CN1355449A - Conformal photosensitive compoistion and lithographic printing plate made by it - Google Patents

Abstract

A positive photosensitive composition for infrared laser and the planographic plate with a photosensitive layer made of the said composition are disclosed. The said composition contains alkaline water-soluble high-molecular compound, light-eat converting agent and phenol derivative. The planographic plate is prepared by coating the said composition on a hydrophilic carrier. Its advantages include with developed are, lowered reduction of development performance after storage, and direct plate-making.

Description

Conformal photosensitive compoistion and with its lithographic plate of making

The invention relates to infrared laser irritability conformal photosensitive compoistion, and can use these materials to accept the infrared laser eurymeric planographic printing plate of digital signals such as computing machine with the made direct plate-making usefulness of direct plate-making formula.

As the planographic printing plate system of directly being made a plate by the numerical data of computing machine, the application of laser is very noticeable.Aspect laser, alarming development has been arranged in recent years, particularly had near infrared when the output of the high-energy in infraluminescence field and small-sized solid state laser semiconductor laser are very easy to obtain.Therefore, as laser, be very useful by the exposure light source of the direct making sheet of numerical data.

May write down the made lithographic plate of photosensitive compoistion of the infrared laser of the light source that is used for directly making a plate with serving as reasons, as reporting and United States Patent (USP) 5 at Japanese kokai publication hei 7-20629 branch, 372, shown in No. 907, propose by containing infrared absorbent, phenolics, novolac resin and being heated and lithographic plate that the photographic layer of acidic latency Bronsted acid is made.Putting down in writing after the infrared laser exposure, the temperature range heating video picture from 75 ℃ to 150 ℃, exposed portion is difficult to dissolving in alkaline imaging liquid, and unexposed portion has then increased dissolubility, thereby has formed the lithography of minus.

Such minus thermal laser is plate offscreen, owing to heat the needs of engineering, sizable firing equipment be arranged, so exist space and energy consumption or the like problem after exposure.Particularly, the problem that can not obtain good picture part/non-picture part is arranged then if temperature control is not good at.

The eurymeric thermal laser that does not need heat treated after the exposure offscreen plate also has numerous schemes.At above-mentioned Japanese kokai publication hei 7-20629 number and United States Patent (USP) 372, represented in No. 907 communiques, the eurymeric lithography that after exposure, need not heat and carry out alkaline video picture, owing to be subjected to the influence of time of developing, temperature and alkali concn easily, the interval of possible video picture is very narrow, is difficult to use in practice.

At Japanese kokai publication hei 7-285275 number and United States Patent (USP) 5,840, in No. 467 communiques, once proposed to have in the alkali soluble resin of phenol hydroxy to having novolac resin etc., add material and all salt and the quinone diacid compounds class etc. of absorbing light heating, constitute the picture recording materials with these materials, use directly plate-making formula of infrared laser light source eurymeric plate printing plate in order to make.

After the exposed portion absorbing light of these picture recording materials, in fact salt, two nitrogen salts, quinone diacid compounds etc. make the aqueous alkaline solution-soluble dissolving resin very low, play the effect of dissolving inhibitor, both having made is heated does not also dissolve, form picture part, in unexposed portion, decompose, find that dissolving stops energy because of being heated, in the video picture process, be removed, and form non-picture part and picture part.With such some recording materials,, take place also need compose with a large amount of heat energy for decomposing because of heating decomposes salt etc. and the formation of non-picture part.In addition, for the salt that will prevent to decompose etc. and alkali-soluble novolac resin again association reaction also have difficulties, thereby improve sensitivity and also be restricted.Particularly, also just like the time will keeping hot and humid condition to exposure behind the photosensitive coated layer, and the low inferior variety of problems of video picture performance exists.

In the WO97/39894 communique, relevant in order can under incandescent lamp, to use, use in the eurymeric lithographic plate at the infrared laser that does not contain two nitrogen salts, quinone diacid compounds and so on, use the scheme of non-photosensitive video picture inhibitor the ultraviolet light photoactive substance.But have also such as imaging liquid when tired that video picture is very low, coating after after a while also can video picture problems such as low and video picture scope is narrow exist.

Noted earlier and problem, with following, aforementioned infrared laser has in essence different with the plate-making mechanism of eurymeric lithographic plate formula printing plate material and aforementioned eurymeric planographic printing plate material of being made a plate by ultraviolet photoetching.

Before the eurymeric planographic printing plate material of the ultraviolet photoetching making sheet addressed be, with alkaline aqueous solution soluble binding agent resin and salt or quinone diacid compounds etc. as essential composition.Herein, when the eurymeric planographic printing plate material with ultraviolet photoetching plate-making exposes, aforesaid salt or quinone diacid body compound are aspect non-exposed portion (picture part), with aforesaid infrared laser with the eurymeric planographic printing plate material the same play the dissolving inhibitor effect, aspect exposed portion (non-picture part), different with aforementioned infrared laser with eurymeric lithographic plate formula printing plate material, decompose generation acid by illumination, played the dissolution accelerator of aforesaid adhesive resin.So in this eurymeric planographic printing plate material with ultraviolet light plate-making, its exposed portion and non-exposed portion are very big for the dissolubility difference of alkaline imaging liquid.

With respect to this situation, aforesaid infrared laser uses the eurymeric planographic printing plate material when exposure, in exposed portion (non-picture part), because infrared ray dyestuffs etc. are very weak with the interaction of aforesaid adhesive resin, this infrared ray dyestuff is not the effect as the dissolution accelerator of bonding agent, and therefore the dissolubility difference of non-exposed portion and exposed portion is very little.

Therefore, for infrared laser eurymeric planographic printing plate material,, promptly be in order to increase exposed portion and the deliquescent difference of non-exposed portion, needn't to use the material that improves solubility for alkaline imaging liquid for improving the difference of picture.If used such material, under the high situation of the activity degree of imaging liquid, non-desired non-exposed portion (picture part) dissolves.The ultraviolet photoetching eurymeric planographic printing plate that uses with convention in the past compares, and the interval of video picture is very narrow.Consequently, in the storage after making, reduced residual solvent, increased the situation that bonding agent combines with hydrogen, it is low to have produced video picture.Just made and under same video picture condition, carry out stable video picture after after a while and have any problem.

Therefore purpose of the present invention is to enlarge the interval of video picture, reduces the low of video picture after storing, improves printing adaptability, and the infrared laser that direct version usefulness is provided is version offscreen.

The all colleague of the present invention makes great efforts the result of research repeatedly, in the photosensitive compoistion that contains alkali-soluble macromolecular compound, photo-thermal conversion agent and illuminating colour, has added and has phenol OH and have-CH in molecule ₂The compound of OR (R=alkyl, acyl group) owing to the adding of these compounds, increases substantially the interval of video picture, has obtained the good infrared laser conformal photosensitive compoistion of coating back bin stability, finishes the present invention.

Conformal photosensitive compoistion of the present invention contains (A) alkaline water soluble high-molecular compound, (B) photo-thermal conversion agent, and (C) in molecule, have phenol OH and-CH ₂The phenol derivatives of OR (R=alkyl, acyl group) is its feature.

In addition, the lithographic plate in the application item 2 of the present invention is to be coated with the photographic layer that the infrared laser that contains following (A)～(C) is used conformal photosensitive compoistion on hydrophilic carrier, is its feature.

(A) alkaline water soluble high-molecular compound

(B) photo-thermal conversion agent

(C) molecule contain phenol OH and-CH ₂The phenol derivatives of OR (R=alkyl, acyl group).

Herein, (A) be novolac resin as alkaline water soluble high-molecular compound.(B) as photo-thermal conversion agent, preferably from have cyanine dye, merocyanine dyes or the pyrans based dye that absorbing wavelength is 700～1300nm light wave ability, to select more than one.

