CN1603956A - Image-forming composition for heat-sensitive CTP image base, acid generating source for the composition and preparation thereof - Google Patents
Image-forming composition for heat-sensitive CTP image base, acid generating source for the composition and preparation thereof Download PDFInfo
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Abstract
This invention provides a high sensitivity image forming composition used in heat sensitive CTP plate and its acid generating source preparation method. The said composition comprises the following countered by weight: 1 to 20 percent of heat acid generating source; 50 to90 percent of filming resin; 1 to 20 percent of cross linker; 1 to 10 percent of light to heat translation substance; 0.2 to 2 percent of color dye; and 10 to 30 percent of solvent, wherein the said weight percent values are based on the composition total mass.
Description
Technical field
The invention belongs to the synthetic preparation and the applied technical field of optical information recording material.More particularly, the present invention relates to print the photosensitive composition of lithographic plate, be used for the product acid source and the preparation thereof of said composition, the CTP forme that obtains the method for dissimilar CTP formes and obtain thus with above-mentioned composition with sense ultraviolet light, infrared light responsive.
Technical background
Nineteen nineties, Kodak has taken the lead in inventing the directly plate of plate-making of temperature-sensitive digitizing, is called for short thermal CTP plate material (US 5340699, and US 5491046, and US 5466557).This plate is made film-forming resin with phenol resin, (resol) makes crosslinking chemical with the hydroxymethyl phenol resin, produce acid source with salt compounded of iodine or trichloromethyl compound in triazine class as light, with benzindole is that cyanine dye (can absorb the near infrared light of 830nm) is as the photo-thermal transformation substance, and the adding coloring background dye, form negative heat cross-linking type heat-sensitive CTP plate image forming composition.When infrared laser (830nm) by computer control, carry out image scanning when exposure on plate, the infrared light that the sweep test infrared absorbing dye absorbs 830nm is converted into heat energy, causes to be scanned portion temperature and to be increased to more than the threshold temperature, cause light to produce the acid source thermal decomposition and produce acid, generate sub-image; Then, with plate preheating between 110-130 ℃, make sub-image that sufficient cross-linking and curing reaction partly take place, enter in the developer solution and develop, the part of scanning curing is not obtained negative heat cross-linking type thermosensitive CTP forme by flush away.This can be described as nineteen ninety-five so far, the most original background technology of hundreds of thermosensitive CTP patents of invention.But, the preceding preheating procedure of a development is arranged in this technology, not only need cost expensive preheating and cooling device, and operation is prolonged, plate-making speed reduces.Afterwards, people have proposed positive without preheating thermosensitive CTP plate-making scheme, and have proposed tens of patented claims by KPG company, Agfa Corp., Fuji Photo Film Co., Ltd., Mitsubishi Chemical Ind etc.The characteristics of this technology are the preheating procedures that has saved in the negative heat cross-linking type thermal CTP plate material plate-making process, obtain the positive forme.In this technology, have plenty of based on physical change and finish imaging plate-making, have plenty of based on chemical change and finish imaging plate-making.Based on the imaging process of physical change, the composition of image forming composition is simple, and plate stability is better, and still, the dissolving contrast before and after the heat scan in developer solution is less, and image quality is not high.Formation method based on chemical change, though overcome disadvantage based on the physical change formation method, extensively promote the use of at present, but, this forme is being compared certain gap is still arranged (Yu Shangxian, Yang Jinrui: thermosensitive CTP technology and thermographic material with the negative heat cross-linking stencilling material that preheating is arranged aspect resolution, site reductibility and the press resistance rate, " printing today ", No.9,2002).
In Drupa printing exhibition in 2000, Mitsubishi chemical company has put on display negative without preheating heat cross-linking type thermal CTP plate material.Afterwards, some patents are also disclosed in the world, generally be select for use can acid catalyzed polymerization or the resin of free-radical-initiated polymerization as film-forming resin, add light inlet and produce acid source and thermal initiator, and infrared absorbing dye is as the photo-thermal transformation substance, and forms image forming composition.When infrared photoscanning, photo-thermal transformation substance absorbing light and change into heat, heat cause produces acid source or thermal initiator decomposes, and produces proton or free radical, and then cause cationic polymerization or Raolical polymerizable, make to be scanned the partially polymerized undissolvable imaging area in developer solution that is solidified into.But, this plate, what have encounters problems aspect storage stability, and have be difficult in the diluted alkaline water to develop obtains image clearly, and press resistance rate is not high after the imaging that has.So the industrialization of this plate so far, commercialization actual achievement are not good.
