm-450nm is had enough photosensitive Photoepolymerizationinitiater initiater also not by known to the people up at present.

As high-speed relatively Photoepolymerizationinitiater initiater, be well known that to be used in combination the Photoepolymerizationinitiater initiater that comprises a kind of particular dye and a kind of titanium luxuriant (titanocene) compound.The dyestuff of Ju oxazolidine acid core and the composition of triazine Photoepolymerizationinitiater initiater are disclosed in JP-B-61-9621 (term " JP-B " refers to " Jap.P. of having examined is open " at this), but consider that from the production aspect problem herein is that this compound is wanting in storage stability.

In addition, in JP-A-8-272096 (term " JP-A " refers to " the Jap.P. published of examination is open " at this), disclose the composition of the dyestuff of Ju You azolactone acid core and titanocene compound and in JP-A-10-101719, disclose the dyestuff of acid core and the composition of titanocene compound with 5-unit heterocycle.Though these compound speed are quite high, speed and has the 450nm wavelength or more during short wavelength's LASER Light Source, in fact can not obtain enough photonasty when using not enough, and they are not suitable for short wavelength light source.

In addition, at JP-A-9-328505, the concrete carbocyanine and the composition of titanocene compound are disclosed among JP-A-8-272096 and the JP-A-8-262715.Though these compound speed are quite high, in fact speed not enough, and they are not suitable for short wavelength light source.In JP-B-143299 and JP-A-2-216154, disclose and comprised as the N-alkyl indolinylidene of photosensitizer or the inferior benzothiazolyl alkane ketone (N-alkylbenzothiazolylidenealkanone) of N-alkyl with as the photopolymerisable compositions of the Hexaarylbiimidazole of activator, but in fact these photopolymerisable compositions can not show enough light sensitivity, and it also has problems aspect storage stability.

Though disclose the composition of carbazole derivates and the luxuriant Photoepolymerizationinitiater initiater of titanium in JP-A-9-230913, this herein compound has long absorbing wavelength, so they are not suitable for short wavelength light source.Disclose the composition of styryl dye and titanocene compound in JP-A-9-80750, this composition speed is quite high, but speed is high not enough.The composition of carbazole derivates and triazine Photoepolymerizationinitiater initiater is disclosed in JP-A-62-212643 and JP-A-63-32540, the composition of carbazole derivates and salt compounded of iodine Photoepolymerizationinitiater initiater is disclosed in JP-A-63-32539, with the composition that in JP-A-63-325401, discloses carbazole derivates and thioxanthones Photoepolymerizationinitiater initiater, but in fact any light sensitivity in these compounds is not enough, and it also has problems aspect storage stability.

The object of the invention provides a kind of photosensitive composition with good workability, economic benefit and storge quality, said composition can be used as the planographic printing plate precursor material of the scan exposure that is applicable to the CTP system, or is the planographic printing plate precursor material of the planographic printing plate precursor of high sensitization for the vibration wavelength of cheap short wavelength's semiconductor laser.

Another object of the present invention provides a kind of containing the photosensitive composition at the novel Photoepolymerizationinitiater initiater of the high sensitization of the wide wavelength coverage of 350nm-450nm.

In order to achieve the above object, the present inventor has been found that photopolymerisable compositions comprises (i) sensitizing dye by following formula (I-1) expression, (ii) but titanocene compound and (iii) a kind of vibration wavelength for short wavelength's semiconductor laser have the addition polymerization compound with at least a ethylenical unsaturated double bonds of enough light sensitivity, and it has excellent storage stability, therefore finishes the present invention:

Wherein A ' and B represent respectively-S-, NR ₃, or NR ₄R ₃And R ₄That each representative replaces or unsubstituted alkyl, or that replace or unsubstituted aryl; Y ₁And Y ₂Each representative and adjacent A ' or B and adjacent carbon atom form the non-metal atom group of dyestuff alkalescence nuclear together; R ₁And R ₂Each represents the non-metal atom group of unit price, or R ₁And R ₂Bonding forms ring fat or fragrance mutually.

In addition, in order to achieve the above object, the present inventor has been found that, when mix using by the carbazole compound of following formula (II-1) expression and titanocene compound, can obtain having the Photoepolymerizationinitiater initiater of good light sensitivity and stability, particularly can obtain being suitable for Photoepolymerizationinitiater initiater in the exposure of 350nm-450nm wavelength.Inventor of the present invention further finds to be used to the photosensitive composition of photopolymerization planographic printing plate precursor, photosensitive composition comprise this Photoepolymerizationinitiater initiater and with free radical or acid reaction to change or to keep the compound of physics or chemical characteristic, but the addition polymerization compound that has at least a ethylenical unsaturated double bonds specifically, can obtain having enough light sensitivity for the vibration wavelength of short wavelength's semiconductor laser, and the planographic printing plate precursor that can under bright safety lamp, handle, therefore finish the present invention:

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Each represents hydrogen atom, or the monovalent nonmetallic atomic radical, and precondition is R ¹And R ³In at least one be the organic residue of unit price by following partial structurtes formula (1) expression, and R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Separately each other bonding with form fat with the group of fragrance;

In it and R ¹⁰Represent hydrogen atom, or the monovalent nonmetallic atomic radical; The Z representative need form divalence non-metal atom group with the first ring of substituent 5-acid core and R with adjacent atomic radical ¹⁰Can with R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸Or R ⁹Bonding with form fat with the ring of fragrance;

In order to achieve the above object, the present inventor has been found that to adopt and comprises (i) sensitizing dye by following formula (III-1) expression, (ii) titanocene compound, but the addition polymerization compound that (iii) has ethylenical unsaturated double bonds, can obtain having the photosensitive composition of enough light sensitivity and good shelf-stability, therefore finish the present invention for the vibration wavelength of short wavelength's semiconductor laser:

Wherein the A representative can have substituent aromatic rings or heterocycle; The X represention oxygen atom, sulphur atom or-N (R ₃)-; R ₁, R ₂And R ₃Each represents hydrogen atom, or the non-metal atom group of unit price, A and R ₁, and R ₂And R ₃Bonding is to form group fat or fragrance mutually respectively, and in the photosensitive composition composition of 100 weight %, the sensitizing dye of formula (III-1) expression is 0.05-30 weight %, and titanocene compound is 0.5-80 weight %,

But the addition polymerization compound with ethylenical unsaturated double bonds is 5-80 weight %.

In above-mentioned photosensitive composition, but described addition polymerization compound with ethylenical unsaturated double bonds is acrylic or methacrylic acid.

In above-mentioned photosensitive composition, but but described addition polymerization compound with ethylenical unsaturated double bonds is a carbamates addition polymerization compound.

A kind of light polymerization process, this method comprise with the laser beam with wavelength 350nm-450nm above-mentioned photosensitive composition exposure.

To describe the present invention in detail below.

Photopolymerisable compositions

Photopolymerisable compositions of the present invention contains (A) Photoepolymerizationinitiater initiater (sensitizing dye and titanocene compound) as basis, but the addition polymerization compound (hereinafter referring to " but addition polymerization compound ") that (B) has at least a ethylenical unsaturated double bonds, if necessary, can contain (C) binder polymer.To specify every kind of composition below.

(A) Photoepolymerizationinitiater initiater

Contain (i) as the Photoepolymerizationinitiater initiater (hereinafter referring to " light trigger " sometimes) of photopolymerisable compositions basis of the present invention and have the sensitizing dye of special construction and (ii) titanocene compound.Can think that the main absorbing light of sensitizing dye produces with the titanocene compound that promotes coexistence and causes free radical (this method refers to " dye sensitization " hereinafter) in light trigger of the present invention.One of reason that sensitizing dye of the present invention is superior is that its absorbing wavelength is in the scope of 350nm to 450nm.In addition, though a large amount of titanocene compound described later has weak absorbance and also has photonasty in same zone in the wavelength region may of ultraviolet to contiguous 500nm in essence, but the present invention has the photonasty that the sensitizing dye of special construction has greatly improved titanocene compound, on the other hand, by control titanocene compound consumption to relatively small amount, in short wavelength range, can fully improve photonasty, simultaneously, on the other hand, can pass through titanocene compound itself, make in the photonasty in 500nm zone low, therefore, can improve the safety light adaptability (the use adaptability under amber light, or the like) of photopolymerisable compositions.In addition, though it is unclear the present invention with especially good dye sensitization to be had the dye sensitization mechanism of sensitizing dye of special construction, can infer as follows.Just, sensitizing dye of the present invention has high relatively radiation (fluorescence or phosphorescence), impels the life-span of dyestuff excited state long, makes the efficient of dye sensitization reaction uprise.In addition, demonstrate high relatively fluorescence,, can produce wholesome effect to dye sensitization efficient on the practical work though dyestuff is triplet state (triple state) compound group with good formation efficient as sensitizing dye of the present invention.

(i) sensitizing dye

The used sensitizing dye of the present invention is represented by formula (I-1):

Wherein A ' and B represent respectively-S-, NR ₃, or NR ₄R ₃And R ₄That each representative replaces or unsubstituted alkyl, or that replace or unsubstituted aryl; Y ₁And Y ₂Each representative and adjacent A ' or B and adjacent carbon atom form the non-metal atom group of dyestuff alkalescence nuclear together; R ₁And R ₂Each represents the non-metal atom group of unit price, or R ₁And R ₂Bonding forms ring fat or fragrance mutually.

To describe formula (I-1) below in detail.

A ' and B represent respectively-S-, NR ₃, or NR ₄R ₃And R ₄That each representative replaces or unsubstituted alkyl, or that replace or unsubstituted aryl.

Specify by R below ₃And R ₄The preferred example of the not substituted alkyl of representative.The preferred example of substituted alkyl is not the alkyl of straight chain, side chain or ring with 1-20 carbon atom, and concrete example comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, the second month in a season-butyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl and 2-norborny (norbornyl).

By R ₃And R ₄The substituent preferred example of the substituted alkyl of representative is the monovalent nonmetallic atomic radical except hydrogen atom; its preferred example comprises 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, N-dialkyl amido, 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 sulphur oxygen base (alkylsulfoxy); aryl sulphur oxygen base, acyl group thio group, acyl amino; N-alkyl acyl amino; N-aryl-acyl amino, 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, 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; formoxyl; acyl group, carboxyl, alkoxy carbonyl; aryloxycarbonyl; carbamyl, 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; the alkyl sulfinyl, aryl sulfinyl, alkyl sulphonyl; aryl sulfonyl, thio group (SO ₃H) and its conjugation base (hereinafter referring to the sulfonation base), alcoxyl sulfonyl, fragrant oxygen sulfonyl, sulfinyl (sulfinamoyl); the 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; the N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N; N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono (PO ₃H ₂) and its conjugation base (hereinafter referring to the phosphine base), dialkyl phosphine acyl group (PO ₃(alkyl) ₂), diaryl phosphono (PO ₃(aryl) ₂), alkylaryl phosphono (PO ₃(alkyl) (aryl)), monoalkyl phosphono (PO ₃H (alkyl)) and its conjugation base (hereinafter referring to the alkylphosphines base), single aryl phosphine acyl group (PO ₃H (aryl)) and its conjugation base (hereinafter referring to the aryl phosphine base), phosphonato (OPO ₃(H) ₂) and its conjugation base (hereinafter referring to alkyl phosphine oxygen base), dialkyl phosphine acyloxy (OPO ₃(alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), alkylaryl phosphonato (OPO ₃(alkyl) (aryl)), monoalkyl phosphonato (OPO ₃H (alkyl)) and its conjugation base (hereinafter referring to alkyl phosphine oxygen base), single aryl phosphine acyloxy (OPO ₃H (aryl)) and its conjugation base (hereinafter referring to aryl phosphine oxygen base), cyano group, nitro, aryl, heteroaryl, alkenyl, alkynyl.

As the object lesson of alkyl in the substituting group of substituted alkyl, what can enumerate is above-mentioned alkyl.As the object lesson of aryl in the substituting group of substituted alkyl, what can enumerate is phenyl, diphenyl, naphthyl; tolyl, xylyl, 3,5-dimethylbenzene methyl; cumenyl, chlorphenyl, bromophenyl, chloromethyl phenyl; hydroxyphenyl, anisyl, ethoxyphenyl; phenoxy phenyl, acetyl oxygen phenyl, benzoyl oxygen phenyl; the methyl thio-phenyl, phenyl thio-phenyl, methylamino phenyl; dimethylaminophenyl, acetyl-amino phenyl, carboxyl phenyl; the methoxycarbonyl group phenyl, carbethoxy phenyl, carbobenzoxy phenyl; N-phenyl amino formoxyl phenyl, cyano-phenyl, thio-phenyl; the sulfonation phenyl, phosphono phenyl, phosphine phenyl.

As the object lesson of heteroaryl in the substituting group of substituted alkyl, operable is to contain at least one nitrogen-atoms, and the aromatic rings of the monocycle of oxygen atom and sulphur atom or many rings preferably uses the aromatic rings of 5-or 6-unit, furans for example, pyrroles or pyridine.

Object lesson as alkenyl in the substituting group of substituted alkyl, what can enumerate is vinyl, the 1-propenyl, the 1-butenyl group, cinnamyl and 2-chloro-1-vinyl are ethinyls as the object lesson of alkynyl in the substituting group of substituted alkyl, the 1-propinyl, the 1-butynyl, the trimethyl silyl ethinyl.

As acetyl group (G in the substituting group of substituted alkyl ¹CO-) G in ¹Object lesson, what can enumerate is hydrogen atom and abovementioned alkyl and aryl.

In these substituting groups, preferred example comprises halogen atom (F ,-Br ,-Cl;-I), alkoxy, aryloxy group, alkyl thio-base; the aryl thio group, N-alkyl amino, N, N-dialkyl amido; acyloxy, N-alkyl carbamoyloxy base, N-arylamino formyloxy, acyl amino; formoxyl, acetyl group, carboxyl, alkoxy carbonyl; aryloxycarbonyl, carbamyl, N-alkyl-carbamoyl; N, N-dialkyl amido formoxyl, N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl, thio group, sulfonation base; sulfamoyl, N-alkylsulfamoyl group, N; the N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl; phosphono, phosphine base, dialkyl phosphine acyl group; the diaryl phosphono, monoalkyl phosphono, alkylphosphines base; single aryl phosphine acyl group, aryl phosphine base, phosphonato; the phosphine oxygen base, aryl, alkenyl.

On the other hand, as the alkylidene in the substituted alkyl, what can enumerate is to obtain alkylidene by remove any one hydrogen atom on the alkyl of the above-mentioned 1-20 of a having carbon atom to form residue of divalent, preferably have 1-12 carbon atom straight-chain alkyl-sub-, have 3-12 carbon atom branched alkylidene, have the cyclic alkylidene of 5-10 carbon atom.

Comprise chloromethyl by object lesson, bromomethyl, 2-chloroethyl in conjunction with above-mentioned substituting group and the resultant preferred substituted alkyl of alkylidene; trifluoromethyl, methoxyl methyl, methoxyethoxy ethyl; allyl oxygen methyl; Phenoxymethyl, methylthiomethyl, tolyl sulphomethyl; the ethylamino ethyl; the diethylamino propyl group, morpholine propyl group, acetyl-o-methyl; benzoyl oxygen methyl; N-cyclohexyl carboxyamide oxygen ethyl, N-phenyl amino methanoyl ethyl, acetyl-amino ethyl; with N-methyl benzoyl aminopropyl; the 2-oxoethyl, 2-oxopropyl, carboxyl propyl group; the methoxycarbonyl group ethyl; the allyloxycarbonyl butyl, chlorobenzene oxygen carbonyl methyl, carbamyl ylmethyl; N-methylamino formoxyl ethyl; N, N-dipropyl carbamyl ylmethyl, N-anisyl) the carbamyl ethyl; N-methyl-N-thio-phenyl) carbamyl ylmethyl; the sulfo-butyl, sulfonation butyl, sulfonamide butyl; N-ethyl sulfonamide methyl; N, N-dipropyl sulfonamide propyl group, N-methyl-N-phosphono phenyl) the sulfonamide octyl group; N-methylamino sulfonyl propyl group; phosphono (phosphono) butyl; phosphineization (phosphonato) hexyl, diethyl phosphono butyl, diphenyl phosphono propyl group; methyl phosphono butyl; the methylphosphine butyl, tolyl phosphono hexyl, tolylphosphine hexyl; phosphono oxygen propyl group; the phosphine oxygen butyl, benzyl, phenethyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenethyl, to methyl-benzyl, cinnamyl; allyl; 1-propenyl methyl, 2-butenyl group, 2-methacrylic; 2-metering system ylmethyl; 2-propynyl, 2-butynyl, 3-butynyl.

By R ₃And R ₄The concrete preferred example of unsubstituting aromatic yl of expression is the condensed ring that formed by 1-3 phenyl ring and by phenyl ring and the formed condensed ring of the first unsaturated ring of 5-, and concrete example comprises phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, and fluorenyl.Wherein, more preferably phenyl and naphthyl.

By R ₃And R ₄The preferred example of the substituted aryl of expression is those groups that have the monovalent nonmetallic atom except hydrogen atom on above-mentioned one-tenth ring carbon atom as substituent aryl.The substituent preferred example that can exemplify is above-mentioned alkyl, substituted alkyl and above-mentioned those substituent examples in substituted alkyl.The preferred example of these substituted aryls comprises diphenyl, tolyl, xylyl; 3,5-dimethylbenzene methyl, cumenyl; chlorphenyl, bromophenyl, fluorophenyl; chloromethyl phenyl, trifluoromethyl, hydroxyphenyl; anisyl, methoxy (ethoxy) phenyl, allyl oxygen phenyl; phenoxy phenyl, methyl thio-phenyl, tolyl thio-phenyl; the ethylamino phenyl, diethylamino phenyl, morpholinyl phenyl; acetyl oxygen phenyl, benzoyl oxygen phenyl, N-cyclohexyl carboxyamide oxygen phenyl; N-phenyl amino methanoyl phenyl, acetyl-amino phenyl, N-methyl benzoyl aminophenyl; carboxyl phenyl; the methoxycarbonyl group phenyl, allyloxycarbonyl phenyl, chlorobenzene oxygen carbonyl phenyl; the carbamyl phenyl; N-methylamino formoxyl phenyl, N, N-dipropyl carbamyl phenyl; N-(anisyl) carbamyl phenyl; N-methyl-N-(thio-phenyl) carbamyl phenyl, thio-phenyl, sulfonation phenyl; sulfamoyl phenyl; N-ethyl sulfamoyl phenyl, N, N-dipropyl sulfamoyl phenyl; N-tolyl sulfamoyl phenyl; N-methyl-N-(phosphono phenyl) sulfamoyl phenyl, phosphono (phosphono) phenyl, phosphineization (phosphonato) phenyl; diethyl phosphono phenyl; diphenyl phosphono phenyl, methyl phosphono phenyl, methylphosphine phenyl; tolyl phosphono phenyl; the tolylphosphine phenyl, allyl, 1-propenyl methyl; the 2-butenyl group; 2-methacrylic phenyl, 2-methylpropenyl phenyl, 2-propynyl phenyl; 2-butynyl phenyl, 3-butynyl phenyl.

Hereinafter with the R in the formula (I-1) ₁And R ₂R ₁And R ₂Each represents the non-metal atom group of unit price, or R ₁And R ₂Bonding forms ring fat or fragrance mutually.R ₁And R ₂Each preferably represents hydrogen atom, replacement or unsubstituted alkyl, or that replace or unsubstituted aryl, or pass through R ₁And R ₂That replace or unsubstituted alkylidene bonding each other forms ring fat or fragrance etc.Work as R ₁And R ₂When bonding encircled to form each other, this ring can be by the oxygen atom except that carbon atom, nitrogen-atoms, and sulphur atom forms.The preferred example of ring comprises by that replace or unsubstituted alkylidene, ehter bond, ester bond, formed ring such as amido bond.That the preferred example that can exemplify comprises replacement or unsubstituted alkyl, aryl replacement or unsubstituted, specifiable is R at formula (I-1) ₃And R ₄Described in identical group.

Hereinafter with the Y in the formula (I-1) ₁And Y ₂Y ₁And Y ₂Each representative and adjacent A or B and adjacent carbon atom form the non-metal atom group of dyestuff alkalescence nuclear together.As such heterocycle, can exemplify is the 5-that contains nitrogen-atoms, oxygen atom and sulphur atom, 6-, 7-unit heterocycle, the heterocycle of preferred 5-or 6-unit.

As the example that contains the nitrogen-atoms heterocycle of preferred use, be known at L.G.Brooker etc., J.AM.Chem.Soc., 73, in merocyanine dyes, constitute those of alkalescence nuclear described in pp.5326 to 5358 (1951) and the bibliography quoted.Concrete example comprises thiazoles (thiazole for example, 4-methylthiazol, 4-phenyl thiazole, the 5-methylthiazol, 5-phenyl thiazole, 4, the 5-dimethylthiazole, 4,5-diphenyl thiazole, 4,5-two (right-anisyl) thiazole, 4-(2-thienyl) thiazole, or the like), benzothiazoles (benzothiazole for example, 4-chloro benzothiazole, the 5-chloro benzothiazole, 6-chloro benzothiazole, 7-chloro benzothiazole, the 4-methylbenzothiazole, the 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromo benzothiazole, 4-phenyl benzothiazole, 5-phenyl benzothiazole, 4-methoxyl benzo thiazole, 5-methoxyl benzo thiazole, 6-methoxyl benzo thiazole, 5-iodobenzene and thiazole, 6-iodobenzene and thiazole, 4-ethoxyl benzo thiazole, the 5-ethoxyl benzo thiazole, tetrahydro benzothiazol, 5,6-dimethoxy benzo thiazole, 5,6-dioxy methylene benzo thiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylamino benzothiazole, 5-ethoxy carbonyl benzothiazole, or the like), (for example naphthalene [1 for the naphthothiazoles class, 2] thiazole, naphthalene [2,1] thiazole, 5-methoxynaphthalene [2,1] thiazole, 5-ethoxy naphthalene [2,1] thiazole, 8-methoxynaphthalene [1,2] thiazole, 7-methoxynaphthalene [1,2] thiazole, or the like), thianaphtheno-7 ', 6 ' 4,5-thiazoless (4 '-methoxyl thianaphtheno-7 ' for example, 6 ' 4,5-thiazole or the like), azole (4-methyl azoles for example, 5-methyl azoles, 4-phenyl azoles, 4,5-diphenyl azoles, 4-ethyl azoles, 4,5-dimethyl azoles, 5-phenyl azoles or the like), benzo azole (benzo azoles for example, 5-chlorobenzene and azoles, 5-methyl benzo azoles, 5-phenyl benzo azoles, 6-methyl benzo azoles, 5,6-dimethylbiphenyl azoles, 4,6-dimethylbiphenyl azoles, 6-methoxyl benzo azoles, 5-methoxyl benzo azoles, 4-ethoxy benzo azoles, 5-hydroxy benzo azoles, 6-hydroxy benzo azoles, or the like), naphtho- azole (naphtho-[1,2] azoles for example, naphtho-[2,1] azoles, or the like), selenazoles class (4-methyl selenazoles for example, 4-phenyl selenazoles, or the like), benzo selenazoles class (benzo selenazoles for example, 5-chlorobenzene and selenazoles, 5-methoxyl benzo selenazoles, 5-hydroxy benzo selenazoles, the tetrahydro benzo selenazoles, or the like), (for example naphtho-[1 for the naphthalene selenazole class, 2] selenazoles, naphtho-[2,1] selenazoles, or the like), Thiazoling type (thiazoline for example, 4-methylthiazol quinoline, or the like), 2-quinolines (quinoline for example, the 3-methylquinoline, the 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, the 6-chloroquinoline, the 8-chloroquinoline, 6-methoxy quinoline, 6-ethoxyquinoline, the 6-hydroxyquinoline, oxine, or the like), 4-quinolines (quinoline for example, the 6-methoxy quinoline, the 7-methylquinoline, the 8-methylquinoline, or the like), 1-iloquinoline derivative (isoquinoline for example, 3, the 4-dihydro-isoquinoline, or the like), 3-iloquinoline derivative (isoquinoline for example, or the like), benzimidazole (for example 1,3-diethyl benzo imidazoles, 1-ethyl-3-phenyl benzimidazole, or the like), 3,3-dialkyl group indolenine class (for example 3,3-dimethyl indolenine, 3,3, the 5-tri-methyl indole false, 3,3, the 7-tri-methyl indole false, or the like), with 2-pyridines (pyridine for example, the 5-picoline, or the like), 4-pyridines (for example pyridine or the like).These alkalescence are endorsed and are used as di-H alkylene derivative in the present invention.