Secondly, the functional group-CH of phenol derivatives ₂R among the OR, preferably carbon number is 1～4 alkyl, perhaps the acyl group of selecting from formoxyl, acetyl group, bytyry, benzoyl, cinnamoyl and valeryl.

Effect of the present invention is not clear and definite as yet, but work out: because (A) buck soluble high-molecular compound and (C) specific phenol derivatives are existed jointly, by with the molecular memory of phenol derivatives the interaction of phenol hydroxy, maintain the video picture of appropriateness, so the video picture of alkaline water imaging liquid is good.And, because contain-CH ₂The OR base and contains methylol (CH ₂OH) compound compares, and the interaction that the alkaline water soluble resin combines with hydrogen is not strong, so the strong stability of hydrophobicity better.Because both balance, make between sensitivity, imaged sector, particularly the photographic layer bin stability after the coating all improves, and because the surface hydrophobic of picture part is more intense, picture have excellent printing ink to be subjected to capacitive in printing process.

Below describe the present invention in detail.Photosensitive compoistion of the present invention as mentioned above, it is the infrared ray photosensitive compoistion of having known in the past, promptly, contain in the infrared ray photosensitive compoistion of absorbing light pyrogen, also add (C) molecule and contain phenol OH and CH with (B) at the macromolecular compound of (A) alkali soluble ₂The phenol derivatives of OR (R=alkyl, acyl group) (following be called aptly specific phenol derivatives) is its feature.

At first, (C) specific phenol derivatives is illustrated.This phenol derivatives, its molecule contain phenol hydroxyl and-CH ₂OR (R=alkyl, acyl group).Such compound is widely used phenol derivatives, as with following structural formula represented contain methylol (CH ₂OH) compound relatively a little less than the interaction that the alkaline water soluble resin combines with hydrogen slightly, thereby has stronger hydrophobic property.[changing 1]

Aforesaid-CH ₂The OR base has one at least for well in molecule, but from the viewpoint of effect, contains plural-CH ₂The OR base is better.

-CH ₂R in the OR base, as alkyl with methyl, ethyl, just-a straight chain shape or a chain of propyl group, isopropyl, just-butyl, isobutyl, t-butyl etc., have carbon number and be 1～4 alkyl for well.As acyl group, then with formoxyl, acetyl group, bytyry, benzoyl, cinnamoyl and valeryl for well.

Contain phenol OH and-CH at molecule ₂The compound of OR base (R=H or alkyl, acyl group); for example; that is put down in writing in Japanese kokai publication sho 57-111529 communique or Japanese kokai publication hei 6-282067 communique is such, is 10～60 ℃ with phenol derivatives and formaldehyde in temperature range, and 1～30 hour reaction time is resulting in the highly basic.So, at first, make and contain-CH ₂The compound of OH base, with alcohol or and acid reaction, make methylol generation esterification or etherification reaction, obtain on the position of R, having alkyl, acylated compound.

Contain more like this-CH ₂OR base or-CH ₂The phenol derivatives of OH base, be to contain the adjuvant as the positive light sensitivity lithographic plate formula print format of photonasty composition such as quinone diacid with ultraviolet source exposure, after having opened known in clear 57-111529 communique or the Japanese kokai publication hei 6-282067 communique, photographic layer video picture by aforesaid spy, during high-temperature heating treatment, improve printability resistance, also improved anti-pollution degree thereby very suitable.In order to improve printability resistance, shown in communique, more favourable when R is alkyl or acyl group not as being H.As shown in the present, be applicable to the situation of the conformal photosensitive compoistion of infrared laser irritability, exceed accident, have-CH ₂The compound of OH base does not have effect when R is H.Have only as the aforementioned that R is the material of alkyl or acyl group, have between the imaged sector of raising, the printing ink when improving bin stability and improving printing is subjected to the effect of capacitive (ink adhesion).

Below list in the present invention and to use, contain intramolecular phenol OH and-CH ₂The concrete example of compound of OR base and (R=alkyl, acyl group).The present invention is not restricted to these compounds.

As the addition of (C) specific phenolic derivant, with respect to (A) alkaline water soluble high-molecular compound, with 2～30 weight % for well, 5～20 weight % more preferably.If addition is very few, and it is little then to improve the video picture effect, and the effect that bin stability improves is also little.And if addition is too much, and video picture, bin stability have all improved, during the imaging liquid high activity, necessary anti-video picture be difficult to, minimum site is easily by at random, also has simultaneously when printing and the low tendency of printing performance.

Secondly, (A) alkali soluble macromolecular compound is illustrated.

Employed in the present invention alkaline aqueous solution soluble high-molecular compound (following be called simply [alkali-soluble macromolecule]).For example as, phenolics, m-cresol-formaldehyde resin, p-cresol-formaldehyde resin, m-/P-cresols-formaldehyde resin, phenol/cresols (m-, it is any that p-or m-/p-mix) mix the novolac resin of formaldehyde resin, xylenol resin etc.

The alkali-soluble macromolecule here, its weight-average molecular weight are 500～20,000, and number-average molecular weight is 200～10, and 000 is advisable.

And United States Patent (USP) the 4th, 123 is put down in writing in No. 279 instructionss, and t-butylphenol formaldehyde resin, octyl phenol formaldehyde resin etc. are such, contains substituting group and be the phenol of alkyl of carbon number 3～8 and the condensation product of formaldehyde, also can merge use.Foregoing alkali-soluble macromolecule can use separately, and also using more than two kinds might as well.

In the present invention, aforesaid (A) alkali-soluble macromolecule such as EP330, in 239A2 number put down in writing, (1) is contained in a part, the monomer of the sulfonamido that combines with a hydrogen atom at least on the nitrogen-atoms (below, be called [monomer of (1)]).(2) contain in a part the monomer (below, be called [monomers of (2)]) of the represented active imino group of formula as described above.(3) each monomer that contains the phenol hydroxyl as, acrylamide, Methacrylamide, acrylate, methacrylate or hydroxy styrenes (below, be called [monomers of (3)]).With wherein at least a as the copolymerization composition and contain 10 moles of copolymers (below, be called [specific interpolymer]) more than the % and can and use.

Aforesaid specific copolymer is to be its copolymerization composition with aforementioned (1) is at least a in (3), with contain 20 moles more than the % for well.The copolymerization composition is as being less than 10 moles of %, then contain between the macromolecule of phenol hydroxyl do mutually not obvious, narrower between its imaged sector.

In addition, aforesaid specific copolymer, contain except that aforementioned (1) other copolymerization composition to the monomer of (3) (below, be called [other copolymerization composition]) also passable.

The monomer of aforementioned (1); it is the sulfonamido that in a part, combines with a hydrogen atom at least on its nitrogen-atoms; be the degraded monomer that is constituted that closes simultaneously with unsaturated link of more than one possibility polymerization; therein, with the amino-sulfonyl that contains acryloyl group, allyl or ethoxy and displacement or single displacement or the low molecular compound of the sulphonyl imino group of displacement for well.

Aforementioned (A) alkali-soluble macromolecule can be used in combination more than a kind or 2 kinds separately, and it is in photosensitive compoistion total solid composition, and addition is 30-99 weight %, is preferably 40-95 weight %, more preferably 60-90 weight %.The addition of alkali soluble polymer is when being lower than 30 weight %, and the permanance of photographic layer is bad, and when surpassing 99 weight %, sensitivity, this two aspect of permanance are all bad.

In the present invention, aforesaid (B) photo-thermal conversion agent is, can use all pigment or dyestuff that heat takes place after the absorbing light.

