CN101954776B - Heat-sensitive composition for thermosensitive CTP plate, plate-making method using the same and application of amide carboxylic acid ammonium salt in the same - Google Patents
Heat-sensitive composition for thermosensitive CTP plate, plate-making method using the same and application of amide carboxylic acid ammonium salt in the same Download PDFInfo
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- CN101954776B CN101954776B CN 200910158051 CN200910158051A CN101954776B CN 101954776 B CN101954776 B CN 101954776B CN 200910158051 CN200910158051 CN 200910158051 CN 200910158051 A CN200910158051 A CN 200910158051A CN 101954776 B CN101954776 B CN 101954776B
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Abstract
The invention relates to a heat-sensitive composition which comprises the following components: A) 1-5wt% of H2NCO-R-COONH4 compound shown in a formula (I), wherein, R is as defined in specification; B) 87-95wt% of linear phenolic resin; C) 1-5wt% of infrared absorbing dye; and D) 1-3wt% of background dye. The invention further relates to a method for preparing a thermosensitive CTP plate, comprising the following steps: (1) sequentially roughening, anodizing and sealing an aluminum plate base; (2) coating the aluminum plate base after sealing treatment with the heat-sensitive composition; and (3) drying the coated aluminum plate base obtained in step (2) in two sections, wherein, the first section is dried with far infrared ray and the second section is dried with forced hot air, and finally obtaining the thermosensitive CTP plate. In addition, the invention further relates to application of the H2NCO-R-COONH4 compound as a dissolving promoter shown in formula (I) in the heat-sensitive composition. The heat-sensitive composition of the invention has the advantages of simple composition, stable storage and excellent thermosensitive imaging comprehensive performance.
Description
Technical field
The present invention relates to a kind of thermo-sensitive computer digitlization (CTP) plate sensible heat composition of directly making a plate.Particularly, the present invention relates to a kind of amide carboxylic acid ammonium salt that comprises as the thermal CTP plate material of chaotropic agent sensible heat composition.In addition, the invention still further relates to a kind of method of using described thermal CTP plate material to prepare positive image without preheating thermal CTP plate material with the sensible heat composition, and also relate to amide carboxylic acid ammonium salt purposes as chaotropic agent in thermal CTP plate material usefulness sensible heat composition.
Background technology
For the positive-printing heat-sensitive CTP plate material of exploitation to the rapid industrialization beginning of this century that begin one's study from the nineties in last century, the thermographic composition of its use comprises following component usually: a. line style phenol resin; B. the physical change type molten/chaotropic agent of resistance or chemical change type hinder molten/chaotropic agent; C. as the infrared absorbing dye of photo-thermal transformation substance; D. heat is produced acid source; With the e. coloring background dye.Wherein the in the past many employings of the described physical change type of the components b molten/chaotropic agent of resistance can with the material of the phenolic hydroxyl group generation association of line style phenol resin, such as the carbonyls such as ketone, carboxylate, ether compound, tertiary amine compound etc., these several compounds can use separately also can compound use (EP0823327).Some physical change type induced thermal imaging composition systems need not to add in addition the molten/chaotropic agent of physics change type resistance by the molten effect of the resistance of infrared absorbing dye and coloring background dye.It is very effective utilizing the molten/chaotropic agent of normal temperature chemical amplification type resistance in the chemical change type induced thermal imaging composition, and the inventor etc. had once applied for multinomial Chinese patent at this point and obtained the authorization (China Patent No. 01123686.8,02117827.5,02160050.3 and 03143500.9).Be known that the physical change type can also utilize phase change, for example utilize the regular phase change of arranging of crystallization-noncrystalline, regular-non-.Most physical change types and chemical change type scheme nearly all will be used the product acid source in order to accelerate molten, the short molten variation of its resistance, utilize the acid that produces that association or the short molten effect of chemical breakdown occur to separate under the effect of heat.
Mitsubishi chemical Co., Ltd in 1997 utilize the sulfonyl hydrazines compound as the chaotropic agent application driography thermal CTP plate material patent (Unexamined Patent 9-319074).The sulfonyl hydrazines compound can decompose gases such as producing nitrogen under the effect of heat, and discharging simultaneously acidity is not very strong acidic materials, can be developed relatively easily liquid through the part of heat scan and develop and remove.The sensitivity height is the outstanding advantages of this plate, but there is following fatal shortcoming in pure sulfonyl hydrazines compound: this easily decomposes (1) pure sulfonyl hydrazines compound in aqueous slkali, thereby very weak to the molten ability of the resistance of alkaline developer, in developing process, very easily subtract the film loss of gloss, even can't stay image in the situation improperly filling a prescription; (2) the sulfonyl hydrazines compound is comparatively responsive to temperature, although its decomposition temperature is generally more than 140 ℃, but because in fact the impact of environmental factor namely decomposes lentamente since 110 ℃, thereby to utilize the sulfonyl hydrazines compound as chaotropic agent, baking version baking temperature generally be only below 100 ℃ safe; And (3) sulfonyl hydrazines compound hydrogen supply reducing power is extremely strong, the compatibility ion of it and heat-sensitive composition middle infrared absorption dyestuff very easily forms corresponding acid, particularly this effect is more obvious in the presence of proton solvent, thereby the sensible heat composition solution ageing stability extreme difference of preparation, placing the pH value of three days left and right sides sensible heat liquid will be down to about 2 by about 3, sometimes even can drop to about 1～1.5, service life is the longest only has three days, generally only have one day, this is the large fatal shortcoming in its production application process.Same time, Nippon Steel Chemical Co., Ltd once synthesized the hydrazone compounds (Unexamined Patent 9-254542 and Unexamined Patent 9-295463) of a series of sulfohydrazides, their stability is more much better than sulfonyl hydrazines compound, yet Co., Ltd. of Nippon Steel is not used for temperature-sensitive plate aspect with this compounds, but is used for the manufacturing of heat-sensitive paper; And owing to being to use with bi-component, above-mentioned shortcoming is not able to abundant exposure.1998 Dongli Ltd. (Unexamined Patent 11-123885 and Unexamined Patent 11-268437) sulfohydrazide and carbohydrazide structure combined also invented driography CTP plate, the stability of use therein sensible heat composition solution is necessarily improved.But according to the inventor's experiment, this scheme does not also thoroughly solve the stability problem of sensible heat composition solution.In the recent period, domestic have research unit and manufacturer that unifor cyclohexanone hydrazone compounds has been obtained better effects as releasing acid foaming chaotropic agent for the manufacture of thermal CTP plate material, but the service life of used sensible heat composition solution is still shorter, roughly within five days.
Up to the present, the inventor finds that not yet the ammonia (releasing alkali) of releasing that proposes among the present invention produces the short compound that dissolves of acid foaming for the report of sensible heat composition.Based on the problem that exists in the conventional art with after the inventor has studied the unsettled reason of sensible heat composition solution, so the inventor has proposed to release the ideamonger that ammonia (releasing alkali) produces acid foaming chaotropic agent.The proposition of this conception is based on the above-mentioned background technology on the one hand, is based on the other hand the resting form acid agent (or latent curing agent) that adopts when studying the amino-alkyd resin acid cure seventies in last century.
Based in the past used technology and the inventor's in the past invention, an object of the present invention is to provide the sensible heat composition of the thermal CTP plate material with good stability, another purpose of the present invention is the positive PS printing plate version base that utilizes common sealing of hole to cross, and is coated with under the condition that does not add priming coat or transition zone and makes that sensitivity is high, good resolution, development latitude are large, be difficult for loss of gloss subtracts the dirty positive image without preheating thermal CTP plate material of film and the residual end.