By the Y in formula (I-1) ₁And Y ₂With above-mentioned adjacent A ' or B, form together in the above-mentioned example of nitrogenous and sulfur heterocyclic ring with adjacent carbon atom, especially preferably has dyestuff by structure shown in the following formula (I-2), this be because, it has good exposure adaptability at 350nm-450nm, and having high photosensitivity, it can provide a kind of very photopolymerizable composition of excellent storage stability that has in addition.

R wherein ₁, R ₂, R ₃And R ₄Defined equivalent in meaning with formula (I-1) respectively; X ₁And X ₂Each represents the O atom, S atom, Se atom, NR ₉Or CR ₁₀R ₁₁R ₉, R ₁₀And R ₁₁Each representative has the alkyl of 1-6 carbon atom, or that replace or unsubstituted phenyl; And R ₅, R ₆, R ₇And R ₈Each represents hydrogen atom, has the alkyl of 1-6 carbon atom, has the alkoxy of 1-6 carbon atom, phenyl replacement or unsubstituted, chlorine or bromine, and R ₅With R ₆, and R ₇With R ₈Bonding is to form ring fat or fragrance mutually.Bonding can be by the oxygen atom except that carbon atom when forming ring each other when them, and nitrogen-atoms or sulphur atom form and encircle.The preferred example of ring comprises by that replace or unsubstituted alkenyl, ehter bond, ester bond, formed ring such as amido bond.That the preferred example that can exemplify comprises replacement or unsubstituted alkyl, aryl replacement or unsubstituted, specifiable is R at formula (I-1) ₃And R ₄Described in identical group.

In the preferred experimental program of the present invention, X ₁And X ₂Identical, and represent S or C (CH ₃) ₂R ₁+ R ₂(this situation is meant R ₁And R ₂Bonding forms ring each other) be-(CH ₂) ₂-or-(CH ₂CHR ₁₄CH ₂The R of)-wherein ₁₄The expression H or the tert-butyl group); R ₃And R ₄Identical and represent CH ₃Or C ₂H ₅R ₁And R ₂Each represents H; R ₅And R ₆Each represents H, or its each other bonding form aromatic rings; R ₇And R ₈Each represents H, or its each other bonding form aromatic rings.Relevant in formula (I-2), the replacement or unsubstituted alkyl, alkenyl and substituting group, what can enumerate is and the identical group described in the formula (I-1).

Following chemical structural formula (D1)-(D25) is the more detailed example of sensitizing dye of the present invention, yet the used sensitizing dye of the present invention is not limited to the following chemical structure, and any sensitizing dye is as long as it satisfies the said structure key element and just can preferably use.

Can be with base catalyst Claisen-Schmidt condensation prepared in reaction the present invention by the suitable ketone of the suitable aldehyde of 2 equivalents and 1-equivalent with formula (I-1) or (I-2) represented sensitizing dye.The method of producing sensitizing dye by the hydrolysis of carbonyl cyanine dye is disclosed in US patent 3,672,906.At the Khim.Geterotsikl.Soedin. of works such as Slominskii, pp.711 to 712 (1974), and Chem.Abst., and 81, the synthetic method by the condensation reaction of ketone and azo (azothium) salt has been described among the 77828f (1974).

In order to improve the performance of photopolymerisable compositions, can carry out various chemical modifications to relevant sensitizing dye of the present invention.For example will be at photopolymerisable compositions of the present invention as under the situation of photosensitive layer; by means of covalent bonding; but the method for ionic bonding and hydrogen bonding is by the bonding of dyestuff and addition polymerization compound structure (for example acryloyl group and methacrylyl); the film strength of to expose can be improved, and the unnecessary dye precipitated in the caudacoria that exposes can be prevented.In addition, use a spot of light trigger, the part that produces free radical by the described titanocene compound of sensitizing dye and back and other (for example, reduction decomposition part is as alkyl halide,, superoxide, diimidazole etc. and oxicracking part is as borate, amine, the trimethyl silyl methyl, ethyloic, carbonyl, imines, or the like) bonding, can improve the photonasty of photopolymerisable compositions significantly.When photopolymerisable compositions of the present invention is used as planographic printing plate precursor (a kind of preferred using method of the present invention), the hydrophilic segment of introducing (acid free radical or polar group such as carboxyl and its ester, sulfonic group and its ester, oxirane, or the like) flexibility (adaptability) of operation of (alkalescence) aqueous systems developing solution can be improved effectively.Particularly, ester type hydrophilic radical compatibility is good, and this is owing to its hydrophobic relatively structure in photosensitive layer, and makes water wettability improve by the generation of the hydrolysis in developer solution acid free radical.In addition, in order to improve compatibility and the crystal settling that prevents at photosensitive layer, can at random introduce various substituting groups.For example, in the photosensitive system of certain kind, aryl and allylic unsaturated link are extremely effective for improving compatibility sometimes, in addition, with introducing the branched alkyl structure, or the like method, by between the π-plane of the π-plane of dyestuff and other dyestuff, introducing steric hindrance, can suppress crystal settling significantly.In addition, by the introducing phosphate, epoxy radicals, trialkoxysilyl, or the like, can improve metal and metal oxide cohesive to dead matter.In addition, if necessary, can also use the polymerization of sensitizing dye.

But be similar to addition polymerization described below,, can at random use sensitizing dye according to the performance design of photochromics.For example, can improve the compatibility of itself and photopolymerisable compositions by the sensitizing dye that mix to use two or more.When selecting sensitizing dye, except that photonasty, the molar extinction coefficient at used light emitted wavelength place is a key factor.If use dyestuff with big molar extinction coefficient, can reduce the addition of dyestuff relatively, this is economical, also the physical property to the film of photopolymerisable compositions is useful.Because photonasty, resolving power and the physical property of photopolymerisable compositions exposed film are subjected to the influence of optical source wavelength absorbance bigger, therefore, consider from these factors, can select the addition of sensitizing dye arbitrarily.For example 0.1 or lower absorbance zone photonasty reduce.In addition, the influence owing to halation reduces resolving power.Yet this sometimes low absorbance is for improving 5 μ m or more the hardness of thick film is quite effective.When sensitizing dye is used to have the printed panel of the photosensitive layer that comprises photopolymerisable compositions, 3 or higher high absorbance zone, nearly all light is absorbed on the surface of photosensitive layer, therefore, hindered the more curing of nexine of film, and made film strength and the bond strength of matrix is become not enough.When the plate printing plate of the film thickness that sensitizing dye is used to have relative thin, make the absorbance of photosensitive layer become 0.1-1.5, preferably the addition of the sensitizing dye of setting from 0.25-1 is preferred.When sensitizing dye was used for plate printing plate, in the photopolymerisable compositions composition of per 100 weight portions, its amount was generally the 0.05-30 weight portion, is preferably the 0.1-20 weight portion, more preferably the 0.2-10 weight portion.

(ii) titanocene compound

Have no particular limits as the titanocene compound of light trigger being used for the present invention, any compound is as long as when producing living radical during with rayed under itself and the above-mentioned sensitizing dye coexistence situation, just can use this compound.For example, can use arbitrarily at the various known compounds disclosed in the following patent: JP-A-59-152396, JP-A-61-151197, JP-A-63-41483, JP-A-63-41484, JP-A-2-249, JP-A-2-291, JP-A-3-27393, JP-A-3-12403, and JP-A-6-41170.

What can more specifically exemplify is dicyclopentadienyl-Ti-dichloride, the two phenyl of dicyclopentadienyl-Ti-, dicyclopentadienyl-Ti-two-2,3,4,5,6-five fluoro-1-phenyl (hereinafter referring to " T-1 " sometimes), dicyclopentadienyl-Ti-two-2,3,5,6-tetrafluoro-1-phenyl, dicyclopentadienyl-Ti-is two-2,4,6-three fluoro-1-phenyl, dicyclopentadienyl-Ti-is two-2,6-two fluoro-1-phenyl, and dicyclopentadienyl-Ti-two-2,4-two fluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,3,4,5,6-five fluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,3,5,6-tetrafluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,4-two fluoro-1-phenyl and two (cyclopentadienyl group)-two (2,6-two fluoro-3-(1-H-1-pyrrole radicals) phenyl titaniums (hereinafter referring to " T-2 " sometimes).

Be similar to above-mentioned sensitizing dye,, can carry out various chemical modifications titanocene compound of the present invention in order further to improve the characteristic of photopolymerisable compositions.For example, operable method has, but uses the method for unsaturated compound and other generation free radical part bonding of titanocene compound and sensitizing dye addition polymerization; Introduce the method for hydrophilic segment; In order to improve compatibility and to prevent crystal settling, introduce substituent method; In order to improve cohesive, introduce substituent method; The method of polymerization.

About the usage of titanocene compound, but be similar to addition polymerization compound recited above and sensitizing dye,, can also at random use titanocene compound according to the performance design of photochromics.For example, can improve compatibility with photopolymerisable compositions by the compound that mix to use two or more.Usually, consider the large usage quantity of preferred titanocene compound from the photonasty aspect.In the photopolymerisable compositions composition of per 100 weight portions, its amount is the 0.5-80 weight portion, and being preferably the 1-50 weight portion is enough to obtain satisfied photonasty.On the other hand, fundamental purpose of the present invention is to consider under amber light and white lamp to use, because therefore light, consider from the mist aspect that in contiguous 500nm irradiation the consumption of preferred titanocene compound is less.Even the consumption of titanocene compound is reduced to 6 weight portions or still less, further reduce to 1.9 weight portions or still less and further reduce to 1.4 weight portions or still less, can obtain enough photonasty by mixing with sensitizing dye of the present invention to use.

(B) but the addition polymerization compound

From having at least one, but preferably select to have the addition polymerization compound of at least one ethylenical unsaturated double bonds in the compound of two or more terminal unsaturation ethylene linkages.This compound is industrial known, and has no particular limits being used for these compounds of the present invention.For example, this compounds can be monomer, prepolymer (being dipolymer, trimer), oligomer or its potpourri and its multipolymer form.The monomer whose that can exemplify and the example of multipolymer be the unsaturated carboxylic acid class (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid, or the like) and its ester class and amide-type, and preferably use the ester class of unsaturated carboxylic acid and aliph polyols compound, the amide-type of unsaturated carboxylic acid and fat polyamine compound.In addition, also preferred the use has the unsaturated carboxylate type of nucleophilic displacement of fluorine base and the addition reaction product of amide-type and simple function group or many functional group isocyanates's class and epoxies, dehydration condensation product with these compounds and simple function group or polyfunctional carboxylic acids, the example of described nucleophilic displacement of fluorine base is a carboxyl, amino and sulfydryl.The also preferred addition reaction product that uses with the electric substituent unsaturated carboxylate type of parent and amide-type and simple function group or polyfunctional group alcohols, amine and mercaptan, the electric substituent example of described parent is isocyanato-, epoxy radicals, have the substitution reaction product that can discharge substituent unsaturated carboxylate type and amide-type and simple function group or polyfunctional group alcohols, amine and mercaptan with use, described releasable substituent example is halogen and tosyloxy.As other example, can also replace above-mentioned unsaturated carboxylic acid with unsaturated phosphoric acid, styrene, vinyl ether or the like.

The object lesson of the ester monomer of aliph polyols compound and unsaturated carboxylic acid comprises esters of acrylic acid, ethylene glycol diacrylate, diacrylate triglycol ester, diacrylate 1,3-butanediol ester, diacrylate 1,4-butanediol ester, diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethyol propane triacrylate (trimethylolpropane triacrylate), trimethylolpropane tris (acryloyl-oxy propyl group) ether, three acrylic acid trimethylolethane esters, hexanediol diacrylate, diacrylate 1,4-cyclohexanediol ester, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, diacrylate dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, three (acrylyl oxy-ethyl) isocyanates, the polyester acrylic ester oligomer, or the like.

Example as methacrylate comprises dimethacrylate 1, the 4-butanediol ester, the dimethacrylate triglycol ester, the dimethacrylate DOPCP, trihydroxy methyl propane trimethyl acrylate, trimethyl acrylic acid trimethylolethane ester, Ethylene glycol dimethacrylate, dimethacrylate 1,3-butanediol ester, dimethacrylate hexanediol ester, dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, the dimethacrylate dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, trimethyl acrylic acid sorbitol ester, tetramethyl acrylic acid sorbitol ester, two [right-(3-methacryloxypropyl-2-hydroxyl-propoxyl group) phenyl] dimethylmethane, two [right-(3-methacryloxypropyl ethoxy) phenyl] dimethylmethane, or the like.

Example as the itaconate class comprises two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acid 1,3 butylene glycol esters, two itaconic acids 1,4-butanediol ester, two itaconic acids 1,4-butanediol ester, two itaconic acid pentaerythritol esters, four itaconic acid sorbitol esters, or the like.

Example as the crotonates class comprises two crotonic acid glycol esters, two crotonic acids 1, and the 4-butanediol ester, two crotonic acid pentaerythritol esters, four crotonic acid sorbitol esters, or the like.

Example as iso-crotonic acid ester class comprises two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters, and four iso-crotonic acid sorbitol esters, or the like.

Example as the maleate class comprises two maleic acid glycol esters, two maleic acid triglycol esters, and two maleic acid pentaerythritol esters, four maleic acid sorbitol esters, or the like.

Example as other ester, for example can also preferably use in the present invention at JP-B-46-27926, disclosed aliphatic alcohol ester class among JP-B-51-47334 and the JP-A-57-196231, at JP-A-59-5240, disclosed among JP-A-59-5241 and the JP-A-2-226149 have those esters of fragrant skeleton and disclosed those esters that contain amino in JP-A-1-165613.

In addition, can also use the potpourri of above-mentioned ester monomer.

In addition, the object lesson of the amide monomer of fat polyamine compound and unsaturated carboxylic acid comprises methylene two-acrylamide, methylene two-Methacrylamide, 1,6-hexylidene two-acrylamide, 1,6-hexylidene two-Methacrylamide, diethylene triamine three-acrylamide, xylylene two-acrylamide, xylylene two-Methacrylamide, or the like.

As other preferred amide monomer, what can exemplify is disclosed those amide monomers with cyclohexylene structure in JP-B-54-21726.

In addition, but also preferably use in the present invention by the resulting carbamate groups addition polymerization of the addition reaction of isocyanates and hydroxyl compound, as concrete example, can exemplify as the disclosed vinyl carbamate compound that in a molecule, has two or more polymerizable vinyl in JP-B-48-41708, it is to obtain by having by the addition reaction that has the polyisocyanate compound of two or more isocyanate groups in the vinyl monomer with hydroxyl of following formula (V) representative and the molecule.

CH ₂＝C(R)COOCH ₂CH(R’)OH

Wherein R and R ' respectively represent H or CH ₃

In addition, also preferably use in the present invention at JP-A-51-37193, disclosed urethane acrylate class among JP-B-2-32293 and the JP-B-2-16765, with at JP-B-58-49860, JP-B-56-17654, disclosed carbamate compounds among JP-B-62-39417 and the JP-B-62-38418 with oxirane skeleton.

In addition, as at JP-A-63-277653, disclosed among JP-A-63-260909 and the JP-A-1-105238, by use in molecule, have amino structure and thioether (sulfide) but the addition polymerization compound of structure can obtain the hypervelocity photopolymerisable compositions.

As other example, what also can exemplify is multi-functional acrylate's class and methyl acrylic ester, as at JP-A-48-64183, disclosed among JP-B-49-43191 and the JP-B-52-30490, react polyester acrylate class and the epoxy acrylate class that obtains by epoxy resin and (methyl) acrylic acid.Can also exemplify at JP-B-46-43946, among JP-B-1-40337 and the JP-B-1-40336 disclosed special unsaturated compound and in JP-A-2-25493 disclosed vinyl sulfonic acid compound.In addition, preferably use the disclosed structure that contains perfluoro alkyl group in JP-A-61-22048 among the present invention.Have again, can also use Kyokai, Vol.20, No.7, photocurable monomer and the oligomer introduced among the pp.300-308 (1984) at Bulletin of Nihon Setchaku.

But the detailed directions of addition polymerization compound, for example can optionally determine to use according to the characteristic of the photochromics of final design be what structure compound, be to use or to mix compound, the maybe amount that will use used separately.For example, have in mind from following aspect and come alternative condition.For photosensitive speed, preferred per molecule contains the structure of a plurality of unsaturated groups, and preferred in many cases difunctional group or polyfunctional group group.In order to improve the film strength that the image part is promptly solidified, preferred trifunctional or polyfunctional group group, in addition, in potpourri, use different functionality and different polymerizable groups (as, acrylate, methacrylate, distyryl compound, vinyl ether compound) so that both the sense of control photosensitiveness had also been controlled intensity.Though have the compound of macromolecule or have the photosensitive speed and the film strength of high hydrophobicity compound good,, aspect developing powder developer solution and precipitation, consider preferred these compounds sometimes.Photopolymerisable compositions and dispersed aspect, for other composition (as binder polymer, initiating agent, colorant, or the like) compatibility, but the selection of addition polymerization compound and usage are key factors.For example, can improve compatibility by the potpourri that uses low-purity compound or two or more compounds sometimes.In addition, in order to improve carrier and outer field cohesive, also can select to have the compound of special construction.But mixing ratio about addition polymerization compound in photopolymerisable compositions, consumption is the photonasty height greatly then, but sometimes consumption too conference cause the shortcoming that is separated, because the viscosity of photopolymerisable compositions and cause precipitation from developer solution, cause the problem (as the transfer of photochromics composition and bondingly cause producing failure) in production and processing.Consider that from these aspects in many cases, based on each composition of whole composition, but the mixing ratio of preferred addition polymerization compound is the 5-80 weight portion, more preferably the 25-75 weight portion.But but can use the addition polymerization compound separately or mix the addition polymerization compound that uses two or more.In addition, consider oxygen, resolving power, sprayability, index of refraction change and surface adhesion to the interference of the degree of polymerization, but can at random select suitable structure, mixing ratio and the addition of addition polymerization compound.In addition, can determine the coating method of layer structure and priming paint and finish paint according to environment.

(C) binder polymer

When photopolymerisable compositions being used for plate printing plate (optimization test scheme of the present invention), preferred photopolymerisable compositions further contains binder polymer.As binder polymer, preferably use the line style organic high molecular polymer.Can use any " line style organic high molecular polymer ".Preferred select can water development or the water soluble that develops of alkalescent water or soluble line style organic high molecular polymer of alkalescent water or swelling line style organic high molecular polymer.Selected and the line style organic high molecular polymer that uses is not only as the film forming agent of composition, also as water development agent, alkalescent water developer or organic solvent developer.For example, when using the line style organic high molecular polymer of water soluble, make water development become possibility.As the line style organic high molecular polymer, what can exemplify has an addition polymer that has hydroxy-acid group at side chain, for example at JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, disclosed polymkeric substance among JP-A-59-53836 and the JP-A-59-71048, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, the crotonic acid multipolymer, the maleic acid of maleic acid and partial esterification.Can also use the acid cellulose derivant that has hydroxy-acid group at side chain.Except above-mentioned, can also use by in addition polymer, adding the resulting polymkeric substance of cyclic acid anhydride with carboxyl.

In these compounds, particularly therefore [benzyl (methyl) acrylate-(methyl) but other addition polymerization vinyl monomer of acrylic acid-as required] multipolymer and [allyl (methyl) acrylate-(methyl) but other addition polymerization vinyl monomer of acrylic acid-as required] multipolymer balance film intensity, photonasty and development property well help with in the present invention.

Because at JP-B-7-12004, JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, the intensity of disclosed carbamate groups binder polymer with acid free radical is very good among JP-A-1-271741 and the Japanese patent application No.10-116232, therefore helps pressrun and low exposure adaptability.

Disclosed bonding agent with acylamino-had both had good development property in JP-A-11-171907, and good film strength is arranged again.

Except recited above, be useful as the line style organic high molecular polymer polyvinyl pyrrolidone and the polyethylene oxide of water soluble.In order to improve the curing film strength, can also use pure soluble nylon, 2, the polyethers of two (4-hydroxyl-phenyl) propane of 2-and epichlorokydrin.Though in whole composition, can mix these line style organic high molecular polymers, when combined amount surpasses 90% weight, image intensity etc. be had adverse influence with any amount.Preferred amount is 3-85% weight.Preferably having the compound of photopolymerization ethylenical unsaturated double bonds and the weight ratio of line style organic high molecular polymer is 1/9-7/3.In optimization experiment scheme of the present invention, used binder polymer is water-insoluble soluble with alkali basically, wherein can or very little be used as the organic solvent (the undesirable solvent of environment) of developing solution.In this class is used,, suitably select the acid number (acid content of every gram polymkeric substance of representing with chemical equivalent) and the molecular weight of binder polymer from image intensity and the consideration of development property.Acid number is preferably 0.4-3.0meq/g, and more preferably 0.6-2.0meq/g and molecular weight are preferably 3,000-500,000, more preferably 10,000-300,000.

Photosensitive composition in another experimental program of the present invention comprises the carbazole compound (hereinafter referring to " carbazole compound " simply) by formula (II-1) expression, titanocene compound and with free radical or acid reaction to change or to keep the compound of physics or chemical characteristic.

The inventor has been found that by mix using carbazole compound and titanocene compound can improve the present composition significantly in the photonasty corresponding to the wavelength region may of carbazole compound absorption band.Though do not know the effect of these two kinds of compounds in the present invention, play the sensitizing dye effect but can infer carbazole compound, absorb exposure and form excited state and cause free radical (this method hereinafter refers to " dye sensitization effect ") to promote from the coexistence titanocene compound, to produce.

One of reason that sensitizing dye of the present invention is superior is that its absorbing wavelength is in the scope of 350nm to 450nm.In addition, though largest portion titanocene compound described later has weak absorbance and also have photonasty in same zone in the wavelength region may of ultraviolet to contiguous 500nm in essence, but the present invention has the photonasty that the sensitizing dye of special construction has greatly improved titanocene compound, therefore, can pass through the consumption of control titanocene compound on the one hand to relatively small amount, in short wavelength range, can be enough to improve photonasty, simultaneously, on the other hand, can pass through titanocene compound itself, make in the photonasty in 500nm zone lowly, therefore, can improve the safety light adaptability of photopolymerisable compositions.The inventor has been found that when sensitizing dye satisfies following architectural characteristic, can obtain above-mentioned characteristic, thereby has finished the present invention.Just, when having, the alkalescence of styryl type dye nuclear can obtain very high photonasty and good absorbability when carbazole structure and acid core have 5-unit cyclocarbonyl structure.At T.H.James, The Theory of ThePhotographic Process, Fourth Edition, Chapter 8, described the definition of " acid core " among the Macmillan Publishing Co..Sensitizing dye by merocyanine dyes representative has 1 usually endways) alkalescence (electron donor) and 2) acid (electron accepter) heterocycle, and 1) alkalescence (electron donor) heterocycle is called alkalescence nuclear and 2) acidity (electron accepter) heterocycle is called acid core.At T.H.James, The Theory of The PhotographicProcess, Fourth Edition, Chapter 8, describe the example of alkalescence nuclear and acid core among the Macmillan Publishing Co. in detail.

Though it is unclear the present invention to be had the dye sensitization mechanism of sensitizing dye had good especially dye sensitization of special construction, can infer as follows.Just, sensitizing dye of the present invention has high relatively radiation (fluorescence or phosphorescence) spectrum, impels the life-span that has by the dyestuff excited state of partial structurtes formula (1) representative structure long relatively, the result, and dyestuff works and makes itself and activating agent effecting reaction.

The A Photoepolymerizationinitiater initiater

The light polymerization initiator that is used for photosensitive composition of the present invention comprises carbazole sensitizing dye and titanocene compound.