As the pigment of preceding addressing, can use commercially available pigment, or in pigment index (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), [printing-ink technology, the pigment of being put down in writing in (CMC publish, 1984 annuals) etc.

As the kind of aforementioned pigment, can list as: black pigment, yellow uitramarine, orange pigment, brown pigments, red pigment, violet pigment, green pigment, viridine green, fluorescent pigment, metal powder pigment, other and polymkeric substance are in conjunction with pigment.

Specifically can enumerate as: insoluble azo colour, azo lake, condensed azo pigment, chelating AZO pigments, phthualocyanine pigment, anthraquinone pigment, perylene Ji perylene ketone series pigments, thioindigo color, quinoline a word used for translation ketone series pigments, dioxazine pigment, iso-dihydro-indole series pigments, quinone o-hydroxyacetophenone series pigments, be infected with mordant pigment, azine pigment, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment, carbon black etc.

To these pigment in use, without surface treatment or all right through surface treatment.The surface-treated method can list: with resin or cured surface coated method, and the method for adhering to surfactant, method that combines with surface of pigments with reactive materials (for example, silane coupling agent or epoxy compound, polyisocyanate etc.) etc.Above-mentioned surface treatment method is recorded in [character of metallic soap class and application] (good fortune study), [printing-ink technology] (CMC publication, 1986 annuals) and [up-to-date pigment applications technology] (CMC publication, 1984 annuals) and [up-to-date pigment applications technology] (CMC publication, 1986 annuals).

The particle diameter of aforementioned pigment, for well, 0.05～1 μ m is better with 0.01～10 μ m, and 0.1～1 μ m is best.

When the particle diameter of aforementioned pigment was lower than 0.01 μ m, its stability of dispersion thing in photosensitive layer coating liquid was poor, and not good enough if surpass the homogeneity of 10 μ m photographic layers.

As aforementioned dispersing of pigments method, can use manufacturing printing ink or manufacturing toner etc. used, the dispersion technology that is known.As disperse machinery can enumerate as: ultrasonic decollator, muller, sand grains reeler, pearly-lustre mill, supermicro mill, bowl mill, fan mill, dispersion mill, KD mill, colloid mill, dynatron, triple-roller mill, add voltage-controlled and machine etc.Write up is in [up-to-date pigment applications technology] (CMC publication, 1986 annuals).

Before the dyestuff addressed, can use commercially available dyestuff, and the dyestuff of the record in the document (for example, [dyestuff brief guide] Synthetic Organic Chemistry association compiles, clear and 45 annuals).

As object lesson, can enumerate as: azo dyes, the wrong salt azo dyes of metal, pyrazolone azo dyes, anthraquinone dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine dyes, cyanine dye etc.

As absorbing infrared ray, perhaps near infrared pigment, carbon black are optimum uses.In addition, as can absorb infrared ray or near infrared example as: Japanese kokai publication sho 58-125246 number, the spy opens clear 59-84356 number, the spy opens clear 59-202829 number, the spy opens the cyanine dye of being put down in writing in the clear 60-78787 grade, Japanese kokai publication sho 58-173696 number, the spy opens clear 58-181690 number, the spy opens the methine dyes of being put down in writing in the clear 58-194595 grade, Japanese kokai publication sho 58-112793 number, the spy opens clear 58-224793 number, the spy opens clear 59-48187 number, the spy opens clear 59-73996 number, the spy opens clear 60-52940 number, the spy opens the naphthoquinone dyestuff of being put down in writing in the clear 60-63744 grade, the spiny dogfish pyrans pigment of being put down in writing among the Japanese kokai publication sho 58-112792 etc., 434, No. 875 contained cyanine dyes of BrP etc.

In addition, for aforesaid dyestuff, United States Patent (USP) the 5th, 156, the near infrared of being put down in writing in No. 938 reclaims the very suitable use of sensitizer, and United States Patent (USP) the 3rd, 881, aryl benzo (sulphur) pyralium salt of the replacement of being put down in writing in No. 924, Japanese kokai publication sho 57-142645 number (United States Patent (USP) the 4th, 327,169) the trimethylene thiophene pyralium salt of being put down in writing in, the spy opens clear 58-181051 number, with 58-220143 number, with 59-41363 number, with 59-84248 number, with 59-84249 number, with 59-146063 number, with the pyrans based compound of being put down in writing in 59-146061 number, the spy opens the anthocyanidin of being put down in writing in clear 59-216146 number, United States Patent (USP) the 4th, 283, the pentamethylene sulfuration pyralium salt of being put down in writing in No. 475 etc., Japan special fair 5-13514 number, with the pyrylium compound that shows of opening in the 5-19702 communique, Epolight III-178, Epolight III-130, Epolight III 125 grades (Ai Bailin society system) are particularly suitable.

Other the degree of photo-thermal preferably changes agent, has absorbing light and gives birth to the character of heat, and have the absorption territory in 700～1200nm wavelength coverage, particularly can mix with alkali-soluble macromolecule chemical combination is fine, as the following basic-dyeable fibre that proposes.This dyestuff has, and can interactional base take place with the alkali-soluble macromolecule at its intramolecular ammonium, imido grpup etc., interacts with aforesaid (A) alkali-soluble macromolecule, can suppress this alkali-soluble.

Can enumerate as following general formula (Z), as the example of this dyestuff.(changing 3)

In the above-mentioned general formula (Z), R ²¹～R ²⁴Representative be respectively hydrogen atom independently, or with carbon number be 1～12 for suitable alkyl, thiazolinyl, alkoxy, naphthenic base, aryl as sub stituent, R ¹And R ²², R ²³And R ²⁴Separately in conjunction with being the ring structure that forms.

In the formula, R ²⁵～R ³⁰Represented is each independently, can have substituent carbon number and be 1～12 alkyl, these bases can have substituting group.

In the formula, R ³¹～R ³³Represented is each independently hydrogen atom, halogen atom or can to have substituent carbon number be 1～8 alkyl, above-mentioned R ³²Can with above-mentioned R ³¹Or R ³³In conjunction with and form ring structure, m＞2 o'clock, the R of plural number ³²Can be each other in conjunction with forming ring structure.

In the formula, R ³⁴～R ³⁵Represented is each independently hydrogen atom, halogen atom or can to have substituent carbon number be 1～8 alkyl, above-mentioned R ³⁴Can with R ³⁵In conjunction with and form ring structure, during the situation of m＞2, the R of plural number ³⁴Can be each other in conjunction with forming ring structure.

Above-mentioned each substituting group can be listed below, for example: halogen atom, carbonyl, nitro, itrile group, sulfonyl, carboxyl, the ester that contains carbonic acid, sulphonic acid ester etc.

In addition, m is with 1～8 integer representation, wherein with 1～3 for well.

In the formula, X-represents negative ion, can give an example as: cross chloric acid, tetrafluoride boric acid, phosphorus hexafluoride acid, triisopropyl naphthalene sulfonic acids, 5-nitro-O-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-acid dimethyl, 2,4,6-tri-methyl p-toluenesulfonate, 2-nitrobenzene-sulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzene sulfonic acid, 2-fluoridize octyl group naphthalene sulfonic acids, dodecylbenzene sulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxyl-4-hydroxyl-5-benzoyl benzene sulfonic acid and p-toluenesulfonic acid etc.

The represented compound of above-mentioned general formula (Z) is the compound that generally is referred to as cyanine dye, and the compound of cyanine dye A～E as shown below is fit to use, and the present invention does not limit these compounds.Change 4

Change agent as the photo-thermal degree that can be applicable to the cyanine based dye, to represented dyestuff of top described general formula and following cyanine dye F, G etc. all are suitable for.Change 5

Above-mentioned photo-thermal conversion agent (B), for the total solid composition of photosensitive compoistion, the ratio of adding in photosensitive compoistion is 0.01～50 weight %, be preferably 0.1～10 weight %, and the preferred adding proportion of dyestuff is 0.5～10 weight %, and the preferred adding proportion of pigment is 3.1～10 weight %.