Summary of the invention
The technological means of dealing with problems
In order to realize above-mentioned purpose of the present invention, the present invention has mainly adopted the chaotropic agent of being used the sensible heat composition by the amide carboxylic acid ammonium salt of acid anhydrides and ammonia synthesis as thermal CTP plate material.This compounds slowly discharges ammonia (releasing alkali) at the heating initial stage (when temperature is not bery high), and meanwhile carboxyl discharges formation acid amides carboxylic acid and produces acid.Amide carboxylic acid ammonium salt is a kind of extraordinary acid-base buffer agent, thereby can make the pH value of sensible heat composition solution keep stable within considerable time.The ammonia that produces during thermal decomposition makes the rete foaming, particularly makes soon the rete foaming because of aerogenesis speed after reaching decomposition point.The foaming effect of ammonia and because it self alkalescence and can produce the molten effect of urging with the compound with phenol ammonia structure that film-forming resin forms, and the acid amides carboxylic acid that produces forms the salt such as carboxylic acid sodium salt and can further strengthen this molten effect of urging in alkaline developer.Even the temperature of rete rises to such an extent that the higher acid amides carboxylic acid that makes further generates acid imide in the scanning process, because steaming rapidly also of the steam that produces can produce foaming effect, and acid imide self is acidic materials, also is very easy to be dissolved in the alkaline developer.Above-mentioned each factor makes the sensible heat composition have huge poor solubility through behind the heat scan in alkaline developer, is very beneficial for forming the positive image image.The new concept of Here it is thinking of the present invention and thermographic is not report in all patents of invention in the past.
Detailed Description Of The Invention
According to a first aspect of the invention, provide a kind of thermal CTP plate material sensible heat composition, based on the gross weight of this sensible heat composition, it comprises following component:
A) the amide carboxylic acid ammonium salt compound of at least a general formula (I) of 1～5 % by weight is as chaotropic agent,
H
2NCO-R-COONH
4(I)
Wherein R is that the anhydride compound of following dicarboxylic acids does not contain the residue that anhydride group obtains: 1,2,3, on 6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, the phenyl ring with on the phthalic anhydride of a methyl substituents, the phenyl ring with phthalic anhydride, the 5-ENB-2 of 1,2,3 or 4 chlorine and/or fluoro substituents, 3-dicarboxylic acid anhydride, 2,3-naphthalic anhydride, Malaysia eleostearate, maleic rosin, Malaysia laccol or anthracene-9,10-dihydro bridged ring-α, β-succinic anhydride;
B) the line style phenol resin of 87～95 % by weight is as film-forming resin;
C) 1～5 % by weight has the infrared absorbing dye of absworption peak in 790～830nm optical wavelength range; And
D) coloring background dye of 1～3 % by weight.
Component A
Use in the sensible heat composition at thermal CTP plate material of the present invention, comprise the amide carboxylic acid ammonium salt of formula (I) as component A, it is especially released ammonia and produces acid foaming chaotropic agent as chaotropic agent.The Main Function of this compound is: produce acidic materials acid amides carboxylic acid after the heat scan when producing ammonia in the rete; The ammonia that discharges particularly when reaching decomposition temperature, because rate of release is very fast, causes rete foaming puffing, thereby adding that a part of ammonia is stayed in the rete can develop to rapidly picture with the film-forming resin effect in alkaline developer; In addition, the acid amides carboxylic acid that produces forms the salts such as carboxylic acid sodium salt in alkaline developer, and these salts also have extremely strong short molten effect; Also have, even the scanning temperature is higher, imidization reaction further occurs and forms acid imide in the acid amides carboxylic acid, on the one hand, acid imide self is acidic materials, thereby is easy to develop and removes, on the other hand, the steam that produces at higher temperature also can make rete foaming puffing, thereby promotes to develop.Therefore, formula used according to the invention (I) compound is that collection produces acid, produces alkali and short molten the acting on all over the body of foaming, and becomes the key component of thermographic composition.
Sensible heat composition of the present invention comprises releases ammonia and produces acid foaming chaotropic agent-amide carboxylic acid ammonium salt-can be based on traditional method preparation for preparing the amide carboxylic acid ammonium salt compound.To the present invention advantageously, the anhydride compound of the dicarboxylic acids that amide carboxylic acid ammonium salt synthetic of the present invention uses, such as 1,2,3,6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, 5-ENB-2,3-dicarboxylic acid anhydride and 2,3-naphthalic anhydride etc., necessary purity is higher, and anhydride content requires more than 95 % by weight.Suction becomes corresponding dicarboxylic acids if acid anhydrides is placed for a long time, then needs to make its dehydration become acid anhydrides in about one hour in baking under 140～160 ℃ the temperature and re-uses.
The amide carboxylic acid ammonium salt that the present invention uses both can adopt the method for bibliographical information synthetic, and following four kinds of methods that also can adopt the inventor to propose are synthetic:
(1) acid anhydrides with dicarboxylic acids is dissolved in weight in its organic solvent of 2～5 times, obtain the organic solution of acid anhydrides, under strong agitation, this acid anhydrides solution is added drop-wise in the ammonia spirit of 15～25 % by weight, the temperature of control reactant liquor is 10～40 ℃ in this adding procedure, the amount of ammoniacal liquor is so that the mole of ammonia is 2.5～3 times of acid anhydrides mole, time for adding is 0.5～1 hour, the gained reactant mixture was reacted under 50～65 ℃ temperature 1～2 hour, majority of organic solvent and the part moisture of use are removed in distillation (for example decompression distillation) under 60～70 ℃ temperature afterwards, the concentrate that cooling obtains is separated out amide carboxylic acid ammonium salt, suction filtration, drying obtains the amide carboxylic acid ammonium salt product.
(2) and the proportion scale in the said method (1) identical, just under strong agitation be in the anti-acid anhydrides organic solution that splashes into by the dicarboxylic acids of the described preparation of method (1) of the ammonia spirit of 15～25 % by weight with concentration, time for adding is still 0.5～1 hour, then described in method (1), carry out post processing, obtain the amide carboxylic acid ammonium salt product.
(3) under agitation pass into the ammonia of q.s in the acid anhydrides organic solution by the dicarboxylic acids of the described preparation of method (1), be generally at least 3 times of acid anhydrides mole, the temperature of reactant liquor remains 20～40 ℃ in passing into the process of ammonia, and it is 1～2 hour that the flow of control ammonia makes the time that passes into ammonia.Ammonia passes into was down to room temperature with reactant liquor after complete in 0.5～1.5 hour, then further fully cool off to separate out product, pour out mother liquor and concentrated mother liquor (for example concentrated by decompression distillation) further to separate out product, all products that drying is separated out obtain the amide carboxylic acid ammonium salt product.
(4) acid anhydrides with dicarboxylic acids is ground into fine powder, then under strong agitation, join the ammonia mole in the ammonia spirit of its 15～25 % by weight of 2.5～3.0 times, the temperature of reactant liquor is controlled to be 10～40 ℃ when adding acid anhydrides, the interpolation time is 0.5～1 hour, the gained reactant mixture was reacted under 50～70 ℃ temperature 1～2 hour, cool off afterwards reactant liquor and separate out amide carboxylic acid ammonium salt, and with mother liquor concentrated (for example concentrated by decompression distillation), crystallisation by cooling is separated out product again, all products that drying is separated out obtain the amide carboxylic acid ammonium salt product.
In above-mentioned four kinds of methods first three planted the solvent that chemical reaction does not occur with this acid anhydrides again the acid anhydrides all used organic solvent, this solvent to select can to dissolve the dicarboxylic acids that the present invention uses under the reaction condition of method (1)-(3).As the example of this solvent, can mention dioxane, oxolane, dimethyl formamide (DMF), methyl-sulfoxide (DMS), trichloro-ethylene, chloroform and chlorobenzene equal solvent, they can use separately, also can compound use.But the acid anhydrides of considering the dicarboxylic acids that the present invention uses in these solvents dissolubility and drip ammoniacal liquor or pass into ammonia after the compatibility of ammonia and water, preferentially select dioxane and/or oxolane.
