CN1221862C - Sensitive or thermal-induction image forming material - Google Patents

Abstract

The present invention provides a photosensitive or heat sensitive image forming material capable of making plates by infrared laser, obtaining images with high quality and storing favorable stability. The present invention is characterized in that a recording layer which can change a composition soluble to water or water containing soda by light functions or heat functions is arranged on a supporter; a middle layer which has the same functions as the recording layer and has higher sensitivity to the light functions or the heat functions than the recording layer is arranged between the supporter and the recording layer. The image forming material preferably contains an infrared absorbing agent so as to record with high sensitivity by utilizing the infrared laser.

Description

Sensitization or thermonasty Image forming material

The invention relates to the sensitization or the thermonasty Image forming material that can be used as lithographic printing plate material, color proof, photoresist and color filter, particularly about carrying out infrared laser scanning and the minus directly plate-making, that can be used as the lithographic printing plate material that directly to make a plate or the sensitization or the thermonasty Image forming material of eurymeric according to the digital signal of computing machine etc.

In recent years, the research of laser technology has obtained breakthrough, particularly the ultrared solid state laser of emission wavelength 760nm to 1200nm and semiconductor laser (following be called for short sometimes " iraser ") can be easy to obtain high-output power and small-sized product.These irasers can be used as recording light source when the numerical data of utilizing computing machine etc. is directly carried out galley plate-making.Therefore, for to the high photosensitive polymer combination of the susceptibility of this class infrared ray recording light source, promptly cause photochemical reaction etc. and the demand that changes greatly for the photosensitive polymer combination of the solubility of imaging liquid increases year by year by infrared radiation.

The recording materials of induction take place for these laser, people have carried out various researchs, representative research results wherein, as can be with the material of infrared laser more than wavelength photoreceptor 760nm record, the minus recording materials of the acid catalysis cross-linking type of putting down in writing among the eurymeric recording materials put down in writing among the US4708925 and the flat 8-276558 of Te Kai etc. be arranged.

In addition, as the ultraviolet light of 300nm-700nm or the recording materials of the corresponding type of visible light laser, described in US2850445 and special public clear 44-20189, the minus recording materials of many free radical polymerization types etc. are arranged.The recording materials that utilize free radical polymerization like this can be realized high sensitivity, but because the polymerization inhibiting effect of oxygen, susceptibility greatly reduces.

These Image forming materials all are to form 1 layer of recording layer with single composition on supports such as aluminium.The individual layer recording layer that constitutes by the composition of homogeneous, because the influence of photoactive substance, the effect of the energy-ray that sends from light source, more little from the surface of photographic layer to its effect of the past more depths of support, be reduced to minimum at close support near interface.In addition, in the occasion of using infrared ray to expose, because to the thermal diffusion of the support back side, above-mentioned tendency is further aggravated.

In order to alleviate the problems referred to above, can take to improve the way of the susceptibility of recording layer itself, but the susceptibility of height can cause that storage stability reduces under high humidity environment, causes going wrong in the practicality, therefore presses for high image quality and storage stability preferable image and forms material.

On the other hand, the material that can utilize following short-wavelength light of 300nm and electron beam to write down is a particular importance as the photoresist material.In recent years, the integrated level of integrated circuit is more and more higher, in the manufacture process of the Semiconductor substrate of super LSI etc., also need to carry out the processing of the superfine graph that constitutes by the live width below half micron, in order to address that need, the use wavelength of exposure device that is used for photoetching is shorter and shorter, people have inquired into extreme ultraviolet light and excimer laser (XeCl, KrF, ArF etc.), have begun now to inquire into to utilize electron beam to form ultramicrofine figure.Electron beam promises to be the light source of figure formation technology of future generation especially.

The common issue of these Image forming materials is, how to enlarge above-mentioned various energy exposure portion and not irradiation portion be the ON-OFF of the image of image portion and non-image portion, in this regard, also there are some problems in recording layer with single composition recited above, for example, in the Image forming material of minus, the adhesion deficiency of support and image portion, in the Image forming material of eurymeric, owing to not enough the causing of the video picture of image portion left residual film on support.On these problems, can not meet the demands fully, thereby need the unexistent in the past new technology of development.

The objective of the invention is, a kind of sensitization or thermonasty Image forming material are provided, for this Image forming material, use ultrared solid state laser of irradiation and semiconductor laser can be directly to make a plate according to the numerical data of computing machine etc., be formed on the images with high image quality that does not have residual film in the minus on the image adhesion power support good, non-image portion in eurymeric, and storage stability is good.

The inventor starts with from the layer formation of the recording layer of Image forming material and has carried out deep research, found that, by have the recording layer of common susceptibility, between recording layer and support, be provided with and have more high sensitive recording layer being provided with near the plane of exposure for exposure light source, can adopt infrared laser to carry out record, form images with high image quality, and can solve the problem of storage stability, thereby finished the present invention.

Promptly, the present invention is sensitization or thermonasty Image forming material, it is characterized in that, on support, be provided with by effect and change the recording layer that the composition for the solubility of water or buck constitutes by light or heat, between this support and recording layer, be provided with and have with the recording layer said function and for the susceptibility of the effect of light or heat middle layer than this record floor height.

In above-mentioned sensitization or thermonasty Image forming material, add infrared absorbent, can utilize infrared laser to carry out the record of high sensitivity.

Effect Ji Lishang of the present invention is not fully aware of, it is believed that, adopt Image forming material of the present invention, the layer have with the more hypersensitivity of recording layer said function is set as the middle layer between support and the recording layer, can make the rerum natura of support near interface change increase, show high image quality (for minus and the adhesion of Yan Shigao, for eurymeric and the residual film of Yan Shigao is eliminated property).

In addition; usually; if high sensitive recording layer is set; stability when preserving under high humidity can reduce; the humidity that the reduction of this stability is actually owing to the recording layer surface is that the influence that moisture soaks in recording layer causes; therefore; as the recording layer that directly contacts with external environment condition; the recording layer that has good stability that configuration has common susceptibility; like this; the layer of hypersensitivity is protected, even also can keep good storage stability under the condition of high humility.

Therefore, adopt this structure can take into account two aspects of storage stability under high image quality and the high humility.

In addition, in the present invention, sensitization or thermonasty Image forming material (being designated hereinafter simply as Image forming material) also comprise the Image forming material of not only sensitization but also sensible heat.

[working of an invention mode]

Explain the present invention below.

Image forming material of the present invention, so long as on support stacked that be used to write down, get final product for 2 layers of different recording layer of susceptibility of light or heat, have no particular limits for the formation of recording layer.

Operable recording layer in Image forming material of the present invention for instance, can be enumerated known free radical polymerization system, the crosslinked system of acid catalysis (comprising cationic polymerization) recording layer as the recording layer of minus.In these recording layers, the free radical or the acid that produce by rayed or heating become initiating agent or catalyzer, make the compound polymerization reaction take place that constitutes recording layer, cross-linking reaction and solidify, and form image portion.In addition, can enumerate known acid catalyzed decomposition as the recording layer of eurymeric is, interacts and remove system's (sensible heat eurymeric).In these recording layers, by acid or the heat energy that rayed or heating produce, the feasible key that has formed the macromolecular compound of layer is disengaged, and becomes water soluble and buck, is removed by video picture, forms non-image portion.

The present invention is this principle of difference of utilizing recording layer susceptibility (reactivity) to each other, is not constituted the influence of the kind of the sensitization of recording layer or sensible heat material.

Below, specifically describe the various formations of Image forming material of the present invention.

Image forming material of the present invention, be on support, to be provided with to change the recording layer that the composition for the solubility of water or buck constitutes by effect and form by light or heat, this recording layer contains water insoluble usually and dissolves in the macromolecule of buck, effect by light or heat, the high molecular key that constitutes this layer is cut off, perhaps key is strengthened or newly forms and solidify, and causes dissolubility for the alkali imaging liquid to increase or reduces.

In addition, in the present invention, water insoluble and macromolecule that dissolve in buck abbreviates " buck soluble high-molecular " sometimes as.

Adopt the image forming method of Image forming material of the present invention and this material of use, in the occasion of carrying out the minus record, because the effect of light or heat, recording layer reduces for the dissolubility of alkali imaging liquid, can also contain the crosslinked compound of useful acid in the above-mentioned buck soluble high-molecular and the acidic compound by heat.In addition, in the occasion of carrying out the eurymeric record, because the effect of light or heat, recording layer increases for the dissolubility of alkali imaging liquid, consider from the liquefiable angle that promotes above-mentioned buck soluble high-molecular, can use the infrared absorbent of father-in-law's salt type as infrared absorbent.