The above-mentioned pigment or the addition of dyestuff, then sensitivity is low to be lower than 0.01 weight %, but if surpass 50 weight %, photographic layer can lose homogeneity, the permanance of photographic layer also degenerates.

Above-mentioned pigment or dyestuff, add to other composition with also passable in one deck, it is also passable to add other set one deck to.What is called is added other one deck to, that is to say to add the material in fact very low with containing the dissolubility that makes cementing agent to, be in the adjoining course of such one deck that pyrolytic and undecomposed state are arranged and go.In addition, above-mentioned pigment or dyestuff and cementing agent are preferably in same one deck, be added on other the layer also passable.

Infrared laser conformal photosensitive compoistion of the present invention serves as beyond the essential composition with aforementioned (A)～(C), in the scope of not damaging effect, can add known all adjuvants.

For example: have pyrolytic at salt, quinone two acids, aromatic series sulfo group compound, aromatic sulphonic acid ester compounds etc., but be under the undecomposed state, in fact the material that reduces with the dissolubility that makes the aqueous alkaline solution-soluble macromolecular compound merges when using, seek in the imaging liquid for non-exposure part (picture part), it is satisfactory to improve dissolving inhibition aspect.

As aforesaid salt, can list: diazo salt, ammonium salt, microcosmic salt, salt compounded of iodine, sulfonium salt, salt, clock salt etc.

The suitable example of above-mentioned salt is lifted as follows: S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal et al, Polymer, 21,423 (1980), the diazo salt of being put down in writing in the Japanese kokai publication hei 5-158230 communique, United States Patent (USP) the 4th, 069, No. 055, with 4,069, No. 056, the ammonium salt of the record in Te Kaiping 3-140140 number the instructions, D.C.Necker et al, Macromolecules, 17,2468 (1984), C.S.Wen et al, Teh.Proc.Conf.Rad.Curing ASIA, P478 Tokyo, Oct (1988), United States Patent (USP) the 4th, 069, No. 055, the microcosmic salt of being put down in writing in same 4,069, No. 056, J.V.Crivello et al, macromorecnles, 10 (6), 1307 (1977), Chem﹠amp; Eng.News, Nov.28, P31 (1988), No. the 104th, 143, Europe patent, No. the 339th, 049, United States Patent (USP), with the 410th, No. 201, Te Kaiping 2-150848 number, the salt compounded of iodine of being put down in writing in Te Kaiping 2-296514 number, J.V.Crivello etal, Polymer J.17,73 (1985), J.V.Crivello et al.J.Org.Chem., 43,3055 (1978), W.R.Watt et al, J.Polymer Sci., polymer Chem.Ed., 22,1789 (1984), J.V.crivelloet al, Polymer Bull., 14,279 (1985), J.V.Crivello et al, Macromorecules, 14 (5), 1141 (1981), J.V.Crivello et al, J.Polymer Sci., polymer Chem.Ed., 17,2877 (1979), European patent the 370th, No. 693, with 233, No. 567, with 297, No. 443, with 297, No. 442, United States Patent (USP) the 4th, 933, No. 377, with 3,902, No. 144, with 410, No. 201, with 339, No. 049, with 4,760, No. 013, with 4,734, No. 444, with 2,833, No. 827, Deutsche Bundespatent the 2nd, 904, No. 626, with 3,604, No. 580, with 3, the sulfonium salt of being put down in writing in 604, No. 581, J.V.Crivello et al, Macromorecules, 10 (6), 1307 (1977), J.V.Crivello et al, J.Polymer Sci., Polymerchem.Ed., the salt of record in 17,1047 (1977), C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, the clock salt of being put down in writing among the Oct (1988) etc.

(quinone two acids)

In above-mentioned quinone two acids, preferred O-quinone diacid compounds.

Above-mentioned O-quinone diacid compounds, the compound that employing is made of at least one O-quinone diacyloxy, can increase the compound of the different structure of alkali-soluble owing to thermal decomposition, that is to say, owing to the thermal decomposition of O-quinone diacid loses the inhibition dissolving power of bonding agent, thereby help improve the dissolubility of photographic layer.

Above-mentioned O-quinone diacid compounds for example as: the husky work of J. fruit " photosensitivity system " (John Wiley﹠amp; Sons.Inc.) compound of being enumerated in the 339-352 page or leaf, particularly with the sulphonic acid ester of the O-quinone diacid of various aromatic polyhydroxy compounds or aromatic amino compound and reaction, and sulfonic acid amides etc. is all good.In addition, benzoquinones-(1,2)-diacid-5-sulfonic acid chloride of being put down in writing in the special public clear 43-28403 communique, perhaps naphthoquinones-(1,2)-diacid-5-sulfonic acid chloride reaches pyrogallol one acetone resin and ester thereof, United States Patent (USP) the 3rd, reach for 046, No. 120 with the 3rd, 188, the benzoquinones of being put down in writing in No. 210-(1,2)-diacid monosulfonic acid chloride and naphthoquinones-(1,2)-diacid-5-sulfonic acid chloride and phenol-formaldehyde resin and ester class thereof be.

In addition, can also list some preferably as: naphthoquinones-(1,2)-diacid-4-sulfonic acid chloride and phenol-formaldehyde resin, or cresol-formaldehyde resin and ester thereof, naphthoquinones-(1,2)-diacid-4-sulfonic acid chloride, and pyrogallol-acetone resin and ester class thereof.

The O-quinone diacid compounds that some other is useful can be by knowing in numerous patent reports.For example exist: Japanese kokai publication sho 47-5303 number, the spy opens clear 48-63802 number, the spy opens clear 48-63803 number, the spy opens clear 48-96575 number, the spy opens clear 49-38701 number, the spy opens clear 48-13354 number, special public clear 41-11222 number, special public clear 45-9610 number, special public clear 49-17481 number, United States Patent (USP) the 2nd, 797, No. 213, with the 3rd, 454, No. 400, with the 3rd, 544, No. 323, with the 3rd, 573, No. 917, with the 3rd, 674, No. 495, with the 3rd, 785, No. 825, BrP the 1st, 227, No. 602, with the 1st, 251, No. 345, with the 1st, 267, No. 005, with the 1st, 329, No. 888, with the 1st, 330, No. 932, Deutsche Bundespatent waits cited record in each instructions for the 854th, No. 890.

The addition of above-mentioned O-quinone diacid compounds for the total solid composition that photonasty is formed, suits in 1～10 weight % scope.These compounds can independent a kind of use, also can merge use more than two kinds.

As with the corresponding ion of above-mentioned salt; can list: tetrafluoride boric acid, phosphorus hexafluoride acid, triisopropyl naphthalene sulfonic acids, 5-nitro-O-toluenesulfonic acid, 5-sulfosalicylic acid, 2; 5-acid dimethyl, 2; 4,6-tri-methyl p-toluenesulfonate, 2-nitrobenzene-sulfonic acid, 3-Benzene Chloride sulfonic acid, 3-bromobenzene sulfonic acid, 2-fluoridize caprylyl naphthalene sulfonic acids, dodecylbenzene sulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxyl-4-hydroxyl-5-benzoyl-benzene sulfonic acid, p-toluenesulfonic acid etc.

In above each compound, particularly preferred as phosphorus hexafluoride acid, triisopropyl naphthalene sulfonic acids or 2, the alkyl aryl sulfonate of 5-acid dimethyl etc.