In said method (1)～(4), if the anhydride compound of dicarboxylic acids contains solid impurity, advantageously first with reacted reacting liquid filtering, carry out again afterwards distillation and concentration and process.The amide carboxylic acid ammonium salt product should carry out drying not being higher than under 60 ℃ the low temperature, and some dry temperature are higher than 60 ℃, and the small part ammonium salt decomposition reaction can occur forms the acid amides carboxylic acid.
The anhydride compound of the available dicarboxylic acids of amide carboxylic acid ammonium salt that synthetic the present invention uses has a lot, can mention 1,2,3,6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, on the phenyl ring with the phthalic anhydride (comprising 3-and 4-methyl nadic anhydride) of a methyl substituents, on the phenyl ring with 1,2, the phthalic anhydride of 3 or 4 chlorine and/or fluoro substituents (for example 3-and 4-chloro-phthalic anhydride, 3,4-, 3,5-, 3,6-and 4,5-two chloro-phthalic anhydrides, 3,4,5-and 3,4,6-three chloro-phthalic anhydrides, 3,4,5, the 6-tetrachlorophthalic tetrachlorophthalic anhydrid, 3-and 4-difluorophthalic anhydride, 3,4-, 3,5-, 3,6-and 4,5-difluorophthalic anhydride, 3,4,5-and 3,4,6-trifluoro-phthalic acid acid anhydride, 3,4,5, the 6-ptfe phthalic anhydride, 3-chloro-6-difluorophthalic anhydride and 4-chloro-5-difluorophthalic anhydride etc.), 5-ENB-2, the 3-dicarboxylic acid anhydride, 2,3-naphthalic anhydride, the Malaysia eleostearate, maleic rosin, Malaysia laccol and anthracene-9,10-dihydro bridged ring-α, β-succinic anhydride.Preferably, the acid anhydrides of dicarboxylic acids used according to the invention is to be selected from least a in lower group: 1,2,3,6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, 5-ENB-2,3-dicarboxylic acid anhydride and 2,3-naphthalic anhydride.Therefore, correspondingly, the R in formula (I) compound is preferably
-CH
2CH
2-,
Or
As component A, it both can use single kind according to amide carboxylic acid ammonium salt of the present invention, also can use two or more different amide carboxylic acid ammonium salt.
In sensible heat composition of the present invention, be generally 1～5 % by weight as the consumption of the amide carboxylic acid ammonium salt of component A based on the sensible heat composition total weight, be preferably 1～3 % by weight.
B component
Use in the sensible heat composition at thermal CTP plate material of the present invention, comprise the line style phenol resin as B component, it is the component of content maximum in the sensible heat composition of the present invention, as film-forming resin.The selection principle of B component should be so that it be good with the compatibility of component A, C and three components of D, particularly has good compatibility with chaotropic agent as component A, and does not contain the impurity that causes this chaotropic agent decomposition.As the B component of line style phenol resin, its selection is conventional, and available phenol resin has a lot.As an example, can mention poly(4-hydroxystyrene), orthoresol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-paracresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, orthoresol-phenol-formaldehyde resin, paracresol-phenol-formaldehyde resin, tertiary butyl phenol-phenol-formaldehyde resin, orthoresol-paracresol-phenol-formaldehyde resin and metacresol-paracresol-phenol-formaldehyde resin.Poly(4-hydroxystyrene) is during as film-forming resin, and preferably its weight average molecular weight is 8000～20000, and M
w/ M
nBe 1.1～1.3, the listed various linear phenol-aldehyde resins in front are during as film-forming resin, and preferably their weight average molecular weight separately are 3000～10000, and M
w/ M
nBe 3～10.The line style phenol resin can use separately, also can compound use.(metacresol-paracresol-formaldehyde resin, the mol ratio of metacresol and paracresol are 6: 4, and weight average molecular weight is 5000-6000, and M to be applicable to linear phenol-aldehyde resin of the present invention and for example to be BTB-25 that sky, Weihai becomes chemical industry Co., Ltd to produce
w/ M
nBe 4～6), (paracresol-phenol-formaldehyde resin, the mol ratio of paracresol and phenol are 2: 1 to BTB-27, and weight average molecular weight is about 4000, and M
w/ M
nBe 3～4), (orthoresol-paracresol-formaldehyde resin, the mol ratio of orthoresol and paracresol are 3: 1 to BTB-28F, and weight average molecular weight is 8000, and M
w/ M
nBe 3.2), (metacresol-paracresol-formaldehyde resin, the mol ratio of metacresol and paracresol are 7: 3 to BTB-29, and weight average molecular weight is about 9000, and M
w/ M
nBe 9～10), (metacresol-paracresol-formaldehyde resin, the mol ratio of metacresol and paracresol are 7: 3 to BTB-29 (L), and weight average molecular weight is 5000～6000, and M
w/ M
nBe 5～6) and BTB-211 (paracresol-phenol-metacresol-formaldehyde resin, the mol ratio of paracresol, phenol and metacresol are 6: 3: 1, and weight average molecular weight is 3000～4000, and M
w/ M
nBe 3～3.5).
In sensible heat composition of the present invention, be generally 87～95 % by weight as the consumption of the line style phenol resin of B component based on the sensible heat composition total weight, be preferably 92～95 % by weight.
Component C
Thermal CTP plate material of the present invention with the sensible heat composition in, be included in infrared absorbing dye that 790～830nm optical wavelength range has absworption peak as component C, such dyestuff is a class photo-thermal transformation substance.It is infrared absorbing dye that this infrared absorbing dye can select commercially available colored cyanines system and section to spend cyanines both at home and abroad.The absworption peak wavelength of these infrared absorbing dyes is generally 800～830nm, and the absworption peak of usually measuring in alcohol solvent is 815～820nm, and the absworption peak of measuring in the sensible heat composition is generally about 830nm.The infrared absorbing dye that is fit to sensible heat composition of the present invention has NK-2014, NK-2268, the HCD-21 of Lin Yuan company, the PS-101 of Japanese chemical drug, PS-102, and the infrared absorbing dyes such as S 0094 of FEWCHEMICALS company.
In sensible heat composition of the present invention, be generally 1～5 % by weight as the consumption of the infrared absorbing dye of component C based on the sensible heat composition total weight, be preferably 2～4 % by weight.Consumption during greater than 5 % by weight heating temp too high, for chaotropic agent of the present invention, only need 170～250 ℃ and get final product, temperature is too high to tend to produce some side reactions.In addition, infrared absorbing dye self is a kind of stronger resistance solvent, and consumption too conference causes certain difficulty to development.Generate heat when consumption is lower than 1% too low, the temperature that is scanned part is not enough, and the sensitivity of sensible heat composition is too low so that amide carboxylic acid ammonium salt of the present invention decomposes, and under the scanning energy of regulation, particularly not thorough in close aluminum substrate punishment solution, developing, it is dirty to be easy to keep on file.
Component D
Use in the sensible heat composition at thermal CTP plate material of the present invention, comprise coloring background dye as component D.The selection of this coloring background dye is conventional, and available background dye has a lot, and general conventional PS version and heat-sensitive CTP plate all are fit to coloring background dye.Component D preferably comprises and is selected from lower group one or more as main dyestuff: solvent blue, alkaline bright blue, Victoria's ethereal blue, malachite green, blackish green, crystal violet, ethyl violet and crystal violet, preferred Victoria's ethereal blue and/or alkaline bright blue are as main dyestuff, and this component D randomly also comprises the auxiliary dyestuff of one or more conducts that is selected from lower group: dimethyl yellow, curcumin and sudan black.Coloring background dye as component D both can have been used single kind of dyestuff, also can use two or more different dyes.
In sensible heat composition of the present invention, be generally 1～3 % by weight as the consumption of the coloring background dye of component D based on the sensible heat composition total weight, be preferably 1～2 % by weight.