(A1) sensitizing dye

The carbazole sensitizing dye that is configured for photosensitive composition light trigger of the present invention is represented by following formula (II-1):

R wherein ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Each represents hydrogen atom, or the monovalent nonmetallic atomic radical, and precondition is R ¹And R ³In at least one be the organic residue of unit price by following partial structurtes formula (1) expression, and R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸And R ⁹Separately each other bonding with form fat with the group of fragrance;

In it and R ¹⁰Represent hydrogen atom, or the monovalent nonmetallic atomic radical; The Z representative need form divalence non-metal atom group with the first ring of substituent 5-acid core and R with adjacent atomic radical ¹⁰Can with R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸Or R ⁹Bonding with form fat anti-with ring fragrance;

To describe formula (II-1) and local structural formula (1) below in detail.

R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Each represents hydrogen atom, or monovalent nonmetallic atomic radical, that replace with preferred representative respectively or unsubstituted alkyl, that replace or unsubstituted alkenyl, that replace or unsubstituted aryl, that replace or unsubstituted aromatic heterocycle residue, alkoxy replacement or unsubstituted, replacement or unsubstituted alkyl thio group, hydroxyl or halogen atom.

Specify R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Preferred example.Alkyl comprises straight chain, side chain or the naphthenic base with 1-20 carbon atom, and concrete example comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, the second month in a season-butyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl and 2-norborny (norbornyl).In these groups, more preferably have the straight chained alkyl of 1-12 carbon atom, have the branched alkyl of 3-12 carbon atom and have the naphthenic base of 5-10 carbon atom.

The substituent example of substituted alkyl is the monovalent nonmetallic atomic radical except hydrogen atom; its preferred example comprises halogen atom (F;-Br;-Cl;-I), hydroxyl, alkoxy; aryloxy group; sulfydryl, alkyl thio-base, aryl thio group; alkyl two thio groups; aryl two thio groups, amino, N-alkyl amino; N; the N-dialkyl amido, 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 sulphur oxygen base (alkylsulfoxy); aryl sulphur oxygen base; the acyl group thio group, acyl amino, N-alkyl acyl amino; N-aryl-acyl amino; 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, formoxyl, acyl group; carboxyl; alkoxy carbonyl group, aryloxy carbonyl, carbamyl; the N-alkyl-carbamoyl; N, N-dialkyl amido formoxyl, N-aryl-amino-carbonyl; N; N-ammonia diaryl base formoxyl, N-alkyl-N-aryl-amino-carbonyl, alkyl sulfinyl; the aryl sulfinyl; alkyl sulphonyl, aryl sulfonyl, thio group (SO ₃H) and its conjugation base (hereinafter referring to the sulfonation base), alcoxyl sulfonyl, fragrant oxygen sulfonyl, sulfinyl (sulfinamoyl); the 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; the N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N; N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono (PO ₃H ₂) and its conjugation base (hereinafter referring to the phosphine base), dialkyl phosphine acyl group (PO ₃(alkyl) ₂), diaryl phosphono (PO ₃(aryl) ₂), alkylaryl phosphono (PO ₃(alkyl) (aryl)), monoalkyl phosphono (PO ₃H (alkyl)) and its conjugation base (hereinafter referring to the alkylphosphines base), single aryl phosphine acyl group (PO ₃H (aryl)) and its conjugation base (hereinafter referring to the aryl phosphine base), phosphonato (OPO ₃(H) ₂) and its conjugation base (hereinafter referring to alkyl phosphine oxygen base), dialkyl phosphine acyloxy (OPO ₃(alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), alkylaryl phosphonato (OPO ₃(alkyl) (aryl)), monoalkyl phosphonato (OPO ₃H (alkyl)) and its conjugation base (hereinafter referring to the alkylphosphines acyloxy), single aryl phosphine acyloxy (OPO ₃H (aryl)) and its conjugation base (hereinafter referring to aryl phosphine oxygen base), cyano group, nitro, aryl, heteroaryl, alkenyl, alkynyl.

As the object lesson of alkyl in these substituting groups, what can exemplify is above-mentioned alkyl.As the object lesson of aryl, what can exemplify is phenyl, diphenyl, naphthyl; tolyl, xylyl, 3,5-dimethylbenzene methyl; cumenyl, chlorphenyl, bromophenyl, chloromethyl phenyl; hydroxyphenyl, anisyl, ethoxyphenyl; phenoxy phenyl, acetyl oxygen phenyl, benzoyl oxygen phenyl; the methyl thio-phenyl, phenyl thio-phenyl, methylamino phenyl; dimethylaminophenyl, acetyl-amino phenyl, carboxyl phenyl; the methoxycarbonyl group phenyl, carbethoxy phenyl, carbobenzoxy phenyl; N-phenyl amino formoxyl phenyl, cyano-phenyl, thio-phenyl; the sulfonation phenyl, phosphono phenyl, phosphine phenyl.

As the object lesson of heteroaryl, can use and contain at least one nitrogen-atoms, the aromatic rings of the monocycle of oxygen atom and sulphur atom or many rings, the example of the preferred especially heteroaryl that uses comprises thiophene, thianthrene, furans, pyrans, isobenzofuran, chromene, xanthene, fen piperazine, pyrroles, pyrazoles, isothiazole ， isoxazole, para-diazines, pyrimidine, pyridazine, indolizine, different indolizine, indoles, indazole, purine, quinolizine, isoquinoline, phthalazines, 1,5-benzodiazine, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthrene, acridine, perimidine, phenanthroline, phthalazines, phenarsazine, fen piperazine, furazan and fen piperazine.Further benzo condensation or these groups can have substituting group with these groups.

As the example of alkenyl, what can exemplify is vinyl, the 1-propenyl, and the 1-butenyl group, cinnamyl and 2-chloro-1-vinyl, as the object lesson of alkynyl, what can exemplify is ethinyl, 1-propinyl, 1-butynyl, trimethyl silyl ethinyl.

As acetyl group (G ¹CO-) G in ¹, what can exemplify is hydrogen atom and abovementioned alkyl and aryl.

In these substituting groups, preferred example comprises halogen atom (F ,-Br ,-Cl;-I), alkoxy, aryloxy group, alkyl thio-base; the aryl thio group, N-alkyl amino, N, N-dialkyl amido; acyloxy, N-alkyl carbamoyloxy base, N-arylamino formyloxy, acyl amino; formoxyl, acetyl group, carboxyl, alkoxy carbonyl; aryloxycarbonyl, carbamyl, N-alkyl-carbamoyl; N, N-dialkyl amido formoxyl, N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl, thio group, sulfonation base; sulfamoyl, N-alkylsulfamoyl group, N; the N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl; phosphono, phosphine base, dialkyl phosphine acyl group; the diaryl phosphono, monoalkyl phosphono, alkylphosphines base; single aryl phosphine acyl group, aryl phosphine base, phosphonato; the phosphine oxygen base, aryl, alkenyl.

On the other hand, as the alkenyl in the substituted alkyl, what can exemplify is to obtain alkenyl by remove any one hydrogen atom on the alkyl of the above-mentioned 1-20 of a having carbon atom to form residue of divalent, the straight alkenyl that preferably has 1-12 carbon atom, have the branched alkenyl of 3-12 carbon atom and have the closed chain thiazolinyl of 5-10 carbon atom.

Though it is resulting by R by mixing above-mentioned substituting group and alkenyl ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰The substituting group of represented preferred substituted alkyl is arbitrarily, but the object lesson of preferred substituted alkyl comprises chloromethyl, bromomethyl; the 2-chloroethyl, trifluoromethyl, methoxyl methyl; the methoxyethoxy ethyl, allyl oxygen methyl, Phenoxymethyl; methylthiomethyl, tolyl sulphomethyl, ethylamino ethyl; the diethylamino propyl group; the morpholine propyl group, acetyl-o-methyl, benzoyl oxygen methyl; N-cyclohexyl carboxyamide oxygen ethyl; N-phenyl amino methanoyl ethyl, acetyl-amino ethyl and N-methyl benzoyl aminopropyl; the 2-oxoethyl; the 2-oxopropyl, carboxyl propyl group, methoxycarbonyl group ethyl; the allyloxycarbonyl butyl; chlorobenzene oxygen carbonyl methyl, carbamyl ylmethyl, N-methylamino formoxyl ethyl; N; N-dipropyl carbamyl ylmethyl, N-(anisyl) carbamyl ethyl, N-methyl-N-(thio-phenyl) carbamyl ylmethyl; the sulfo-butyl; the sulfonation butyl, sulfonamide butyl, ethyl sulfonamide methyl; N; N-dipropyl sulfonamide propyl group, N-tolyl sulfonamide propyl group, N-methyl-N-(phosphono phenyl) sulfonamide octyl group; phosphono (phosphono) butyl; phosphineization (phosphonato) hexyl, diethyl phosphono butyl, diphenyl phosphono propyl group; methyl phosphono butyl; the methylphosphine butyl, tolyl phosphono hexyl, tolylphosphine hexyl; phosphono oxygen propyl group; the phosphine oxygen butyl, benzyl, phenethyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenethyl, to methyl-benzyl, cinnamyl; allyl; 1-propenyl methyl, 2-butenyl group, 2-methacrylic; 2-metering system ylmethyl; 2-propynyl, 2-butynyl, 3-butynyl.

By R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰The preferred example of represented aryl is that concrete example comprises phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, and fluorenyl by 1-3 the formed condensed ring of phenyl ring with by phenyl ring and the formed condensed ring of the 5-unsaturated ring of unit.Wherein, more preferably phenyl and naphthyl.

By R ¹, R ², R ³, R ⁴, R ⁵, R ⁷, R ⁸, R ⁸, R ⁹And R ¹⁰The object lesson of represented preferred substituted aryl is to become those groups of the monovalent nonmetallic atom that has on the ring carbon atom except hydrogen atom as substituent at above-mentioned aryl.The substituent preferred example that can exemplify is above-mentioned alkyl, substituted alkyl and above-mentioned those substituent examples in substituted alkyl.The object lesson of preferred these substituted aryls comprises diphenyl, tolyl, xylyl; 3,5-dimethylbenzene methyl, cumenyl; chlorphenyl, bromophenyl, fluorophenyl; chloromethyl phenyl, trifluoromethyl, hydroxyphenyl; anisyl, methoxy (ethoxy) phenyl, allyl oxygen phenyl; phenoxy phenyl, methyl thio-phenyl, tolyl thio-phenyl; the ethylamino phenyl, diethylamino phenyl, morpholinyl phenyl; acetyl oxygen phenyl, benzoyl oxygen phenyl, N-cyclohexyl carboxyamide oxygen phenyl; N-phenyl amino methanoyl phenyl, acetyl-amino phenyl, N-methyl benzoyl aminophenyl; carboxyl phenyl; the methoxycarbonyl group phenyl, allyloxycarbonyl phenyl, chlorobenzene oxygen carbonyl phenyl; the carbamyl phenyl; N-methylamino formoxyl phenyl, N, N-dipropyl carbamyl phenyl; N-(anisyl) carbamyl phenyl; N-methyl-N-(thio-phenyl) carbamyl phenyl, thio-phenyl, sulfonation phenyl; sulfamoyl phenyl; N-ethyl sulfamoyl phenyl, N, N-dipropyl sulfamoyl phenyl; N-tolyl sulfamoyl phenyl; N-methyl-N-(phosphono phenyl) sulfamoyl phenyl, phosphono (phosphono) phenyl, phosphineization (phosphonato) phenyl; diethyl phosphono phenyl; diphenyl phosphono phenyl, methyl phosphono phenyl, methylphosphine phenyl; tolyl phosphono phenyl; the tolylphosphine phenyl, allyl, 1-propenyl methyl; the 2-butenyl group; 2-methacrylic phenyl, 2-methylpropenyl phenyl, 2-propynyl phenyl; 2-butynyl phenyl, 3-butynyl phenyl.

Hereinafter with the Z in the partial structurtes formula (1) of formula (II-1).The Z representative need form the divalence non-metal atom group with the first ring of substituent 5-acid core with adjacent atomic radical.The object lesson of acid core is 1,3-dicarbapentaborane nuclear (for example, 1,3-(1,2-) dihydroindene diketone, 1,3-two oxirane-4, the 6-diketone, or the like), pyrazolone nuclear (for example, 3-methyl isophthalic acid-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1-(2-[4-morpholinodithio base)-3-antazoline-5-ketone, or the like), different azoles quinoline ketone nuclear (for example, the different azoles quinoline of 3-phenyl-2--5-ketone, the different azoles quinoline of 3-methyl-2--5-ketone, or the like), oxyindole nuclear (for example, 1-alkyl-2,3-dihydro-2-oxyindole, or the like), 2-sulfo--2,4-thiazolidinedione nuclear (for example, the derivant that rhodanine and its N-replace, for example 3-methyl rhodanine, 3-ethyl rhodanine, 3-phenyl rhodanine, 3-allyl rhodanine, 3-benzyl rhodanine, 3-ethyloic rhodanine, 3-carboxyethyl rhodanine, 3-methoxycarbonylmethy-rhodanine, 3-hydroxyethyl rhodanine, 3-morpholine ethyl rhodanine, or the like), 2-sulfo--2,4- oxazolidinedione is examined (promptly, 2-sulfo--2,4-3H, 4H)- azoles diketone nuclear, for example, 2-ethyl-2-sulfo--2,4- oxazolidinedione, or the like), thianaphthenone (is for example examined, 3 (2H)-thianaphthenones, 3 (2H)-thianaphthenones-1, the 1-dioxide, or the like), 2-sulfo--2,5-thiazolidinedione nuclear (for example, 3-ethyl-2-sulfo--2,5-thiazolidinedione, or the like), 2,4-thiazolidinedione nuclear (for example, 2, the 4-thiazolidinedione, 3-ethyl-4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, or the like), thiazolidone nuclear (for example, 4-thiazolidone, 3-ethyl-4-thiazolidone, 2-ethyl sulfydryl-4-thiazolidone, 2-aminomethyl phenyl amino-4-thiazolidone, or the like), 2-imino acid-2- azoles quinoline-4-ketone is examined (promptly, false hydantoins nuclear), 2,4-imidazolinedione nuclear (that is hydantoins nuclear,, for example 2, the 4-imidazolinedione, 3-ethyl-2,4-imidazolinedione, 1,3-diethyl-2, the 4-imidazolinedione, or the like), 2-sulfo--2,4-imidazolinedione nuclear (be thio-hydantoin nuclear, 2-sulfo--2 for example, 4-imidazolinedione, 3-ethyl-2-sulfo--2, the 4-imidazolinedione, 1,3-diethyl-2-sulfo--2, the 4-imidazolinedione, or the like), imidazoline-5-ketone nuclear (for example, 2-propyl group sulfydryl-2-imidazoline-5-ketone, or the like), furans-5-ketone nuclear and thioindoxyl nuclear (for example, 5-methyl thioindoxyl, or the like), and these acid are endorsed further to have substituting group.

In above-mentioned carbazole sensitizing dye by formula (II-1) and local structural formula (1) expression, because have by following formula (II-2), (II-3), (II-4), (II-5) or (II-6) dyestuff of expression structure has high photosensitivity and the photosensitive composition with good shelf-stability can be provided, so especially preferably use such dyestuff in the present invention.

At formula II-2)-(II-6) in, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Respectively with (II-1) and local structural formula (1) in defined identical; X ¹, X ², X ³And X ⁴Each represents the O atom, S atom, or NR ²⁰Represent the O atom with Y, S atom, or NR ²¹And R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Each represents hydrogen atom, or the monovalent nonmetallic atomic radical, they each other bonding have substituent fat and ring fragrance separately to form.

Below detailed description formula (II-2)-(II-6).

In formula (II-2)-(II-6), R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Respectively with (II-1) and local structural formula (1) in defined identical.R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Each represents hydrogen atom, or monovalent nonmetallic atomic radical, and each preferably represents replacement or unsubstituted alkyl, that replace or unsubstituted alkenyl, that replace or unsubstituted aryl, heteroaryl replacement or unsubstituted, alkoxy replacement or unsubstituted, that replace or unsubstituted alkyl thio group, hydroxyl or halogen atom.R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸And R ¹⁹Bonding has substituent fat and ring fragrance separately to form each other.As R ¹¹, R ¹², R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ¹⁹, R ²⁰And R ²¹Preferred example, what can exemplify is and R at formula (II-1) ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹And R ¹⁰Described in identical instances.

In formula (II-2)-(II-6), X ¹, X ², X ³And X ⁴Each represents the O atom, S atom, or NR ²⁰Y represents the O atom, S atom, or NR ²¹

By above-mentioned acid core with active methylene group and replacement or not the condensation reaction of substituted carbazole carbonyl acetaldehyde (carboaldehyde) can obtain sensitizing dye by formula (II-2)-(II-6) representative, and can be with reference to synthetic these dyestuffs of JP-B-59-28329.

Preferably as follows by the object lesson of (D1)-(D3) compound of formula (II-1) expression, but the invention is not restricted to these compounds.In addition, the isomeride that connects acid core and carbazole skeleton with two keys is indefinite, and the present invention is not subjected to the restriction of each isomeride.

With regard to the carbazole sensitizing dye that is contained in the photosensitive composition of the present invention, wherein photosensitive composition is used as planographic printing plate precursor, in order to improve the performance of photosensitive layer, can carry out various chemical modifications to sensitizing dye.For example; by means of covalent bonding, the method for ionic bonding and hydrogen bonding, but and the bonding by sensitizing dye and addition polymerization compound structure (for example acryloyl group and methacrylyl); can improve the film strength and preventing of to expose from the unnecessary dye precipitated of exposing in the caudacoria.In addition, use a spot of light trigger, the part that produces free radical by the described titanocene compound of sensitizing dye and back and other (for example, reduction decomposition part is as alkyl halide,, superoxide, diimidazole etc. and oxicracking part is as borate, amine, the trimethyl silyl methyl, ethyloic, carbonyl, imines, or the like) bonding, can improve the photonasty of photosensitive composition significantly.In order to improve the planographic printing plate precursor (a kind of preferred using method of the present invention) that uses photosensitive composition of the present invention flexibility (adaptability) of operation for (alkalescence) aqueous systems developing solution, introduce hydrophilic segment (acid free radical or polar group such as carboxyl and its ester, sulfonic group and its ester, oxirane, or the like) be effective.Particularly, ester type hydrophilic radical compatibility is good, and this is owing to its relative hydrophobic structure in the photosensitive layer of planographic printing plate precursor, and makes water wettability improve by the generation of the hydrolysis in developer solution acid free radical.In addition, in order to improve compatibility and the crystal settling that prevents in the photosensitive layer of planographic printing plate precursor, can at random introduce various substituting groups.For example, in the photosensitive system of certain kind, aryl and allylic unsaturated link are extremely effective for improving compatibility sometimes, in addition, with introducing the branched alkyl structure, or the like method, by between the π-plane of the π-plane of dyestuff and other dyestuff, introducing steric hindrance, can suppress crystal settling significantly.In addition, by the introducing phosphate, epoxy radicals, trialkoxysilyl, or the like, can improve the cohesive between metal and metal oxide and the dead matter.In addition, if necessary, can also use the polymerization of sensitizing dye.

The concrete use of sensitizing dye for example according to the last design of photochromics performance, can at random be set the structure of compound used therefor, is to use independent dyestuff also to be to use the potpourri of two or more dyestuffs or the consumption of dyestuff.For example, can improve compatibility with the photosensitive layer of planographic printing plate precursor by the sensitizing dye that mix to use two or more.When selecting sensitizing dye, except that photonasty, the molar extinction coefficient at used light emitted wavelength place is a key factor.If use dyestuff with big molar extinction coefficient, can reduce the addition of dyestuff relatively, this is economical, also the physical property to the film of photosensitive layer is useful.Because photonasty, resolving power and the physical property of the exposed film of photosensitive layer are subjected to the influence of optical source wavelength absorbance bigger, therefore, consider from these factors, can select the addition of sensitizing dye arbitrarily.For example 0.1 or lower absorbance zone photonasty reduce.In addition, the influence owing to halation reduces resolving power.Yet this sometimes low absorbance is for improving 5 μ m or more the hardness of thick film is quite effective.When using sensitizing dye, when for example being used for printed panel, 3 or higher high absorbance zone, nearly all light is absorbed on the surface of photosensitive layer, therefore, has hindered the more curing of nexine of film, and film strength and with the bond strength deficiency of matrix.When the planographic printing plate precursor of the film thickness that sensitizing dye is used to have relative thin, make the absorbance of photosensitive layer become 0.1-1.5, preferably the addition of the sensitizing dye of setting from 0.25-1 is preferred.When sensitizing dye was used for planographic printing plate precursor, in the photosensitive layer composition of per 100 weight portions, its amount was generally the 0.05-30 weight portion, is preferably the 0.1-20 weight portion, more preferably the 0.2-10 weight portion.

(A2) titanocene compound

To being used for photosensitive composition of the present invention, have no particular limits as the titanocene compound of light trigger, any compound just can use this compound as long as under itself and above-mentioned sensitizing dye coexistence situation, can produce living radical during with rayed.For example, can use arbitrarily at the various known compounds disclosed in the following patent: JP-A-59-152396, JP-A-61-151197, JP-A-63-41483, JP-A-63-41484, JP-A-2-249, JP-A-2-291, JP-A-3-27393, JP-A-3-12403, and JP-A-6-41170.

What can more specifically exemplify is dicyclopentadienyl-Ti-dichloride, the two phenyl of dicyclopentadienyl-Ti-, dicyclopentadienyl-Ti-two-2,3,4,5,6-five fluoro-1-phenyl (hereinafter referring to " T-1 " sometimes), dicyclopentadienyl-Ti-two-2,3,5,6-tetrafluoro-1-phenyl, dicyclopentadienyl-Ti-is two-2,4,6-three fluoro-1-phenyl, dicyclopentadienyl-Ti-is two-2,6-two fluoro-1-phenyl, and dicyclopentadienyl-Ti-two-2,4-two fluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,3,4,5,6-five fluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,3,5,6-tetrafluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,4-two fluoro-1-phenyl and two (cyclopentadienyl group)-two (2,6-two fluoro-3-(1-H-1-pyrrole radicals) phenyl titaniums (hereinafter referring to " T-2 " sometimes).

When being used as the photosensitive layer of planographic printing plate precursor, be similar to above-mentioned sensitizing dye, in order to improve the characteristic of photosensitive composition, can carry out various chemical modifications to the relevant titanocene compound that is contained in the photosensitive composition of the present invention.For example, operable method has: but the method for the unsaturated compound of usefulness titanocene compound and sensitizing dye addition polymerization and other generation free radical part bonding; Introduce the method for hydrophilic segment; In order to improve compatibility and to prevent crystal settling, introduce substituent method; In order to improve cohesive, introduce substituent method; The method of polymerization.

About the usage of titanocene compound, but be similar to addition polymerization compound recited above and sensitizing dye,, can also at random use titanocene compound according to the performance design of photochromics.For example, can improve compatibility with the photosensitive layer of planographic printing plate precursor by the compound that mix to use two or more.Usually, consider the large usage quantity of preferred titanocene compound from the photonasty aspect.In the photosensitive layer composition of per 100 weight portions, its amount is the 0.5-80 weight portion, and being preferably the 1-50 weight portion is enough to obtain satisfied photonasty.On the other hand, fundamental purpose of the present invention is to consider under amber light and white lamp to use, because therefore light, consider from the mist aspect that in contiguous 500nm irradiation the consumption of preferred titanocene compound is less.Even the consumption of titanocene compound is reduced to 6 weight portions or still less, further reduce to 1.9 weight portions or still less and further reduce to 1.4 weight portions or still less, can obtain enough photonasty by mixing to use with above-mentioned sensitizing dye.

B. with free radical or acid reaction to change and to keep the compound of physics or chemical characteristic

Except above-mentioned light trigger, photosensitive composition of the present invention contain with free radical or acid reaction to change and to keep the compound of physics or chemical characteristic.