The bonding agent macromolecule that uses among the present invention can use the known macromolecular compound of the various different occasions that are suitable for minus or eurymeric.According to the different separately occasions of minus or eurymeric, can use macromolecular compound described below.

The macromolecule that uses in the recording layer as the Image forming material of minus can be enumerated the aromatic hydrocarbon ring that has hydroxyl or the direct combination of alkoxy on side chain or main chain.Described alkoxy is considered from the angle of susceptibility, preferably 20 alkoxys that carbon atom is following.In addition, described aromatic hydrocarbon ring is considered from the angle that raw material is convenient to obtain, preferably phenyl ring, naphthalene nucleus or anthracene nucleus.These aromatic hydrocarbon rings also can have the substituting group beyond hydroxyl or the alkoxy, substituting group such as halogen radical, cyano group for example, and the angle of the susceptibility of not associating considers, preferably do not have the substituting group beyond hydroxyl or the alkoxy.

Operable in the present invention binder polymer is to have by phenolics such as polymkeric substance that constitutes the unit shown in the following general formula (III) or novolac resins.

[changing 1]

General formula (III)

In the formula, Ar ²Expression phenyl ring, naphthalene nucleus or anthracene nucleus.R ⁴Expression hydrogen atom or methyl.R ⁵Expression hydrogen atom or 20 alkoxys that carbon atom is following.X ¹Atom more than a kind and the carbon number representing to contain singly-bound or be selected among C, H, N, O, the S are the concatenating group of 0-20 divalent.K represents the integer of 1-4.

Below, at first enumerate the example ([BP-1]-[BP-6]) by the formation unit of general formula (III) expression that can be suitable in the present invention, but the present invention is not subjected to the restriction of these examples.

[changing 2]

[changing 3]

Have the polymkeric substance that these constitute unit, can be by using corresponding monomer, adopting in the past known method to carry out free radical polymerization to obtain.

In the present invention,, only can use the homopolymer that constitutes by the formation unit shown in the general formula (III), also can use to have this specific formation unit and by the multipolymer that constitutes the unit of other known monomer derived as binder polymer.Other known monomer that use this moment can be enumerated: esters of acrylic acids such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-EHA, cyclohexyl acrylate, acrylic acid 2-hydroxyl ethyl ester, benzyl acrylate; Methyl acrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid 2-Octyl Nitrite, cyclohexyl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, benzyl methacrylate; Styrene, vinyl cyanide and acrylic acid, methacrylic acid etc. have the monomer of acidic groups; The salt of the strong acid such as sylvite of the alkali metal salt of the sodium salt of p styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, tetraalkylammonium salt, 3-sulfopropyl acrylate.

Use the ratio that contains in the multipolymer of these monomers to be advisable, preferably 60-100% (weight) at 50-100% (weight) by the formation unit of general formula (III) expression.

In addition, the weight-average molecular weight of the polymkeric substance that uses among the present invention is advisable below 1-5000, and preferably 10,000-300,000, number-average molecular weight is being advisable more than 1000, and preferably 2000-25 ten thousand.Polydispersity (weight-average molecular weight/number-average molecular weight) is being advisable more than 1, preferably the scope of 1.1-10.

These polymkeric substance can be any in atactic polymers, block polymer, the graft polymer etc., preferably atactic polymers.

Employed solvent for example can be enumerated during the polymkeric substance that uses in synthetic the present invention: tetrahydrofuran, dichloroethylene, cyclohexanone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, acetate 2-methoxy ethyl ester, diethylene glycol dimethyl ether, 1-methoxyl-2-propyl alcohol, 1-methoxyl-2-propyl-acetic acid ester, N, dinethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water etc.These solvents may be used alone, can also be two or more kinds in combination.

The initiating agent of employed free radical polymerization can use known compounds such as azo-initiator, peroxide initiator during the polymkeric substance that uses in synthetic the present invention.

Narrate the novolac resin class below.The novolac resin that can be suitable among the present invention can enumerate linear phenol-aldehyde resin, neighbour-,-, the novolac resin of the phenol that replaced by halogen atom, alkyl etc. of right-various cresols linear phenol-aldehyde resins and multipolymer thereof, utilization.

The weight-average molecular weight of these novolac resins is being advisable more than 1000, preferably the scope of 2000-2 ten thousand.Number-average molecular weight is being advisable more than 1000, preferably the scope of 2000-15000.Polydispersity is being advisable more than 1, preferably the scope of 1.1-10.

In addition, be suitable as add novolac resin that polymkeric substance uses can enumerate linear phenol-aldehyde resin, neighbour-,-, the novolac resin of the phenol that replaced by halogen atom, alkyl etc. of right-various cresols linear phenol-aldehyde resins and multipolymer thereof, utilization.

The weight-average molecular weight of these novolac resins is being advisable more than 1000, preferably the scope of 2000-200000 ten thousand.Number-average molecular weight is being advisable more than 1000, preferably the scope of 2000-150000.Polydispersity is being advisable more than 1, preferably the scope of 1.1-10.

Secondly, as the macromolecular compound of the Image forming material that can be used for eurymeric, be included on main chain in the macromolecule and/or the side chain and contain the homopolymer of acidic groups, their multipolymer and their potpourri.

Wherein, from for the dissolubility of alkaline imaging liquid and demonstrate dissolving suppress can angle consider that the compound that has the described acidic groups in following (1)-(6) in high molecular main chain and/or side chain is optimal.

(1) phenolic group (Ar-OH)

(2) sulfonamido (SO ₂NH-R)

(3) sulfonamide of Qu Daiing is acidic group (hereinafter to be referred as " an active imino group ")

[-SO ₂NH COR-SO ₂NHSO ₂R-CONHSO ₂R]

(4) carboxylic acid group (CO ₂H)

(5) sulfonic group (SO ₃H)

(6) phosphate (OPO ₃H ₂)

In above-mentioned (1)-(6), Ar represents to have the aryl concatenating group of substituent divalent, and R represents to have substituent alkyl.

In having the buck soluble high-molecular that is selected from the acidic groups in above-mentioned (1)-(6), the buck soluble high-molecular that preferably has (1) phenolic group, (2) sulfonamido and (3) active imino group, consider from the angle of guaranteeing dissolubility, video picture tolerance and film strength, preferably select buck soluble high-molecular for use with (1) phenolic group or (2) sulfonamido for alkaline imaging liquid.

Buck soluble high-molecular with the acidic groups that is selected from above-mentioned (1)-(6) for example can be enumerated as follows:

(1) as having the buck soluble high-molecular of phenolic group, for example can enumerate: the condensed polymer of the condensed polymer of the condensed polymer of phenol and formaldehyde, metacresol and formaldehyde, paracresol and formaldehyde ,/to the condensed polymer of cresols and formaldehyde, phenol and cresols (between can being, to or/in mixing any) and the condensed polymer of novolac resin such as the condensed polymer of formaldehyde and Pyrogallol and acetone.Can also enumerate in addition and make the compound copolymerization that has phenolic group on the side chain and the multipolymer that obtains.Perhaps, the multipolymer that can also use the compound copolymerization that has phenolic group on the side chain to obtain.

Above-mentioned compound with phenolic group can be enumerated acrylamide, Methacrylamide, acrylate, methacrylate or the hydroxy styrenes etc. with phenolic group.

The weight-average molecular weight of buck soluble high-molecular is 5.0 * 10 ²-2.0 * 10 ⁴, consider that from the angle of image formation property preferably number-average molecular weight is 2.0 * 10 ²-1.0 * 10 ⁴These macromolecules not only may be used alone, two or more kinds can also be used in combination.In the occasion that is used in combination, can also simultaneously and have the condensed polymer of the alkyl of 3-8 carbon atom as substituent phenol and formaldehyde with the condensed polymer of tertiary butyl phenol described in the US4123279 and formaldehyde and the condensed polymer of octyl phenol and formaldehyde etc.