For the application of making a plate, sensible heat composition of the present invention need to be mixed with the solution form usually.The available main body solvent of preparation sensible heat composition solution has ethylene glycol monomethyl ether, ethylene glycol monoemethyl ether, the only methyl ether of propane diols and cyclohexanone etc., these solvents can use separately, also can compound use, for example use the mixed solvent of ethylene glycol monomethyl ether and the only methyl ether of propane diols.In addition, butanone, gamma-butyrolacton and/or dioxane etc. can be used as secondary solvent.The preferred butanone of the present invention is used in conjunction with as secondary solvent and aforementioned body solvent, and butanone generally accounts for 15～25 % by weight of solvent gross weight.
Solvent load is decided on the viscosity of the required coating fluid of coating machine usually, and the solid content of general sensible heat composition solution is between 10～15 % by weight, and viscosity is at 3～5mm
2S
-1Between.Advantageously, before coating plate-making, the sensible heat composition solution generally will be successively carries out three-stage filtration through the filter membrane (for example teflon membrane filter) in 10 μ m, 2 μ m and 0.5 μ m aperture, and the filtrate that obtains can be coated with within 10 days.
During preparation sensible heat composition solution, each component is preferably dissolved according to following order: generally be the infrared absorbing dye that dissolves first than indissoluble, after infrared absorbing dye dissolves fully, add again coloring background dye and film-forming resin, add at last according to amide carboxylic acid ammonium salt compound of the present invention.If also comprise the molten/chaotropic agent of normal temperature chemical amplification type resistance in the sensible heat composite formula, then the dissolving sequencing of each component is preferably infrared absorbing dye, coloring background dye, amide carboxylic acid ammonium salt, film-forming resin and the molten/chaotropic agent of normal temperature chemical amplification type resistance.This be because: the molten/chaotropic agent of normal temperature chemical amplification type resistance is easy to form acid and acidolysis reaction occurs with the compatibility ion of infrared absorbing dye, cause the sensible heat composition solution to lose efficacy ahead of time, and amide carboxylic acid ammonium salt has preferably buffer effect of fuluic acid, thereby dissolves first the acid amides carboxylic acid can effectively avoid the sensible heat composition solution to lose efficacy ahead of time before the molten/chaotropic agent of dissolving normal temperature chemical amplification type resistance.
According to another aspect of the present invention, the invention provides a kind of method of using thermal CTP plate material of the present invention to prepare positive image without preheating thermal CTP plate material with the sensible heat composition, the method comprises the steps:
(1) aluminum substrate being carried out successively roughening treatment, anodized and sealing of hole processes;
(2) will use through the aluminum substrate that sealing of hole was processed thermal CTP plate material of the present invention to carry out coated version with the sensible heat composition; And
The aluminum substrate through applying that (3) will obtain in step (2) carries out the two-part drying, and wherein first paragraph adopts FAR INFRARED HEATING to carry out drying, and second segment adopts forced air dry, thereby obtains positive image without preheating thermal CTP plate material.
In method for platemaking of the present invention, the version base of the positive image without preheating thermal CTP plate material of employing is aluminum substrate.Before coating thermal CTP plate material of the present invention was with the sensible heat composition, this aluminum substrate need to carry out roughening treatment, anodized and sealing of hole successively to be processed.
For the roughening treatment in the step (1), the purpose of this processing is to enlarge the specific area of version base, thereby improves absorption affinity.Roughening treatment both can be mechanical roughening treatment, also can be that electrolyzing and coarsening is processed, and perhaps comprised this two kinds of roughening treatments, under a rear situation, preferably carried out first mechanical roughening treatment, after carry out electrolyzing and coarsening and process.For electrolyzing and coarsening, its method commonly used is the alternating current roughening method,, two aluminium plates is put into the electrolyte of hydrochloric acid or nitric acid that is, connects AC power, makes the Grains that the aluminium plate surface formation depth and fineness are moderate, be evenly distributed.For the anodized in the step (1), the purpose of this processing is to make the aluminium plate surface to form one deck densification, crackless pellumina.It is darker that Grains on this pellumina has, and what have is irregular, if when directly being coated with heat sensing layer and might causing developing the residual end dirty, particularly evident when CTP.For addressing this problem and in the situation that without the primary coat processing, in method for platemaking of the present invention, also must carrying out sealing of hole and process.
Process for the aluminum substrate that will obtain after the anodized carries out sealing of hole, the version base of this processing can be delivered in the sealing of hole groove that pore-sealing liquid is housed and be carried out sealing of hole.Usually, the temperature of sealing of hole groove remains 50～80 ℃, and the speed of a motor vehicle of sealing of hole time during on coating decided, and may be selected to be 20～40 seconds.For the present invention, being used for the pore-sealing liquid of sealing of hole can be based on following hole sealing agent: potassium dihydrogen phosphate-potassium fluoride, potassium dihydrogen phosphate-tartaric acid list sodium salt-potassium fluoride, potassium dihydrogen phosphate-sodium metasilicate-potassium fluoride, sodium dihydrogen phosphate-sodium fluoride, sodium metaaluminate-sodium fluoride, sodium dihydrogen phosphate-β-I is peaceful, sodium metasilicate-sodium fluoride, sodium metaaluminate, sodium potassium tartrate tetrahydrate-tartaric acid and/or sodium metasilicate-tartaric acid etc.Preferably phosphoric acid potassium dihydrogen-potassium fluoride of the present invention (weight ratio is 100: 1.2～100: 1.5) or sodium dihydrogen phosphate-sodium fluoride (weight ratio is 100: 1.2～100: 1.5) are as hole sealing agent.Pore-sealing liquid is generally by preparing aforementioned hole sealing agent can obtain with deionized water and/or distilled water.Based on the gross weight of whole pore-sealing liquid, the hole sealing agent concentration of the pore-sealing liquid of preparing is generally 5～15 % by weight, preferred 8～10 % by weight.
Hole-sealing technology of the present invention is the process procedure an of necessity for method for platemaking of the present invention, can not remove this hole-sealing technology as conventional positive PS printing plate, otherwise that the plate that is coated with is easy to the residual end is dirty.More external thermal CTP plate material manufacturers except adopting hole-sealing technology, add priming coat or transition zone toward contact for addressing this problem, and the processing version base that the present invention only needs sealing of hole to obtain to meet the demands.
Depend on the circumstances the processing of carrying out needing before the coated version except above-mentioned, aluminum substrate also comprises other conventional treatment.For example when the space of a whole page of aluminum substrate has grease, need to carry out first ungrease treatment to the version base, this is for example by using aqueous slkali, for example sodium hydrate aqueous solution soaks to realize, also can be by soaking to realize with acid solution such as diluted nitric acid aqueous solution, preferably first with soaking with acid solution after the aqueous slkali soaking.In addition, also being included in flushing, neutralization and the optional drying of having carried out after every processing processes.
For example, before aluminum substrate coating sensible heat composition, typically aluminum substrate can be handled as follows successively:
(1) make the aluminum substrate degreasing with dilute NaOH solution, for example lower to NaOH solution immersion 30 seconds in 60～70 ℃;
(2) water flushing;
(3) use rare HNO
3Solution (3% HNO for example
3Solution) soak the space of a whole page;
(4) water flushing;
(5) roughening treatment;
(6) water flushing;
(7) neutralize with alkali lye;
(8) water flushing;
(9) anodized;
(10) water flushing;
(11) sealing of hole is processed; And
(12) use in the phosphoric acid,diluted and remaining alkali, clean again oven dry.