But this compounds is the special addition polymerization compound with at least one ethylenical unsaturated double bonds, and it is selected from has at least one, preferably the compound of two or more terminal unsaturation ethylene linkages.This compounds is industrial known, and has no particular limits being used for these compounds of the present invention.For example, this compounds can be the chemical species of monomer, prepolymer (being dipolymer, trimer), oligomer or its potpourri and multipolymer.The monomer whose that can exemplify and the example of multipolymer be the unsaturated carboxylic acid class (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid, or the like) and its ester class and amide-type, and preferably use the ester class of unsaturated carboxylic acid and aliph polyols compound, the amide-type of unsaturated carboxylic acid and fat polyamine compound.

In addition, also preferred the use has the unsaturated carboxylate type of nucleophilic displacement of fluorine base and the addition reaction product of amide-type and simple function group or many functional group isocyanates's class and epoxies, the example of described nucleophilic displacement of fluorine base is a carboxyl, the dehydration condensation product of amino and sulfydryl and these compounds and simple function group or polyfunctional carboxylic acids.The also preferred addition reaction product that uses with the electric substituent unsaturated carboxylate type of parent and amide-type and simple function group or polyfunctional group alcohols, amine and mercaptan, the electric substituent example of described parent is isocyanato-, epoxy radicals, with have the substitution reaction product that can discharge substituent unsaturated carboxylate type and amide-type and simple function group or polyfunctional group alcohols, amine and mercaptan, can discharge substituting group such as halogen and tosyloxy.As other example, can also replace above-mentioned unsaturated carboxylic acid with unsaturated phosphoric acid, styrene, vinyl ether or the like.

The object lesson of the ester monomer of aliph polyols compound and unsaturated carboxylic acid comprises esters of acrylic acid, ethylene glycol diacrylate, diacrylate triglycol ester, diacrylate 1,3-butanediol ester, diacrylate 1,4-butanediol ester, diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethyol propane triacrylate (trimethylolpropane triacrylate), trimethylolpropane tris (acryloyl-oxy propyl group) ether, three acrylic acid trimethylolethane esters, hexanediol diacrylate, diacrylate 1,4-cyclohexanediol ester, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, diacrylate dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, three (acrylyl oxy-ethyl) isocyanates, the polyester acrylic ester oligomer, or the like.

Example as methacrylate comprises dimethacrylate 1, the 4-butanediol ester, the dimethacrylate triglycol ester, the dimethacrylate DOPCP, trihydroxy methyl propane trimethyl acrylate, trimethyl acrylic acid trimethylolethane ester, Ethylene glycol dimethacrylate, dimethacrylate 1,3-butanediol ester, dimethacrylate hexanediol ester, dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, the dimethacrylate dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, trimethyl acrylic acid sorbitol ester, tetramethyl acrylic acid sorbitol ester, two [right-(3-methacryloxypropyl-2-hydroxyl-propoxyl group) phenyl] dimethylmethane, two [right-(3-methacryloxypropyl ethoxy) phenyl] dimethylmethane, or the like.

Example as the itaconate class comprises two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acid 1,3 butylene glycol esters, two itaconic acids 1,4-butanediol ester, two itaconic acids 1,4-butanediol ester, two itaconic acid pentaerythritol esters, four itaconic acid sorbitol esters, or the like.

Example as the crotonates class comprises two crotonic acid glycol esters, two crotonic acids 1, and the 4-butanediol ester, two crotonic acid pentaerythritol esters, four crotonic acid sorbitol esters, or the like.

Example as iso-crotonic acid ester class comprises two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters, and four iso-crotonic acid sorbitol esters, or the like.

Example as the maleate class comprises two maleic acid glycol esters,, two maleic acid triglycol esters, two maleic acid pentaerythritol esters, four maleic acid sorbitol esters, or the like.

Example as other ester, for example can also preferably use in the present invention at JP-B-46-27926, disclosed aliphatic alcohol ester class among JP-B-51-47334 and the JP-A-57-196231, at JP-A-59-5240, disclosed among JP-A-59-5241 and the JP-A-2-226149 have those esters of fragrant skeleton and disclosed those esters that contain amino in JP-A-1-165613.

In addition, can also use the potpourri of above-mentioned each ester monomer.

In addition, the object lesson of the amide monomer of fat polyamine compound and unsaturated carboxylic acid comprises methylene two-acrylamide, methylene two-Methacrylamide, 1,6-hexylidene two-acrylamide, 1,6-hexylidene two-Methacrylamide, diethylene triamine three-acrylamide, xylylene two-acrylamide, xylylene two-Methacrylamide, or the like.

As other preferred amide monomer, what can exemplify is disclosed those amide monomers with cyclohexylene structure in JP-B-54-21726.

In addition, also preferably use in the present invention by the resulting carbamate groups addition polymerization of the addition reaction of isocyanates and hydroxyl compound, as concrete example, can exemplify as the disclosed vinyl carbamate compound that in a molecule, has two or more polymerizable vinyl in JP-B-48-41708, it is to obtain by having by the addition reaction that has the polyisocyanate compound of two or more isocyanate groups in the vinyl monomer with hydroxyl of following formula (V) representative and the molecule.

CH ₂＝C(R)COOCH ₂CH(R’)OH

Wherein R and R ' respectively represent H or CH ₃

In addition, also preferably use in the present invention at JP-A-51-37193, disclosed urethane acrylate class among JP-B-2-32293 and the JP-B-2-16765, with at JP-B-58-49860, JP-B-56-17654, disclosed carbamate compounds among JP-B-62-39417 and the JP-B-62-39418 with oxirane skeleton.

In addition, as at JP-A-63-277653, disclosed among JP-A-63-260909 and the JP-A-1-105238, by use in molecule, have amino structure and thioether (sulfide) but the addition polymerization compound of structure can obtain the hypervelocity photopolymerisable compositions.

As other example, what also can exemplify is multi-functional acrylate's class and methyl acrylic ester, as at JP-A-48-64183, disclosed among JP-B-49-43191 and the JP-B-52-30490, by epoxy resin and (methyl) acrylic acid reaction resulting polyester esters of acrylic acid and epoxy acrylate class.Can also exemplify at JP-B-46-43946, among JP-B-1-40337 and the JP-B-1-40336 disclosed special unsaturated compound and in JP-A-2-25493 disclosed vinyl sulfonic acid compound.In addition, preferably use the disclosed structure that contains perfluoro alkyl group in JP-A-61-22048 among the present invention.Have again, can also use Kyokai, Vol.20, No.7, photocurable monomer and the oligomer introduced among the pp.300-308 (1984) at Bulletin of Nihon Setchaku.

But the detailed directions of addition polymerization compound, for example can optionally determine to use according to the characteristic of the photochromics of final design be what structure compound, be to use or to mix use, the maybe amount that will use separately.For example, have in mind from following aspect and come alternative condition.For photosensitive speed, preferred per molecule contains the structure of a plurality of unsaturated groups, and preferred in many cases difunctional group or polyfunctional group group.When but the addition polymerization compound is used to the photosensitive layer of planographic printing plate precursor, in order to improve the film strength that the image part is promptly solidified, preferred trifunctional or polyfunctional group group, in addition, in potpourri, use different functionality and different polymerizable groups (as, acrylate, methacrylate, distyryl compound, vinyl ether compound) so that both the sense of control photosensitiveness had also been controlled intensity.Though have the compound of macromolecule or have the photosensitive speed and the film strength of compound of high hydrophobicity good,, aspect developing powder developer solution and precipitation, consider preferred these compounds sometimes.Photosensitive layer and dispersed aspect, for the compatibility of other composition (binder polymer as hereinafter described, the described colorant in above-mentioned light trigger and back, or the like), but the selection of addition polymerization compound and usage are key factors.For example, can improve compatibility by the potpourri that uses low-purity compound or two or more compounds sometimes.In addition, in order to improve carrier and outer field cohesive, also can select to have the compound of special construction.But mixing ratio about addition polymerization compound in photosensitive layer, consumption is the photonasty height greatly then, but sometimes consumption too conference cause the shortcoming that is separated because the viscosity of photosensitive layer causes the problem (as the transfer of each composition of photochromics and bondingly cause producing failure) in production and processing and causes precipitation from developer solution.Consider that from these aspects in many cases, based on the composition of whole compositions, but the mixing ratio of preferred addition polymerization compound is the 5-80 weight portion, more preferably the 25-75 weight portion.But but can use the addition polymerization compound separately or mix the addition polymerization compound that uses two or more.In addition, consider oxygen, resolving power, sprayability, index of refraction change and surface adhesion to the interference of the degree of polymerization, but can at random select suitable structure, mixing ratio and the addition of addition polymerization compound.In addition, can determine the coating method of layer structure and priming paint and finish paint according to environment.

(C) binder polymer

When photosensitive composition of the present invention being used for the photosensitive layer of plate printing plate (optimization test scheme of the present invention), but preferred photosensitive compositions further contains the binder polymer except above-mentioned light trigger and addition polymerization compound.As binder polymer, preferably use the line style organic high molecular polymer.Can use any " line style organic high molecular polymer ".Preferred select can water development or the water soluble that develops of alkalescent water or soluble line style organic high molecular polymer of alkalescent water or swelling line style organic high molecular polymer.Selected and the line style organic high molecular polymer that uses is not only as the film forming agent of composition, also as water development agent, alkalescent water developer or organic solvent developer.For example, when using the line style organic high molecular polymer of water soluble, make water development become possibility.As the line style organic high molecular polymer, what can exemplify has an addition polymer that has hydroxy-acid group at side chain, for example at JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, disclosed polymkeric substance among JP-A-59-53836 and the JP-A-59-71048, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, the crotonic acid multipolymer, the maleic acid of maleic acid and partial esterification.Can also use the acid cellulose derivant that has hydroxy-acid group at side chain.Except above-mentioned, can also use by in addition polymer, adding the resulting polymkeric substance of cyclic acid anhydride with carboxyl.

In these compounds, particularly therefore [benzyl (methyl) acrylate-(methyl) but other addition polymerization vinyl monomer of acrylic acid-as required] multipolymer and [allyl (methyl) acrylate-(methyl) but other addition polymerization vinyl monomer of acrylic acid-as required] multipolymer balance (in the balance) film strength, photonasty and development property well help with in the present invention.

Because at JP-B-7-12004, JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, the intensity of the binder polymer of disclosed carbamate groups with acid free radical is very good among JP-A-1-271741 and the Japanese patent application No.10-116232, therefore helps pressrun and low exposure adaptability.

Disclosed bonding agent with acylamino-had both had good development property in JP-A-11-171907, and good film strength is arranged again.

Except recited above, be useful as the polyvinyl pyrrolidone and the oxirane of the line style organic high molecular polymer of water soluble.In order to improve the curing film strength, can also use pure soluble nylon, 2, the polyethers of two (4-hydroxyl-phenyl) propane of 2-and epichlorokydrin.Though in whole composition, can mix these line style organic high molecular polymers, when combined amount surpasses 90% weight, image intensity etc. be had adverse influence with any amount.Preferred amount is 3-85% weight.Preferably having the compound of photopolymerization ethylenical unsaturated double bonds and the weight ratio of line style organic high molecular polymer is 1/9-7/3.In optimization experiment scheme of the present invention, used binder polymer is water-insoluble soluble with alkali basically, wherein can or be limited in few consumption for the organic solvent (environment is undesirable) as developing solution.In this class is used,, suitably select the acid number (acid content of every gram polymkeric substance of representing with chemical equivalent) and the molecular weight of binder polymer from image intensity and the consideration of development property.Acid number is preferably 0.4-3.0meq/g, and more preferably 0.6-2.0meq/g and molecular weight are preferably 3,000-500,000, more preferably 10,000-300,000.

Photosensitive composition in another experimental program of the present invention comprises (A) Photoepolymerizationinitiater initiater, (B) with free radical or acid at least a reaction to change or to keep the compound as basis of at least a physics or chemical characteristic, if desired, (C) binder polymer.To specify every kind of composition below.

(A) Photoepolymerizationinitiater initiater

As the Photoepolymerizationinitiater initiater (light trigger) of photosensitive composition basis of the present invention comprise (I) have special construction sensitizing dye and (II) titanocene compound.Can think that in light trigger of the present invention, the main absorbing light of sensitizing dye is to promote producing initiation free radical (this method refers to " dye sensitization " hereinafter) from the titanocene compound of coexistence.One of reason that sensitizing dye of the present invention is superior is that its absorbing wavelength is in the regional extent of 350nm to 450nm.In addition, though a large amount of titanocene compound described later has weak absorption and also has photonasty in same zone in the wavelength region may of ultraviolet to contiguous 500nm in essence, but because the present invention has the photonasty that the sensitizing dye of special construction has greatly improved titanocene compound, on the other hand, by control titanocene compound consumption to relatively small amount, in short wavelength range, can be enough to improve photonasty, simultaneously, on the other hand, can pass through titanocene compound itself, make in the photonasty in 500nm zone lowly, therefore, can improve the safety light adaptability of photosensitive composition.

The inventor has been found that when sensitizing dye satisfies following architectural characteristic, can obtain above-mentioned characteristic, thereby has finished the present invention.Just, when having, the acid core of dyestuff can obtain very high photonasty and good absorbability when azoles 5-unit ring (having one or more carbonyls or thiocarbonyl) structure and alkalescence nuclear have aromatic rings or heterocycle.At T.H.James, The Theory of The Photographic Process, FourthEdition, Chapter 8, described the definition of " acid core " and " alkalescence nuclear " among the Macmillan Publishing Co..Sensitizing dye by merocyanine dyes representative has 1 usually endways) alkalescence (electron donor) and 2) acid (electron accepter) heterocycle, and 1) alkalescence (electron donor) heterocycle is called alkalescence nuclear and 2) acidity (electron accepter) heterocycle is called acid core.At T.H.James, The Theory of The Photographic Process, FourthEdition, Chapter 8, describe the example of alkalescence nuclear and acid core among the Macmillan Publishing Co. in detail.

Though it is unclear the present invention to be had the dye sensitization mechanism of sensitizing dye had good especially dye sensitization of special construction, can infer as follows.Just, sensitizing dye of the present invention has high radiation (fluorescence or phosphorescence) spectrum, impels the sensitizing dye of the present invention with above-mentioned partial structurtes formula long relatively in the life-span of excited state, the result, and dyestuff works and makes itself and activating agent effecting reaction.

(A1) sensitizing dye

The used sensitizing dye of the present invention is represented by formula (III-1):

Wherein the A representative can have substituent heterocycle or aromatic rings; The X represention oxygen atom, sulphur atom or-N (R ₃)-; R ₁, R ₂And R ₃Each represents the non-metal atom group of hydrogen atom or unit price, A and R ₁, and R ₂And R ₃Respectively mutually bonding to form fat or aromatic group.

To describe the represented compound of formula (III-1) below in detail.

R ₁, R ₂And R ₃Each represents the non-metal atom group of hydrogen atom or unit price, and preferred representative respectively replaces or unsubstituted alkyl, that replace or unsubstituted alkenyl, that replace or unsubstituted aryl, that replace or unsubstituted aromatic heterocycle residue, that replace or unsubstituted alkoxy, replacement or unsubstituted alkyl thio group, hydroxyl or halogen atom.

Specify R below ₁, R ₂And R ₃Preferred example.The preferred example of alkyl comprises the alkyl of straight chain, side chain or ring with 1-20 carbon atom, and concrete example comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, the second month in a season-butyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, the 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl and 2-norborny.In these groups, more preferably have the straight chained alkyl of 1-12 carbon atom, have the branched alkyl of 3-12 carbon atom and have the naphthenic base of 5-10 carbon atom.

The substituent example of substituted alkyl is the monovalent nonmetallic atomic radical except hydrogen atom; its preferred example comprises 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, N-dialkyl amido, 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 sulphur oxygen base (alkylsulfoxy); aryl sulphur oxygen base, acyl group thio group, acyl amino; N-alkyl acyl amino; N-aryl-acyl amino, 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, 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; formoxyl; acyl group, carboxyl, alkoxy carbonyl; aryloxycarbonyl; carbamyl, 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; the alkyl sulfinyl, aryl sulfinyl, alkyl sulphonyl; aryl sulfonyl, thio group (SO ₃H) and its conjugation base (hereinafter referring to the sulfonation base), alcoxyl sulfonyl, fragrant oxygen sulfonyl, sulfinyl (sulfinamoyl); the 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; the N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N; N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono (PO ₃H ₂) and its conjugation base (hereinafter referring to the phosphine base), dialkyl phosphine acyl group (PO ₃(alkyl) ₂), diaryl phosphono (PO ₃(aryl) ₂), alkylaryl phosphono (PO ₃(alkyl) (aryl)), monoalkyl phosphono (PO ₃H (alkyl)) and its conjugation base (hereinafter referring to the alkylphosphines base), single aryl phosphine acyl group (PO ₃H (aryl)) and its conjugation base (hereinafter referring to the aryl phosphine base), phosphonato (OPO ₃(H) ₂) and its conjugation base (hereinafter referring to alkyl phosphine oxygen base), dialkyl phosphine acyloxy (OPO ₃(alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), alkylaryl phosphonato (OPO ₃(alkyl) (aryl)), monoalkyl phosphonato (OPO ₃H (alkyl)) and its conjugation base (hereinafter referring to alkyl phosphine oxygen base), single aryl phosphine acyloxy (OPO ₃H (aryl)) and its conjugation base (hereinafter referring to aryl phosphine oxygen base), cyano group, nitro, aryl, heteroaryl, alkenyl, alkynyl.

As the object lesson of alkyl in these substituting groups, what can exemplify is above-mentioned alkyl.As the object lesson of aryl, what can exemplify is phenyl, diphenyl, naphthyl; tolyl, xylyl, 3,5-dimethylbenzene methyl; cumenyl, chlorphenyl, bromophenyl, chloromethyl phenyl; hydroxyphenyl, anisyl, ethoxyphenyl; phenoxy phenyl, acetyl oxygen phenyl, benzoyl oxygen phenyl; the methyl thio-phenyl, phenyl thio-phenyl, methylamino phenyl; dimethylaminophenyl, acetyl-amino phenyl, carboxyl phenyl; the methoxycarbonyl group phenyl, carbethoxy phenyl, carbobenzoxy phenyl; N-phenyl amino formoxyl phenyl, cyano-phenyl, thio-phenyl; the sulfonation phenyl, phosphono phenyl, phosphine phenyl.

As the object lesson of heteroaryl, can use and contain at least one nitrogen-atoms, the aromatic rings of the monocycle of oxygen atom and sulphur atom or many rings, the preferred especially heteroaryl that uses comprises thiophene, thianthrene, furans, pyrans, isobenzofuran, chromene, xanthene, fen piperazine, pyrroles, pyrazoles, isothiazole ， isoxazole, para-diazines, pyrimidine, pyridazine, indolizine, different indolizine, indoles, indazole, purine, quinolizine, isoquinoline, phthalazines, 1,5-benzodiazine, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthrene, acridine, perimidine, phenanthroline, phthalazines, phenarsazine, fen piperazine, furazan and fen piperazine.These groups can be further by the benzo condensation or have substituting group.

As the object lesson of alkenyl, what can exemplify is vinyl, the 1-propenyl, and the 1-butenyl group, cinnamyl and 2-chloro-1-vinyl, as the object lesson of alkynyl, what can exemplify is ethinyl, 1-propinyl, 1-butynyl, trimethyl silyl ethinyl.As acetyl group (G ¹CO-) G in ¹Object lesson can be hydrogen atom and abovementioned alkyl and aryl.In these substituting groups, preferred example comprises halogen atom (F ,-Br ,-Cl;-I), alkoxy, aryloxy group, alkyl thio-base; the aryl thio group, N-alkyl amino, N, N-dialkyl amido; acyloxy, N-alkyl carbamoyloxy base, N-arylamino formyloxy, acyl amino; formoxyl, acetyl group, carboxyl, alkoxy carbonyl; aryloxycarbonyl, carbamyl, N-alkyl-carbamoyl, N; N-dialkyl amido formoxyl, N-aryl-amino-carbonyl, N-alkyl-N-aryl-amino-carbonyl, thio group; the sulfonation base, sulfamoyl, N-alkylsulfamoyl group; N, N-dialkyl sulfamine, N-ammonia aryl sulfonyl; N, N-ammonia diaryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl; phosphono, phosphine base, dialkyl phosphine acyl group; the diaryl phosphono, monoalkyl phosphono, alkylphosphines base; single aryl phosphine acyl group, aryl phosphine base, phosphonato; the phosphine oxygen base, aryl, alkenyl.

On the other hand, as the alkylidene in the substituted alkyl, obtain alkylidene by on the alkyl of the above-mentioned 1-20 of a having carbon atom, removing any one hydrogen atom to form residue of divalent, preferably have 1-12 carbon atom straight-chain alkyl-sub-, have 3-12 carbon atom branched alkylidene, have the cyclic alkylidene of 5-10 carbon atom.

By resulting by R in conjunction with above-mentioned substituting group and alkylidene ₁, R ₂And R ₃The object lesson of the preferred substituted alkyl of representative comprises chloromethyl, bromomethyl, 2-chloroethyl; trifluoromethyl, methoxyl methyl, methoxyethoxy ethyl; allyl oxygen methyl, Phenoxymethyl, methylthiomethyl; the tolyl sulphomethyl, ethylamino ethyl, diethylamino propyl group; the morpholine propyl group, acetyl-o-methyl, benzoyl oxygen methyl; N-cyclohexyl carboxyamide oxygen ethyl, N-phenyl amino methanoyl ethyl, acetyl-amino ethyl; with N-methyl benzoyl aminopropyl, 2-oxoethyl, 2-oxopropyl; the carboxyl propyl group, methoxycarbonyl group ethyl, allyloxycarbonyl butyl; chlorobenzene oxygen carbonyl methyl, carbamyl ylmethyl, N-methylamino formoxyl ethyl; N, N-dipropyl carbamyl ylmethyl, N-(anisyl) carbamyl ethyl; N-methyl-N-(thio-phenyl) carbamyl ylmethyl; the sulfo-butyl, sulfonation butyl, sulfonamide butyl; ethyl sulfonamide methyl; N, N-dipropyl sulfonamide propyl group, N-aminomethyl phenyl amino-sulfonyl; N-methyl-N-(phosphono phenyl) sulfonamide octyl group; phosphono (phosphono) butyl; phosphineization (phosphonato) hexyl, diethyl phosphono butyl, diphenyl phosphono propyl group; methyl phosphono butyl; the methylphosphine butyl, tolyl phosphono hexyl, tolylphosphine hexyl; phosphono oxygen propyl group; the phosphine oxygen butyl, benzyl, phenethyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenethyl, to methyl-benzyl, cinnamyl; allyl; 1-propenyl methyl, 2-butenyl group, 2-methacrylic; 2-metering system ylmethyl; 2-propynyl, 2-butynyl, 3-butynyl.

By R ₁, R ₂And R ₃The preferred example of aryl of expression is the condensed ring that formed by 1-3 phenyl ring and by phenyl ring and the formed condensed ring of the first unsaturated ring of 5-, and concrete example comprises phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, and fluorenyl.Wherein, more preferably phenyl and naphthyl.

By R ₁, R ₂And R ₃The preferred object lesson of the substituted aryl of expression is those groups that have the monovalent nonmetallic atom except hydrogen atom on above-mentioned one-tenth ring carbon atom as substituent aryl.The substituent preferred example that can exemplify is above-mentioned alkyl, substituted alkyl and above-mentioned those substituent examples in substituted alkyl.The preferred object lesson of these substituted aryls comprises diphenyl, tolyl, xylyl; 3,5-dimethylbenzene methyl, cumenyl; chlorphenyl, bromophenyl, fluorophenyl; chloromethyl phenyl, trifluoromethyl, hydroxyphenyl; anisyl, methoxy (ethoxy) phenyl, allyl oxygen phenyl; phenoxy phenyl, methyl thio-phenyl, tolyl thio-phenyl; the ethylamino phenyl, diethylamino phenyl, morpholinyl phenyl; acetyl oxygen phenyl, benzoyl oxygen phenyl, N-cyclohexyl carboxyamide oxygen phenyl; N-phenyl amino methanoyl phenyl, acetyl-amino phenyl, N-methyl benzoyl aminophenyl; carboxyl phenyl; the methoxycarbonyl group phenyl, allyloxycarbonyl phenyl, chlorobenzene oxygen carbonyl phenyl; the carbamyl phenyl; N-methylamino formoxyl phenyl, N, N-dipropyl carbamyl phenyl; N-(anisyl) carbamyl phenyl; N-methyl-N-(thio-phenyl) carbamyl phenyl, thio-phenyl, sulfonation phenyl; sulfamoyl phenyl; N-ethyl sulfamoyl phenyl, N, N-dipropyl sulfamoyl phenyl; N-tolyl sulfamoyl phenyl; N-methyl-N-(phosphono phenyl) sulfamoyl phenyl, phosphono (phosphono) phenyl, phosphineization (phosphonato) phenyl; diethyl phosphono phenyl; diphenyl phosphono phenyl, methyl phosphono phenyl, methylphosphine phenyl; tolyl phosphono phenyl; the tolylphosphine phenyl, allyl, 1-propenyl methyl; the 2-butenyl group; 2-methacrylic phenyl, 2-methylpropenyl phenyl, 2-propynyl phenyl; 2-butynyl phenyl, 3-butynyl phenyl.