(2) conduct has the buck soluble high-molecular of sulfonamido, for example can enumerate with the minimum that is obtained by the compound with sulfonamido to constitute the polymkeric substance that the unit constitutes as the main composition composition.Such compound can enumerate have respectively in the molecule more than 1 on nitrogen-atoms at least in conjunction with the compound of the sulfonamido of 1 hydrogen atom and unsaturated group that can polymerization.Wherein preferentially select the low molecular compound that has acryloyl group, allyl or ethyleneoxy and replacement or a substituted-amino sulfonyl or substituted sulphonyl imino group in the molecule for use, for example the compound of representing by following general formula 1-5.

General expression 1

General expression 2

General expression 3

General expression 4

General expression 5

In the formula, X ¹, X ²Respectively independently expression-O-or-NR ²⁷-.R ²¹, R ²⁴, respectively represent independently hydrogen atom or-CH ₃R ²², R ²⁵, R ²⁹, R ³²And R ³⁶Represent to have alkylidene, ring alkylidene, arlydene or the inferior aralkyl of substituent carbon number 1-12 respectively independently.R ²³, R ²⁷And R ³³Represent hydrogen atom, the alkyl that can have substituent carbon number 1-12, naphthenic base, aryl or aralkyl respectively independently.In addition, R ²⁶, R ³⁷Represent to have alkyl, naphthenic base, aryl, the aralkyl of substituent carbon number 1-12 respectively independently.R ²⁸, R ³⁰And R ³⁴Represent independently respectively hydrogen atom or-CH ₃R ³¹, R ³⁵Represent singly-bound respectively independently or can have substituent carbon number 1-12 alkylidene, the ring alkylidene, arlydene or inferior aralkyl.Y ³, Y ⁴Represent independently respectively singly-bound or-CO-.

In the compound of representing by general formula 1-5; for eurymeric lithography material of the present invention, especially preferentially select an amino-sulfonyl phenyl methyl acrylate, N-(to the amino-sulfonyl phenyl) Methacrylamide, N-(to the amino-sulfonyl phenyl) acrylamide etc. for use.

(3) conduct has the buck soluble high-molecular of active imino group, for example can enumerate with the minimum that is obtained by the compound with active imino group to constitute the polymkeric substance that the unit constitutes as the main composition composition.Such compound can be enumerated the compound of the active imino group of being represented by following structural that has respectively in the molecule more than 1 and unsaturated group that can polymerization.

[changing 5]

Specifically, can use N-(p-toluenesulfonyl) Methacrylamide, N-(p-toluenesulfonyl) acrylamide etc.

(4) as having carboxylic acid group's buck soluble high-molecular, the minimum that for example can enumerate to be obtained by the compound that has carboxylic acid group more than 1 and polymerisable unsaturated group in the molecule respectively constitutes the polymkeric substance of unit as the main composition composition.

(5) as having sulfonic buck soluble high-molecular, the minimum that for example can enumerate to be obtained by the compound that has sulfonic group more than 1 and polymerisable unsaturated group in the molecule respectively constitutes the polymkeric substance of unit as the main composition composition.

(6) as having the buck soluble high-molecular of phosphate, the minimum that for example can enumerate to be obtained by the compound that has phosphate more than 1 and polymerisable unsaturated group in the molecule respectively constitutes the polymkeric substance of unit as the main composition composition.

Be formed in the minimum unit buck soluble high-molecular, that have the acidic groups that is selected from above-mentioned (1)-(6) that uses in the Image forming material of eurymeric, not necessarily only be a kind, also can use will have more than 2 kinds the minimum of the same acidic groups minimum that constitutes the unit or have different acidic groups more than 2 kinds constitute the unit copolymerization and the product that obtains.

The method of copolymerization can adopt known in the past grafting copolymerization process, segment copolymerization method or random copolymerization method.

Above-mentioned multipolymer should contain the compound above copolymerization of 10% (mole), that have the acidic groups that is selected from (1)-(6) in multipolymer, preferably contain more than 20% (mole).When being lower than 10% (mole), often can not fully improve the video picture tolerance.

It is fashionable to use infrared laser to write on Image forming material of the present invention, considers from the angle of susceptibility, preferably contains infrared absorbent in recording layer.

Infrared absorbent has the function that the infrared ray that will absorb is transformed into heat, at this moment, in the recording materials of minus, because the heat that produces is decomposed acid forming agent described below, generates acid, and cross-linking reaction takes place in recording layer, in addition, in the recording materials of eurymeric, by laser scanning generation photochemical reaction, feasible dissolubility for imaging liquid increases greatly.

The infrared absorbent that uses among the present invention is ultrared dyestuff or the pigment of absorbing wavelength 760nm-1200nm effectively, preferably has the dyestuff or the pigment of absorption maximum at the 760nm-1200nm wavelength.

Explain below at Image forming material of the present invention and have the infrared absorbent that the occasion of minus recording layer can be suitable for.

The known dyestuff that above-mentioned dyestuff can use commercially available dyestuff and for example put down in writing in the document such as " dyestuff brief guide " (Synthetic Organic Chemistry association compiles, clear and 45 annuals).Specifically can enumerate dyestuffs such as azo dyes, metal complex salts azo dyes, pyrazolone azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine type dye, cyanine dyestuff, this Valley, storehouse pigment, pyralium salt, metal mercaptide salt ligand.

Preferred dyestuff for example can be enumerated: the spy opens clear 58-125246, spy and opens clear 59-84356, spy and open the cyanine dyestuff that clear 59-202829, spy open record among the clear 60-78787 etc.; The spy opens clear 58-173696, spy and opens the methine type dye that clear 58-181690, spy open record among the clear 58-194595 etc.; The spy opens clear 58-112793, spy and opens clear 58-224793, spy and open clear 59-48187, spy and open clear 59-73996, spy and open the naphthoquinone dyestuff that clear 60-52940, spy open record among the clear 60-63744 etc.; The spy opens black nurse (ス Network ワ リ リ ウ system) pigment in this Valley, storehouse of middle records such as clear 58-112792; The cyanine dyestuff of putting down in writing among the GB434875 etc.

In addition, can also use the near infrared absorption sensitizer of putting down in writing among the US5156938, can use aryl benzo (sulfo-) pyralium salt of the replacement of putting down in writing among the US3881924 in addition, the spy opens three methine thia pyralium salts of record among the clear 57-142645 (US4327169), the spy opens clear 58-181051, the spy opens clear 58-220143, the spy opens clear 59-41363, the spy opens clear 59-84248, the spy opens clear 59-84249, the spy opens clear 59-146063, the spy opens the pyrans based compound of putting down in writing among the clear 59-146061, the spy opens the peaceful pigment of the match of putting down in writing among the clear 59-216146, the five methine sulfo-pyralium salts of putting down in writing among the US4283475 etc., perhaps special fair 5-13514, the pyrylium compound of putting down in writing among the special fair 5-19702.

In addition, as other preferred example of dyestuff, can enumerate in the instructions of US4756993 (I) and (II) hear-infrared absorption dye shown in the formula.

In these dyestuffs, especially preferentially select the peaceful pigment of match, this Valley, storehouse pigment, pyralium salt, mercaptan nickel ligand for use.

The pigment that uses among the present invention, can adopt commercially available pigment and カ ラ-イ Application デ Star Network ス (C.I.) brief guide, " up-to-date pigment brief guide " (Japanese pigment technology association compiles, 1977 annuals), " up-to-date pigment applications technology " (CMC publishes, 1986 annuals) are arranged, CMC publishes " printing イ Application キ technology ", 1984 annuals) in the pigment of record.

The kind of pigment can be enumerated black pigment, yellow uitramarine, orange pigment, brown pigments, red pigment, violet pigment, green pigment, viridine green, fluorescent pigment, metal powder pigment etc., also has polymer scale to close pigment in addition.Specifically, can use insoluble azo colour, mordant pigment, condensed azo pigment, chelating AZO pigments, titanium cyanines series pigments, anthraquione pigmentss, perylene system and Suo Lan intellectual circle series pigments, thioindigo series pigments, quinoline pyridine ketone series pigments, dioxazine series pigments, isoindoline ketone series pigments, Kui phthalein ketone series pigments, dye and pay a mordant pigment, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment, carbon black etc.Preferentially select carbon black in these pigment for use.