In the preferred embodiment of method for platemaking of the present invention, aluminum substrate after roughening treatment and anodic oxidation, the R of gained version base
aValue is 0.4～0.6 μ m, R
h(R
z) value is 2～3 μ m, and the amount of pellumina is 2.5～3.0g/m
2The R of gained version base after sealing of hole is processed
h(R
z) value is 1.8～2.5 μ m, and its R
aThe amount of value and pellumina and sealing of hole are basic identical before processing, that is, and and R
aValue is 0.4～0.6 μ m, and the amount of pellumina is 2.5～3.0g/m
2
After the aluminum substrate sealing of hole is processed, if necessary after the remaining basic species that neutralized, that aluminum substrate is clean, dry, carry out coated version with sensible heat composition of the present invention afterwards.For this reason, for example can send it to and can control coated version in the airtight extrusion coated device of coating weight by measuring pump and spraying nozzle slit, solid rete coating weight (in solid content) preferably is controlled to be 1.6～1.8g/m
2
After according to step (2) coated version, the aluminum substrate through applying is carried out drying.According to the present invention advantageously, before the aluminum substrate through applying in step (2) carries out the drying of step (3), with it through levelling section levelling.Described drying is carried out with the two-part drying according to the present invention, and wherein first paragraph adopts FAR INFRARED HEATING to carry out drying, and second segment adopts forced air dry, thereby obtains positive image without preheating thermal CTP plate material.Preferably, this two-part drying is carried out in the dry road of two-part, and the first paragraph in this drying road adopts FAR INFRARED HEATING, and second segment adopts forced air to carry out drying; Usually, the dry road length of first paragraph FAR INFRARED HEATING drying is generally 10～15 meters.This FAR INFRARED HEATING can utilize far-infrared heating tube to produce.The far infrared illumination of first paragraph far infrared drying is the same with conventional PS version production line, and far infrared drying efficient is higher, is difficult for producing " cloud and mist " phenomenon that the forced air drying is brought.Although rear one section hot air flow is larger, because through the far infrared drying of first paragraph, most solvents boil off, good apparently form, thereby can not cause " cloud and mist " phenomenon or other apparent bad phenomenon.And, aforementioned two-part drying process can make the solvent of space of a whole page coating be down to after Two stage dryer and be no more than 5 % by weight, even do not surpass 3 % by weight, thereby can not produce that the heat sensing layer that causes because the space of a whole page is overheated decomposes or the problem such as crosslinked, thereby guaranteed not only to be not easy to subtract the film loss of gloss but also to be not easy to keep on file dirty in the developing process.This two-part drying process obtains good thermal CTP plate material very favorable condition is provided for coating after sealing of hole with common PS version.The Length Ratio of far infrared drying section and forced air dryer section is 1.5: 1～1: 1.In the far infrared drying section, answer so that space of a whole page temperature is no more than 120 ℃ when dry, and the gas flow temperature of forced air dryer section should be 105-120 ℃, preferably about 110 ℃.
Dimensions according to plate after the cooling cuts, and the scale error that cuts preferably is controlled in the 0.3mm, obtains positive image without preheating thermal CTP plate material.
In a preferred embodiment of the inventive method, the heat sensing layer thickness of the positive image without preheating thermal CTP plate material for preparing is 1.6～1.8g/m
2, and solvent is no more than 3 % by weight of heat sensing layer weight in the heat sensing layer.
As mentioned above, adopt the amide carboxylic acid ammonium salt compound of formula of the present invention (I) as the chaotropic agent of thermal CTP plate material with the sensible heat composition, after with this plate heat scan, this amide carboxylic acid ammonium salt can produce the acid amides carboxylic acid as acidic materials in rete, this amide carboxylic acid ammonium salt also can produce ammonia simultaneously, the ammonia that discharges, particularly when reaching decomposition temperature, because rate of release is very fast, cause rete foaming puffing, thereby adding that a part of ammonia is stayed in the rete can develop to rapidly picture with the film-forming resin effect in alkaline developer.In addition, the acid amides carboxylic acid that produces forms the salts such as carboxylic acid sodium salt in alkaline developer, and these salts also have extremely strong short molten effect.Also have, even the scanning temperature is higher, imidization reaction further occurs and forms acid imide in the acid amides carboxylic acid, on the one hand, acid imide self is acidic materials, thereby is easy to develop and removes, on the other hand, the steam that produces at higher temperature also can make rete foaming puffing, thereby promotes to develop.Therefore, formula used according to the invention (I) compound is that collection produces acid, produces alkali and short molten the acting on all over the body of foaming, and becomes the key component of thermographic composition.
Therefore, in accordance with a further aspect of the present invention, the amide carboxylic acid ammonium salt compound that the invention provides general formula (I) thermal CTP plate material with the sensible heat composition in as the purposes of chaotropic agent,
H
2NCO-R-COONH
4(I)
Wherein R is that the anhydride compound of following dicarboxylic acids does not contain the residue that anhydride group obtains: 1,2,3, on 6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, the phenyl ring with on the phthalic anhydride of a methyl substituents, the phenyl ring with phthalic anhydride, the 5-ENB-2 of 1,2,3 or 4 chlorine and/or fluoro substituents, 3-dicarboxylic acid anhydride, 2,3-naphthalic anhydride, Malaysia eleostearate, maleic rosin, Malaysia laccol or anthracene-9,10-dihydro bridged ring-α, β-succinic anhydride.
In a preferred embodiment of purposes of the present invention, R is preferably
-CH
2CH
2-,
Or
Set forth the present invention below by embodiment, but these embodiment should not be construed as limitation of the scope of the invention.
Synthetic example
Measure infrared spectrogram (the FTIR-8400s Fourier infrared spectrograph of synthetic product of the present invention, Japan Shimadzu company), element forms (VarioE1 type elemental analyser, Germany Elementar company), fusing point (Tyke, Beijing XT-4 binocular micro melting point apparatus) and Thermal Synthetic Analysis collection of illustrative plates (ZRY-2P Thermal Synthetic Analysis instrument, Shanghai Precision Scientific Apparatus Co., Ltd) contrasts for the composition structure of determining product, and with the result of standard diagram, physical chemistry handbook and relevant paper and patent.
The pH that gas phase is released ammonia and the residue aqueous solution adopts the method for inventor's foundation to test: 0.02g amide carboxylic acid ammonium salt product sample is placed on the micro melting point apparatus, and above sample, add a cover the surface plate that is stained with moistening extensive test paper, heat up gradually, when extensive test paper becomes blueness, prove that sample begins to discharge alkaline gas.Stopped heating heats up when treating that the micro melting point apparatus temperature rises to 260 ℃, residue decomposition is taken out be cooled to room temperature, then all residue decompositions is put into the distilled water of 1ml, and is the pH value of the residue aqueous solution with the pH value of extensive test paper mensuration obtained aqueous solution.
Determine that according to the Thermal Synthetic Analysis collection of illustrative plates and in conjunction with the temperature range of product release alkaline gas temperature (Tv) and the amide carboxylic acid ammonium salt compound of amide carboxylic acid ammonium salt compound slow evaporation release ammonia decompose rapidly the temperature (Td) that discharges ammonia.
The thermal CTP plate material master that coats is developed in the goldstar of Kodak premium developer solution in 25 ℃, observe master and begin the time (s) that loss of gloss subtracts film, represent the anti-developer solution performance of plate with this.Thermal CTP plate material behind the abundant heat scan is developed in the goldstarpremium of Kodak developer solution in 25 ℃, observe the time (s) of thoroughly cleaning, represent the aobvious clean performance of plate with this.Sensitivity (mJ/cm at the Trendsetter 800 II Quantum thermosensitive CTPs plate-making aircraft measurements plate of the imperial PS version printing material of Guangxi Yulin gold Co., Ltd
2), and resolution wire spoke (μ m) and dot reproduction percentage (%) under observation optimum scanning energy and the best development conditions.
Synthesis example 1.1
Get 15.2g (0.1mol) 1,2,3,6-tetrabydrophthalic anhydride (analyzing pure) is dissolved in the 50g dioxane (analyzing pure), and is for subsequent use until thoroughly dissolving in the dropping funel that filters afterwards the 100ml that packs into.The ammoniacal liquor 20.4g (containing ammonia 0.3mol) that in the four-hole boiling flask that agitator, condenser pipe, dropping funel and thermometer are housed, adds 25 % by weight.Strong agitation limit in limit drips the dioxane solution of acid anhydrides in cold bath, and the control reaction temperature is 15～35 ℃, dropwises in 1 hour.Keep reaction 1 hour 50～60 ℃ of stirrings after dropwising, then be warming up to 60～70 ℃ and vacuumize steaming except most of dioxane and part moisture, concentrate poured in the beaker cool off, separate out the high viscosity mucus, suction filtration, with this mucus product pour in the enamel tray be lower than under 55 ℃ the temperature dry, crystallization is placed in cooling, obtain product TAG-1.1, be white powder, productive rate is 89%.