Hereinafter with the A in the formula (III-1).The A representative has substituent heterocycle or aromatic rings.As object lesson with substituent heterocycle or aromatic rings, group that can exemplify and R ₁, R ₂And R ₃Described in identical.

By above-mentioned acid core with active methylene group and replacement or not the condensation reaction of substituted aroma ring or heterocycle can obtain sensitizing dye by formula (III-1) representative, and can be with reference to synthetic these dyestuffs of JP-B-59-28329.

Preferably as follows by the object lesson of (D1)-(D28) compound of formula (III-1) expression, but the invention is not restricted to these compounds.In addition, the isomeride that connects acid core and alkalescence nuclear with two keys is indefinite, and the present invention is not subjected to the restriction of each isomeride.

As under the situation of planographic printing plate precursor,, can carry out various modifications at sensitizing dye to relevant sensitizing dye of the present invention in order to improve the performance of photosensitive layer.For example; by means of covalent bonding; the method of ionic bonding and hydrogen bonding, but the film strength of will exposing can be improved by the bonding of sensitizing dye and addition polymerization compound structure (for example acryloyl group and methacrylyl), and can prevent the unnecessary dye precipitated in the caudacoria that exposes.In addition, use a spot of light trigger, the part that produces free radical by the described titanocene compound of sensitizing dye and back and other (for example, reduction decomposition part is as alkyl halide,, superoxide, diimidazole etc. and oxicracking part is as borate, amine, the trimethyl silyl methyl, ethyloic, carbonyl, imines, or the like) bonding, can improve the photonasty of photosensitive composition significantly.

In order to improve the planographic printing plate precursor that uses photosensitive composition of the present invention flexibility (adaptability) of operation to (alkalescence) aqueous systems developing solution (a kind of preferred using method of the present invention), the hydrophilic segment of introducing (acid free radical or polar group such as carboxyl and its ester, sulfonic group and its ester, oxirane, or the like) flexibility (adaptability) of operation can be improved effectively.Particularly, ester type hydrophilic radical compatibility is good, and this is owing to its hydrophobic relatively structure in the photosensitive layer of planographic printing plate precursor, and makes water wettability improve by the generation of the hydrolysis in developer solution acid free radical.In addition, in order to improve compatibility and the crystal settling that prevents at photosensitive layer, can at random introduce various substituting groups.For example, in the photosensitive system of certain kind, aryl and allylic unsaturated link are extremely effective for improving compatibility sometimes, in addition, with introducing the branched alkyl structure, or the like method, by between the π-plane of the π-plane of dyestuff and other dyestuff, introducing steric hindrance, can suppress crystal settling significantly.In addition, by the introducing phosphate, epoxy radicals and trialkoxysilyl, or the like, can improve the cohesive between metal and metal oxide and the dead matter.In addition, if necessary, can also use the polymerization of sensitizing dye.

The detailed directions of sensitizing dye, for example can optionally determine to use according to the characteristic of the photochromics of final design be what structure dyestuff, be to use or to mix dyestuff, the maybe amount that will use used separately.For example, can improve the compatibility of itself and photosensitive composition by the sensitizing dye that mix to use two or more.When selecting sensitizing dye, except that photonasty, the molar extinction coefficient at used light emitted wavelength place is a key factor.When being used for the offset printing precursor, if use dyestuff, can reduce the addition of dyestuff relatively with big molar extinction coefficient, this is economical, also the physical property to the film of photosensitive layer is useful.Because the influence that photonasty, resolving power and the physical property of photosensitive layer exposed film are absorbed by optical source wavelength is bigger, therefore, consider from these factors, can select the addition of sensitizing dye arbitrarily.For example 0.1 or lower absorbance zone photonasty reduce.In addition, the influence owing to halation reduces resolving power.

Yet this sometimes low absorbance is for improving 5 μ m or more the hardness of thick film is quite effective.When using sensitizing dye in printed panel, 3 or higher high absorbance zone, nearly all light is absorbed on the surface of photosensitive layer, therefore, has hindered the more curing of nexine of film, and film strength and with the bond strength deficiency of matrix.When the plate printing plate of the film thickness that sensitizing dye is used to have relative thin, make the absorbance of photosensitive layer become 0.1-1.5, preferred 0.25-1 and the addition of the sensitizing dye set is preferred.When sensitizing dye was used for plate printing plate, in the photosensitive layer composition of per 100 weight portions, its amount was generally the 0.05-30 weight portion, is preferably the 0.1-20 weight portion, more preferably the 0.2-10 weight portion.

(A2) titanocene compound

Have no particular limits as the titanocene compound of light trigger being used for the present invention, any compound is as long as when producing living radical during with rayed under itself and the above-mentioned sensitizing dye coexistence situation, just can use this compound.For example, can use arbitrarily at the various known compounds disclosed in the following patent: JP-A-59-152396, JP-A-61-151197, JP-A-63-41483, JP-A-63-41484, JP-A-2-249, JP-A-2-291, JP-A-3-27393, JP-A-3-12403, and JP-A-6-41170.

What can more specifically exemplify is dicyclopentadienyl-Ti-dichloride, the two phenyl of dicyclopentadienyl-Ti-, dicyclopentadienyl-Ti-two-2,3,4,5,6-five fluoro-1-phenyl (hereinafter referring to " T-1 " sometimes), dicyclopentadienyl-Ti-two-2,3,5,6-tetrafluoro-1-phenyl, dicyclopentadienyl-Ti-is two-2,4,6-three fluoro-1-phenyl, dicyclopentadienyl-Ti-is two-2,6-two fluoro-1-phenyl, and dicyclopentadienyl-Ti-two-2,4-two fluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,3,4,5,6-five fluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,3,5,6-tetrafluoro-1-phenyl, dimethyl cyclopentadienyl group-Ti-two-2,4-two fluoro-1-phenyl and two (cyclopentadienyl group)-two (2,6-two fluoro-3-(1-H-1-pyrrole radicals) phenyl titaniums (hereinafter referring to " T-2 " sometimes).

Be similar to above-mentioned sensitizing dye, when when the planographic printing plate precursor, in order further to improve the characteristic of photosensitive layer, the various chemical modifications that can carry out titanocene compound of the present invention.For example, operable have: but the method for the unsaturated compound of titanocene compound and sensitizing dye addition polymerization and other generation free radical part bonding; Introduce the method for hydrophilic segment; In order to improve compatibility and to prevent crystal settling, introduce substituent method; In order to improve cohesive, introduce substituent method; The method of polymerization.

About the usage of titanocene compound, but be similar to addition polymerization compound recited above and sensitizing dye,, can also at random use titanocene compound according to the performance design of photochromics.For example, can improve compatibility with photosensitive composition by the compound that mix to use two or more.Usually, consider the large usage quantity of preferred titanocene compound from the photonasty aspect.In the photosensitive layer composition of per 100 weight portions, its amount is the 0.5-80 weight portion, and being preferably the 1-50 weight portion is enough to obtain satisfied photonasty.On the other hand, fundamental purpose of the present invention is to consider under amber light and white lamp to use, because light considers from the mist aspect that in contiguous 500nm irradiation the consumption of therefore preferred titanocene compound is less.Even the consumption of titanocene compound is reduced to 6 weight portions or still less, further reduce to 1.9 weight portions or still less and further reduce to 1.4 weight portions or still less, also can obtain enough photonasty by mixing with sensitizing dye of the present invention to use.

(B) with free radical or acid at least a reaction to change or to keep the compound of at least a physics or chemical characteristic

The 3rd basis of the present invention (iii) is because the effect of active seed has changed compound and its physics of maintenance or the compound of chemical characteristic of its physics or chemical characteristic, and active seed is that the light reaction by above-mentioned light trigger produces.Composition is (iii) had no particular limits, can use as long as have any compound of this class character.For example, in many cases, the above-mentioned compound as light trigger that exemplifies itself has this class character.Can be by the free radical that results from light trigger, the effect of acid and/or alkali and the composition characteristic (iii) that changes comprises the physical property such as the absorption spectrum (color) of molecule, chemical constitution and polarizability, physical property such as solubleness with material, intensity, index of refraction, flowability and cohesive.

For example, (iii) the time, can change the color of exposed portion independently, and this composition can be used as image forming material as the composition that from light trigger, produces acid or alkali when the compound that will change absorption spectrum by PH (as the PH indicator).Similarly, when the compound that will change absorption spectrum by oxidation reaction/reduction reaction or nucleophilic addition as composition (iii) the time, the oxidation or the reducing action that cause by free radical can form image.For example at J.Am.Chem.Soc., 108,128 (1986), J.Imaging Sci., 30,215 (1986) and IsraelJ.Chem., this class example described in 25 264 (1986).

In addition, but by mixing, can form light-curable resin or negativity photopolymer as composition addition polymerization compound (iii) or compound and light trigger that can polycondensation.

As composition (iii), can use be the free redical polymerization compound (for example, compound with ethylenic unsaturated bond, or the like), cationically polymerizable compound (for example, epoxy compound, vinyl ether compound, methylol compound, or the like) but and anionic polymerization compound (for example, epoxy compound, or the like), at that edits, Photopolymer Handbook by the Photopolymer Meeting, Kogyo Chosa-Kai (1989), and Kobunshi, the example of these compounds has been described in 45,786 (1996).Comprise as composition (iii) mercaptan compound and the composition of the optical free radical propellant of form of mixtures also be known.

It also is useful that the compound that decomposes as composition theobromine (iii) combines with the photosensitive acid propellant.For example, the macromolecular compound material that uses its side chain and main chain to be decomposed by acid, and can change its solubleness, water wettability and hydrophobicity by light, but this material can be by actual in photolysis photosensitive resin and positivity photopolymer widely.For example at ACS.Symp.Ser., 242,11 (1984), JP-A-60-3625, U.S.Patents5,102,771,5,206,317,5,212,047, JP-A-4-26850, JP-A-3-1921731, the object lesson of these compounds of describing among JP-A-60-10247 and the JP-A-62-40450.

But will describe addition polymerization compound composition below in detail (iii), this composition is the good composition that is used for high speed planographic printing plate precursor of the present invention.

(B-1) but the addition polymerization compound

From having at least one, but the addition polymerization compound of preferably selecting to have at least one ethylenical unsaturated double bonds in the compound of two or more terminal unsaturation ethylene linkages as composition of the present invention (iii).This compound is industrial known, and has no particular limits being used for these compounds of the present invention.For example, this compounds can be monomer, prepolymer (being dipolymer, trimer, oligomer or its potpourri) and its multipolymer.The monomer whose that can exemplify and the example of multipolymer be the unsaturated carboxylic acid class (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid, or the like) and its ester class and amide-type, and preferably use the ester class of unsaturated carboxylic acid and aliph polyols compound, the amide-type of unsaturated carboxylic acid and fat polyamine compound.In addition, also preferred the use has the unsaturated carboxylate type of nucleophilic displacement of fluorine base and the addition reaction product of amide-type and simple function group or many functional group isocyanates's class and epoxies, the example of described nucleophilic displacement of fluorine base is a carboxyl, amino and sulfydryl and the also preferred dehydration condensation product that uses these compounds and simple function group or polyfunctional carboxylic acids.

The also preferred addition reaction product that uses with the electric substituent unsaturated carboxylate type of parent and amide-type and simple function group or polyfunctional group alcohols, amine and mercaptan, the electric substituent example of described parent is isocyanate group, epoxy radicals, have the substitution reaction product that can discharge substituent unsaturated carboxylate type and amide-type and simple function group or polyfunctional group alcohols, amine and mercaptan with use, described releasable substituent example is halogen and tosyloxy.As other example, can also replace above-mentioned unsaturated carboxylic acid with unsaturated phosphoric acid, styrene, vinyl ether or the like.

The object lesson of the ester monomer of aliph polyols compound and unsaturated carboxylic acid comprises esters of acrylic acid, ethylene glycol diacrylate, diacrylate triglycol ester, diacrylate 1,3-butanediol ester, diacrylate 1,4-butanediol ester, diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, trimethyol propane triacrylate (trimethylolpropane triacrylate), trimethylolpropane tris (acryloyl-oxy propyl group) ether, three acrylic acid trimethylolethane esters, hexanediol diacrylate, diacrylate 1,4-cyclohexanediol ester, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, diacrylate dipentaerythritol ester, six acrylic acid dipentaerythritol ester, three acrylic acid sorbitol esters, tetrapropylene acid sorbitol ester, five acrylic acid sorbitol esters, six acrylic acid sorbitol esters, three (acrylyl oxy-ethyl) isocyanates, the polyester acrylic ester oligomer, or the like.

Example as methacrylate comprises dimethacrylate 1, the 4-butanediol ester, the dimethacrylate triglycol ester, the dimethacrylate DOPCP, trihydroxy methyl propane trimethyl acrylate, trimethyl acrylic acid trimethylolethane ester, Ethylene glycol dimethacrylate, dimethacrylate 1,3-butanediol ester, dimethacrylate hexanediol ester, dimethacrylate pentaerythritol ester, trimethyl acrylic acid pentaerythritol ester, pentaerythritol tetramethacrylate, the dimethacrylate dipentaerythritol ester, hexamethyl acrylic acid dipentaerythritol ester, trimethyl acrylic acid sorbitol ester, tetramethyl acrylic acid sorbitol ester, two [right-(3-methacryloxypropyl-2-hydroxyl-propoxyl group) phenyl] dimethylmethane, two [right-(3 methacryloxypropyl ethoxy) phenyl] dimethylmethane, or the like.

Example as the itaconic acid class comprises two itaconic acid glycol esters, two itaconic acid propylene glycol esters, two itaconic acid 1,3 butylene glycol esters, two itaconic acids 1,4-butanediol ester, two itaconic acids 1,4-butanediol ester, two itaconic acid pentaerythritol esters, four itaconic acid sorbitol esters, or the like.

Example as the crotonates class comprises two crotonic acid glycol esters, two crotonic acids 1, and the 4-butanediol ester, two crotonic acid pentaerythritol esters, four crotonic acid sorbitol esters, or the like.

Example as iso-crotonic acid ester class comprises two iso-crotonic acid glycol esters, two iso-crotonic acid pentaerythritol esters, and four iso-crotonic acid sorbitol esters, or the like.

Example as the maleate class comprises two maleic acid glycol esters, two maleic acid triglycol esters, and two maleic acid pentaerythritol esters, four maleic acid sorbitol esters, or the like.

Example as other ester, for example can preferably use in the present invention at JP-B-46-27926, disclosed aliphatic alcohol ester class among JP-B-51-47334 and the JP-A-57-196231, at JP-A-59-5240, disclosed among JP-A-59-5241 and the JP-A-2-226149 have those esters of fragrant skeleton and disclosed those esters that contain amino in JP-A-1-165613.

In addition, can also use the potpourri of above-mentioned ester monomer.

In addition, the object lesson of the amide monomer of fat polyamine compound and unsaturated carboxylic acid comprises methylene two-acrylamide, methylene two-Methacrylamide, 1,6-hexylidene two-acrylamide, 1,6-hexylidene two-Methacrylamide, diethylene triamine three-acrylamide, xylylene two-acrylamide, xylylene two-Methacrylamide, or the like.

As other preferred amide monomer, what can exemplify is disclosed those amide monomers with cyclohexylene structure in JP-B-54-21726.

In addition, but also preferably use in the present invention by the resulting carbamate groups addition polymerization of the addition reaction of isocyanates and hydroxyl compound, as concrete example, can exemplify as the disclosed vinyl carbamate compound that in a molecule, has two or more polymerizable vinyl in JP-B-48-41708, it is to obtain by having by the addition reaction that has the polyisocyanate compound of two or more isocyanate groups in the vinyl monomer of the hydroxyl of following formula (2) representative and the molecule.

CH ₂＝C(R)COOCH ₂CH(R’)OH (2)

Wherein R and R ' respectively represent H or CH ₃

In addition, preferably use in the present invention at JP-A-51-37193, disclosed urethane acrylate class among JP-B-2-32293 and the JP-B-2-16765, with at JP-B-58-49860, JP-B-56-17654, disclosed carbamate compounds among JP-B-62-39417 and the JP-B-62-38418 with oxirane skeleton.

In addition, disclosed among JP-A-63-260909 and the JP-A-1-105238 as at JP-A-63-277653, by use in molecule, have amino structure and thioether (sulfide) but the addition polymerization compound of structure can obtain the hypervelocity photosensitive composition.

As other example, what also can exemplify is multi-functional acrylate's class and methyl acrylic ester, as at JP-A-48-64183, disclosed among JP-B-49-43191 and the JP-B-52-30490, react polyester acrylate class and the epoxy acrylate class that obtains by epoxy resin and (methyl) acrylic acid.Can also exemplify at JP-B-46-43946, among JP-B-1-40337 and the JP-B-1-40336 disclosed special unsaturated compound and in JP-A-2-25493 disclosed vinyl sulfonic acid compound.In addition, preferably use the disclosed structure that contains perfluoroalkyl in JP-A-61-22048 among the present invention.Have again, can also use Kyokai, Vol.20, No.7, photocurable monomer and the oligomer introduced among the pp.300-308 (1984) at Bulletin ofNihon Setchaku.

But the detailed directions of addition polymerization compound, for example can optionally determine to use according to the characteristic of the photochromics of final design be what structure compound, be to use or to mix use, the maybe amount that will use separately.For example, have in mind from following aspect and come alternative condition.For photosensitive speed, preferably each molecule contains the structure of many unsaturated groups, and preferred in many cases difunctional group or polyfunctional group group.In order to improve the film strength that the image part is promptly solidified, preferably trifunctional or polyfunctional group group, in addition, in potpourri, use different functionality and different polymerizable groups (as, acrylate, methacrylate, distyryl compound, vinyl ether compound) so that both the sense of control photosensitiveness had also been controlled intensity.Though have the compound of macromolecule or have the photosensitive speed and the film strength of compound of high hydrophobicity good,, aspect developing powder developer solution and precipitation, consider preferred these compounds sometimes.

Photosensitive composition and dispersed aspect, for with other composition (as binder polymer, initiating agent, colorant, or the like) compatibility, but the selection of addition polymerization compound and usage are key factors, for example, can improve compatibility by the potpourri that uses low-purity compound or two or more compounds sometimes.In addition, but when addition polymer is used to planographic printing plate precursor,, also can select to have the compound of special construction in order to improve carrier (back is described) and outer field cohesive.But mixing ratio about addition polymerization compound in photosensitive composition, the big more then photonasty of consumption is high more, but measure too conference sometimes and cause the shortcoming that is separated, when but addition polymer is used to planographic printing plate precursor, because the viscosity of photosensitive composition causes problem (as the transfer of photochromics composition and bondingly cause producing failure) and the precipitation from developer solution in production and processing.Consider that from these aspects in many cases, based on each composition of whole composition, but the mixing ratio of preferred addition polymerization compound is the 5-80 weight portion, more preferably the 25-75 weight portion.But but can use the addition polymerization compound separately or mix the addition polymerization compound that uses two or more.In addition, consider the interference of oxygen, resolving power, atomizing (fogging) property, index of refraction variation and surface adhesion, but can at random select suitable structure, mixing ratio and the addition of addition polymerization compound the degree of polymerization.In addition, can determine the coating method of layer structure and priming paint and finish paint according to environment.

(C) binder polymer

When photosensitive composition being used for plate printing plate (optimization test scheme of the present invention), preferred photosensitive layer further contains binder polymer.As binder polymer, preferably use the line style organic high molecular polymer.Can use any " line style organic high molecular polymer ".Preferred select can water development or the water soluble that develops of alkalescent water or soluble line style organic high molecular polymer of alkalescent water or swelling line style organic high molecular polymer.Selected and the line style organic high molecular polymer that uses is not only as the film forming agent of composition, also as water development agent, alkalescent water developer or organic solvent developer.For example, when using the line style organic high molecular polymer of water soluble, make water development become possibility.As the line style organic high molecular polymer, what can exemplify has an addition polymer that has hydroxy-acid group at side chain, for example at JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, disclosed polymkeric substance among JP-A-59-53836 and the JP-A-59-71048, i.e. methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, the crotonic acid multipolymer, the maleic acid of maleic acid and partial esterification.Can also use the acidic cellulose derivative that has hydroxy-acid group at side chain.Except above-mentioned, can also use by in addition polymer, adding the resulting polymkeric substance of cyclic acid anhydride with carboxyl.

In these compounds, particularly therefore [benzyl (methyl) acrylate-(methyl) but other addition polymerization vinyl monomer of acrylic acid-as required] multipolymer and [allyl (methyl) acrylate-(methyl) but other addition polymerization vinyl monomer of acrylic acid-as required] multipolymer balance film intensity, photonasty and development property well help with in the present invention.

Because at JP-B-7-120041, JP-B-7-120042, JP-B-8-12424, JP-A-63-287944, JP-A-63-287947, the intensity of disclosed carbamate groups binder polymer with acid free radical is very good among JP-A-1-271741 and the Japanese patent application No.10-116232, therefore helps pressrun and low exposure adaptability.

Disclosed bonding agent with acylamino-had both had good development property in JP-A-11-171907, and good film strength is arranged again.

Except recited above, polyvinyl pyrrolidone and polyethylene oxide can be used as the line style organic high molecular polymer of water soluble.In order to improve the curing film strength, can also use pure soluble nylon, 2, the polyethers of two (4-hydroxyl-phenyl) propane of 2-and epichlorokydrin.Though in whole composition, can mix these line style organic high molecular polymers, when combined amount surpasses 90% weight, image intensity be had adverse influence with any amount.Preferred amount is 3-85% weight.Preferably having the compound of photopolymerization ethylenical unsaturated double bonds and the weight ratio of line style organic high molecular polymer is 1/9-7/3.

In optimization experiment scheme of the present invention, used binder polymer is water-insoluble soluble with alkali basically, wherein can or be limited to the organic solvent (the undesirable solvent of environment) that very little uses as developing solution.In this class is used,, suitably select the acid number (acid content of every gram polymkeric substance of representing with chemical equivalent) and the molecular weight of binder polymer from image intensity and the consideration of development property.Acid number is preferably 0.4-3.0meq/g, and more preferably 0.6-2.0meq/g and molecular weight are preferably 3,000-500,000, more preferably 10,000-300,000.

Other composition except above-mentioned principal ingredient will be described below.

D. other composition

When photosensitive composition of the present invention is used as the photosensitive layer of planographic printing plate precursor, can at random use each production method and various other composition of being suitable for using.Institute's preferred additives is as follows.

(D1) be total to photosensitizer

By the adjuvant (hereinafter referring to " photosensitizer altogether ") that uses certain kind, can further improve the photonasty of photosensitive layer.Though its mechanism is unclear, can infers and be based on following chemical process.Just, in the light reaction procedure that light absorption caused, produce various middle spike (free radicals by above-mentioned light trigger, superoxide, oxygenant, reductive agent, or the like), therefore its photosensitizer reaction and continue polyaddition reaction together forms new living radical.Can be categorized as (a) can produce free radical by reducing action compound with being total to photosensitizer, (b) can produce the compound of free radical by oxidation, (c) can convert the compound of high mars free radical to, or play the compound of chain-transferring agent effect with the low activity free radical reaction.Yet in many cases, which class what compound is belonged to does not have common standard (view).