These pigment can not carry out surface treatment just to be used, and also can carry out using after the surface treatment.The surface-treated method can adopt, the method for surface coated resin or wax, and the method for attaching surface activating agent perhaps makes reactive materials (for example organosilane coupling agent, epoxy compound, polyisocyanate etc.) be attached to method on the surface of pigments etc.Above-mentioned surface treatment method is documented in " metal crystal soda character と application " (good fortune study), " printing イ Application キ technology " (CMC publication, 1984 annuals) and " up-to-date pigment applications technology " (CMC publication, 1986 annuals).

The particle diameter of pigment is advisable in the 0.01-10 mu m range, preferably 0.05-1 μ m, preferably 0.1-1 μ m.The particle diameter of pigment is during less than 0.01 μ m, disperse thing stable bad in the image recording layer coating fluid, otherwise during above 10 μ m, the homogeneity of image recording layer is also bad.

With the method for pigment dispersing, can adopt the known dispersion technology that in printing ink manufacturing and toner manufacturing etc., uses.Can enumerate ultrasonic disperser, puddle mixer, attitor, pearl grinding machine, horizontal sand mill, bowl mill, cut open sand machine, dispersing mixer, KD grinding machine, colloid mill, dynatron, triple-roller mill, pressurization kneader etc. as dispersion machine.The details of these technology is documented in " up-to-date pigment applications technology " (CMC publication, 1986 annuals).

Solid shape with respect to recording layer coating liquid is divided total amount, and the addition of these dyestuffs or pigment is advisable at 0.01-30% (weight).

The following describes the operable infrared absorbent of occasion that has the recording layer of eurymeric at Image forming material of the present invention.

In the eurymeric recording layer, use the occasion of infrared absorbent, (unexposed portion is rasterized inhibition must to produce positive interaction by the interaction with the binder polymer with particular functional base, exposure portion is removed, promote video picture), therefore, especially preferentially select the infrared absorbent of father-in-law's salt type structure for use, specifically, in the infrared absorbent that the occasion of above-mentioned minus is used, can select the peaceful pigment of match, pyralium salt especially for use.The details of matching peaceful pigment and pyralium salt as previously described.

In addition, also can use the anionic property infrared absorbent described in the flat 10-237634 of special Willing.This anionic property infrared absorbent is meant, do not have cationic structural in fact in the parent nucleus that absorbs ultrared pigment, has the infrared absorbent of anion structure.

For example can enumerate (a-1) anionic property metal ligand, (a-2) cationic carbon black, (a-3) anionic property phthalocyanine.

(a-1) anionic property metal ligand described here is meant that the central metal of light absorbing coordination body and dentate in fact all become anionic metal ligand.

(a-2) the anionic property carbon black can be enumerated, and combines the carbon black of anion bases such as sulfonic acid, carboxylic acid, phosphonate group as substituting group.For these bases are imported in carbon blacks, can be described according to the 12nd page of カ-ボ Application Block ラ Star Network brief guide the 3rd edition (カ-ボ Application Block ラ Star Network association compiles, April 5 nineteen ninety-five カ-ボ Application Block ラ Star Network association distribution), with the acid of regulation with methods such as carbon black oxidations.

(a-3) the anionic property phthalocyanine is meant, the anion base of being enumerated in (a-2) above combining as substituting group on the skeleton of phthalocyanine becomes anionic phthalocyanine on the whole.

Furtherly, can enumerate record in [0014] to [0105] of the flat 10-237634 of special Willing by [Ga ^--M-Gb] _mX ^M+[Ga-represents anionic substituent to the anionic property infrared absorbent of expression, and Gb represents neutral substituting group, X ^M+Expression contains the kation of the 1-m valency of proton, and m represents the integer of 1-6].

In addition, as the example of the infrared absorbent that uses among the present invention, can enumerate below shown in the infrared absorbent with salt structure.The object lesson of such infrared absorbent can be enumerated (A-1～A-56), but the invention is not restricted to these examples.

[changing 6]

[changing 7]

[changing 8]

[changing 9]

[changing 10]

[changing 11]

[changing 12]

[changing 13]

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

In the structural formula of A-1～A-56, T ^-The counter anion of representing 1 valency, preferably halide anion (F ^-, Cl ^-, Br ^-, I ^-), Lewis acid anion (BF ₄ ^-, PF ₆ ^-, SbCl ₆ ^-, ClO ₄ ^-), alkyl sulfonic acid negative ion, aryl sulfonic acid negative ion.

Here said alkyl is meant the alkyl of straight chain shape, a chain or the ring-type of 1-20 carbon atom, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, cetyl, octadecyl, eicosyl, isopropyl, isobutyl, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 1-methyl butyl, isohesyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norborny particularly.Wherein, preferentially select the straight chain shape of 1-12 carbon atom, a chain of a 3-12 carbon atom and the cyclic alkyl of 5-10 carbon atom for use.

Aryl recited above in addition, be meant that the aryl that is made of 1 phenyl ring, 2 or 3 phenyl ring form the aryl that the aryl of condensed ring, phenyl ring and 5 Yuans unsaturated rings form condensed ring, can enumerate phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl particularly, wherein preferably phenyl, naphthyl.

Image forming material of the present invention is used as the occasion of eurymeric, the addition of above-mentioned infrared absorbent can according to determine in method same described in the Image forming material of minus.

In order further to improve susceptibility and video picture tolerance, can also contain the peaceful pigment of above-mentioned match, pyralium salt, negative ion in the recording layer of minus in the present invention and be (operable infrared absorbents in the above-mentioned negative light-sensitive resin combination) such as other dyestuff beyond the pigment or pigment.

Utilizing infrared laser irradiation that Image forming material of the present invention is formed aspect the image, must accomplish: as the occasion of the minus recording materials use that alkali imaging liquid dissolubility is reduced, its recording layer, except the content of thickness and infrared absorbent, can use employed recording layer in the known minus recording materials, have no particular limits.

Buck dissolubility for the buck soluble high-molecular compound that reduces exposed portion can contain in the minus recording layer: decompose acidic acid forming agent and utilize the acid that generates that cross-linking reaction takes place, make the acid crosslinking agent of bonding agent polymeric hardener by the effect of light or heat; Perhaps, the effect by light or heat produces the compound of free radical and utilizes the free radical that generates and the compound of polymerization, curing etc.

Described acid forming agent is meant by the rayed of 200-500nm wavelength or the heating more than 100 ℃ and acidic compound, for example can enumerate known acid forming agent that uses in light depigmenting agent, phototropic agent or the little resistance of light trigger, pigment of light trigger, the polymerization of photoionization base of light cationic polymerization etc., the acidic compound of known thermal decomposition and their potpourri.The acid that produces can be that pKa such as sulfonic acid, hydrochloric acid are at the strong acid below 2.

Operable acid forming agent can be enumerated father-in-law's salt such as iodonium salt, sulfonium salt, phosphonium salt, diazo salt among the present invention.Can enumerate the compound of putting down in writing among the flat 7-20629 of US4708925 and Te Kai particularly.Preferably with salt compounded of iodine, sulfonium salt, the diazo salt of sulfonate ion as counter ion counterionsl gegenions.Diazo-compounds of putting down in writing among the diazo-compounds that diazo salt is preferably put down in writing among the US3867147, the US2632703 and the special diazo resin of putting down in writing among flat 1-102456 and the flat 1-102457 of Te Kai of opening.In addition, the benzyl sulfonic acid esters of putting down in writing among US5135838 in addition that preferentially selects for use and the US5200544.In addition, the spy opens flat 2-100054 in addition, the spy opens active sulphonic acid ester and the disulfonyl based compound class of putting down in writing among flat 2-100055 and the flat 8-9444 of special Willing.The S-triazines that the haloalkyl that in addition can also adopt the spy to open to put down in writing among the flat 7-271029 replaces.

These compounds may be used alone, two or more kinds can also be used in combination.

In the present invention, divide total amount with respect to the solid shape of recording layer, the adding proportion that these oxygen generate agent is 0.01-50% (weight), preferably 0.1-25% (weight), preferably 0.5-20% (weight).When addition is lower than 0.01% (weight), can not get image, otherwise when addition surpassed 50% (weight), non-image produced pollution during printing, therefore all inadvisable.

In addition, as acid crosslinking agent, methylol compound of in the flat 9-234404 of special Willing, putting down in writing or (alkoxymethyl)-2 based compound, the resol etc., can also enumerate the following compounds of putting down in writing among the flat 11-151412 of special Willing.