Summary of the invention
In view of the aforementioned techniques background, the present inventor is based on 2,1,4-diazonium naphthoquinone sulphonate compounds is easy to take place sulphonic acid ester and decomposes the fact (G.Buhr that produces sulfonic acid behind ultraviolet photoetching, H.Lenz and S.Scheler, Image Reversal Resists for g-line Exposure:Chemistry andLithography, J.Photopolym.Sci.Technol., 1989,2 (3): 417-428) and the patent (Mitsubishi Chemical Ind of the high sensitivity negative heat cross-linking type heat-sensitive CTP plate once applied for of Mitsubishi Chemical Ind, Te Kaiping-11-119428,11-24248 etc., photosensitive composite and photosensitive lithographic plate), light in the photosensitive composition is wherein produced acid source to be produced acid source with photo-thermal and substitutes, and with the phenol resin of industrialization as film-forming resin, adjust the set of dispense ratio of photosensitive composition, cooperate different mask-making technologies, for example earlier with after the black light blanket exposure, carry out the infrared laser method for scanning again, obtain dissimilar CTP formes, these formes have extraordinary application prospect as negative heat cross-linking type thermal CTP plate material and negative without preheating heat cross-linking type thermal CTP plate material.(Te Kaiping-11-119428) invention of high sensitivity thermal CTP plate material has more outstanding advantage compared with Mitsubishi Chemical Ind.Based on this, the present invention is accomplished.
The purpose of this invention is to provide a kind of novel thermosensitive CTP plate image forming composition, it comprises film-forming resin, produces acid source, crosslinking chemical, photo-thermal conversion material, coloring background dye and solvent, uses said composition can obtain sensitivity height, good resolution, higher negative heat cross-linking type thermal CTP plate material, negative without preheating heat cross-linking type thermal CTP plate material and the positive without preheating thermal CTP plate material of pressrun.
Another object of the present invention provides and is used for above-mentioned thermal CTP plate material novel product acid source compound of image forming composition and preparation method thereof.
A further object of the present invention provides a kind of method that is prepared the CTP plate by CTP plate of the present invention with image forming composition.
An also purpose of the present invention provides the CTP plate that is made with image forming composition by CTP plate of the present invention.
Therefore, one aspect of the present invention provides a kind of novel thermosensitive CTP plate image forming composition, comprises following component:
1) photo-thermal of 1-20% weight produces acid source;
2) film-forming resin of 50-90% weight;
3) crosslinking chemical of 1-20% weight;
4) photo-thermal conversion material of 1-10% weight;
5) coloring background dye of 0.2-2% weight; With
6) making the solid content of described composition is the solvent of 10-30% weight, and wherein said percent by weight is based on the solid gross mass of described composition.
The present invention provides the novel product acid source compound shown in the following general formula on the other hand:
General formula 1 general formula 2 general formulas 3
Wherein R is
Or
, R
1Be H or C
1-C
4Alkyl, n are 2-5,2n=m+p, and m 〉=p, and p is not equal to 0.
Further aspect of the present invention provides the preparation method of above-mentioned novel product acid source compound, comprise 2,1,4-diazo naphthoquinone sulfonic acid chloride or paratoluensulfonyl chloride and be selected from the esterification of linear phenolic resin or reaction of grafting parent and the separating obtained product that N-hydroxyl acid imide material, polyhydroxy phenol compounds and weight-average molecular weight are 2000-4000.
The present invention also provides the CTP plate that is prepared the method for CTP plate and obtain thus with image forming composition by above-mentioned thermal CTP plate material on the one hand.