(a) can produce the compound of free radical by reducing action

Compound with carbon-halogen bond: can think carbon-halogen bond reduction fracture and produce living radical.Particularly, for example preferably use trihalomethyl-s-triazine and San halogen Jia oxadiazole.

Compound with nitrogen-nitrogen key: can think nitrogen-nitrogen key reduction fracture and produce living radical.Particularly, for example preferably use six allyl diimidazoles.

Compound with o-o bond: can think o-o bond reduction fracture and produce living radical.Particularly, for example preferably use organic peroxide.

Compound: can think carbon-heterodesmic and oxygen-nitrogen key reduction fracture and produce living radical.Particularly, for example preferably use diaryl group iodized salt, triaryl matte, N-alkoxy pyridines (adinium) salt.

Ferrocene, the aromatic hydrocarbons iron complex: reduction produces living radical.

(b) can produce the compound of living radical by oxidation

Alkylates complex: can think by oxidation carbon-heterodesmic fracture and generation living radical.

Particularly, for example preferably use the triaryl alkyl borate.

Alkyl ammonium compounds: can think that by oxidation the C-X bond rupture on the carbon atom adjacent with nitrogen-atoms also produces living radical.Preferred X is a hydrogen atom, carboxyl, trimethyl silyl, benzyl or the like.Particularly, ethanolamines for example, N-phenylglycine class, N-trimethyl silyl methylaniline.

Sulfocompound, sn-containing compound: by similar effect, the nitrogen-atoms in the amine can be produced living radical by the compound of sulphur atom or tin atom replacement.In addition, be known that by S-S fracture and can also make compound have photonasty with S-S key.

The methyl carbonyls that a-replaces: make the bond rupture between carbonyl-α carbon bond produce living radical by oxidation.Its carbonyl is also demonstrated identical effect by the compound that oxime ether replaces.Particularly, 2-alkyl-1-[4-(alkylthio) phenyl]-2-morpholino purone-1 (morpholinopuronone) compound, what can exemplify is these compounds and hydramine reaction, the resulting oxime ether of etherificate N-OH then.

Sulfinate: the living radical that reduction is produced.Particularly, what can exemplify is aryl sulfinic acid sodium, or the like.

(c) can become the compound of high mars free radical with the living radical reaction conversions, or play the compound of chain-transferring agent effect

For example can use to have SH PH, SiH, the compound of GeH.These compounds produce free radical by hydrogen being given low activity free radical seed, or can produce free radical by removing proton after the oxidation.Particularly, can exemplify as 2-mercaptobenzimidazole.

The example that many conducts more specifically improve the common photosensitizer of photonasty adjuvant is for example disclosed in JP-A-9-236913.Provide the part of these common photosensitizers below, but the present invention is not limited to these common photosensitizers.

Be similar to above-mentioned sensitizing dye,, can carry out various chemical modifications these common photosensitizers for the characteristic of the photosensitive layer that improves planographic printing plate precursor.For example, but spendable method of modifying is to produce the method for free radical part bonding with the unsaturated compound of sensitizing dye, titanocene compound addition polymerization and other; Introduce the method for hydrophilic segment; Improve the method for compatibility, prevent that crystal settling from introducing substituent method; Introduce substituent method in order to improve cohesive; Polymerization.

These common photosensitizers can use separately or two or more mix use.Per 100 weight portions have in the compound of ethylenical unsaturated double bonds, and the suitable consumption of photosensitizer is the 0.05-100 weight portion altogether, is preferably the 1-80 weight portion, more preferably the 3-50 weight portion.

(D2) polymerization inhibitor

Except above-mentioned principal ingredient, preferred photosensitive composition of the present invention contains the small amount of thermal polymerization inhibitor, and this polymerization inhibitor is used for producing and the unwanted heat polymerization with ethylenic unsaturated bond compound of storage process inhibition.As suitable hot polymerization inhibitor, what can exemplify is quinhydrones, p methoxy phenol, two-tert-butyl group-paracresol, 1,2, the 3-trihydroxy benzene, the tert-butyl catechol, benzo quinone, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol) and N-nitroso-phenyl hydramine primary (primary) cerium salt.Based on the weight of whole composition, the addition of preferred polymerization inhibitor is the about 5 weight % of about 0.01 weight %-.In addition, when photosensitive composition of the present invention is coated with the photosensitive layer of making planographic printing plate precursor, if necessary, in order after coating, to suppress the impairment of oxygen to polyreaction, in the dry run, can add advanced higher fatty acid derivative such as docosanoic acid and docosanoic acid acid amides with the fixing surface of photosensitive layer.Based on whole composition, the addition of advanced higher fatty acid derivative is preferably about 0.5 weight %-10 weight %.

(D3) colorant, or the like

When photosensitive composition of the present invention is coated with the photosensitive layer of making planographic printing plate precursor etc.,, can wherein add dyestuff or pigment in order to give photosensitive layer painted in the past.Because the adding of colorant can improve so-called flat board-inspections performance as making a plate into visibility behind the planographic printing plate precursor and the improvement adaptability to image light density., especially preferably use pigment to make colorant because but many dyestuffs are easy to reduce the photonasty of the photosensitive layer of photosensitive polymerization.The object lesson of colorant comprises, for example pigment such as phthalocyanine color, AZO pigments, carbon black and titanium dioxide; With dyestuff such as Ethyl Violet, Crystal Violet, azo dyes, anthraquinone dye and cyanine dye.Based on whole composition, the addition of dyestuff and pigment is preferably about 0.5 weight %-5 weight %.

(D4) other adjuvant

When photosensitive composition of the present invention is coated with photosensitive layer of making planographic printing plate precursor etc., photosensitive composition can further contain the inorganic filler of various known additives as the physical property that is used to improve cured film, can improve other plastifier and the sensitizer of the printing ink bond properties on photosensitive layer surface.

As plastifier, what can exemplify is phthalic acid two octanol esters, dilauryl phthalate, triethylene glycol dieaprylate, dimethyl glycol phthalic ester, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, the triacetyl glycerine, and when using binder polymer, based on the total amount of compound with ethylenic unsaturated bond and binder polymer, the addition of plastifier is 10 weight % or still less.

For the film strength (prolongation of pressrun) of the photosensitive layer that improves planographic printing plate precursor, after the development, ultraviolet (UV) initiating agent and thermal cross-linking agent can also be joined in the photosensitive composition to strengthen the effect of heating/exposure.

In addition, remove the performance of unexposed photosensitive layer, can add adjuvant or a middle layer is provided for the cohesive of improving photosensitive layer and carrier with in order to improve by developing.The compound at relative strong interface is for example arranged by adding or primary coat and the described carrier in back, can improve cohesive and improve pressrun, for example can use compound and phosphine compound with two N structures.On the other hand, by adding or primary coat hydrophilic polymer such as polyacrylic acid and poly-sulfonic acid, can improve the development and anti-the embrocating property (being anti fouling performance) of no image section.

When photopolymerizable composition of the present invention or photosensitive composition being coated on the carrier as photosensitive layer, before using with composition dissolves in various organic solvents.The example of solvent for use comprises acetone, MEK, cyclohexane, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate, glycol monomethyl isopropyl ether, ethylene glycol monomethyl ether acetate, 3-methoxypropanol, methoxy methyl oxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxycarbonyl propyl acetic acid esters, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, methyllactic acid ester, the Solactol ester, or the like.These solvents can use or do admixture solvent separately and use.The concentration of solid content is generally 2 weight %-50 weight % in coating solution.

The coating content of photosensitive layer mainly influences the photonasty of photosensitive layer on carrier, development, and therefore exposure film strength, and pressrun, preferably select the amount of coating arbitrarily according to purposes.The amount of coating is too little, can cause pressrun not enough.But when its consumption was too big, shortcoming was that photonasty descends, and the exposure required time is long, and the processing required time that develops is long.When photosensitive composition of the present invention being used as the planographic printing plate precursor of scan exposure (fundamental purpose of the present invention), the amount of preferred coatings (with dry weight basis) is about 0.1g/m ²-Yue 10g/m ², 0.5g/m more preferably ²-Yue 5g/m ²

Carrier

A purposes of photosensitive composition of the present invention provides a kind of planographic printing plate precursor, preferably provides a kind of at the lip-deep photosensitive layer that comprises photopolymerisable compositions or photosensitive composition of hydrophilic support.Can be without any restrictedly using the known hydrophilic support that is used for planographic printing plate precursor.Being preferred for carrier of the present invention is the template carrier with dimensional stability.The for example paper that can exemplify is with plastics (for example, tygon, polypropylene, polystyrene or the like) laminated paper, sheet metal (for example aluminium, zinc-copper etc.), plastic foil is (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate (CAB), cellulose nitrate, polyethylene terephthalate, tygon, polystyrene, polypropylene, polycarbonate, polyvinyl acetal etc.) and lamination or deposit to paper or plastic foil on the above-mentioned metal.If necessary, for possess hydrophilic property or improvement intensity, can carry out chemical treatment or physical treatment to the surface of these carriers with known method.

In the present invention, preferably use paper, polyester film and aluminium sheet especially preferably use aluminium sheet in above-mentioned all material, and this is because its dimensionally stable and relatively cheap, and in addition, by the surface treatment of carrying out as required, it can provide hydrophilic and firm surface.Also preferred disclosed composite plate in JP-B-48-18327, composite plate is included in the polyethylene terephthalate film on the aluminium sheet.

Preferred aluminium sheet is pure aluminium sheet or contains as the aluminium of principal ingredient and the alloy sheets of trace independent elements, can also use the plastic foil of pressing or depositing with aluminium lamination.The example of contained independent elements comprises silicon in aluminium alloy, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium etc.The content of independent elements is maximum 10 weight % or still less in aluminium alloy.Particularly preferred in the present invention aluminium is fine aluminium, but refinement technique is difficult to produce 100% fine aluminium, therefore can contain the independent elements of minute quantity.As mentioned above, unqualified to the composition of aluminium sheet used among the present invention, can use usual known aluminium sheet and common used material arbitrarily.Used in the present invention aluminium plate thickness is about 0.1-0.6mm, is preferably 0.15-0.4mm, is preferably 0.2-0.3mm especially.

For metallic carrier, particularly have under the situation of carrier on aluminium surface, preferably carry out surface treatment such as roughening and handle (embossing), dip treating in the aqueous solution of sodium silicate, potassium zirconium fluoride, phosphate etc., or anodized.

The surperficial roughening of carrying out aluminium sheet that can in all sorts of ways is handled, for example mechanical roughening method, the electrochemical method of dissolving roughening and the chemical method of selective dissolution.Can use known mechanical means such as ball grinding method in the present invention, brush wiping method, blasting method, finishing method.As electrochemical method, can use and apply alternating current or galvanic method on the aluminium sheet in electrolytic solutions such as hydrochloric acid, nitric acid.In addition, as disclosed in JP-A-54-63902, mechanical roughening method and galvanochemistry roughening method are used in combination.If necessary, before the surface of aluminum plate roughening, be with degreasing as surfactant, organic solvent or alkaline aqueous solution to remove at the lip-deep rolling oil of plate.

In addition, after roughening is handled, preferably in the aqueous solution of sodium silicate, aluminium sheet is flooded.As disclosed in JP-B-47-5125, preferably in the aqueous solution of alkali silicate, aluminium sheet is carried out dip treating.In electrolytic solution, the aluminium sheet electric current of making anode by conversion carries out anodized, electrolytic solution comprises aqueous solution or non-aqueous solution single or two or more mineral acids or organic acid or its salt, mineral acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid or the like, organic acid such as oxalic acid, sulfaminic acid or the like.

Disclosed silicate electrodeposition process also is preferred in U.S. patent 3,658,662.

At JP-B-46-27481, disclose among JP-A-52-58602 and the JP-A-52-30503 carrier has been carried out the electrolysis texturizing method, can also be used in combination above-mentioned anodized and sodium silicate processing carrying out surface treatment.

In addition, can also preferably use disclosed technology in JP-A-56-28893, technology to comprise in proper order in the present invention and carry out mechanical surface roughening processing, chemical etching, the electrolysis embossing, anodized and sodium silicate are handled.

After carrying out above-mentioned each processing, also preferred in the present invention the use with water soluble resin (polymkeric substance and the multipolymer that for example on side chain, have tygon phosphate group, sulfonic acid group), polyacrylic acid, water-soluble metal salt (as Firebrake ZB), yellow dye, the carrier of ammonia salt or the like primary coat

Also preferred the use carried out the carrier that colloidal sol is handled among the present invention, handles by this colloidal sol, can make functional group can carry out addition polymerization by covalent bonding, as disclosed among the JP-A-7-159983.

As other preferred example, what can exemplify is any carrier of making superficial layer on the waterproof hydrophilic layer.As this class superficial layer, can exemplify for example in U.S. patent 3,055,295 and JP-A-56-13168 in the disclosed layer that comprises inorganic pigment and bonding agent, disclosed hydrophilic expanding layer in JP-A-9-80744, with the disclosed titanium dioxide that comprises in JP-W-8-507727, the dissolved glue film of polyvinyl alcohol (PVA) and silicic acid.

This hydrophilic treatment not only is used for the hydrophilic treatment of carrier surface, and is used to prevent the adverse reaction of photosensitive layer on the carrier (on carrier), and is used to improve the cohesive of photosensitive layer.

Protective seam

Be used for the planographic printing plate precursor of scan exposure; preferred photopolymerisable compositions of the present invention or the photosensitive composition of using; owing in air, expose usually, so preferably provide a kind of protective seam comprising on the layer of photopolymerisable compositions or photosensitive composition.Protective seam prevents that airborne oxygen and lower-molecular substance such as alkaline matter (these materials hinder exposure causes the imaging reaction in photosensitive layer) are mixed in the photosensitive layer, and makes that exposure becomes possibility in air.Therefore, as the needed characteristic of protective seam, protective seam preferably has the low-permeability of low molecular weight compound such as oxygen, does not hinder the back transmission of exposure basically; Has good cohesive with photosensitive layer; And after exposure, remove easily in the developing process.Up to now, these schemes have been attempted and disclose in U.S. patent 3,458,311 and JP-A-55-49729.

As the material that is used for protective seam, preferably use the high molecular polymer of the goodish water soluble of crystallinity, water-soluble polymers particularly, polyvinyl alcohol (PVA) for example, polyvinylpyrrolidone, acid cellulose, gelatin, gum arabic, polyacrylic acid are known.In these compounds, when polyvinyl alcohol (PVA) when the principal ingredient, remove at fundamental characteristics such as oxygen-free with by development and can obtain best result aspect the protective seam.For the performance of the cut-out oxygen that obtains needing and water-soluble,,, just can partly be substituted in polyvinyl alcohol used in the protective seam as long as it contains unsubstituted vinyl alcohol units for ester, ether and acetal.In addition, part polyethylene alcohol can have other multipolymer composition.As the object lesson of polyvinyl alcohol, what can exemplify is to have hydrolysis rate 71-100% and molecular weight 300-2, those polyvinyl alcohol (PVA) of 400.

What specifically can routine exemplify is PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, and L-8 (by Kuraray Co., Ltd. produces).

Except the performance of getting rid of oxygen with develop and remove the property, consider that mist formation, cohesive and scratch resistance select the consumption of each composition of protective seam (selecting the adjuvant of PVA and use) and coating.Usually, the hydrolysis rate of used PVA high more (substituted ethylene alcohol unit content is not higher in protective seam) and bed thickness are thick more, and the performance of then getting rid of oxygen just uprises, and therefore is of value to photonasty.But,, can in production and storage process, produce undesired polymerization, or when imaging exposes, produce increasing the weight of of unwanted mist and image line if oxygen-free is too high.

When handling printed panel, with the cohesive and the scratch resistance of image section be epochmaking characteristic, promptly, when the hydrophilic layer that will comprise water-soluble polymers is laminated on the oleophilic layer, because cohesive is not enough, and peeling off of film easily take place, the polymerization that causes because of oxygen of released part simultaneously is obstructed and is produced the such defective of sclerosis failure such as film.

In order to improve the cohesive between photosensitive layer and the protective seam, people had proposed various countermeasures.For example, in U.S. patent 292,501 and 44, disclosed in 563, by in the hydrophilic polymer that mainly comprises polyvinyl alcohol (PVA), mixing acryl emulsion or the water-insoluble vinyl pyrrolidone/vinyl acetate copolymer of 20-60 weight %, and resulting product layer is pressed onto on the polymeric layer, can obtain enough cohesives.Any using on the protective seam of the present invention in the technology that can these are known.At for example U.S.3,458,311 and JP-A-55-49729 in the coating method of these protective seams is disclosed in detail.

Can further give protective seam other function.For example,, can absorb 500nm or long wavelength's light more effectively, can further improve safety light adaptability and do not reduce photonasty by adding the colorant (water-soluble dye, or the like) that the light of 350nm-450nm exposure is had good transmissibility.

When the photochromics that comprises photosensitive composition of the present invention is used as image forming material, obtain image by image exposure usually, remove the unexposed portion of photosensitive layer then with developer solution.When photosensitive composition was used as planographic printing plate precursor, disclosed developer solution can be used as preferred developer solution in JP-B-57-7427, preferably used the aqueous solution of inorganic alkaline metal salt, ammoniacal liquor and organic basic reagent such as monoethanolamine or triethanolamine, wherein inorganic alkaline metal salt such as sodium silicate, potassium silicate, NaOH, potassium hydroxide, lithium hydroxide, tertiary sodium phosphate, disodium hydrogen phosphate, triammonium phosphate, Diammonium phosphate (DAP), sodium silicate, sodium bicarbonate.Add these inorganic or organic alkaline reagents and make the concentration of alkaline solution become 0.1-10 weight %, be preferably 0.5-5 weight %.

If necessary, alkaline aqueous solution can contain for example benzylalcohol of a spot of surfactant and organic solvent, the 2-phenoxetol, and butoxy ethanol, or the like.For example, what can exemplify is in U.S. patent 3,375,171 and 3,615, disclosed compound in 480.

In addition, can also be preferably at JP-A-50-26601, JP-A-58-54341, disclosed developer solution among JP-B-56-39464 and the JP-B-56-42860.

In addition, the process of carrying out plate printing plate plate-making from planographic printing plate precursor with photosensitive layer (it uses photosensitive composition of the present invention), if necessary, before exposure, exposure process neutralization heater plate surface always from be exposed to developing process.By adding the imaging reaction that heat energy promotes photosensitive layer, this can improve photonasty and pressrun and photosensitive stabilization.In addition, in order to improve image intensity and pressrun, the image after developing is carried out after the entire image heating or the entire image exposure is effective.Before development, usually preferably at 150 ℃ or more heat under the appropriate condition of low temperature.If temperature is too high, can there be the problem of image blur.Heating after developing in very harsh conditions is promptly usually 200-500 ℃ of heating.Low temperature can not obtain enough image intensification effects, and higher temperature can make the thermal decomposition of carrier degraded and image section.

Can expose to planographic printing plate precursor with the known method that does not add restriction with photosensitive layer (it uses photosensitive composition of the present invention).The wavelength of preferred use light source is 350nm-450nm, uses InGan series semiconductor laser especially.Exposure machine can be interior cylinder type, outer cylinder type, or any in plate.Because each composition of photosensitive layer is a highly-water-soluble, it also dissolves in neutral water and the alkalescent water.After being loaded on the printing machine, the planographic printing plate precursor with this formation needs pressure (on-press) exposure imaging system.

As other exposure radioactive ray that are used for photopolymerisable compositions of the present invention, can use the mercury lamp of UHV (ultra-high voltage), high pressure, middle pressure and low pressure, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp and visible lamp and Ultra-Violet Laser lamp, daylight lamp, tungsten lamp and daylight.

As the LASER Light Source of useful 350nm-450nm, can use following light source.

As gas laser: argon (Ar) ion laser (364nm, 351nm, 10mW-1W), krypton (Kr) ion laser (356nm, 351nm, 10mW-1W), helium-cadmium (He-Cd) laser instrument (441nm, 325nm, 1mW-100mW),

As solid-state laser: 2 times Nd./YAG (YVO ₄) and the combination of SHG crystal (355nm, 5mW-1W), the combination of Cr/LiSAF and SHG crystal (430nm, 10mW),

As semiconductor laser: KNbO ₃Ring resonator (430nm, 30mW), waveguide type wavelength conversion equipment and AlGaAs, and the semi-conductive combination of InGaAs (380nm-450nm, 5mW-100mW), waveguide type wavelength conversion equipment and AlGaInP, the semi-conductive combination of AlGaAs (300nm-350nm, 5mW-100mW), AlGaInN (350nm-450nm, 5mW-30mW) and

As other pulsed laser: N ₂Laser instrument (337nm, pulse 0.1-10mJ), XeF (351nm, pulse 10-250mJ).

Consider from wavelength characteristic and expense aspect, and preferred especially AlGaInN semiconductor laser (available InGaN series semiconductor laser instrument on the market, 400nm-410nm, 5mW-30mW).

As the scan exposure type exposure sources of planographic printing plate precursor, exposure machine can be interior cylinder type, outer cylinder type, or plate, preferably use in the above-mentioned light source can continuous shaking those light sources.In fact, consider preferred especially following exposure sources from the photonasty and the relation between the plate-making time of photochromics.

With Dan Shu to three beam exposure apparatus of one or more gas lasers or solid-state laser light source, make total output become 20mW or higher by interior cylinder type equipment.

With multi beam (1-10 bundle) exposure device of one or more semiconductor lasers, gas laser or solid-state laser light source, make total output become 20mW or higher by plate equipment.

With multi beam (1-9 bundle) exposure device of one or more semiconductor lasers, gas laser or solid-state laser light source, make total output become 20mW or higher by outer cylinder type equipment.

With the multi beam of one or more semiconductor lasers, gas laser or solid-state laser light source (10 bundles or more multi beam) exposure device, make total output become 20mW or higher by outer cylinder type equipment.

Described in the above by in directly drawing type of the laser beam plate printing plate, the photonasty X (J/cm of photochromics ²), the exposure area S (cm of photochromics ²), a kind of energy q (W) of LASER Light Source, the quantity n of laser beam and total time shutter t (s) satisfy equation (eq1):

X·S＝n·q·t (eq1)

I) under interior cylinder type situation (Dan Shu):

Laser revolution f (resolution Z (point/centimetre) and total time shutter t (s) satisfy equation (eq2) for radian/s), the sub-sweep length Lx (cm) of photochromics:

f·Z·t＝Lx (eq2)

Ii) (multi beam) under the cylinder type situation outside:

Drum revolution F (radian/s), the sub-sweep length Lx (cm) of photochromics, resolution Z (point/centimetre), the total time shutter t (s) and the quantity n of laser beam, satisfy equation (eq3):

F·Z·n·t＝Lx (eq3)

Iii) under plate situation (multi beam):

The revolution H of polygon prism (radian/s), the sub-sweep length Lx (cm) of photochromics, resolution Z (point/centimetre), the total time shutter t (s) and the quantity n of laser beam, satisfy equation (eq4):

H·Z·n·t＝Lx (eq4)

By the required resolution of substitution actual print plate in above-mentioned equation (2,560dpi), board size (A1/B1,421 inches of sub-sweep lengths), about 20/hour conditions of exposure and the light sensitive characteristic of photosensitive composition of the present invention (photosensitive wavelength, photonasty: about 0.1mJ/cm ²), can think that the combining of multi beam exposure system that the photochromics that uses photosensitive composition of the present invention and use always are output as 20mW or higher laser is particularly preferred.In addition, consider operability and expense, outer cylinder type is most preferred with the combining of semiconductor laser exposure device of multi beam (10 bundle or more).

Except being used for the scan exposure plate printing plate, photopolymerisable compositions of the present invention or photosensitive composition can not add the light-curable resin field that is widely used in of restriction, for example, as required, when composition is used to be mixed with the liquid photopolymerisable compositions of ion polymerizable compound, can obtain the high-speed light image forming material.In addition, change with photopolymerization reaction by making refraction index, can be with said composition as the hologram image material.By surface adhesion is changed, said composition can also be used for different material for transfer (peeling off photographic material, the toner, developer material).The photocuring that also can be used as microcapsules.Also can be further used for producing the light-curable resin material of electronic material such as photoresist and printing ink, coating and bonding agent.