1. the aromatics that replaces with alkoxy methyl or hydroxymethyl

2. the compound that has N-methylol, N-alkoxy methyl or N-acyloxy methyl

3. go back oxygen compound

1. the aromatics that replaces with alkoxy methyl or hydroxymethyl, for example can enumerate with methylol, acetoxy-methyl or polysubstituted aromatics of alkoxy methyl and heterogeneous ring compound, preferably [the changing 14] of this patented claim and the compound described in [changing 15].In above-mentioned chemical formula, L ₁～L ₈Represent hydroxymethyl or alkoxy methyl that methoxy, ethoxyl methyl replace with the following alkoxy of 18 carbon atoms like that respectively independently.

2. the compound that has N-hydroxymethyl, N-alkoxy methyl or N-acyloxy methyl can be enumerated among EP-A-0133216, DE3634671, the DE3711264 disclosed alkoxy substituted compound among disclosed monomer and oligomer-carbamide condensation product and urea-formaldehyde condensation products, the EP-A-0212482.

Preferred example for example can be enumerated the carbamide derivant that has 2 free N-methylols, N-alkoxy methyl or N-acyloxy methyl at least, wherein particularly preferably is N-(alkoxymethyl)-2 radical derivative.

3. epoxy compound can be enumerated the epoxy compound of the monomer that contains the alkoxy more than 1, dipolymer, oligomer, polymkeric substance shape.For example, the resultant of reaction of the resultant of reaction of bisphenol-A and epichlorokydrin, low-molecular-weight phenol-formaldehyde resin and epichlorokydrin etc., the epoxy resin that can enumerate record among US4026705, the GB1539192 in addition, uses.

Below 1. the operable crosslinking chemical of the present invention-3. is 5-80% (weight), preferably 10-75% (weight), preferably 20-70% (weight) with respect to the solid shape of minus recording layer is divided total amount.When the addition of crosslinking chemical was lower than 5% (weight), the photographic layer permanance of resulting original edition for lithographic printing plate worsened, otherwise, when being higher than 80% (weight), stable bad during preservation.

In addition, can also enumerate the phenol derivatives shown in [0078] to [0084] of the flat 11-151412 of above-mentioned special Willing as acid crosslinking agent.

In the recording layer of Image forming material of the present invention, can also add above-mentioned all cpds in addition as required.

For example, can use the dyestuff that in visible-range, has bigger absorption colorant as image.Specifically can enumerate Oil Yellow#101, Oil Yellow#103, Oil Pink#312, Oil Green BG, Oil Blue BOS, Oil Blue#603, Oil BlackBY, Oil Black BS, Oil Black T-505 (above is オ リ エ Application ト chemical industry (strain) manufacturing), Victoria's ethereal blue, crystal violet (CI42555), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170B), peacock green (CI42000), methylenum careuleum (CI52015), AIZEN SPLON BLUE-C-RH (protecting native ケ paddy chemistry (strain) manufacturing) etc., and the special dyestuff of putting down in writing among the clear 62-293247 of opening.

By adding these dyestuffs, it is more clear with the difference of non-image portion that image forms back image portion, thereby preferably interpolation.With respect to the total amount that the solid shape of recording layer is divided, its addition is 0.01-10% (weight).

In addition, in order to increase Treatment Stability for the video picture condition, in recording layer of the present invention, can also add the spy open clear 62-251740 or special open the non-ionic surfactant put down in writing among the flat 3-208514 and specially open clear 59-121044, the spy opens the amphoteric surfactant of putting down in writing among the flat 4-13149.

The object lesson of non-ionic surfactant can be enumerated anhydrosorbitol tristearate, anhydrosorbitol monopalmitate, anhydrosorbitol trioleate, stearic acid glyceryl monoacetate, polyoxyethylene nonylplenyl ether etc.

The object lesson of amphoteric surfactant can be enumerated alkyl two (amino-ethyl) glycocoll, alkyl polyamino ethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethyl imidazole betaine salt, N-myristyl-N, N-betaine type (for example trade name ア モ one グ Application K, first industry (strain) are made) etc.

Non-ionic surfactant and amphoteric surfactant shared ratio in recording layer is 0.05-15% (weight), preferably 0.1-5% (weight).

In addition, in order to give flexibility of filming etc., in the recording layer of Image forming material of the present invention, can add plastifier, for example polyglycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexylphthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate etc.

In Image forming material of the present invention, above-mentioned each composition is dissolved in the solvent, then it is coated on the suitable support that has formed the recording layer of hypersensitivity (middle layer) more described below, thereby forms recording layer.

Employed solvent can be enumerated: ethylene dichloride, cyclohexanone, methyl ethyl ketone, methyl alcohol, ethanol, propyl alcohol, ethylene glycol monomethyl ether, 1-methoxyl-2-propyl alcohol, 2-methoxy ethyl acetic acid esters, 1-methoxyl-2-propyl-acetic acid ester, dimethoxy-ethane, methyl lactate, ethyl lactate, N, N-dimethyl acetamide, N, dinethylformamide, tetramethylurea, N-Methyl pyrrolidone, dimethyl sulfoxide, sulfolane, gamma-butyrolacton, toluene, water etc., but be not limited to these.These solvents can be used alone or as a mixture.The concentration of the mentioned component in the solvent (the full shape branch admittedly that comprises adjuvant) is 1-50% (weight).

The coating weight of the recording layer among the present invention (Gu shape branch) is according to purposes and difference generally is adjusted into 0.01-3.0g/m ²Scope.

Coating can be adopted the whole bag of tricks, the excellent blade coating that for example winds the line, rotary coating, spraying, curtain coating, dip coated, air knife blade coating, blade coating, roller coat etc.Along with the minimizing of coating weight, apparent susceptibility increases, but being reduced by membrane property of image recording film.

Can add the surfactant that is used to improve coating in recording layer of the present invention, for example special to open the fluorine of putting down in writing among the clear 62-170950 be surfactant.In the solid shape of full recording layer was divided, its addition was 0.01-1% (weight), preferably 0.05-0.5% (weight).

Below, illustrate between support and above-mentioned recording layer, be provided with, have with the recording layer said function and for the susceptibility of the effect of light or heat than the middle layer (hereinafter to be referred as the middle layer) of this record floor height.This middle layer can directly form on the support that has formed undercoat as required.

Middle layer of the present invention, the product that can utilize the recording materials that form principle by the identical primary image of above-mentioned recording layer to improve its susceptibility and obtain, for example: the middle layer that constitutes in the radical polymerization system that forms on the support, the recording layer that the polymerization of susceptibility specific ionization base is the low crosslinked system of acid catalysis is set on this layer, thereby the variety classes recording materials are used in combination by hypersensitivity more.

Consider that from the fusion character at interface and the angle of manufacturing the middle layer of the recording materials identical with recording layer is preferably used in above-mentioned middle layer.

In addition, the difference of susceptibility for light or heat in recording layer and middle layer should be 1.3 times at least.The difference of susceptibility is during less than 1.3 times, and the effect that constitutes rhythmo structure is insufficient.The susceptibility in recording layer and middle layer can be by forming independent layer, measures susceptibility under the same conditions respectively and obtain.

The following describes raising susceptibility method when using recording materials of the same race to be, the middle layer.These class methods for example can be enumerated: adopt the video picture of the bonding agent in the method adjustment formation middle layer that changes water wettability base, the hydrophobicity base that imports or change molecular weight, improve the method for susceptibility; Adjust the sensitization or the thermonasty compound concentrations that contain in (increase) middle layer, improve the method for susceptibility; Perhaps, in the middle layer, add to promote what reaction that the effect by light or heat takes place or rerum natura changed; Such as sensitizing auxiliary agents such as infrared absorbents, improve the method for susceptibility etc.

The coating weight in the middle layer among the present invention (Gu shape branch) is according to purposes and difference generally is adjusted into 0.01-3.0g/m ²Scope.

Can be coated with the middle layer among the present invention, the support of recording layer, be the plate object of dimensionally stable, for example paper, stacked plastics (tygon for example, polypropylene, polystyrene etc.) paper, sheet metal (aluminium for example, zinc, copper etc.), plastic sheeting (cellulose diacetate for example, Triafol T, cellulose propionate, cellulose butyrate, cellulose acetate-butyrate, cellulose nitrate, polyethylene terephthalate, tygon, polystyrene, polypropylene, polycarbonate, polyvinyl acetate etc.), lamination or evaporation the paper of above-mentioned metal or plastic sheeting etc.