Detailed Description Of The Invention
Thermal CTP plate material of the present invention is the novel product acid source compound shown in the following general formula with used product acid source compound in the image forming composition:
General formula 1 general formula 2 general formulas 3
Wherein R is
Or
, R
1Be H or C
1-C
4Alkyl, n are 2-5,2n=m+p, and m 〉=p, and p is not equal to 0.
Gordian technique of the present invention be this novel photo-thermal produce the design of acid source, synthetic with and application in photosensitive composition.Certainly, light used in Mitsubishi Chemical Ind's patent produces acid source 3, and the two trichloromethyl-1-of 5-replace described photo-thermal to produce acid source to the light product acid source that the used conventional light product acid sources such as diphenyl iodnium of methoxy styryl compound in triazine class and Kodak all can be used as in the image forming composition of the present invention undoubtedly with part.The amount ranges that these conventional light produce acid source generally accounts for 1-10% weight in image forming composition solid gross mass.But, only produce acid source with the general light of these thermal CTP plate materials, can only obtain the negative heat cross-linking type heat-sensitive CTP plate of preheating, be difficult to obtain positive or negative without preheating thermal CTP plate material.Innovation part of the present invention is: at first, and based on 2,1, the 4-diazonium naphthoquinone sulphonate is after UV-irradiation, and the diazo naphthoquinone base decomposes, isomerization, become indenes acid structure after, the ester group of sulphonic acid ester also is easy to decompose and produces sulfonic acid, and this is the work reported of someone in the past.We are valuable imagination: the sulphonic acid ester that becomes indenes acid structure should be under the effect of heat, and than 2,1, the easier decomposition of 5-diazonium naphthoquinone sulphonate produces sulfonic acid.The second, we affirm that this photo-thermal produces acid source, and a process by resistance solvent change chaotropic agent can take place, and has very large dissolving contrast in developer solution, thereby is very beneficial for forming positive without preheating thermal CTP plate material before and after the effect of light and heat.The 3rd, we have used for reference structures such as phthalimide, naphthalimide and have been easy to phenolics the insoluble process of certain buck take place under the effect of heat, and this structure is imported in the sulphonic acid ester, constitute the composite crosslinking curing system with hexamethoxymethyl melamine.Thereby this sulphonic acid ester had both been done the product acid source, done the molten/chaotropic agent of resistance again, doublely done auxiliary crosslinking and curing agent, successfully obtained negative without preheating heat cross-linking type thermal CTP plate material.At last, we find that also corresponding p-toluenesulfonic esters also has similar performance.
Above-mentioned novel product acid source compound can be by comprising 2,1,4-diazo naphthoquinone sulfonic acid chloride or paratoluensulfonyl chloride and be selected from the esterification of linear phenolic resin that N-hydroxyl acid imide material, polyhydroxy phenol compounds and weight-average molecular weight are 2000-4000 or the method preparation of reaction of grafting parent and separating obtained product.
2,1, in 4-diazonium naphthoquinone sulphonate or the p-toluenesulfonic esters class material there be much required esterification parent, as mentioned above, the esterification parent that the present invention uses has three classes: 1. N-hydroxyl acid imide material, and as N-hydroxyphthalimide, N-hydroxyl naphthalimide, N-hydroxy tetrahydro phthalimide, N-hydroxyl norborene dicarboximide, N-maloyl imines etc.Consider from aspects such as its solvent nature, reaction complexity and imaging characteristics, recommend to use the N-hydroxyphthalimide.2. the polyhydroxy phenol compounds that obtains by resorcinol condensation or addition, as addition product, resorcinol and the tung oil of condensation product, resorcinol and the rosin of condensation product, resorcinol and the benzil acid of condensation product, resorcinol and the cyclohexanone of resorcinol and acetone or eleostearic acid and with addition product of laccol etc.These polyhydroxy phenol analog derivatives are with 2,1, need not be as the first kind material when 4-diazo naphthoquinone sulfonic acid chloride or paratoluensulfonyl chloride esterification 100% esterification, only need 〉=50% phenolic hydroxyl group esterification is got final product.3. weight-average