In addition, be included in the light polymerization initiator that comprises carbazole compound and titanocene compound in photopolymerisable compositions of the present invention and the photosensitive composition photonasty and have good stability, except being used for top described photosensitive composition, also can be used for various uses.For example, can make triphenyl methane series leuco dye with the high photosensitivity heat-tinting with the free radical that light produced efficiently.In addition, by free radical addition, Photoepolymerizationinitiater initiater of the present invention can be so that the decoloring reaction of the polymethine series dyes of certain kind.Because light polymerization initiator of the present invention not only produces free radical by light, and produce sour composition simultaneously, so by with the mixing energy production high speed imaging material of following compositions, these compositions are compounds of changing with acid of its absorbance, cause the resin combination of cross-linking reaction or because the resin combination that improves solubleness is decomposed in acid by acid.

Embodiment

To describe the present invention in detail with reference to each embodiment, but the present invention is not limited to these embodiment.

Example I-1 is to I-8, comparative example I-1 to I-3

The preparation of carrier

The aluminium sheet of thick 0.3mm was soaked for 25 seconds to finish etch in the sodium hydrate aqueous solution of 60 ℃ 10 weight %,,, wash with water then in order to neutralize with the salpeter solution washing of 20 weight % then with the flowing water washing.In 1 weight % aqueous solution of nitric acid, use sine wave alternating current, with 300 coulombs/decimeter ²Anode current aluminium sheet is carried out the coarse processing of electrolytic surface.Then, plate was soaked for 5 seconds in 40 ℃ 1 weight % sodium hydrate aqueous solution, in the aqueous sulfuric acid of 60 ℃ 30 weight %, soak then and carried out decontamination in 40 seconds and handle.Then, in 20 weight % aqueous sulfuric acids, with current density 2A/cm ²Plate is carried out anodized 2 minutes, make the thickness of anode oxide film reach 2.7g/m ²Through measuring, surfaceness is 0.3 μ m (by JIS B0601 method, representing with Ra).

Use the rod-type coating machine, following colloidal sol reaction solution be coated onto the back side of the plate of so handling, at 100 ℃ with dry 1 minute of coated plate.Thereby obtain having dried coating content is 70mg/m ²The carrier of back coating.

The colloidal sol reaction solution

50 heavy parts of tetraethyl-metasilicates

Water 20 weight portions

Methyl alcohol 15 weight portions

Phosphoric acid 0.05 weight portion

Above-mentioned each composition is mixed and stirring, begin to produce heat after about 5 minutes.Reaction continued after 60 minutes, and the solution below adding in reaction solution obtains the back coating coating solution thus.

The back coating coating solution

1,2,3-trihydroxy benzene-formaldehyde condensation resins (molecular weight: 2000) 4 weight portions

Repefral 5 weight portions

Fluorochemical surfactant 0.7 weight portion

(multipolymer of acrylic acid N-butyl PFO sulfonamide ethyl ester/acrylic acid polyoxyethylene ester, molecular weight: 20,000)

Methyl alcohol silicasol 50 weight portions

(by Nissan Chemical Industries, Ltd produces methyl alcohol: 30%)

Methyl alcohol 800 weight portions

The preparation of photosensitive layer

With following photopolymerisable compositions, be 1.0g/m with dried coating content ²Be coated onto on the aluminium sheet of handling like this,,, form photosensitive layer thus dry 2 minutes of the plate that was coated with at 80 ℃.

Pentaerythritol tetracrylate 20 weight portions

Multipolymer 20 weight portions of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Light trigger (shown in Table I-1)

Sensitizing dye

Titanocene compound

Be total to photosensitizer

Fluorine-based non-ionic surfactant (F-177P) 0.3 weight portion

Hot polymerization inhibitor, N-nitroso-phenyl hydramine aluminium salt 0.1 weight portion

Pigment dispersion 0.6 weight portion

The composition of pigment dispersion

Composition/pigment orchid: 1,5/6 15 weight portion

Copolymer 10 weight portion of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Cyclohexanone 15 weight portions

Acetate methoxyl propyl ester 20 weight portions

Propylene glycol monomethyl ether 40 weight portions

Methyl ethyl ketone 20g

Propylene glycol monomethyl ether 20g

The preparation of protective seam

(saponification degree: 98mol%, the degree of polymerization: aqueous solution 550) is 2g/m with dried coating content with 3 weight % polyvinyl alcohol (PVA) ²Be coated onto on the photosensitive layer, and 100 ℃ of dryings 2 minutes.

The adaptive evaluation of photonasty and safety light

With ladder indicator (step guide) (by Fuji Photo Film Co., Ltd., produce, the gray level indicating gauge is shown in the discontinuous variation that Δ D=0.15 place optical density is transmitted) closely touch on the above-mentioned resulting photochromics, by light filter (Kenko-BP-40), expose with xenon lamp, make it reach known exposure energy.In order to assess the exposure adaptability to the shortwave semiconductor laser, the Kenko-BP-40 that will use the exposure of 400nm monochromatic light is as light filter.Then,, soaked for 10 seconds in the developer solution by composition below having, photochromics is developed at 25 ℃.Mxm. when image is completely removed (shown in Table I-1) calculates photonasty (clear photonasty)." clear photonasty " is meant and forms the required minimum energy of image, and the value of being somebody's turn to do is low more, and photonasty is high more.

Table I-1

Embodiment	Initiating agent (based on the addition of total solid content in photosensitive layer, weight %)			Clear photonasty (mJ/cm 2)
					Sensitizing dye	Titanocene compound	Be total to photosensitizer
	Example I-1	D3(1.0)	T-1(1.0)					H-1(5.0)	0.2
Example I-2				D1(1.0)	T-2(1.3)	H-1(2.0)	0.1
	Example I-3	D2(1.5)	T-2(1.8)					H-2(5.0)	0.1
Example I-4				D13(1.2)	T-2(0.9)	Do not have	0.3
	Example I-5	D14(1.0)	T-2(2.8)					H-1(10)	0.2
Example I-6				D18(1.2)	T-1(1.8)	Do not have	0.3
	Example I-7	D10(0.8)	T-1(1.8)					H-2(3.0)	0.1
Example I-8				D22(0.9)	T-1(0.5)	Do not have	0.3
	Comparative example I-1	Do not have	T-2(1.8)					Do not have	1.5
Comparative example I-2				Do not have	T-2(2.8)	H-1(5.0)	0.7
	Comparative example I-3	D1(1.0)	H-3(1.0) *					H-2(3.0)	1.0

^*Replace titanocene compound embodiment as a comparison with Hexaarylbiimidazole.

From Table I-1 as can be seen, plate printing plate of the present invention has very high speed and demonstrates enough light sensitivity for the scan exposure system.

In addition, compare with the situation of not using sensitizing dye, light trigger of the present invention is at a high speed, particularly, even when the addition of titanocene compound is very little, also demonstrate enough photonasty.

Developer solution in Table I-1

Comprise that following component and pH value are 13 aqueous solution.

1K potassium silicate 3.0 weight portions

Potassium hydroxide 1.5 weight portions

Compound 0.2 weight portion by following formula 1 expression

Water 95.3 weight portions

The compound of formula 1

Example I-9

With preparing planographic printing plate precursor with example I-1 to the identical method of I-8.Different is that the variation of light trigger composition is as follows, and the thickness of photosensitive layer becomes 1.5g/m ²

Photoepolymerizationinitiater initiater

(based on the addition of total solid content in photosensitive layer)

Sensitizing dye D1 1.2 weight %

Titanocene compound T-2 1.5 weight %

Be total to photosensitizer H-1 7.0 weight %

Use has the InGaN semiconductor laser of vibration wavelength 400nm, is shining on the 25 μ m printed panels and exposure energy density 0.2mJ/cm ²Condition under, the planographic printing plate precursor that so obtains is carried out scan exposure.Then, 100 ℃ to 10 seconds kinds of plate heating after, carry out above-mentioned development processing.

Obtain the plate printing plate of the good blue image of visibility.By KOR-D printing machine (producing), use the plate printing plate that so obtains to carry out lithography by Heidelberg Co..Can obtain surpassing 50,000 good image density and the anti-printed matter of embrocating.

Example I-10

At 45 ℃, under the mandatory condition of 65%RH, will in example I-9, store 3 days by prepared planographic printing plate precursor.With the method identical, use this plate to make a plate and print with example I-9.Obtain being similar to the good result of example I-9.

Example I-11

Measure the emission intensity plot of used usually safety light and measure the emission intensity plot position that shows (end of shortwave) in the shortwave branch.In addition, comment the working ability of explaining archaic or dialectal words in current language under each safety light.

Table I-2

Safety light	The end (nm) of shortwave emission	Working ability
			White lamp	400	Well
Amber light	520	Enough bright for making sheet processing
			The orange lamp	570	Quite dark, and be difficult to processing, than conventional long processing time
Red light	600	Very dark, this processing needs skill

Therefore, consider that from the working ability aspect amber light is needed.Requirement under amber light accessible material at 520nm at least, preferred 490nm or more the long wavelength have low photosensitivity.Have absorption maximum in contiguous 400nm dye groups of the present invention, so advantage of the present invention is also aspect this.

Example I-12

Prepare planographic printing plate precursor with the method identical with example I-9.Different is that the variation of light trigger composition is as follows, and the thickness of photosensitive layer becomes 2.0g/m ²

Light trigger

(based on the addition of total solid content in photosensitive layer)

Sensitizing dye D8 1.5 weight %

Titanocene compound T-2 1.5 weight %

Be total to photosensitizer H-1 5.0 weight %

Use has the InGaN semiconductor laser of vibration wavelength 400nm, is shining on the 25 μ m printed panels and exposure energy density 0.15mJ/cm ²Condition under, the planographic printing plate precursor that so obtains is carried out scan exposure.Then, 100 ℃ to 10 seconds kinds of plate heating after, carry out above-mentioned development processing.Obtain having the plate printing plate of the good blue image of visibility.At 300 ℃ above-mentioned resulting plate was further heated 5 minutes, and carry out lithography with KOR-D printing machine (producing) by Heide lberg Co..Can obtain surpassing 200,000 the good image density and the printed matter of anti-embrocating property (that is anti fouling performance).

Example I-13

Before scan exposure, planographic printing plate precursor prepared in example I-9 was exposed 30 minutes with amber light.With the method identical, use this plate to make a plate and print with example I-9.Obtain and the identical good result of example I-9.

Comparative example I-4

Prepare planographic printing plate precursor with the method identical with example I-9.Different is with sensitizing dye D1 (maximum absorption wavelength: 410nm) replace H4 (maximum absorption wavelength: 500nm).Use has the InGaN semiconductor laser of vibration wavelength 400nm, uses the method plate-making identical with example I-9 to make image mobile (that is image disappearance).In addition, use the method identical, before scan exposure, to prepared planographic printing plate precursor exposure 30 minutes, and use the method identical to make a plate and print with example I-9 with amber light with example I-13.The whole surface of printed matter is solid and fuzzy.

Planographic printing plate precursor of the present invention has the enough photonasty that is suitable for short wavelength semiconductor laser such as InGaN scan exposure, and a kind of have good pressrun and anti-embrocating property (that is anti fouling performance) are provided.Under amber light, can improve the mist that the present invention is used for the planographic printing plate precursor of scan exposure significantly, therefore can greatly improve the working ability of handling printed panel.In addition, photopolymerisable compositions of the present invention not only has good photonasty, and has excellent storage stability.

Example II-1 is to II-8, comparative example II-1 to II-6

The preparation of carrier

With preparing each carrier with example I-1 to the I-8 method identical with comparative example I-1 to I-3.

The preparation of photosensitive layer

With following photopolymerisable compositions, be 1.0g/m with dried coating content ²Be coated onto on the aluminium sheet of above-mentioned processing,,, form photosensitive layer thus dry 2 minutes of the plate that was coated with at 80 ℃.

Pentaerythritol tetracrylate 1.5g

The multipolymer 2.0g of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Light trigger (shown in Table II-1)

Sensitizing dye

Titanocene compound

Be total to photosensitizer

Fluorine-based non-ionic surfactant (F-177P) 0.02g

Hot polymerization inhibitor, N-nitroso-phenyl hydramine aluminium salt 0.01g

Pigment dispersion 2.0g

The composition of pigment dispersion

Composition/pigment orchid: 1,5/6 15 weight portion

Copolymer 10 weight portion of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Cyclohexanone 15 weight portions

Acetate methoxyl propyl ester 20 weight portions

Propylene glycol monomethyl ether 40 weight portions

Methyl ethyl ketone 20.0g

Propylene glycol monomethyl ether 20.0g

The preparation of protective seam

With forming each protective seam with example I-1 to the I-8 method identical with comparative example I-1 to I-3.

The adaptive evaluation of photonasty and safety light

With with example I-1 to I-8, the method that comparative example I-1 to I-3 is identical is estimated.

The result is shown in following Table II-1.

Table II-1

Embodiment	Initiating agent (based on the addition of the total solid content in photosensitive layer, weight %)			Clear photonasty (mJ/cm 2)
					Sensitizing dye	Titanocene compound	Be total to photosensitizer
	Example II-1	D4(1.0)	T-1(1.0)					H-1(5.0)	0.2
Example II-2				D21(1.3)	T-2(1.8)	H-2(2.0)	0.1
	Example II-3	D18(1.2)	T-2(0.9)					Do not have	0.3
Example II-4				D6(1.0)	T-2(2.8)	H-1(10)	0.2
	Example II-5	D17(1.2)	T-1(1.8)					Do not have	0.3
Example II-6				D25(0.8)	T-1(1.8)	H-2(3.0)	0.1
	Example II-7	D14(0.9)	T-2(0.5)					Do not have	0.1
Example II-8				D1(1.2)	T-1(1.8)	Do not have	0.3
	Comparative example II-1	D7(2.5)	Do not have					Do not have	Can not form image
Comparative example II-2				Do not have	T-2(1.8)	Do not have	1.5
	Comparative example II-3	Do not have	T-2(2.8)					H-1(5.0)	0.7
Comparative example II-4				H6(0.9)	T-2(0.5)	Do not have	0.9
	Comparative example II-5	H5(1.2)	T-1(1.8)					Do not have	1.2
Comparative example II-6				D14(1.0)	H-3(1.0) *	Do not have	1.4

^*Replace titanocene compound example II-6 as a comparison with triaizine compounds.

Result from Table II-1 uses the planographic printing plate precursor of photosensitive composition of the present invention to have very high speed and demonstrate enough light sensitivity for the scan exposure system as can be seen.

In addition, compare with the situation of not using sensitizing dye, the photosensitive composition of the present invention that contains light trigger is at a high speed, and particularly, even when the addition of titanocene compound is very little, it also demonstrates enough photonasty.

At example II-1 used developer solution to II-8 and the comparative example II-1 to II-6 is to comprise that following component and pH value are 13 aqueous solution.

1K potassium silicate 3.0 weight portions

Potassium hydroxide 1.5 weight portions

Compound 0.2 weight portion by following formula 1 expression

Water 95.3 weight portions

The compound of formula 1

Example II-9 is to II-16, comparative example II-7

Prepare each planographic printing plate precursor by following procedure, and estimate printing performance.The result is shown in Table II-2.

The pre-service of carrier

With the suspending liquid of No. 8 nylon brusses and 800 order float stones and water, the 1S aluminium sheet of thick 0.30mm is brushed decorations handle, and the surface of the thorough clean plate of water.By plate was soaked for 60 seconds in the sodium hydrate aqueous solution of 70 ℃ 10 weight %, finish etch.Further water flushing with the neutralization of 20 weight % salpeter solutions, then washes with water then.Using V _AUnder the sine wave alternating current condition for 12.7V, in 1 weight % aqueous solution of nitric acid, use sine wave alternating current, with 300 coulombs/decimeter ²Anode current plate is carried out the coarse processing of electrolytic surface.The surfaceness that records is 0.45 μ m (by JIS B0601 method, representing with Ra).

The hydrophilic treatment of carrier surface

's tetrasilicic acid sodium (the SiO of 11.2 2.5 weight % with above-mentioned carrier at 70 ℃, pH value ₂: 28-30%, Na ₂O:9-10%, Fe:0.02% or still less) soaked for 13 seconds in the aqueous solution, wash with water then.Measure its lip-deep Si element by fluorescent X-ray analysis, the amount that obtains going up silicate in its surface is 10mg/m ²

Interior coating

The coating solution A that preparation has following component, and with phenyl-phosphonic acid 20mg/m ²Coating content, be that the roller (wheeler) of 180rpm is coated onto it on water-wetted surface of above-mentioned carrier with rotational speed, then 80 ℃ of 30 seconds of drying.

Internal layer coating solution A

Phenyl-phosphonic acid 0.07-1.4g

Methyl alcohol 200g

The coating of photosensitive layer

With 1.0-2.0g/m ²Coating content, the photosensitive layer coating solution that will have following component with roller (wheeler) was coated onto on the above-mentioned carrier with internal layer, and at 100 ℃, with dry 1 minute of this photosensitive layer.

The photosensitive layer coating solution

But addition polymerization compound (compound shown in the Table II-2) 1.5g

Binder polymer (compound shown in the Table II-2) 2.0g

Sensitizing dye (compound shown in the Table II-2) 0.1g

Activator (compound shown in the Table II-2) 0.1g

Be total to photosensitizer (compound shown in the Table II-2) 0.3g

Pigment dispersion 2.0g

The composition of pigment dispersion

Composition/pigment orchid: 1,5/6 15 weight portion

Copolymer 10 weight portion of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Cyclohexanone 15 weight portions

Acetate methoxyl propyl ester 20 weight portions

Propylene glycol monomethyl ether 40 weight portions

Hot polymerization inhibitor, N-nitroso-phenyl hydramine aluminium salt 0.01g

Surfactant, Megafac F-177

(by Dainippon Chemicals﹠amp; Ink Co., Ltd. produces) 0.02g

Methyl ethyl ketone 20.0g

Propylene glycol monomethyl ether 20.0g

The preparation of protective seam

(saponification degree: 98mol%, the degree of polymerization: aqueous solution 550) is 2g/m with dried coating content with 3 weight % polyvinyl alcohol (PVA) ²Be coated onto on the photosensitive layer, and 100 ℃ of dryings 2 minutes.

The exposure of planographic printing plate precursor

With 400nm monochromatic light light source, to the planographic printing plate precursor exposure that so obtains, the control exposure makes the exposure energy density of plate become 200 μ J/cm ², under the condition of 175 line/inches, make the plate exposure by solid state image exposure and per 1% half luminous point imaging exposure for 1%-99%.

Develop and plate-making

With the preparation developer solution (shown in the Table II-2) and Finisher FP-2W (by Fuji Photo Film Co., Ltd., produce) be put into automatic processor LP-850 (by Fuji Photo Film Co., Ltd., produce) in, under 30 ℃ of developing solution temperature and 18 seconds condition of development time, exposed plate is developed/makes a plate.Therefore, obtain plate printing plate.

The pressrun test

Use R201 (by Roland Co., Ltd. produces) printing machine and GEOS-G (N) (by DainipponChemicals﹠amp; Ink Co., Ltd. produces) printing ink.Observe the printed matter of solid state image part and estimate pressrun by the number that fogs.This value is high more, and pressrun is good more.

The pressure test of half luminous point pressrun

Use R201 (by Roland Co., Ltd. produces) printing machine and GEOS-G (N) (by DainipponChemicals﹠amp; Ink Co., Ltd. produces) printing ink.Begin after 5,000 of printings from printing,, PS board cleaning agent CL-2 (by Fuji Photo Film Co., Ltd. produces) is executed on the printing sponge, and eliminate half luminous point part in order to remove the printing ink on printed panel.Then, print 10,000, and the omission of half luminous point on printed matter that detects by an unaided eye (that is, disappearing).

Embrocating property test (that is contaminative)

Use R201 (by Roland Co., Ltd. produces) printing machine and GEOS-G (N) (by DainipponChemicals﹠amp; Ink Co., Ltd. produces) printing ink.Observe the no image section (unexposed portion) of printed matter and estimate embrocating property (that is contaminative).

Table II-2

Embodiment number	Photosensitive layer						The composition of developer solution	Printing performance
											But the compound of addition polymerization	Binder polymer	Sensitizing dye	Titanocene compound	Be total to photosensitizer	Coating content (mg/m 2)	The pressrun of image section	The pressrun of half luminous point part	The embrocating property of non-imaging moiety
	Example II-9	M-I	B-1	D-3	T-1	H-8		1.5	DV-1	100,000										Well	Well
Example II-10							M-2				B-1	D-22	T-2	H-8	2	DV-2	70,000	Well	Well
	Example II-11	M-2	B-2	D-14	T-2	H-2		1.8	DV-3	200,000										Well	Well
Example II-12							M-1				B-2	D-1	T-2	H-2	2.5	DV-1	80,000	Well	Well
	Example II-13	M-1	B-1	D-17	T-1	H-2		1	DV-1	70,000										Well	Well
Example II-14							M-2				B-3	D-25	T-1	H-2	1	DV-3	50,000	Well	Well
	Example II-15	M-2	B-3	D-4	T-2	H-7		2.5	DV-3	50,000										Well	Well
Example II-16							M-2				B-1	D-21	T-1	H-8	1.8	DV-1	80,000	Well	Well
	Comparative example II-7	M-1	B-1	Do not have	T-2	H-2		1.5	DV-1	Image flows										Image flows	Well

But the addition polymerization compound in Table II-2

M-1: pentaerythritol tetracrylate (by Shin-Nakamura Kagaku Kogyo Co., Ltd., the ester A-TMMT that NK produces)

M-2: dimethacrylate glycerine ester cyclohexylene diisocyanate carbamate prepolymer (by KyoeiChemical Co., Ltd., UA101H)

Binder polymer in Table II-2

B-1: allyl methyl acrylate/methacrylic acid/N-N-isopropylacrylamide multipolymer (the copolyreaction mol ratio: 67/13/20), by the resulting acid number of NaOH titration: 1.15meq/g, the weight-average molecular weight that records with GPC: 130,000.

B-2: allyl methyl acrylate/methacrylic acid copolymer (the copolyreaction mol ratio: 83/17), by the resulting acid number of NaOH titration: 1.55meq/g, the weight-average molecular weight that records with GPC: 125,000.

B-3: the urethane resin of the polycondensation product of following diisocyanate and glycol: methyl diphenylene diisocyanate (MDI), hexylidene diisocyanate (HMDI), polypropylene glycol (PPG1000, weight-average molecular weight: 1,000), 2, two (methylol) propionic acid (DMPA) of 2-, copolyreaction mol ratio (MDI/HMDI/PPG1000/DMPA): 40/10/15/35, by the resulting acid number of NaOH titration: 1.05meq/g, the weight-average molecular weight that records with GPC: 45,000.

Developer solution in Table II-2

DV-1

Comprise that following component and pH value are 10 aqueous solution.

Monoethanolamine 0.1 weight portion

Triethanolamine 1.5 weight portions

Compound 4.0 weight portions by following formula 1 expression

Compound 2.5 weight portions by following formula 2 expressions

Compound 0.2 weight portion by following formula 3 expressions

Water 91.7 weight portions

DV-2

Comprise that following component and pH value are 10 aqueous solution.

Sodium bicarbonate 1.2 weight portions

Sodium carbonate 0.8 weight portion

Compound 3.0 weight portions by above-mentioned formula 1 expression

Compound 2.0 weight portions by above-mentioned formula 2 expressions

Compound 0.2 weight portion by above-mentioned formula 3 expressions

Water 92.8 weight portions

DV-3

Comprise that following component and pH value are 13 aqueous solution.

1K potassium silicate 3.0 weight portions

Potassium hydroxide 1.5 weight portions

Compound 0.2 weight portion by above-mentioned formula 3 expressions

Water 95.3 weight portions

From the result of Table II-2 as can be seen, under can the condition of Plate making printing plate with scan exposure, even under extremely low exposure energy condition, planographic printing plate precursor of the present invention can provide to high productivity good plate printing plate.On the other hand, in not using the comparative example II-7 of light trigger of the present invention, can not obtain can practical plate printing plate.