Preferred support can be enumerated mylar or aluminium sheet, wherein preferential especially preferred dimension good stability, the cheap aluminium sheet of price comparison.Suitable aluminium sheet is pure aluminum plate and is principal ingredient and the alloy sheets that contains other element of trace with aluminium, the plastic foil of aluminium that can also adopt lamination or evaporation.Other contained yuan have silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium etc. in the aluminium alloy.Other element total content in the alloy is below 10% (weight).Particularly preferred aluminium is fine aluminium among the present invention, but pure aluminium is had any problem on the refining manufacturing technology fully, therefore also can be with containing the aluminium alloy of other element on a small quantity.The aluminium sheet that is suitable among the present invention, its composition has no particular limits, and can use known in the past aluminium sheet.The thickness that is used as the aluminium sheet of support in the present invention is about 0.1-0.6mm, preferably 0.15-0.4mm, preferably 0.2-0.3mm.

Before making the surface coarsening of aluminium sheet, for example can carry out ungrease treatment as required, to remove the rolling oil on surface with surfactant, organic solvent or alkaline aqueous solution etc.

The roughening treatment of surface of aluminum plate can adopt the whole bag of tricks to carry out, and for example the method for mechanical alligatoring makes surface dissolution and the method for alligatoring with electrochemical method, and with the method on chemical method selective dissolution surface.The method of machinery can adopt known method such as ball-milling method, brushing method, abrasive blasting method, polishing polishing.The method that useful interchange of electrochemical surface roughening method or direct current carry out in hydrochloric acid or nitric acid electrolytic solution.In addition, open described in the clear 54-63902, can also adopt method the two combination as the spy.

Aluminium sheet through such alligatoring carries out caustic corrosion processing and neutralisation treatment as required, then, carries out anodized for the water-retaining property and the wearing quality that improve the surface as required.The electrolyte that is used for the anodized of aluminium sheet can use the various electrolyte that form porous matter oxide film thereon, generally adopts sulfuric acid, phosphoric acid, oxalic acid, chromic acid or their acid mixture.These electrolytical concentration can suitably be determined according to electrolytical kind.

The condition of anodized changes along with employed electrolyte, cannot treat different things as the same, and generally can adopt following condition: electrolyte concentration 1-80% (weight), 5-70 ℃ of liquid temperature, current density 5-60A/dm ², voltage 1-100V, electrolysis time 10 seconds-5 minutes.The amount of anodic oxidation coating is less than 1.0g/m ²The time, anti-film deficiency, perhaps non-image position is easy to generate scuffing, particularly in the occasion of original edition for lithographic printing, scratches part during printing and adheres to printing ink easily, produces so-called " scratch and pollute ".

Through after the anodized, as required hydrophilicity-imparting treatment is carried out on the aluminium surface.The hydrophilicity-imparting treatment that can adopt among the present invention has, disclosed alkali silicate among US2714066, US3181461, US3280734 and the US3902734 (for example sodium silicate aqueous solution) method.In the method, support is placed in dip treating or electrolytic treatments in the sodium silicate aqueous solution.In addition, can also adopt the method that disclosed polyphosphonic acid vinyl acetate is handled among disclosed potassium fluorozirconate, US3276868, US4153461, the US4689272 among the special public clear 36-22063.

Be coated with before the above-mentioned recording layer, as required undercoat can be set on support.

The composition of undercoat can use various organic compounds, for example can select from following compounds: the methylcellulose that contracts, dextrin, gum arabic, 2-ciliatine etc. have amino phosphonic acid based; Can have organic phospho acids such as substituent phenyl-phosphonic acid, naphthyl phosphonic acids, alkyl phosphonic acid, glycerine phosphonic acids, methylenediphosphonate and ethylidene diphosphonic acid; Can have organic phosphoric acids such as substituent phosphenylic acid, naphthyl phosphoric acid, alkyl phosphoric acid and phosphoglycerol; Can have organic phosphinic acids such as substituent phenyl phosphinic acid, naphthyl phosphinic acids, alkyl phosphinic acid and glycerine phosphinic acids; Amino acids such as glycocoll or Beta-alanine; And the hydrochloride of triethanolamine etc. has the hydrochloride etc. of the amine of hydroxyl.They also can mix use more than 2 kinds.In addition, it is desirable to the above-mentioned diazo-compounds of primary coat.

The amount of coating of organic undercoat is 2-200mg/m ², 5-100mg/m preferably ²This amount of coating is less than 2mg/m ²The time, can not obtain enough films, greater than 200mg/m ²The time also be same.

This organic undercoat can adopt following method to form.Above-mentioned organic compound is dissolved in organic solvent such as water or methyl alcohol, ethanol, methyl ethyl ketone or their mixed solvent, the resulting solution of coating on aluminium sheet, dry then; Perhaps above-mentioned organic compound is dissolved in organic solvents such as water or methyl alcohol, ethanol, methyl ethyl ketone or their mixed solvent, aluminium sheet is put into this solution to be flooded, make it to adsorb above-claimed cpd, wash then, drying, form organic undercoat.In preceding a kind of method, can adopt the whole bag of tricks to be coated with the solution of 0.005-10% (weight) concentration of above-mentioned organic compound.In a kind of method in back, the concentration of solution is 0.01-20% (weight), 0.05-5% (weight) preferably, and dipping temperature is 20-90 ℃, preferably 25-50 ℃, dip time is 0.1 second-20 minutes, preferably 2 seconds-1 minute.Can solution be adjusted into pH1-12 with alkaline matters such as ammoniacal liquor, triethylamine, potassium hydroxide or acidic materials such as hydrochloric acid, phosphoric acid.In addition, when using recording layer of the present invention, can also add yellow uitramarine in order to improve tone rendering as original edition for lithographic printing.

Before address, Image forming material of the present invention can be used as original edition for lithographic printing.This Image forming material can carry out record with infrared laser, as mentioned above, can use the energy density of per 1 beam to be 15000mJ/s cm ²More than, 20000mJ/s cm particularly ²The high-output power infrared laser carry out record.Specifically, can adopt the ultrared solid state laser of emission wavelength 760-1200nm and semiconductor laser to carry out image exposure.Energy density is at lip-deep output power of Image forming material and the numerical value of this beam in the lip-deep area decision of recording layer by per 1 beam line, for example, under the 38mW energy intensity, the laser energy density of the space of a whole page area that 1.5 μ m are square is 17000mJ/s cm ²

Have the occasion of above-mentioned eurymeric or minus recording layer at Image forming material of the present invention, water or alkali imaging liquid carry out the video picture processing after the exposure.Video picture is handled and can be carried out immediately after exposure, also can carry out heat treated between exposure process and video picture operation.Condition during heat treated is to carry out in 60-150 ℃ of scope 5 seconds-5 minutes.The method of heating can adopt known in the past the whole bag of tricks, for example, adopts radiant panel well heater or ceramic heater, makes it to contact the method that heats with recording materials, perhaps utilizes lamp or hot blast to carry out the method for noncontact heating.Write down needed laser energy in the time of laser radiation can being reduced by heat treated.

In the occasion of using alkaline aqueous solution, can use known in the past aqueous alkali as imaging liquid and additional liquid, for example sodium silicate, potassium silicate, tribasic sodium phosphate, three generations's potassium phosphate, ammonium tertiary phosphate, sodium orthophosphate dimetallic, two generation potassium phosphate, ammonium secondary phosphate, sodium carbonate, sal tartari, hartshorn salt, sodium bicarbonate, saleratus, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, NaOH, ammonium hydroxide, potassium hydroxide and inorganic base salts such as lithium hydroxide.Can also use monomethyl amine, dimethyl amine, Trimethylamine, an ethylamine, diethylamide, triethylamine, an isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, an isopropanolamine, diisopropanolamine, piperazine, 1 in addition, organic alkaline agents such as 2-ethylenediamine, pyridine.

These alkaline agents can use separately, perhaps are used in combination more than 2 kinds.

In these alkaline agents, an example of particularly preferred imaging liquid is aqueous silicate solutions such as sodium silicate, potassium silicate.This be because, by the silicon oxide sio of silicate composition ₂With alkali metal oxide M ₂Ratio and the concentration of O (M represents alkaline metal) can be regulated video picture, for example can use the spy to open the alkali silicate of putting down in writing among clear 54-62004, the special public clear 57-7427.