Synthesis example 1.2
Identical with the proportion scale of synthesis example 1.1, just acid anhydrides solution is put into four-hole boiling flask, the anti-ammoniacal liquor that drips is in acid anhydrides solution under strong agitation.Other operating procedure is fully with synthesis example 1.1.Obtain product TAG-1.2, be white powder, productive rate is 90%.
Synthesis example 1.3
Get 15.2g (0.1mol) 1,2,3,6-tetrabydrophthalic anhydride (analyzing pure) is dissolved in the 50g dioxane (analyzing pure), filter to pack into after thorough dissolving and be equipped with in the four-hole boiling flask of conduit, agitator, condenser pipe and thermometer, described conduit is connected with pressure-reducing valve with the control gas flow.Under agitation ammonia is passed in the four-hole boiling flask from conduit, the ammonia amount that passes into is 6.72L (0.3mol).The logical ammonia time is 1 hour, and the temperature of reactant liquor is controlled to be 25～40 ℃ in passing into the process of ammonia.Ammonia passes into was down to room temperature with reactant liquor after complete gradually in 1 hour, then reactant mixture is poured in the beaker, and further abundant cooling crystallize out pours out mother liquor and concentrated mother liquor with further crystallize out product.The crystal that obtains for twice is merged and in 55 ℃ of dryings, obtain product TAG-1.3, be white powder, productive rate is 93%.
Synthesis example 1.4
The ammoniacal liquor (containing ammonia 0.3mol) that in the four-hole boiling flask that agitator, condenser pipe and thermometer are housed, adds 34g 15 % by weight, again with 15.2g (0.1mol) 1,2,3,6-tetrabydrophthalic anhydride (analyzing pure) fine powder joins in the four-hole boiling flask under strong agitation gradually.The temperature of reactant liquor is controlled to be 20～35 ℃ when adding the acid anhydrides fine powder, adds in 1 hour, then 50～60 ℃ of lower stirring reactions 1 hour.Afterwards reactant liquor is poured in the beaker, the stickiness product is separated out in cooling, pour out mother liquor, and the vacuum distillation mother liquor boils off moisture, crystallisation by cooling more afterwards merges the product of so separating out and the stickiness product that obtains previously and in 55 ℃ of dryings, obtains product TAG-1.4, be white powder, productive rate is 90%.
Synthesis example 2
Get succinic anhydride 10g (0.1mol) and be dissolved in the 50g dioxane (analyzing pure), for subsequent use until thoroughly dissolving in the dropping funel that filters afterwards the 100ml that packs into.Preparation subsequently and aftertreatment technology are fully with synthesis example 1.1.Obtain product TAG-2, be white powder, productive rate is 92%.The Physics chemical property of product TAG-2 is listed in the table 1.
Synthesis example 3
Get 5-ENB-2,3-dicarboxylic acid anhydride 16.4g (0.1mol) is dissolved in the 60g dioxane (analyzing pure), and is for subsequent use in the dropping funel of the 100ml that packs into after thoroughly dissolving.Preparation subsequently and aftertreatment technology are fully with synthesis example 1.1.Obtain product TAG-3, be white powder, productive rate is 93%.The Physics chemical property of product TAG-3 is listed in the table 1.
Synthesis example 4
Get the pure phthalic anhydride 14.8g of analysis (0.1mol) and be dissolved in the 50g dioxane (analyzing pure), until thoroughly the rear filtration of dissolving is for subsequent use in packing the 100ml dropping funel into.Preparation subsequently and aftertreatment technology are fully with synthesis example 1.1.Obtain product TAG-4, be white powder, productive rate is 90%.The Physics chemical property of product TAG-4 is listed in the table 1.
Synthesis example 5
Get 2,3-naphthalic anhydride 19.8g (0.1mol) and be dissolved in the 80g dioxane (analyzing pure), until thoroughly the rear filtration of dissolving is for subsequent use in packing the 100ml dropping funel into.Preparation subsequently and aftertreatment technology are fully with synthesis example 1.1, but the reaction temperature of reactant liquor need rise to 65 ℃.Obtain product TAG-5, be white powder, productive rate is 93%.The Physics chemical property of product TAG-5 is listed in the table 1.
With the product TAG-1.1～TAG-1.4 and the TAG-2～TAG-5 that make in aforementioned each synthesis example carry out separately the infrared spectrum map analysis, Elemental Composition is analysed and Thermal Synthetic Analysis, and with various measurement results and standard diagram, physical chemistry handbook and document contrast.Found that: the result of infrared spectrum map analysis, elementary analysis and the Thermal Synthetic Analysis of these four kinds of products of TAG-1.1～TAG-1.4 is identical, all show product that synthesis example 1.1～1.4 these four kinds of methods obtain all be shown in hereinafter structural formula 11,2,3, the amide carboxylic acid ammonium salt of 6-tetrabydrophthalic anhydride, the Physics chemical property of this product is all listed in the table 1 with TAG-1; In addition, test result also shows, the structure of product TAG-2～TAG-5 is respectively shown in hereinafter structural formula 2-5.
Formula 1 formula 2 formulas 3
Formula 4 formulas 5
Application Example 1
With 2.0g TAG-1,2.5g infrared absorbing dye HCD-21 (Lin Yuan company), (sky, Weihai becomes chemical industry Co., Ltd to 1.5g Victoria ethereal blue (soil conservation paddy BHO) with 94g linear phenol-aldehyde resin BTB-29, metacresol-paracresol-formaldehyde resin, the mol ratio of metacresol and paracresol is 7: 3, weight average molecular weight is about 9000, and M
w/ M
nBe 9～10) be dissolved in the mixed solvent of 400g ethylene glycol monomethyl ether and the only methyl ether of 400g propane diols, carry out three-stage filtration with the teflon membrane filter of 10 μ m, 2 μ m and 0.5 μ m successively afterwards, obtain sensible heat composition solution TCL-1.
The aluminum substrate that 0.3mm is thick carries out mechanical alligatoring → electrolyzing and coarsening → anodic oxidation → sealing of hole processing → washing and drying, the aluminum substrate that obtains handling well, its R successively
aValue is 0.58 μ m, R
h(R
z) value is 2.5 μ m, the amount of pellumina is 3.0g/m
2Used pore-sealing liquid is dissolved in double centner potassium dihydrogen phosphate and 1.4 kilograms of potassium fluorides in 1 cubic metre of deionized water and makes.The sealing of hole slot length is 3 meters, and the pore-sealing liquid temperature is 60 ℃.The version base of handling well is directly delivered to extrusion coated section coating, and dispense tip adopts closed extrusion coated head.By the flow of control measuring pump and the gap width of dispense tip nozzle, make coating weight (in solid content) be controlled at 1.6～1.8g/m
2Enter dry road dry behind levelling section levelling, dry road total length is 25 meters, and front 15 meters are adopted the heating of far infrared drying pipe, and this mode of heating is so that space of a whole page temperature is no more than 120 ℃, and rear 10 meters are adopted about 110 ℃ forced air dry.Obtain positive image without preheating thermal CTP plate material master TPS-1 after the drying, the solvent of its sensible heat coating is no more than 3 % by weight based on the weight of whole coating.
Plate master TPS-1 is carried out the dependent imaging performance test, and the results are shown in Table 2.
Application Example 2
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1 still change TAG-1 and make TAG-2, obtain sensible heat composition solution TCL-2 and plate master TPS-2, and the dependent imaging performance of this plate master is listed in the table 2.