Adjuvant beyond the above-mentioned O-quinone diacid compounds, its addition is that 1～10 weight % scope is advisable.Above-mentioned adjuvant and bonding agent are to be advisable containing with one deck.

In addition, as other above-mentioned composition, be purpose to improve sensitivity, can add ring-type acid dehydrate class, phenol and organic acid etc.

Dehydrate as ring-type acid, can enumerate as United States Patent (USP) the 4th, 115, No. 128 instructionss are put down in writing: dehydration phthalic acid, dehydration tetrahydrophthalic acid, dehydration hexahydrophthalic acid, dehydration 3,6-is inside and outside-and Δ 4-tetrahydrophthalic acid, dehydration tetrachloro be for phthalic acid, dehydration maleic acid, dehydration chloromaleic acid, α-phenol maleic acid, dehydration succinic acid, dehydration 1,2,4,5 benzenetetracarboxylic acids etc.

(surfactant)

In addition, in photosensitive compoistion of the present invention, in order to improve Treatment Stability, add and open as Japanese kokai publication sho 62-251740 communique, spy that the non-ionic surfactant, the spy that are put down in writing in the flat 3-208514 communique open clear 59-121044 communique, the spy opens the amphoteric surfactant of being put down in writing in the flat 4-13149 communique the video picture condition.

As the concrete illustration of non-ionic surfactant, can enumerate as Arlacel-65, Arlacel-40, sorbitan trioleate, glyceryl monostearate, polyoxyethylene nonylplenyl ether etc.

Concrete illustration as amphoteric surfactant, can enumerate as alkyl two (amino-ethyl) glycocoll, alkyl polyamino ethyl glycine hydrochloride, 2-alkyl-N-hydroxyethyl-N-hydroxyethyl imidazole quinoline base betaine, or N-four decyls-N, the N-betaine type is (for example: trade name [Ah not 's root K]; First industrial group's system) etc.In addition, can also add that all colleagues of the present invention are put down in writing in flat 10～No. 364061 of the Japanese Patent Application of in the past being filed an application, be to aggregate into the high molecular surfactant that branch becomes with (methyl) acrylate monomer with fluoro-alkyl.

Above-mentioned surfactant is shared ratio in photosensitive compoistion total solid composition, for well, and serves as better with 0.1～5 weight % with 0.05～15 weight %.

Can also in photosensitive compoistion of the present invention, add the picture colorant.As the picture colorant, can add aforesaid salt and form the property organic dyestuff, also can be with other dyestuff.As the suitable dyestuff that contains salt formation property organic dyestuff, can enumerate following oil-soluble dyes and basic-dyeable fibre.

Concrete example: can enumerate as follows; Oil yellow #101, oil yellow #103, the red #312 of oil-bound distemper, glossy dark green BG, oily blue BOS, oily blue #603, glossy black BY, glossy black BS, glossy black T-505 (above) by Orient Chemical Ind's system, the pure orchid of Victoria, liposoluble purple (CI42555), methyl violet (CI42535), ethyl violet, rhodamine B (CI145170B), peacock green (CI142000), serge blue (CI52015) etc.In addition, the spy opens the dyestuff particularly suitable of being put down in writing on the clear 62-29324 communique.

These dyestuffs add the ratio in the photosensitive compoistion to, for photosensitive compoistion total solid composition, are generally 0.01～10 weight %, are preferably 0.1～3 weight %.

In addition, as required, flexibility of filming for increase etc. adds plasticizer in photosensitive compoistion of the present invention.As plasticizer, specifically can be listed below: the oligomer of butyl phthalyl, polyglycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexylphthalate, o-phthalic acid dibutyl ester, tricresyl phosphate, oleic acid tetrahydrofuran ester, acrylic or methacrylic acid and condensate etc.

Infrared laser of the present invention contains above-mentioned various constituent with conformal photosensitive compoistion, can well use as the material of the formation photographic layer of original edition for lithographic printing plate.Below, describe the lithographic plate formula galley master that uses photosensitive compoistion of the present invention in detail.

Aforesaid original edition for lithographic printing plate is the photographic layer that has the aforementioned photosensitive compoistion of coating on carrier.In addition, also has other layer as required.

Usually, aforementioned photosensitive compoistion is dissolved in the appropriate solvent, is coated on then on the suitable carrier and forms as lithographic plate.

Aforesaid solvent might not limit especially.For example can enumerate: dichloro-ethene, cyclohexanol, methyl ethyl ketone, methyl alcohol, ethanol, propyl alcohol, glycol monomethyl methyl esters, 1-methoxyl-2-propyl alcohol, 2-methoxyacetic acid ethyl ester, 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 (DMSO), tetramethylene sulfone, gamma-butyrolacton, toluene etc.These solvents can use separately, also can mix use.The concentration (the total solid composition that contain adjuvant) of solvent in aforementioned photosensitive compoistion is that 1～50 weight % is advisable.Coating, dry back coating weight (solid constituent) of gained on carrier are different because of purposes, to the photosensitive printing version generally with 0.5～5.0 gram/rice ²Be advisable.

As method, can use various methods to the carrier coating.Can give an example as: vacuum coated, revolution coating, hydrojet coating, hang coating, dip coated, air and blow coating, rotary coating, cylinder coating etc.

Along with the minimizing of coating weight, can be observed sensitivity and increase, but the epithelium characteristic of light-sensitive surface is low.

In aforesaid photographic layer, be added to the surfactant that improves coating, for example opening the fluorine of being put down in writing in the clear 62-170950 communique the spy is surfactant.Suitable addition is 0.01～1 weight % with respect to photographic layer all solids component, more preferably 0.05～0.5 weight %.

As the used carrier of lithographic plate, be plate object with good dimensional stability.For example; Paper, plastics (for example: tygon, polypropylene, polystyrene etc.), laminated paper, sheet metal (for example: aluminium, zinc, copper etc.), plastic sheeting (for example: cellulose diacetate, cellulose triacetate, cellulose propionate, acid fiber element, acetate acid fiber element, cellulose nitrate, poly terephthalic acid vinyl acetate, tygon, polystyrene, polypropylene, polycarbonate, polyvinyl acetal etc.), the paper that adheres to as above-mentioned metal laminate plate or evaporation or plastic foil etc.

Stop as above-mentioned carrying, be advisable with polyester film or aluminium sheet, wherein good with dimensional stability again, and more inexpensive aluminium sheet is suitable especially.Suitable aluminium sheet is a pure aluminum plate and be the alloy sheets that principal ingredient contains other element of trace with aluminium, and it is also passable to also have aluminum laminate sheet or evaporation to adhere to the aluminium sheet of plastic sheeting.Other contained in the aluminium alloy yuan have, silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium etc.The amount of other element is below the 10 weight % in the alloy.

To aluminium suitable especially among the present invention is fine aluminium.Because pure aluminium is very difficult at the refining techniques manufacture view fully, so it is also passable only to contain a small amount of other element.Therefore be applicable to aluminium sheet of the present invention, its composition is not particularly limited, and suitably utilizes and is familiar with shared material aluminium sheet.Used aluminium plate thickness can be 0.1～0.6 millimeter among the present invention, and preferred 0.15～0.4 millimeter, more preferably 0.2～0.3 millimeter.

The surface of aluminum plate alligatoring to removed the oils that adhering on surface earlier in the past, for example can carry out ungrease treatment with surfactant, organic solvent, alkaline aqueous solution etc.