In addition,,, the imaging liquid in the video picture groove can be do not needed to change for a long time, a large amount of recording layers can be handled by in imaging liquid, adding the base strength aqueous solution higher (replenishing liquid) than imaging liquid in the occasion of using automatic developing device to carry out video picture.Also can adopt this arbitrary way in the present invention.

Recording layer after using above-mentioned imaging liquid and additional liquid to carry out video picture to handle, water wash water, the rinsing liquid that contains surfactant, the lipoprotein liquid of not feeling that contains gum arabic or starch derivative carry out aftertreatment.In the occasion that recording layer of the present invention is used with plate as printing, these treatment combinations can be got up act on as aftertreatment.

In recent years, particularly in plate-making, printing industry, for the rationalization and the standardization of the operation that realizes making a plate, the automatic developing device that uses printing to use widely with plate.

This automatic developing device generally is to be made of imaging division and aftertreatment portion, comprising carrying printing with the device of plate, respectively handle liquid bath and jetting system, one side will be through the galley horizontal feed of overexposure, and each treating fluid that one side is drawn by pump by the nozzle winding-up carries out video picture and handles.In addition, also occurred recently a kind ofly utilizing deflector roll etc. will print in being full of the processing liquid bath for the treatment of fluid, to flood the method for carrying and handling with plate.In this automatic processing, can in each treating fluid, add additional liquid according to treatment capacity and running time etc.

In addition, can also adopt the so-called disposable processing mode of handling with untapped treating fluid basically.

With the occasion that the above-mentioned Image forming material that obtains uses as lithographic plate, fat glue is not felt in coating as required, supplies with printing process then and uses.In order further to improve printability resistance, can also carry out calcination process.

When lithographic plate is carried out calcination process, before roasting preferably with special public clear 61-2518, special public clear 55-28062, spy open clear 62-31859, the spy opens whole the liquid of putting down in writing among the clear 61-159655 and handles.

Be coated with the original edition of lithographic printing plate of whole liquid, carried out drying as required, then at calcination process device (the calcination process device sold of Fuji description Off イ Le system (strain) for example: be heated to high temperature BP-1300).The temperature and time of heating depends on the kind of the composition that forms image, generally is at 180-300 ℃ of following 1-20 minute.

Through the lithographic plate of calcination process, can wash, draw habitual in the past processing such as glue as required, contain the occasion of whole liquid of water-soluble high-molecular compound etc. in use, can omit and draw glue etc. not feel the fat processing.

To be installed on the offset press through the lithographic plate that above-mentioned processing obtains, be used for a large amount of printings.

[embodiment]

Explain the present invention below by embodiment, but the present invention is not subjected to the restriction of these embodiment.

(embodiment 1-5, comparative example 1-2: eurymeric)

[making of support]

The aluminium sheet (material 1050) of thick 0.30mm is clean with triclene, degreasing use nylon bruss and 400 purpose float stone-water slurries that sand milling is carried out on its surface then, and water is fully clean.This aluminium sheet was flooded 9 seconds in 45 ℃ 25% sodium hydrate aqueous solution, corrodes, after the washing again at 2%HNO ₃Middle dipping 20 seconds, washing.This moment, the etching extent of sand milling rear surface was about 3g/m ²Subsequently, with 7%H ₂SO ₄As electrolytic solution, with 15A/dm ²Current density, on this plate, form 3g/m ²The dc anodizing tunicle, then the washing, drying.Next, the following primary coat liquid of coating on this aluminium sheet, drying is 30 seconds under 80 ℃.Dried amount of coating is 10mg/m ²

＜primary coat liquid 〉

Beta-alanine 0.10g

Methyl alcohol 40.0g

Pure water 60.0g

(embodiment 1-5: the minus Image forming material)

The minus middle layer of forming shown in below being coated with on above-mentioned support forms solution, and drying is 3 minutes under 100 ℃.Dried weight is 0.5g/m ²Then, the minus recording layer of forming shown in below the coating (acid catalysis cross-linked layer) forms solution, 130 ℃ dry 30 seconds down, obtain the Image forming material of minus, as embodiment 1-5.Dried weight adds up to 2.0g/m ²

(the minus middle layer forms solution 1)

The crosslinking chemical of table 1 [B] 0.8g

The macromolecule of table 1 [C] 1.5g

The acid forming agent of table 1 [Z] 0.20g

The infrared absorbent of table 1 [A] 0.30g

Fluorine is surfactant 0.06g

(メ ガ Off ア Star Network F-177: big Japanese イ Application キ chemical industry (strain) is made)

Methyl ethyl ketone 10.0g

Gamma-butyrolacton 10.0g

1-methoxyl-2-propyl alcohol 7.0g

(minus recording layer (acid catalysis cross-linked layer) forms solution 1)

The crosslinking chemical of table 1 [X] 0.8g

The macromolecule of table 1 [Y] 1.5g

The acid forming agent of table 1 [Z] 0.20g

The infrared absorbent of table 1 [A] 0.15g

Colorant 0.015g

AIZEN SPLON BLUE C-RH: protect native ケ paddy chemistry (strain) manufacturing) fluorine is surfactant 0.06g

(メ ガ Off ア Star Network F-177: big Japanese イ Application キ chemical industry (strain) is made)

Ethyl acetate 15.0g

Methyl alcohol 5.0g

[changing 21]

(B-1) resol (Mw 5000)

[changing 22]

(C-1)

Paraoctyl phenol/metacresol (20 weight %/80 weight %)

Formaldehyde condensation novolac resin (Mw 10000)

(C-2)

Para hydroxybenzene ethylene/methacrylic acid methyl esters

(80 weight %/20 weight %) multipolymer (Mw 30000)

(20 weight %/80 weight %) multipolymer (Mw 50000)

[changing 23]

(X-1) resol (Mw 3000)

[changing 24]

(Y-1)

Phenol formaldehyde (PF) condensation novolac resin (Mw 30000)

(Y-2)

Poly(4-hydroxystyrene) (Mw 50000)

Homopolymer (Mw 20000)

[table 1]

	The recording layer crosslinking chemical	The recording layer macromolecule	Acid forming agent	Infrared absorbent	The middle layer crosslinking chemical	The middle layer macromolecule
							Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5	X-1 X-2 X-3 X-4 X-4	Y-1 Y-2 Y-1 Y-1 Y-3	Z-1 Z-1 Z-2 Z-2 Z-2	A-1 A-1 A-2 A-2 A-2	B-1 B-2 B-3 B-1 B-1	C-1 C-1 C-2 C-3 C-1

(comparative example 1-5)

With embodiment 1 in the same coating used on the support of undercoat, be coated on above-mentioned recording layer (acid catalysis cross-linked layer) and form the masking liquid of allocating crosslinking chemical, macromolecule, infrared absorbent etc. in the solution 1 by the prescription described in the following table 2 into, drying is 3 minutes under 100 ℃, obtain on support, only forming the Image forming material of the recording layer of single composition, with these Image forming materials 1-5 as a comparative example.Dried weight is 1.5g/m ²

[table 2]

	The recording layer crosslinking chemical	The recording layer macromolecule	Acid forming agent	Infrared absorbent
					Comparative example 1 comparative example 2 comparative examples 3	X-1 X-2 X-3	Y-1 Y-2 Y-1	Z-1 Z-1 Z-2	A-1 A-1 A-2

Comparative example 4 comparative examples 5

X-4 X-4

Y-1 Y-3

Z-2 Z-2

A-2 A-2

(comparative example 6-10)

With embodiment 1 in the same coating used on the support of undercoat, be coated in the above-mentioned middle layer formation solution 1 and allocate crosslinking chemical, macromolecule, infrared absorbent etc. into and the masking liquid of formation by the prescription described in the following table 3, drying is 3 minutes under 100 ℃, obtain on support only forming the Image forming material of comparing the recording layer of more high sensitive single composition with the recording layer among the comparative example 1-5, with these Image forming materials 6-10 as a comparative example.Dried weight is 0.5g/m ²

[table 3]

	Acid forming agent	Infrared absorbent	The middle layer crosslinking chemical	The middle layer macromolecule
					Comparative example 6 comparative examples 7 comparative examples 8 comparative examples 9 comparative examples 10	Z-1 Z-1 Z-2 Z-2 Z-2	A-1 A-1 A-2 A-2 A-2	B-1 B-2 B-3 B-1 B-1	C-1 C-1 C-2 C-3 C-1