molecular weight is the linear phenolic resin of 2000-4000, metacresol-formaldehyde resin for example, orthoresol-formaldehyde resin, phenol-metacresol-formaldehyde resin, phenol-paracresol-formaldehyde resin etc., the phenolic hydroxyl group esterification yield in these matrix resins gets final product between 20-50%.From the solvent nature and the imaging performance of the carboxylate that synthesized, preferably use condensation product and some low-molecular-weight linear phenol-aldehyde resin of N-hydroxyphthalimide, resorcinol and acetone or cyclohexanone.By above first to the three class esterification parent and 2,1,4-diazo naphthoquinone sulfonic acid chloride or paratoluensulfonyl chloride reaction photo-thermal synthetic of the present invention produces the Chinese patent Shen green grass or young crops 03156178.0 that the program of acid source can the REFERENCE TO RELATED people be submitted on September 3rd, 2003, and whole disclosures of this application are hereby incorporated by reference.For example, can make above-mentioned first to the three class esterification parent and 2,1,4-diazo naphthoquinone sulfonic acid chloride or paratoluensulfonyl chloride are in being selected from acetone, dioxane, DMF in one or more the solvent, utilize and 2,1, mole such as 4-diazo naphthoquinone sulfonic acid chloride or paratoluensulfonyl chloride or slightly excessive triethylamine are as neutralization reagent or catalyzer, between 0-40 ℃, drip catalyzer, Synthetic 2 thus, 1,4-diazonium naphthoquinone sulphonate or p-toluenesulfonic esters, the esterifying reagent molal quantity is the 50-100% of phenolic hydroxyl group total mole number in the grafting parent.Isolation and purification method is that reactant liquor is injected distilled water more than 10 times, and the evolution reaction product filters, and washes with water repeatedly, between 45-50 ℃ with the product drying.What should emphatically point out is, Synthetic 2, and 1, during 4-diazo naphthoquinone sulphonyl oxygen phthalimide, the double solvents that must use DMF or contain DMF reacts.Shown in the general formula 12,1,2 shown in 4-diazo naphthoquinone sulphonyl oxygen phthalimide (PAG-1), the general formula 2,1, shown in 4-diazonium naphthoquinone sulphonate (PAG-2) and the general formula 32,1,4-diazonium naphthoquinone sulphonate (PAG-3) are that three kinds of recommending to use of the present invention produce acid sources.
PAG-1(PH-NAS-4)????????????????PAG-2(RA-NAS-4)?????????????????????????????PAG-3(BTB-NAS-4)
R
1Be H or C
1-C
4Alkyl, n are 2-5,2n=m+p, and m 〉=p, and p is not equal to 0.
Wherein R is
In image forming composition of the present invention, the total content that above-mentioned photo-thermal produces acid source and the optional conventional light product acid source that uses is 1-20% weight based on the composition solid gross mass, preferred 2-10% weight.
Film-forming resin in the image forming composition of the present invention is generally selected line style phenol resin, for example weight-average molecular weight for use
Be the poly(4-hydroxystyrene) of 5000-20000, poly-o-hydroxy ethene or their modified product.Also has weight-average molecular weight
Be 3000-8000,
Phenol-formaldehyde resin between 3-10, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, phenol-metacresol-formaldehyde resin, phenol-orthoresol-formaldehyde resin, phenol-paracresol-formaldehyde resin, phenol-tert-butyl group resinox, phenol-metacresol-paracresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin and metacresol-tert-butyl group resinox etc.Their content in the imaging constituent is generally the 50-90% weight of composition solid gross mass, is preferably 60-80% weight.If consumption is too big, then a little less than the molten ability of the resistance of image forming composition, poor to the resistivity of alkaline developer, membrane left rate is low in the developing process, not only influences picture resolution and dot reproduction, also can reduce the press resistance rate of the forme that is coated with.Otherwise, consumption very little, crosslinking chemical and other consumptions that hinder molten component must increase, though sensitivity might improve (to negative engraving), its development capability descends, be easy to produce keep on file, residual dirty phenomenon, also can reduce the resolution and the dot reproduction of image.For positive without preheating CTP plate, film forming line style phenol resin is preferably in the main chain or contains a certain amount of acid-decomposed activity ehter bond on the side chain.For the negative heat-sensitive CTP plate, should select the bigger line style phenol resin of alkali solubility height and molecular weight for use.