The surface coarsening of aluminium sheet is handled, and available various methodologies is carried out.For example can select to use: mechanical coarse surface method, electrochemical dissolution surface coarsening method and the selection dissolution method of the surface being carried out chemistry.As Mechanical Method, available ball-milling method, brushing method, abrasive blasting method, polishing polishing or the like method for having known.Also having the electrochemical surface roughening method, is the method for carrying out with interchange or direct current with in hydrochloric acid or nitric acid electrolytic solution.In addition, open the utilization put down in writing in the clear 54-63902 communique with the two method that combines the spy.

Aluminium sheet by above method surface coarsening as required, carries out etching and neutralisation treatment, for obtaining desired surperficial water-retaining property or improving the antifriction consumption, carry out anodized.As the used electrolyte of aluminium sheet anodized, all can use as long as can form the various electrolyte of porous matter oxide scale film.The general acid mixture that uses sulfuric acid, phosphoric acid, oxalic acid, chromic acid or above acid.Electrolytical concentration will suitably be determined according to electrolytical kind.

Anodised treatment conditions can not be decided owing to various use change of electrolyte without exception.In general, be 1～80 weight % solution with electrolyte concentration, the liquid temperature is that 5～70 ℃, current density are 5～60 peace/dm ², 1～100 volt of voltage, electrolysis time is for suitable in 10 seconds～5 minutes scopes.

The amount of anodic oxide coating is less than 1.0 gram/rice ²The time, printability resistance is bad, and lithographic plate formula print format predisposes to damage with the non-picture part of master, and in printing process, undermined part is adhered to printing ink and is easy to produce the infringement contamination.

Implement after the anodized, on demand hydrophilicity-imparting treatment is carried out on the aluminium surface.As aforesaid hydrophilicity-imparting treatment, as United States Patent (USP) 2,714, No. 066, the 3rd, 181, No. 461, the 3rd together, 280, No. 734, and the 3rd, 902, No. 734 in containedly handle with metal silicate (for example sodium silicate aqueous solution) method, according to said method, with carrier sodium silicate aqueous solution dip treating, also can use electrolytic treatments, other as shown in the public clear 36-22063 communique of spy to fluoridize potassium silicate, and United States Patent (USP) the 3rd, 276, No. 868, the same the 4th, 153, No. 461, the same the 4th, shown in 689, No. 272, handle with many vinyl phosphoric acid.

Aforesaid lithographic plate formula galley master must be that structure is established photographic layer on carrier.According to intended purposes, can also establish other each layer of protective seam, middle layer, following coating etc. by structure.In order to improve the characteristic of photographic layer, between carrier and photographic layer, set coating by structure.

Forming the composition of coating down, is various organic compounds.For example: carboxymethyl cellulose, dextrin, Ah perverse uncle natural gum, 2-amino-ethyl phosphonic acids etc. has amino phosphonic acid based, substituent phenyl-phosphonic acid is arranged, the naphthyl phosphonic acids, alkyl phosphonic acid, the glyceryl phosphonic acids, methylenediphosphonate, and organic phospho acid such as vinyl di 2 ethylhexyl phosphonic acid, substituent phenyl phosphate is arranged, Naphthyl phosphate, alkylphosphonate and phosphoglyceride organic phosphoric acid, substituent phosphinic acids phenyl ester is arranged, phosphinic acids naphthalene ester, organic phosphinic acids such as phosphinic acids Arrcostab and phosphinic acids glyceride, the amino acids of glycocoll or alanine etc., vinyl alcohol amine hydrochlorate etc. has the amine hydrochlorate of hydroxyl etc.

Above compound both can use separately, also can merge use more than two kinds.

Particularly, open flat 10-301262 communique as EP871070A2 number or spy and put down in writing, with have acidic group and salt high-molecular compound as under be coated with thing, the residual film after the video picture, residual look all seldom, lowly also reducing of printability resistance, most suitable.

Above-mentioned following coating is made by the following method.

Promptly be, with organic solvents such as water or methyl alcohol, ethanol, methyl ethyl ketones, or their mixed solvent dissolves above-mentioned organic compound, with this solution on aluminium sheet, be coated with, dry method, with organic solvent or its mixed solvents such as water or methyl alcohol, ethanol, methyl ethyl ketones,, then aluminium sheet be impregnated in sorption above-claimed cpd in the solution with above-mentioned organic compound dissolving, then with cleaning, drying such as water and form down the method for coating.

In the former coating process, with the solution of 0.005～10 weight % concentration of above-mentioned organic compound, coating ins all sorts of ways.

In addition, for the latter's dipping method, the concentration of solution is 0.01～20 weight %, 0.05～5 weight % more preferably, and dipping temperature is 20～90 ℃, more preferably 25～50 ℃, dip time is 0.1 second～20 minutes, more preferably 2 seconds～1 minute.Here solutions employed, be with alkaline matters such as ammonia, triethylamine, potassium hydroxide, or acidic materials such as hydrochloric acid, phosphoric acid are adjusted at the pH value of solution in 1～12 the scope, in addition, in order to improve the state repeatability of lithography format, can add some welds with master.

The above-mentioned amount of coating of coating down is with 2～100 milligrams/meter ²For good, more preferably 5～50 milligrams/meter ²If amount of coating is less than 2 milligrams/meter ², then can not obtain sufficient printability resistance.And mend the amount of covering if above 100 milligrams/meter ²Can not obtain sufficient printability resistance equally.

The former format of resulting as described above lithography format, again through the picture exposure, the plate-making process that video picture is handled becomes planographic printing plate usually.

As the light source of the used active ray of picture exposure, to be advisable with light source with emission wavelength near infrared to infrared field, solid state laser, semiconductor laser are for suitable especially.

When handling as the video picture of original edition of lithographic printing plate, used imaging liquid and additional liquid can use the alkaline aqueous solution of knowing.Can list as inorganic bases such as sodium silicate, potassium silicate, sodium tripolyphosphate, tri-potassium phosphate, triphosphoric acid ammonium, second sodium phosphate, second potassium phosphate, second ammonium phosphate, sodium carbonate, sal tartari, hartshorn salt, sodium bicarbonate, saleratus, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate, NaOH, ammonium hydroxide, potassium hydroxide and lithium hydroxides.In addition, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, tri-isopropyl amine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, aziridine, 1, organic bases such as 2-ethylenediamine, pyridine.

Above alkali cpd both can independent a kind of use, also can two or more merging use.

In the above alkali cpd, the imaging liquid of particularly suitable is aqueous silicate solutions such as sodium silicate, potassium silicate.Its reason is, can be according to the silicon oxide sio as the silicate composition ₂With alkali gold oxide M ₂The ratio of O and concentration can be regulated video picture.For example, the spy open put down in writing in the clear 54-62004 communique, special public clear 57-7427 number like that, use alkali silicate effectively.

In addition, using automatic developing device to carry out under the situation of video picture,, need not exchange imaging liquid in the long-time video picture groove, also can handle a large amount of PS versions owing to the aqueous solution (replenishing liquid) higher than imaging liquid alkalescence intensity will be added in the imaging liquid.

In order to promote or to suppress video picture, improve the dispersion of video picture degree and the oleophylic China ink of galley picture part, as required, can and replenish at imaging liquid and add various surfactants or organic solvent in the liquid.Can list as the surfactant that is suitable for: negative ion system, kation system, nonionic system and amphoteric surfactant.In addition, opening polyoxyethylene-polyoxy propane copolymerization mould assembly surfactant etc. of being put down in writing in the polyglycol put down in writing in the clear 61-215554 communique or the special fair 3-54339 communique as the spy all is good adjuvant.

Secondly, as required, can also add quinhydrones, resorcinol in imaging liquid and additional liquid, reductive agents such as the sodium salt of the mineral acid of sulphurous acid, sulphurous acid hydracid etc., sylvite can add organic carbonaceous acid, defoamer, water softening agent etc. in addition.