(embodiment 6-10: the eurymeric Image forming material)

With the foregoing description 1 in same form solution 2 through the following eurymeric of coating middle layer on the support of primary coat, 100 ℃ dry 3 minutes down.Dried weight is 0.5g/m ²Then, be coated with following sensible heat eurymeric recording layer and form solution 2, drying is 30 seconds under 130 ℃, and dried weight adds up to 2.0g/m ²

(the eurymeric middle layer forms solution 2)

The macromolecule of table 4 [Q] 2.0g

The infrared absorbent of table 4 [R] (measuring g shown in the table 4))

The adjuvant of table 4 [S] (measuring g shown in the table 4))

Fluorine is surfactant 0.06g

(メ ガ Off ア Star Network F-177: big Japanese イ Application キ chemical industry (strain) is made)

Methyl ethyl ketone 10.0g

Gamma-butyrolacton 10.0g

1-methoxyl-2-propyl alcohol 7.0g

(sensible heat eurymeric recording layer forms solution 2)

The macromolecule of table 4 [P] 2.0g

The infrared absorbent of table 4 [A] 0.15g

Colorant 0.015g

(AIZEN SPLON BLUE C-RH: protect native ケ paddy chemistry (strain) manufacturing)

Fluorine is surfactant 0.06g

(メ ガ Off ア Star Network F-177: big Japanese イ Application キ chemical industry (strain) is made)

Ethyl acetate 15.0g

Methyl alcohol 15.0g

[changing 25]

(P-1)

Metacresol/paracresol (60 weight %/40 weight %)

Formaldehyde condensation novolac resin (Mw 10000)

(P-2)

3,5-xylenols/metacresol (50 weight %/50 weight %)

Formaldehyde condensation novolac resin (Mw 5000)

(P-3)

The formaldehyde condensation novolac resin of metacresol

[changing 26]

50 parts of (50 weight %/50 weight %) multipolymers (Mw 40000)

Potpourri with 50 parts in (P-1) bonding agent

50 parts of (50 weight %/50 weight %) multipolymers (Mw 50000)

Potpourri with 50 parts in (P-1) bonding agent

(50 weight %/50 weight %)

Formaldehyde condensation novolac resin (Mw 20000)

[table 4]

	The recording layer macromolecule	The middle layer macromolecule	Infrared absorbent (addition) (g)	Adjuvant (addition) (g)
					Embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10	P-1 P-2 P-1 P-2 P-3	Q-1 Q-1 Q-1 Q-2 Q-3	R-1(0.2) R-1(0.3) R-2(0.3) R-3(0.2) R-3(0.2)	S-1 (0.1) S-1 (0.1) S-2 (0.2) S-2 (0.2) does not have

(comparative example 11-15)

With embodiment 1 in the same coating used on the support of undercoat, be coated in the above-mentioned sensible heat eurymeric recording layer formation solution 2 and allocate crosslinking chemical, macromolecule, infrared absorbent etc. into and the masking liquid of formation by the prescription described in the following table 5, drying is 3 minutes under 100 ℃, obtain on support, only forming the Image forming material of the recording layer of single composition, with these Image forming materials 11-15 as a comparative example.Dried weight is 1.5g/m ²

[table 5]

	The recording layer macromolecule	Infrared absorbent
			Comparative example 11 comparative examples 12 comparative examples 13 comparative examples 14 comparative examples 15	P-1 P-2 P-1 P-2 P-3	R-1 R-1 R-2 R-3 R-3

(comparative example 16-20)

With embodiment 1 in the same coating used on the support of undercoat, be coated in the above-mentioned eurymeric middle layer formation solution 2 and allocate crosslinking chemical, macromolecule, infrared absorbent etc. into and the masking liquid of formation by the prescription described in the following table 6, drying is 3 minutes under 100 ℃, obtain on support only forming the Image forming material of comparing the recording layer of more high sensitive single composition with the recording layer among the comparative example 11-15, with these Image forming materials 16-20 as a comparative example.Dried weight is 0.5g/m ²

[table 6]

	The middle layer macromolecule	Infrared absorbent (addition) (g)	Adjuvant (addition) (g)
				Comparative example 16 comparative examples 17 comparative examples 18 comparative examples 19 comparative examples 20	Q-1 Q-1 Q-1 Q-2 Q-3	R-1(0.2) R-1(0.2) R-2(0.3) R-3(0.3) R-3(0.2)	S-1 (0.1) S-1 (0.1) S-2 (0.2) S-2 (0.2) does not have

The adhesion evaluation of＜minus inductive material: the anti-brush of point 〉

The ultrared semiconductor laser that use to produce wavelength 830-850nm carries out scan exposure to the Image forming material of the minus that embodiment 1-5 and comparative example 1-10 obtain, form 1% site (highlight), exposure back with the radiant panel well heater in 120 ℃ of following heat treated 60 seconds, imaging liquid DP-4 (1: 8 the water diluent) video picture of making then with Fuji's description Off イ Le system (strain).Use resulting photosensitive material as galley,, compare with the number of pages of printing index then as adhesion with Ha イ デ Le KOR-D press printing.This index is good 100 above persons.

The residual film property the eliminated evaluation of＜eurymeric inductive material: the pollution during printing 〉

The ultrared semiconductor laser that use to produce wavelength 830-850nm carries out scan exposure to the eurymeric Image forming material that embodiment 6-10 and comparative example 11-20 obtain, form 99% site (shadow), subsequently imaging liquid DP-4 (1: 8 the water diluent) video picture made from Fuji's description Off イ Le system (strain).Use resulting photosensitive material as galley, with Ha イ デ Le KOR-D press printing, the pollution of non-image portion during the investigation printing.

The evaluation of＜storage stability 〉

For above-mentioned each Image forming material, before laser explosure, they were placed 3 down in high-temperature condition (85%RH, 35 ℃), equally the Image forming material after preserving is carried out laser explosure with above-mentioned then, calculate the record energy needed, the energy of obtaining preservation front and back under the high-temperature is than (energy/high-temperature after high-temperature is preserved down is the preceding energy of preservation down).

This energy ratio is more favourable for making below 1.1, and storage stability is also better.

These evaluation results are shown in table 7 and the table 8.

[table 7]

	Adhesion (anti-print index)	Storage stability (susceptibility ratio)
			Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5	110 120 130 130 120	1.1 1.0 1.0 1.0 1.0

Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5	80 80 60 70 80	1.1 1.0 1.0 1.0 1.0
			Comparative example 6 comparative examples 7 comparative examples 8 comparative examples 9 comparative examples 10	80 90 100 90 100	2.0 1.6 1.8 1.6 1.6

[table 8]

	Residual film (printing stain)	Storage stability (susceptibility ratio)
			Embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10	Do not have	1.1 1.0 1.0 1.1 1.0
Comparative example 11 comparative examples 12 comparative examples 13 comparative examples 14 comparative examples 15	Stain stain stain stain stain	1.1 1.0 1.0 1.1 1.0
			Comparative example 16 comparative examples 17 comparative examples 18 comparative examples 19 comparative examples 20	Do not have	1.8 1.6 1.7 1.5 1.6

By table 7 and table 8 as can be seen, Image forming material of the present invention, under the situation of minus, the adhesion of image portion is good, and under the eurymeric situation, non-image is not polluted, can both obtain images with high image quality.In addition, do not find that in the environment of high-temperature susceptibility reduces, and shows good storage stability.

[effect of invention]

Image forming material of the present invention can use irradiation ultrared solid state laser or semiconductor laser, directly carry out record according to the numerical data of computer etc., obtain the image of high image quality, and storage stability is good.

Claims (2)

1, a kind of sensitization or thermonasty Image forming material, its special card is: it comprises support, the recording layer that is made of the composition that changes by light or heat effect for the solubility of water or buck is set on support, between this support and recording layer, be provided with have with recording layer in the same effect of constituent by by light or heat change the middle layer that the constituent for the solubility of water or buck constitutes, the susceptibility in described middle layer is at least 1.3 times with the ratio of recording layer susceptibility.

2, a kind of sensitization according to claim 1 or thermonasty Image forming material is characterized in that: sensitization or thermonasty Image forming material contain infrared absorbent, can utilize infrared laser to carry out record.