Application Example 3
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but 2.0g TAG-1 changed make 5.0g TAG-3, and the amount of linear phenol-aldehyde resin BTB-29 is reduced to 91g, obtain sensible heat composition solution TCL-3 and plate master TPS-3, the dependent imaging performance of this plate master is listed in the table 2.
Application Example 4
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but 2.0g TAG-1 changed make 1.0g TAG-4, and the amount of linear phenol-aldehyde resin BTB-29 is increased to 95g, obtain sensible heat composition solution TCL-4 and plate master TPS-4, the dependent imaging performance of this plate master is listed in the table 2.
Application Example 5
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1 still change TAG-1 and make TAG-5, obtain sensible heat composition solution TCL-5 and plate master TPS-5, and the dependent imaging performance of this plate master is listed in the table 2.
Application Example 6
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but 2.0g TAG-1 is changed the combination of making 1.0g TAG-2 and 1.0g TAG-4, and linear phenol-aldehyde resin BTB-29 changed make linear phenol-aldehyde resin BTB-25 (sky, Weihai becomes chemical industry Co., Ltd, metacresol-paracresol-formaldehyde resin, the mol ratio of metacresol and paracresol is 6: 4, weight average molecular weight is 5000-6000, and M
w/ M
nBe 4～6), obtain sensible heat composition solution TCL-6 and plate master TPS-6, the dependent imaging performance of this plate master is listed in the table 2.
Application Example 7
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but 2.0g TAG-1 is changed the combination of making 1.0g TAG-1 and 0.5g TAG-4, and 94g linear phenol-aldehyde resin BTB-29 changed make 94.5g linear phenol-aldehyde resin BTB-28F (sky, Weihai becomes chemical industry Co., Ltd, orthoresol-paracresol-formaldehyde resin, the mol ratio of orthoresol and paracresol is 3: 1, weight average molecular weight is 8000, and M
w/ M
nBe 3.2), obtain sensible heat composition solution TCL-7 and plate master TPS-7, the dependent imaging performance of this plate master is listed in the table 2.
Use Comparative Examples 1
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but TAG-1 changed make crystal violet (dyestuff factory, Tianjin), obtain sensible heat composition solution TCL-contrast 1 and plate master TPS-contrast 1, the dependent imaging performance of this plate master is listed in the table 2.
This application Comparative Examples is with reference to the scheme of conventional commercially available physical change type thermosensitive CTP.
Use Comparative Examples 2
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but TAG-1 changed make unifor (commercially available blowing agent), obtain sensible heat composition solution TCL-contrast 2 and plate master TPS-contrast 2, the dependent imaging performance of this plate master is listed in the table 2.
This application Comparative Examples designs with reference to the patent JP9319074 of Mitsubishi chemical Co., Ltd's application.
Use Comparative Examples 3
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but TAG-1 changed make unifor cyclohexanone hydrazone, obtain sensible heat composition solution TCL-contrast 3 and plate master TPS-contrast 3, the dependent imaging performance of this plate master is listed in the table 2.
Use Comparative Examples 4
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but TAG-1 changed make triazine B (1-methoxy-naphthyl-3, two (trichloromethyl) triazines of 5-), obtain sensible heat composition solution TCL-contrast 4 and plate master TPS-contrast 4, the dependent imaging performance of this plate master is listed in the table 2.
Use Comparative Examples 5
Technique and the mask-making technology of the preparation sensible heat composition solution described in the repeated application embodiment 1, but 2.0g TAG-1 changed make 10g active etherate V-32 (the full ether compound of the EVE of bisphenol-A, sky, Weihai becomes chemical industry Co., Ltd) and 2.0g 1,3, the combination of 5-three (trichloromethyl) triazine (peak forest chemical company), and linear phenol-aldehyde resin BTB-29 reduced to 84g, obtain sensible heat composition solution TCL-contrast 5 and plate master TPS-contrast 5, the dependent imaging performance of this plate master is listed in the table 2.
This sensible heat composition is with reference to Chinese patent application 200810178143.6.
The invention effect
The present invention as formula (I) the amide carboxylic acid ammonium salt compound collected explanations ammonia (releasing alkali) of chaotropic agent, produce acid and foaming effect.Chemical change occurs in this compound in the heat scan process, cause being scanned the sensible heat coating foaming puffing of part, and discharges the ammonia of alkalescence, and produced simultaneously acid amides carboxylic acid increases the acidity of scanning rete, thereby plays from many aspects short molten effect.
Can clearly be seen that from the data of table 1 and table 2, it is neutral that the chaotropic agent that the present invention uses can impel the pH value of sensible heat composition solution to approach, particularly in use strong acid or super acids during as the infrared absorbing dye of compatibility ion and proton solvent; Change also very little according to sensible heat composition solution placement of the present invention ten days even tens of days pH values.Therefore, sensible heat composition of the present invention has solved sulfonyl hydrazines compound in the past is used for thermal CTP plate material as chaotropic agent stability problem, and the latter's sensible heat composition solution only has 1～3 day service life usually.
Use amide carboxylic acid ammonium salt compound of the present invention high as the sensible heat composition sensitivity that chaotropic agent obtains, generally at 100～120mJ/cm
2Between; Differentiate wire spoke at the heat-sensitive CTP plate base and can reach 10 μ m; The dot reproduction percentage is at least 2～99%, generally can reach 1～99%; Subtract film loss of gloss time and aobvious net time according to master and can find out and develop rapidly, be difficult for keeping on file dirty, development latitude large (master subtracts the ratio of film loss of gloss time and aobvious net time generally greater than 2, and what have reaches more than 2).In addition, the anti-dry grinding of thermosensitive CTP master that obtains is good, just goes out the polishing scratch number of times generally greater than 7 times, and the plate shelf stability is good, surpasses half a year.
Induced thermal imaging composite formula of the present invention is extremely simple, can with the patent EP082327 of Mitsubishi chemical Co., Ltd in the embodiment of physical change stencilling material compare favourably, yet the present invention but belongs to chemical change type scheme.The positive image without preheating thermal CTP plate material that the sensible heat composition of preparing with amide carboxylic acid ammonium salt of the present invention coats need not required " post curing " technique of physical change stencilling material (generally being to add thermal maturation a few hours or tens of hours at 50～80 ℃), do not need as normal temperature chemical amplification type thermal CTP plate material, to add yet expensive resistance molten/chaotropic agent, thereby this plate will have the good market competitiveness.
Use needs only the version base and processes through a sealing of hole according to sensible heat composition of the present invention, can obtain available positive image without preheating thermal CTP plate material, need not bilayer coating or multi-layer coated technique that more domestic and international manufacturers adopt.Adopt elder generation through the drying mode of far infrared drying by heated-air drying, the space of a whole page that obtains is smooth smooth, and homogeneity is good.
Claims (18)
1. thermal CTP plate material sensible heat composition, based on the gross weight of this sensible heat composition, it comprises following component:
A) the amide carboxylic acid ammonium salt compound of at least a general formula (I) of 1～5 % by weight is as chaotropic agent,
H
2NCO-R-COONH
4(I)
Wherein R is that the anhydride compound of following dicarboxylic acids does not contain the residue that anhydride group obtains: 1,2,3, on 6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, the phenyl ring with on the phthalic anhydride of a methyl substituents, the phenyl ring with phthalic anhydride, the 5-ENB-2 of 1,2,3 or 4 chlorine and/or fluoro substituents, 3-dicarboxylic acid anhydride, 2,3-naphthalic anhydride, Malaysia eleostearate, maleic rosin, Malaysia laccol or anthracene-9,10-dihydro bridged ring-α, β-succinic anhydride;
B) the line style phenol resin of 87～95 % by weight is as film-forming resin;
C) 1～5 % by weight has the infrared absorbing dye of absworption peak in 790～830nm optical wavelength range; And
D) coloring background dye of 1～3 % by weight.