Above-mentioned with imaging liquid and replenish liquid and carry out the galley that video picture was handled, also to carry out aftertreatment with rinsing liquid that contains washings, surfactant and the lipoprotein liquid of not feeling that contains A Cibai natural gum or starch derivative.As of the aftertreatment of above-mentioned planographic printing plate, can be used in combination with above-mentioned various disposal routes with master.

In recent years, because the rationalization and the standardization of plate-making operation in plate-making, press has been extensive use of the automatic developing device that galley is used.In general this automatic developing device has visualization portion and aftertreatment part, also has device and the various treatment trough and the spraying plant of conveyance galley.Galley after exposure is finished is flatly carried, and sprays video picture with the various treating fluids of pump suction from the sprayer nozzle simultaneously and handles.Also have, know recently, with deflector roll etc. galley is flooded the disposal route of conveyance in the oriented processing liquid bath of filling treating fluid.In so automatic processing procedure, can in treating fluid, replenish the additional liquid of adding at any time and handle according to treatment capacity or running time etc.

Also have, the processing mode that the what is called of handling with in fact original treating fluid is discarded after a single use also is suitable for.

Picture is scraped type and can (for example unwanted picture occur on lithographic plate through overexposure, video picture, washing and/or rinsing and/or natural gum, the film edge corner angle vestige of original film etc.) situation, so, the process that will carry out cancellation to these unwanted picture part.The method of this cancellation can be used as putting down in writing in the fair 2-13293 communique of spy, be coated on the picture that needn't need with cancellation liquid, after placing through certain hour again with this method of washing.And for example the spy open put down in writing in the flat 59-174842 communique like that, utilize optical fiber to import the method for video picture after the unnecessary picture part of active ray irradiation.

The plain film galley that is obtained as mentioned above with after the coating of insensitive fatization natural gum, can offer printing engineering on request.But when obtaining the planographic printing plate of higher printability resistance, can implement the high-temperature heat treatment method.

When lithographic plate is carried out high-temperature heat treatment, before high-temperature heat treatment, by Japanese Patent Publication 61-2518 number, with 55-28062 number, spy open clear 62-31859 number, with being treated to of being put down in writing in 61-159655 number each communique with whole liquid.

As this method, be coated with lithographic plate with sponge or the absorbent cotton that is soaked with whole liquid, or galley is immersed in the method that is coated with in the groove of filling whole liquid.Or be suitable for to be coated with all with automatic coater.In addition, after coating, use slider or slip to roll roller and make the coating weight homogenising, and obtain result preferably.

The coating weight of above-mentioned whole liquid is generally with 0.03～0.8 gram/rice ²(dry back weight) is for suitable.

The lithographic plate of whole liquid of above-mentioned coating uses high-temperature heat treatment device (the high-temperature heat treatment device [BP-1300] that for example, Fuji's photographic film company sold etc.) to carry out high-temperature heating treatment later in drying if necessary.The temperature and time of heating also according to the kind that forms the picture composition, heats in 180 ℃～300 ℃ scopes and was advisable in 1～20 minute.

Lithographic plate after the high-temperature heat treatment, the frequent in the past disposal routes of using such as foundation need suitably be washed, natural gum is scraped type, if used the situation of whole the liquid that contains water-soluble high-molecular compound matter etc., then can save natural gum and scrape that type etc. is so-called does not feel the fat processing.

This method is handled the lithographic plate of gained, and the offset press that is used for packing into etc. carries out the printing of a lot of numbers.

[embodiment]

Below be the explanation embodiments of the invention, the present invention is not limited to these embodiment.

(embodiment 1)

Thickness is 0.3 millimeter aluminium sheet (material 1050), and with 10% sodium hydroxide solution, in 50 ℃, degreasing in 20 seconds is thoroughly cleaned with water.Wash with water again after neutralizing, clean with 10% salpeter solution then.Use square wave ac once more in containing 15 grams per liter aqueous solution of nitric acid, current density 50 peace/dm carry out the processing of electrolysis asperities.Electrolysis asperitiesization aluminium sheet later, impregnated in 60 ℃, after dissolve crude removal 30 seconds in 20% aqueous sulfuric acid, place 15% aqueous sulfuric acid, reached 2.5 gram/rice with direct current 3 peace/dm anodic oxidations by overlay film weight, after the anodic oxidation, dip treating is 1 minute in 25 ℃ 3% sodium silicate solution, and washing and drying obtains substrate A then.With following coating coating fluid coated substrates A down, obtain substrate B.The amount of coating of filming after the drying is 15 milligrams/meter.

＜following coating coating fluid 〉

Following copolymer 0.3 gram of molecular weight 2.8 ten thousand

(compound of being put down in writing in EP871070A2 number)

Methyl alcohol 100 grams

Water 1 gram [changing 6]

As photosensitive layer coating liquid, be coated with the substrate B of above gained with following photosensitive compoistion 1, formed photographic layer in 1 minute, obtain the lithographic plate among the embodiment 1 in 120 ℃ of dryings.The dried coating amount of coating is 1.8 gram/rice ²

＜photosensitive compoistion 1 (photosensitive layer coating liquid 1) 〉

M, p-cresols-linear phenol-aldehyde resin (m, p than=6/4, weight-average molecular weight 7000, contain unreacted cresols 0.3 weight %) 1 gram

Photo-thermal conversion agent (cyanine dye A) 0.05 gram

P-octyl phenol resin 0.01 gram

Naphthoquinones-1, the carboxylate of 2-diacid-5-sulfonyl chloride and pyrogallic acid acetone resin

0.02 gram

Dehydration tetrahydrophthalic acid 0.07 gram

Being the anionic dyestuff of 1-naphthalene sulfonic aicd 0.03 gram to ion in 2-naphthylamines-7-sulfonic acid ethyl ester

Phenol derivatives (example compound (I)) 0.1 gram

Fluorine is surfactant (the luxuriant and rich with fragrance storehouse F-177 of U.S. coffee, a big Japanese ink chemistry

Industry (strain) system) 0.05 gram

Methyl ethyl ketone 7 grams

1-methoxyl-2-propyl alcohol 4 grams

(comparative example 1)

Form in the used photosensitive compoistion of photographic layer at embodiment 1, in order to replace phenol derivatives (example compound (I)), use aforesaid general phenol derivatives structural formula represented have a methylol (CH ₂OH) phenol derivatives (has-CH in the foregoing example compound (I) ₂OCH ₃,-CH ₂The compound of OH base) in addition, other method is similarly to Example 1 handled, and obtains the lithographic plate of comparative example 1.

Comparative example 2

Form in the used photosensitive compoistion of photographic layer at embodiment 1, except need not adding phenol derivatives (example compound (I)), carrier is used the lithographic plate that obtains comparative example 2 with quadrat method similarly to Example 1.

[video picture evaluation]

After resulting lithographic plate coating, (25 ℃, 60% relative humidity front and back) are stored down and at 45 ℃, were placed three days under 75% relative humidity under ambient temperature and moisture respectively.Then to these versions of handling with semiconductor laser exposure machine (Creo Trendsetter 3244 VFS (40w), wavelength 830nm) with 6W and 140 rev/mins carry out scan exposure (space of a whole page energy be 100 millis burnt/centimetre ²).Again with alkaline imaging liquid HD-P2 (Fuji's photographic film system, eurymeric lithographic printing plate-use) in Unigraph society system automatic developing device, 25 ℃ of 20 seconds of video picture.The conductivity of new imaging liquid is 65ms/ centimetre.Carry out video picture with this new imaging liquid, to the lithographic plate of embodiment 1, no matter with what store under any condition, its video picture state is all good, and comparative example 1 with the lithography of comparative example 2 the bad situation of video picture takes place then.