Example II-17

With preparing each planographic printing plate precursor with example II-1 to the identical method of II-6.Different is that the variation of light trigger composition is as follows, and the thickness of photosensitive layer becomes 1.5g/m ²

Light trigger

(based on the addition of total solid content in photosensitive layer)

Sensitizing dye D14 1.2 weight %

Titanocene compound T-2 1.5 weight %

Be total to photosensitizer H-1 7.0 weight %

Use has the InGaN semiconductor laser of vibration wavelength 400nm, is shining on the 25 μ m printed panels and exposure energy density 0.2mJ/cm ²Condition under, the planographic printing plate precursor that so obtains is carried out scan exposure.Then, 100 ℃ to 10 seconds kinds of plate heating after, carry out above-mentioned development processing.

Obtain the plate printing plate of the good blue image of visibility.By KOR-D printing machine (producing), use the plate printing plate that so obtains to carry out lithography by Heidelberg Co..Can obtain surpassing 50,000 the good image density and the printed matter of anti-embrocating property (that is anti fouling performance).

Example II-18

At 45 ℃, under the mandatory condition of 65%RH, will in example II-17, store 3 days by prepared planographic printing plate precursor.With the method identical, use this plate to make a plate and print with example II-17.Obtain being similar to the good result of example II-17.

Example II-19

Measure the emission intensity plot of used usually safety light and measure the position that shows (end of shortwave) emission intensity plot in the shortwave branch.In addition, comment the working ability of explaining archaic or dialectal words in current language under each safety light.Shown in the gained result following Table II-3.

Table II-3

Safety light	The end (nm) of shortwave emission	Working ability
			White lamp	400	Well
Amber light	520	Enough bright for making sheet processing
			The orange lamp	570	Quite dark, and be difficult to processing, than conventional long processing time
Red light	600	Very dark, this processing needs skill

Therefore, consider that from the working ability aspect amber light is needed.Requirement under amber light accessible material at 520nm at least, preferred 490nm or more the long wavelength have low photosensitivity.Have absorption maximum in contiguous 400nm dye groups of the present invention, so advantage of the present invention is also aspect this.

Example II-20

Prepare planographic printing plate precursor with the method identical with example II-17, different is that the variation of light trigger composition is as follows, and the thickness of photosensitive layer becomes 2.0g/m ²

Light trigger

(based on the addition of total solid content in photosensitive layer)

Sensitizing dye D14 1.5 weight %

Titanocene compound T-2 1.5 weight %

Be total to photosensitizer H-1 5.0 weight %

Use has the InGaN semiconductor laser of vibration wavelength 400nm, is shining on the 25 μ m printed panels and exposure energy density 0.15mJ/cm ²Condition under, the planographic printing plate precursor that so obtains is carried out scan exposure.Then, 100 ℃ to 10 seconds kinds of plate heating after, carry out above-mentioned development processing.Obtain having the plate printing plate of the good blue image of visibility.At 300 ℃ above-mentioned resulting plate was further heated 5 minutes, and carry out lithography with KOR-D printing machine (producing) by Heide lberg Co..Can obtain surpassing 200,000 the good image density and the printed matter of anti-embrocating property (that is anti fouling performance).

Example II-21

Before scan exposure, planographic printing plate precursor prepared in example II-20 was exposed 30 minutes with amber light.With the method identical, use this plate to make a plate and print with example II-20.Obtain and the identical good result of example II-20.

Comparative example II-8

Prepare planographic printing plate precursor with the method identical with example II-17.Different is with sensitizing dye D14 (maximum absorption wavelength: 410nm) replace H4 (maximum absorption wavelength: 500nm).Use has the InGaN semiconductor laser of vibration wavelength 400nm, uses the method plate-making identical with example II-17 to make image mobile (that is image disappearance).In addition, use the method identical, before scan exposure, to prepared planographic printing plate precursor exposure 30 minutes, and use the method identical to make a plate and print with example II-17 with amber light with example II-21.The whole surface of printed matter is solid and fuzzy.

The structure of used in this embodiment carbazyl sensitizing dye is those that are exemplified in instructions of the present invention.Other compound is as follows.

Use the planographic printing plate precursor of photosensitive composition of the present invention to have the enough photonasty that is suitable for short wavelength semiconductor laser such as InGaN scan exposure, and the plate printing plate with good pressrun and anti-embrocating property is provided.Under amber light, can improve the mist that uses photosensitive composition of the present invention to be used for the plate printing plate of scan exposure significantly, therefore can greatly improve the working ability of handling printed panel.In addition, photopolymerisable compositions of the present invention not only has good photonasty, and has excellent storage stability.

EXAMPLE III-1 is to III-6, and Comparative Example III-1 is to III-6

The preparation of carrier

With preparing each carrier with example I-1 to the I-8 method identical with comparative example I-1 to I-3.

The preparation of photosensitive layer

With following photopolymerisable compositions, be 1.0g/m with dried coating content ²Be coated onto on the aluminium sheet of above-mentioned processing,,, form photosensitive layer thus dry 2 minutes of the plate that was coated with at 80 ℃.

Pentaerythritol tetracrylate 1.5g

The multipolymer 2.0g of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Light trigger (shown in Table III-1)

Sensitizing dye

Titanocene compound

Be total to photosensitizer

Fluorine-based non-ionic surfactant (F-177P) 0.02g

Hot polymerization inhibitor, N-nitroso-phenyl hydramine aluminium salt 0.01g

Pigment dispersion 2.0g

The composition of pigment dispersion

Composition/pigment orchid: 1,5/6 15 weight portion

Copolymer 10 weight portion of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Cyclohexanone 15 weight portions

Acetate methoxyl propyl ester 20 weight portions

Propylene glycol monomethyl ether 40 weight portions

Methyl ethyl ketone 20g

Propylene glycol monomethyl ether 20g

The coating of protective seam

With with example I-1 to I-8, the method that comparative example I-1 to I-3 is identical prepares protective seam.

The adaptive evaluation of photonasty and safety light

With with example I-1 to I-8, the method that comparative example I-1 to I-3 is identical is estimated.The gained result is shown in following Table III-1.

Table III-1

Embodiment	Initiating agent (based on the addition of total solid content in photosensitive layer, weight %)			Clear photonasty (mJ/cm 2)
					Sensitizing dye	Titanocene compound	Be total to photosensitizer
	EXAMPLE III-1	D21(0.06)	T-1(0.006)					H-1(0.2)	0.2
EXAMPLE III-2				D10(0.1)	T-2(0.12)	H-2(0.2)	0.1
	EXAMPLE III-3	D12(0.08)	T-2(0.06)					Do not have	0.3
EXAMPLE III-4				D11(0.08)	T-2(0.15)	H-1(0.5)	0.2
	EXAMPLE III-5	D20(0.05)	T-2(0.03)					Do not have	0.4
EXAMPLE III-6				D1(0.1)	T-1(0.1)	Do not have	0.1
	Comparative Example III-1	D4(0.2)	Do not have					Do not have	Can not form image
Comparative Example III-2				Do not have	T-2(0.1)	Do not have	1.8
	Comparative Example III-3	Do not have	T-2(0.15)					H-1(0.2)	0.7
Comparative Example III-4				DR-2(0.05)	T-2(0.03)	Do not have	1.5
	Comparative Example III-5	DR-3(0.1)	T-1(0.1)					Do not have	1.1
Comparative Example III-6				DR-1(0.08)	H-3(0.06) *	Do not have	1.8

^*Replace titanocene compound embodiment as a comparison with triaizine compounds.

From Table III-1 as can be seen, plate printing plate of the present invention has very high speed and demonstrates enough light sensitivity for the scan exposure system.

In addition, compare with the situation of not using sensitizing dye, light trigger of the present invention is at a high speed, particularly, even when the addition of titanocene compound is very little, also demonstrate enough photonasty.

EXAMPLE III-1 to III-8 and Comparative Example III-1 to III-6 in used developer solution be to comprise that following component and pH value are 13 aqueous solution.

1K potassium silicate 3.0 weight portions

Potassium hydroxide 1.5 weight portions

Compound 0.2 weight portion by following formula 3 expressions

(Pelex NBL, by Kao Atlas Co., LTd. produces)

Water 95.3 weight portions

The compound of formula 3 (Pelex NBL)

EXAMPLE III-7 is to III-14 and Comparative Example III-7

Prepare each planographic printing plate precursor according to follow procedure, and estimate printing.The result is shown in following Table III-2.

The pre-service of carrier

With the suspending liquid of No. 8 nylon brusses and 800 order float stones and water, the 1S aluminium sheet of thick 0.30mm is brushed decorations handle, and the surface of the thorough clean plate of water.By plate was soaked for 60 seconds in the sodium hydrate aqueous solution of 70 ℃ 10 weight %, finish etch.Further water flushing with the neutralization of 20 weight % salpeter solutions, then washes with water then.Using V _AUnder the sine wave alternating current condition for 12.7V, in 1 weight % aqueous solution of nitric acid, use sine wave alternating current, with 300 coulombs/decimeter ²Anode current plate is carried out the coarse processing of electrolytic surface.The surfaceness that records is 0.45 μ m (by JIS B0601 method, representing with Ra).

The hydrophilic treatment of carrier surface

's tetrasilicic acid sodium (the SiO of 11.2 2.5 weight % with above-mentioned carrier at 70 ℃, pH value ₂: 28-30%, Na ₂O:9-10%, Fe:0.02% or still less) soaked for 13 seconds in the aqueous solution, wash with water then.Measure its lip-deep Si element by fluorescent X-ray analysis, the amount that obtains going up silicate in its surface is 10mg/m ²

The coating of internal layer

The coating solution A that preparation has following component, and with phenyl-phosphonic acid 20mg/m ²Coating content, be that the roller (wheeler) of 180rpm is coated onto it on water-wetted surface of above-mentioned carrier with rotational speed, then 80 ℃ of 30 seconds of drying.

Internal layer coating solution A

Phenyl-phosphonic acid 0.07-1.4g

Methyl alcohol 200g

The coating of photosensitive layer

With 1.0-2.0g/m ²Coating content, the photosensitive layer coating solution that will have following component with roller (wheeler) was coated onto on the above-mentioned carrier with internal layer, and at 100 ℃, with dry 1 minute of this photosensitive layer.

The photosensitive layer coating solution

But addition polymerization compound (compound shown in the Table III-2) 1.5g

Binder polymer (compound shown in the Table III-2) 2.0g

Sensitizing dye (compound shown in the Table III-2) 0.1g

Activator (compound shown in the Table III-2) 0.1g

Be total to photosensitizer (compound shown in the Table III-2) 0.3g

Pigment dispersion 2.0g

The composition of pigment dispersion

Composition/pigment orchid: 1,5/6 15 weight portion

Copolymer 10 weight portion of allyl methyl acrylate/methacrylic acid

(copolymerization mol ratio: 83/17)

Cyclohexanone 15 weight portions

Acetate methoxyl propyl ester 20 weight portions

Propylene glycol monomethyl ether 40 weight portions

Hot polymerization inhibitor, N-nitroso-phenyl hydramine aluminium salt 0.01g

Surfactant, Megafac F-177

(by Dainippon Chemcals﹠amp; InkCo., Ltd. produces) 0.02g

Methyl ethyl ketone 20.0g

Propylene glycol monomethyl ether 20.0g

The preparation that protective seam is coated with

(saponification degree: 98mol%, the degree of polymerization: aqueous solution 550) is 2g/m with dried coating content with 3 weight % polyvinyl alcohol (PVA) ²Be coated onto on the photosensitive layer, and 100 ℃ of dryings 2 minutes.

The exposure of planographic printing plate precursor

With 400nm monochromatic light light source, to the planographic printing plate precursor exposure that so obtains, the control exposure makes the exposure energy density of plate become 200 μ J/cm ², under the condition of 175 line/inches, make the plate exposure by solid state image exposure and per 1% half luminous point imaging exposure for 1%-99%.

Develop and plate-making

With the preparation developer solution (shown in the Table II-2) and Finsher FP-2W (by Fuji Photo Film Co., Ltd., produce) be put into automatic processor LP-850 (by Fuji Photo Film Co., Ltd., produce) in, under 30 ℃ of developing solution temperature and 18 seconds condition of development time, exposed plate is developed/makes a plate.Therefore, obtain plate printing plate.

The pressrun test

Use R201 (by Roland Co., Ltd. produces) printing machine and GEOS-G (N) (by DainipponChemicals﹠amp; Ink Co., Ltd. produces) printing ink.Observe the printed matter of solid state image part and estimate pressrun by the number that fogs.This value is high more, and pressrun is good more.

The pressure test of half luminous point pressrun

Use R201 (by Roland Co., Ltd. produces) printing machine and GEOS-G (N) (by DainipponChemicals﹠amp; InkCo., Ltd. produces) printing ink.Begin after 5,000 of printings from printing,, PS board cleaning agent CL-2 (by Fuji Photo Film Co., Ltd. produces) is executed on the printing sponge, and eliminate half luminous point part in order to remove the printing ink on printed panel.Then, print 10,000, and the omission of half luminous point on printed matter that detects by an unaided eye (that is, disappearing).

Embrocating property test (that is contaminative)

Use R201 (by Roland Co., Ltd. produces) printing machine and GEOS-G (N) (by DainipponChemicals﹠amp; Ink Co., Ltd. produces) printing ink.Observe the no image section (unexposed portion) of printed matter and estimate embrocating property (that is contaminative).

Table III-2

Embodiment number	Photosensitive layer						The composition of developer solution	Printing performance
											But addition polymerization compound	Binder polymer	Sensitizing dye	Titanocene compound	Be total to photosensitizer	Coating content (mg/m 2)	The pressrun of image section	The pressrun of half luminous point part	The embrocating property of non-imaging moiety
	EXAMPLE III-7	M-1	B-1	D-11	T-1	H-5		1.5	DV-1	100,000										Well	Well
EXAMPLE III-8							M-2				B-1	D-22	T-2	H-5	2	DV-2	70,000	Well	Well
	EXAMPLE III-9	M-2	B-3	D-1	T-2	H-2		1.8	DV-3	200,000										Well	Well
EXAMPLE III-10							M-1				B-2	D-26	T-2	H-2	2.5	DV-1	80,000	Well	Well
	EXAMPLE III-11	M-1	B-1	D-16	T-1	H-2		1	DV-1	70,000										Well	Well
EXAMPLE III-12							M-2				B-3	D-10	T-1	H-2	1	DV-3	50,000	Well	Well
	EXAMPLE III-13	M-2	B-3	D-20	T-2	H-4		2.5	DV-3	50,000										Well	Well
EXAMPLE III-14							M-2				B-1	D-21	T-1	H-5	1.8	DV-1	80,000	Well	Well
	Comparative Example III-7	M-1	B-1	Do not have	T-2	H-2		1.5	DV-1	Image flows										Image flows	Well

But the addition polymerization compound in Table III-2

M-1: pentaerythritol tetracrylate (by Shin-Nakamura Kagaku Kogyo Co., Ltd., the ester A-TMMT that NK produces)

M-2: dimethacrylate glycerine ester cyclohexylene diisocyanate carbamate prepolymer (by KyoeiChemical Co., Ltd., UA101H)

Binder polymer in Table III-2

B-1: allyl methyl acrylate/methacrylic acid/N-N-isopropylacrylamide multipolymer (the copolyreaction mol ratio: 67/13/20), by the resulting acid number of NaOH titration: 1.15meq/g, the weight-average molecular weight that records with GPC: 130,000.

B-2: allyl methyl acrylate/methacrylic acid copolymer (copolyreaction mol ratio: 83/17), cross the resulting acid number of NaOH titration a: 1.55meq/g for logical cun, the weight-average molecular weight 125,000 that records with GPC.

B-3: the urethane resin of the polycondensation product of following diisocyanate and glycol: MDI (MDI), hexylidene diisocyanate (HMDI), polypropylene glycol (PPG1000, weight-average molecular weight: 1,000), 2, two (methylol) propionic acid (DMPA) of 2-, copolyreaction mol ratio (MDI/HMDI/PPG1000/DMPA): 40/10/15/35, by the resulting acid number of NaOH titration: 1.05meq/g, the weight-average molecular weight that records with GPC: 45,000.

Developer solution in Table III-2

DV-1

Comprise that following component and pH value are 10 aqueous solution.

Monoethanolamine 0.1 weight portion

Triethanolamine 1.5 weight portions

Compound 4.0 weight portions by following formula 3 expressions

Compound 2.5 weight portions by following formula 4 expressions

Compound 0.2 weight portion by following formula 5 expressions

Water 91.7 weight portions

(Pelex NBL, by Kao Atlas Co., LTd. produces)

(Nukol B4SN, by Nippon Nyukazai Co., Ltd. produces)

DV-2

Comprise that following component and pH value are 10 aqueous solution.

Sodium bicarbonate 1.2 weight portions

Sodium carbonate 0.8 weight portion

Compound 3.0 weight portions by above-mentioned formula 3 expressions

(Pelex NBL is made by Kao Atlas Co.Ltd)

Compound 2.0 weight portions by above-mentioned formula 4 expressions

(Nukol B4SN is made by Nippon Nyukazai Co.Ltd)

Compound 0.2 weight portion by above-mentioned formula 5 expressions

Water 92.8 weight portions

DV-3

Comprise that following component and pH value are 13 aqueous solution.

1K potassium silicate 3.0 weight portions

Potassium hydroxide 1.5 weight portions

Compound 0.2 weight portion by above-mentioned formula 5 expressions

Water 95.3 weight portions

From the result of Table III-2 as can be seen, under can the condition of Plate making printing plate with scan exposure (that is, even under extremely low-yield conditions of exposure), planographic printing plate precursor of the present invention can provide to high productivity good plate printing plate.On the other hand, in the Comparative Example III of not using light trigger of the present invention-7, can not obtain available plate printing plate.

EXAMPLE III-15

With preparing each planographic printing plate precursor with EXAMPLE III-1 to the identical method of III-6.Different is that the variation of light trigger composition is as follows, and the thickness of photosensitive layer becomes 1.5g/m ²

Light trigger

(based on the addition of total solid content in photosensitive layer)

Sensitizing dye D20 1.2 weight %

Titanocene compound T-2 1.5 weight %

Be total to photosensitizer H-1 7.0 weight %

Use has the InGaN semiconductor laser of vibration wavelength 400nm, is shining on the 25 μ m printed panels and exposure energy density 0.2mJ/cm ²Condition under, the planographic printing plate precursor that so obtains is carried out scan exposure.Then, 100 ℃ to 10 seconds kinds of plate heating after, carry out above-mentioned development processing.

Obtain the plate printing plate of the good blue image of visibility.By KOR-D printing machine (producing), use the plate printing plate that so obtains to carry out lithography by Heidelberg Co..Can obtain surpassing 50,000 the good image density and the printed matter of anti-embrocating property (both, soil resistances).

EXAMPLE III-16

At 45 ℃, under the mandatory condition of 65%RH, will in EXAMPLE III-15, store 3 days by prepared planographic printing plate precursor.With the method identical, use this plate to make a plate and print with EXAMPLE III-15.Obtain being similar to the good result of EXAMPLE III-15.

EXAMPLE III-17

Measure the emission intensity plot of used usually safety light and measure the position that shows (end of shortwave) emission intensity plot in the shortwave branch.In addition, comment the working ability of explaining archaic or dialectal words in current language under each safety light.Shown in the gained result following Table III-3.

Table III-3

Safety light	The end (nm) of shortwave emission	Working ability
			White lamp	400	Well
Amber light	520	Enough bright for making sheet processing
			The orange lamp	570	Quite dark, and be difficult to processing, than conventional long processing time
Red light	600	Very dark, this processing needs skill

Therefore, consider that from the working ability aspect amber light is needed.Requirement under amber light accessible material at 520nm at least, preferred 490nm or more the long wavelength have low photosensitivity.Have absorption maximum in contiguous 400nm dye groups of the present invention, so advantage of the present invention is also aspect this.

EXAMPLE III-18

Prepare planographic printing plate precursor with the method identical with EXAMPLE III-15, different is that the variation of light trigger composition is as follows, and the thickness of photosensitive layer becomes 2.0g/m ²

Light trigger

(based on the addition of total solid content in photosensitive layer)

Sensitizing dye D20 1.5 weight %

Titanocene compound T-2 1.5 weight %

Be total to photosensitizer H-1 5.0 weight %

Use has the InGaN semiconductor laser of vibration wavelength 400nm, is shining on the 25 μ m printed panels and exposure energy density 0.15mJ/cm ²Condition under, the planographic printing plate precursor that so obtains is carried out scan exposure.Then, 100 ℃ to 10 seconds kinds of plate heating after, carry out above-mentioned development processing.Obtain having the plate printing plate of the good blue image of visibility.At 300 ℃ above-mentioned resulting plate was further heated 5 minutes, and carry out lithography with KOR-D printing machine (producing) by Heide lberg Co..Can obtain surpassing 200,000 the good image density and the printed matter of anti-embrocating property (that is soil resistance).

EXAMPLE III-19

Before scan exposure, planographic printing plate precursor prepared in EXAMPLE III-18 was exposed 30 minutes with amber light.With the method identical, use this plate to make a plate and print with EXAMPLE III-18.Obtain and the identical good result of EXAMPLE III-18.

Comparative Example III-8

Prepare planographic printing plate precursor with the method identical with EXAMPLE III-15.Different is with sensitizing dye D20 (maximum absorption wavelength: 395nm) replace the DR-4 maximum absorption wavelength: 500nm).Use has the InGaN semiconductor laser of vibration wavelength 400nm, uses the method plate-making identical with EXAMPLE III-15 to make image mobile (that is image disappearance).In addition, use the method identical, before scan exposure, to prepared planographic printing plate precursor exposure 30 minutes, and use the method identical to make a plate and print with EXAMPLE III-19 with amber light with EXAMPLE III-19.The whole surface of printed matter is solid and fuzzy.

Comparative Example III-9

Make a plate with the method identical with EXAMPLE III-15.Different is that FD-YAG (532nm) replaces laser instrument.Obtain having 1.8mJ/cm ²Clear photosensitive image.But, use the method identical with EXAMPLE III-19, before scan exposure, to prepared planographic printing plate precursor exposure 30 minutes, and use the method identical to make a plate and print with EXAMPLE III-19 with amber light.The whole surface of printed matter is solid and fuzzy.

When photosensitive composition of the present invention is used as the photosensitive layer of planographic printing plate precursor, planographic printing plate precursor has the enough photonasty that is suitable for short wavelength semiconductor laser such as InGaN scan exposure, and the plate printing plate with good pressrun and anti-embrocating property (being pollution resistance) is provided.Under amber light, can improve the mist that uses photosensitive composition of the present invention to be used for the plate printing plate of scan exposure significantly, therefore can greatly improve the working ability of handling printed panel.In addition, photopolymerisable compositions of the present invention has good photonasty to wavelength 350nm-450nm, also has fabulous storage stability simultaneously.

Although understand the present invention in detail with reference to each specific embodiment, the various changes and modifications of carrying out under the situation that does not deviate from the spirit and scope of the present invention are conspicuous to those of ordinary skills.

Claims (4)

1. a photosensitive composition comprises (i) sensitizing dye by following formula (III-1) expression, but (ii) titanocene compound and (iii) have the addition polymerization compound of ethylenical unsaturated double bonds:

Wherein the A representative can have substituent aromatic rings or heterocycle; The X represention oxygen atom, sulphur atom or-N (R ₃)-; R ₁, R ₂And R ₃Each represents hydrogen atom, or the non-metal atom group of unit price, A and R ₁, and R ₂And R ₃Respectively mutually bonding with form fat or fragrance group, in the photosensitive composition composition of 100 weight %, the sensitizing dye of formula (III-1) expression is 0.05-30 weight %, titanocene compound is 0.5-80 weight %, but the addition polymerization compound with ethylenical unsaturated double bonds is 5-80 weight %.

2. the photosensitive composition of claim 1, but described addition polymerization compound with ethylenical unsaturated double bonds is acrylic or methacrylic acid.

3. the photosensitive composition of claim 1, but but described addition polymerization compound with ethylenical unsaturated double bonds is a carbamates addition polymerization compound.

4. light polymerization process, this method comprise with the photosensitive composition exposure of the laser beam with wavelength 350nm-450nm to claim 1.