2. according to claim 1 sensible heat composition, based on the gross weight of this sensible heat composition, it comprises following component:
A) the amide carboxylic acid ammonium salt compound of at least a general formula (I) of 1～3 % by weight is as chaotropic agent,
H
2NCO-R-COONH
4 (I)
Wherein R is that the anhydride compound of following dicarboxylic acids does not contain the residue that anhydride group obtains: 1,2,3, on 6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, the phenyl ring with on the phthalic anhydride of a methyl substituents, the phenyl ring with phthalic anhydride, the 5-ENB-2 of 1,2,3 or 4 chlorine and/or fluoro substituents, 3-dicarboxylic acid anhydride, 2,3-naphthalic anhydride, Malaysia eleostearate, maleic rosin, Malaysia laccol or anthracene-9,10-dihydro bridged ring-α, β-succinic anhydride;
B) the line style phenol resin of 92～95 % by weight is as film-forming resin;
C) 2～4 % by weight has the infrared absorbing dye of absworption peak in 790～830nm optical wavelength range; And
D) coloring background dye of 1～2 % by weight.
3. according to claim 1 sensible heat composition, wherein R is
-CH
2CH
2-,
4. according to claim 2 sensible heat composition, wherein R is
-CH
2CH
2-,
5. according to claim 1 sensible heat composition, wherein the B component as the line style phenol resin is one or more phenol resin that are selected from lower group: poly(4-hydroxystyrene), orthoresol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-paracresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin, orthoresol-phenol-formaldehyde resin, paracresol-phenol-formaldehyde resin, tertiary butyl phenol-phenol-formaldehyde resin, orthoresol-paracresol-phenol-formaldehyde resin and metacresol-paracresol-phenol-formaldehyde resin.
6. according to claim 5 sensible heat composition, wherein the poly(4-hydroxystyrene) weight average molecular weight is 8000～20000, and M
w/ M
nBe 1.1～1.3.
7. according to claim 5 sensible heat composition, wherein linear phenol-aldehyde resin separately weight average molecular weight be 3000～10000, and M
w/ M
nBe 3～10.
8. each sensible heat composition according to claim 1-7, wherein the component C as the infrared absorbing dye that has absworption peak in 790～830nm optical wavelength range is infrared absorbing dye for spending cyanines system and/or section to spend cyanines.
9. each sensible heat composition according to claim 1-7, wherein the component D as coloring background dye is conventional PS version and/or thermal CTP plate material background dye, component D comprises and is selected from lower group one or more as main dyestuff: solvent blue, alkaline bright blue, Victoria's ethereal blue, malachite green, blackish green, crystal violet, ethyl violet and crystal violet, and this component D randomly also comprises and is selected from lower group one or more as auxiliary dyestuff: dimethyl yellow, curcumin and sudan black.
10. each thermal CTP plate material prepares the method for positive image without preheating thermal CTP plate material in the use according to claim 1-9 with the sensible heat composition, and the method comprises the steps:
(1) aluminum substrate being carried out successively roughening treatment, anodized and sealing of hole processes;
(2) each thermal CTP plate material carries out coated version with the sensible heat composition in will using according to claim 1-9 through the aluminum substrate that sealing of hole was processed; And
The aluminum substrate through applying that (3) will obtain in step (2) carries out the two-part drying, and wherein first paragraph adopts FAR INFRARED HEATING to carry out drying, and second segment adopts forced air dry, thereby obtains positive image without preheating thermal CTP plate material.
11. method according to claim 10, after wherein roughening treatment, anodized and the sealing of hole of aluminum substrate in step (1) processed, the R of gained version base
aValue is 0.4～0.6 μ m, R
h(R
z) value is 1.8～2.5 μ m, and the amount of pellumina is 2.5～3.0g/m
2
12. method according to claim 10, the wherein pore-sealing liquid of 5～15 % by weight that obtain for one or more hole sealing agents that are selected from lower group with deionized water and/or distilled water preparation of the pore-sealing liquid that process to use of sealing of hole: potassium dihydrogen phosphate-potassium fluoride, potassium dihydrogen phosphate-tartaric acid list sodium salt-potassium fluoride, potassium dihydrogen phosphate-sodium metasilicate-potassium fluoride, sodium dihydrogen phosphate-sodium fluoride, sodium metaaluminate-sodium fluoride, sodium dihydrogen phosphate-β-I rather, sodium metasilicate-sodium fluoride, sodium metaaluminate, sodium potassium tartrate tetrahydrate-tartaric acid and sodium metasilicate-tartaric acid.
13. method according to claim 12, wherein said pore-sealing liquid are the pore-sealing liquid that contains 8～10 % by weight hole sealing agents.
14. method according to claim 12, wherein hole sealing agent is that weight ratio is sodium dihydrogen phosphate-sodium fluoride that potassium dihydrogen phosphate-potassium fluoride of 100: 1.2～100: 1.5 or weight ratio are 100: 1.2～100: 1.5.
15. method according to claim 10, wherein the drying in the step (3) is carried out in the dry road of two-part, the first paragraph in this drying road adopts FAR INFRARED HEATING dry, the dry road of this section length is 10～15 meters, second segment adopts forced air dry, the Length Ratio in the dry road of FAR INFRARED HEATING dryer section and forced air dryer section is 1.5: 1～1: 1, in the FAR INFRARED HEATING dryer section, space of a whole page temperature is no more than 120 ℃, and the gas flow temperature of forced air dryer section is 105-120 ℃.
16. each method according to claim 10-15, the heat sensing layer thickness of the positive image without preheating thermal CTP plate material that wherein prepares is 1.6～1.8g/m
2, and solvent is no more than 3 % by weight of heat sensing layer weight in the heat sensing layer.
17. the amide carboxylic acid ammonium salt compound of general formula (I) thermal CTP plate material with in the sensible heat composition as the purposes of chaotropic agent,
H
2NCO-R-COONH
4 (I)
Wherein R is that the anhydride compound of following dicarboxylic acids does not contain the residue that anhydride group obtains: 1,2,3, on 6-tetrabydrophthalic anhydride, succinic anhydride, phthalic anhydride, the phenyl ring with on the phthalic anhydride of a methyl substituents, the phenyl ring with phthalic anhydride, the 5-ENB-2 of 1,2,3 or 4 chlorine and/or fluoro substituents, 3-dicarboxylic acid anhydride, 2,3-naphthalic anhydride, Malaysia eleostearate, maleic rosin, Malaysia laccol or anthracene-9,10-dihydro bridged ring-α, β-succinic anhydride.
18. purposes according to claim 17, wherein R is
-CH
2CH
2-,
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| CN 200910158051 CN101954776B (en) | 2009-07-17 | 2009-07-17 | Heat-sensitive composition for thermosensitive CTP plate, plate-making method using the same and application of amide carboxylic acid ammonium salt in the same |
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| CN104831329A (en) * | 2015-05-28 | 2015-08-12 | 西南交通大学 | Sealing treatment method for aluminum alloy anode oxide film |
| CN106364209B (en) | 2016-11-04 | 2018-11-09 | 中国科学院理化技术研究所 | A kind of temperature-sensitive of the protective layer containing sensible heat exempts from planographic printing plate material and the application of processing |
| CN108004579A (en) * | 2017-11-27 | 2018-05-08 | 南京邮电大学 | A kind of seal treatment technique of aluminium alloy anode oxide film |
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| CN1490667A (en) * | 2002-10-17 | 2004-04-21 | 北京师范大学 | Thermal sensitive imaging composition for direct platemaking by positive thermal sensitive computer |
| CN1603956A (en) * | 2003-09-30 | 2005-04-06 | 北京师范大学 | Image-forming composition for heat-sensitive CTP image base, acid generating source for the composition and preparation thereof |
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| CN1490667A (en) * | 2002-10-17 | 2004-04-21 | 北京师范大学 | Thermal sensitive imaging composition for direct platemaking by positive thermal sensitive computer |
| CN1603956A (en) * | 2003-09-30 | 2005-04-06 | 北京师范大学 | Image-forming composition for heat-sensitive CTP image base, acid generating source for the composition and preparation thereof |
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