Secondly, the imagination imaging liquid absorbs carbon dioxide in air, it is bad to cause pH value to reduce video picture, dissolves into carbon dioxide in the imagination imaging liquid and conductivity is reduced and will add the additional liquid HD-P2R higher than imaging liquid alkali concn, and addition is than the susceptible condition of preassigned.Add to replenish after the liquid, conductivity raises, and making conductivity is to change between the 61ms/ centimetre～78ms/ centimetre to carry out the video picture experiment.Version after video picture is handled is by the video picture of its non-picture part, the film minimizing of picture part and the repeatability of 1% site are examined or check.All no problem represents with zero.Its result such as following table 1 are represented.

(table 1)

		Conductivity
											Lithographic plate	Preservation condition	??62	???64	??66	??68	??70	??72	??74	??76	?????78
Embodiment 1	Ambient temperature and moisture	??○	???○	??○	??○	??○	??○	??○	??○	1% site is at random
											45 ℃ of 75%RH 3 days	Video picture is bad	???○	??○	??○	??○	??○	??○	??○	?????○
	Comparative example 1	Ambient temperature and moisture	Video picture is bad	Video picture is bad	Video picture is bad	??○	??○	??○	??○	??○											1% site is at random
45 ℃ of 75%RH 3 days											Video picture is bad	Video picture is bad	Video picture is bad	Video picture is bad	Video picture is bad	Video picture is bad	??○	??○	?????○
		Comparative example 2	Ambient temperature and moisture	Video picture is bad	Video picture is bad	??○	??○	??○	??○	??○										??○	1% site is at random
45 ℃ of 75%RH 3 days	Video picture is bad										Video picture is bad	Video picture is bad	Video picture is bad	Video picture is bad	??○	??○	??○	?????○

Zero represented scope, the conductivity amplitude broadness that good video picture scope is promptly arranged is as judgement wide between imaged sector.Secondly, the sample that ambient temperature and moisture is stored down, the common conductivity amplitude broadness with forcing the sample that (high temperature, high humidity) placed under the cruel condition has shown its stability for storage.Use the lithographic plate of the embodiments of the invention 1 of specific phenol derivatives as can be known from above result, with the comparative example 1 that contains the phenol derivatives of knowing, reach the comparative example 2 that does not contain phenol derivatives and compare, have between broader imaged sector and good storage stability.

[evaluation of printing adaptability]

After exposure, the video picture, be coated with whole liquid BC-7 (Fuji's photographic film system) with automatic coating machine to no problem sample, be heated to 260 ℃ with high-temperature heating equipment BP-1300 again, handled seven minutes, carrying out the space of a whole page in order to water-reducible gummy GU-7 (Fuji's heliotype formula system) solution then handles, place after one day, just print with HAIDEL SOR-M printing machine.Print from the beginning to picture part supply printing ink and estimate its printing ink adherence to the number that acquisition stable printing product are printed.

Secondly, after obtaining stablize printed matter, proceed printing, up to the printing ink concentration reduction of picture part, and printed printed sheet number is estimated itself and printing when can not get the good print product.The result is as shown in table 2 below.

(table 2)

Lithographic plate	Adherence number (opening)	The number of anti-brush the (ten thousand)
			Embodiment 1	?????9	??????30
Comparative example 1	????200	??????32
			Comparative example 2	????100	??????20

The printing ink adherence of lithographic plate that can be known embodiment 1 by table 2 is good, and the printing ink of picture part is subjected to the capacitive excellence.And printability resistance is also good.By above result, can confirm that the imaged sector field width of lithographic plate of the present invention is wide and printing adaptability is also very excellent.

(embodiment 2)

In the pre-treatment identical and smear on the carrier of handling down with embodiment 1, be coated with following photosensitive compoistion 2 (photosensitive layer coating liquid 2), at 130 ℃ of dryings one minute, formation photographic layer, obtain the lithographic plate of embodiment 2.The dried coating amount of coating is 1.1 gram/rice ²

＜photosensitive compoistion 2 (photosensitive layer coating liquid 2) 〉

M, p-cresols phenolic novolac (m, p ratio=6/4, mean molecular weight 3500) 0.5 gram

N-(the amino sulfinyl phenol of p-)

Copolymer 0.5 gram of Methacrylamide and methyl acrylate

(EP 330, put down in writing among the embodiment of No. 2 instructionss of 239A)

Photo-thermal conversion agent (cyanine dye B) 0.07 gram

2-methoxyl-4-phenyl amino benzene phenodiazine hexafluoro phosphate 0.02 gram

Dehydration tetrahydrophthalic acid 0.12 gram

Is anionic dyestuff 0.015 gram of 1-naphthalene sulfonic aicd with the pure orchid-BOH of Victoria to ion

Phenol derivatives (above-mentioned exemplary compounds (II)) 0.1 gram

Fluorine is surfactant (the luxuriant and rich with fragrance storehouse F-177 of U.S. coffee, a big Japanese ink chemistry

Industry (strain) system) 0.05 gram

Gamma-butyrolacton 2 grams

Methyl ethyl ketone 20 grams

1-methoxyl-2-propyl alcohol 1 gram

(comparative example 3)

Form the used photosensitive compoistion 2 of photographic layer according to embodiment 2, other is identical with embodiment 2 except that not adding phenol derivatives (exemplary compounds (II)), obtains the lithographic plate of comparative example 3.

The gained lithographic plate is stored under ambient temperature and moisture identical with embodiment 1 and hot and humid condition.

The semiconductor laser exposure machine that this edition and embodiment 1 usefulness is same exposes, with alkaline imaging liquid LH-DP and additional liquid LH-DPR (Fuji's photographic film system), in the photographic film system automatic developing device LP-900H of Fuji, 30 ℃ of video pictures 12 seconds are filled perhaps in same video picture and to be studied in the scope.The result is shown in following table 3.

(table 3)

		Conductivity
									Lithographic plate	Preservation condition	??39	??41	??43	??45	??47	????49	???51
Embodiment 2	Ambient temperature and moisture	??○	??○	??○	??○	??○	Film slightly reduces
									45 ℃ of 75%RH 3 days	Video picture is bad	??○	??○	??○	??○	????○	???○
	Comparative example 3	Ambient temperature and moisture	Video picture is bad	Video picture is bad	??○	??○	??○	Film slightly reduces
45 ℃ of 75%RH 3 days									Video picture is bad	Video picture is bad	Video picture is bad	Video picture is bad	??○	????○	???○

Can find out that by tabular language the lithographic plate of embodiment 2 is compared with the lithographic plate of the comparative example 3 that does not contain phenol derivatives, broad between its imaged sector, excellent storage stability under harsh storage requirement.

Select photosensitive compoistion of the present invention, and use the digital signal and the iraser that provide by computing machine etc. directly to make a plate, broad between imaged sector, high-storage stability and the good lithographic plate of printing adaptability can be provided.

Claims (2)

1, a kind of infrared laser conformal photosensitive compoistion, it is characterized in that: this constituent contains: (A) alkaline water soluble high-molecular compound, the conversion agent of (B) photo-thermal and (C) in molecule, have a phenol OH, and have-CH ₂The phenol derivatives of OR (R=alkyl, acyl group).

2, a kind of lithographic plate is characterized in that: this lithographic plate is on its hydrophilic carrier, have with the infrared laser that contains following (A)～(C) with the photographic layer that conformal photosensitive compoistion was coated with,

(A) alkaline water soluble high-molecular compound

(B) photo-thermal conversion agent

(C) in molecule, have phenol OH, and have-CH ₂The phenol derivatives of OR (R=alkyl, acyl group).