Crosslinking chemical in the image forming composition of the present invention can have a variety of selections, for example can use methylolation linear phenol-aldehyde resin, methylolation poly(4-hydroxystyrene), methylolation polyphenolic substance.Also can be methylolation melamine, methoxymethylation line style phenol resin, methoxymethylation poly(4-hydroxystyrene), methoxymethylation polyphenolic substance, methoxymethylation melamine etc.Because the polarity of methylolation phenol resin or polyphenolic substance, methylolation melamine is stronger, and is relatively poor to the molten ability of the resistance of alkaline solution, and their thermal stabilitys in image forming composition are not so good; In addition, methoxymethylation phenol resin and polyphenolic substance, the activity that cross-linking reaction takes place under the acid effect is lower, the image taking speed deficiency, so the present invention recommends the hexamethoxymethyl melamine that uses the methoxylation ratio high as far as possible, the etherificate rate of its methoxylation is preferably in about 95%.
The consumption of crosslinking chemical in image forming composition should account for the 1-20% weight of composition solid gross mass, is preferably 5-15% weight.As the image forming composition of positive without preheating heat-sensitive CTP plate, the consumption of crosslinking chemical should be below 5%, and as negative heat cross-linking type heat-sensitive CTP plate image forming composition, dosage of crosslinking agent should be at 5-15%.Consumption is too big, and residual dirty phenomenon easily takes place the difficulty of developing, and influences forme resolution.Consumption very little, the crosslinking curing deficiency not only reduces sensitivity, and influences the press resistance rate of forme.
The synthetic method of the hexamethoxymethyl melamine of the high etherificate rate of using among the present invention can be with reference to the synthetic method of many alkoxymethyl melamines in the traditional paint coating amino resins.Here only need to strengthen the consumption of methyl alcohol, so that obtain the etherificate rate at the hexamethoxymethyl melamine more than 90%.
Photo-thermal conversion material in the image forming composition of the present invention is infrared absorbing dye commonly used, and it can be that used benzindole is cyanine dyes, step cyanine dye and various λ in the traditional thermal CTP plate
MaxThe infrared absorbing dye of=825-840nm (in imaging system).In order to use conventional PS version solvent, can use the PS-101 or the PS-102 of Japanese chemical drug company; In order to reduce the cost of plate, also can use Japanese Lin Yuan commercial NK-2014 of company or NK-2268, and the like product of other companies.Their consumptions in heat-sensitive composition are generally the 1-10% weight of composition total solid quality, preferred 4-8% weight.The temperature-sensitive sensitivity is lower very little for consumption, and image quality is relatively poor; Consumption is too big, because infrared absorbing dye is a kind of alkali insoluble material, develops difficulty takes place, and increased considerably the cost of plate.
Coloring background dye in the image forming composition of the present invention can be selected the diversity of settings dyestuff of traditional PS version and thermal CTP plate material for use.As solvent blue, alkaline bright blue, Victoria's ethereal blue, indigo, methyl violet, crystal violet, malachite green.In addition, also can add some complementary dyestuffs, for example, sudan black, methyl orange, eosin, dimethyl yellow, fluorescein etc.The addition of background dye in photosensitive composition is generally the 0.2-2% weight of solid gross mass, preferred 0.5-1.5% weight.The addition of auxiliary dyestuff is the 20-80% of main body background dye.
Solvent in the image forming composition of the present invention can be selected traditional PS version or CTP version image forming composition solvent, for example cyclohexanone, MEK, ethylene glycol monoethyl ether, dihydroxypropane single-ether, gamma-butyrolacton, ethyl lactate, butyl acetate, dioxane, tetrahydrofuran, triclene, methenyl choloride, methylene chloride etc. for use.They can use separately, also can two or more compound use.When selecting general infrared absorbing dye for use, the main body solvent should be cyclohexanone or MEK, and other solvents can be made secondary solvent.When PS-101 that uses Japanese chemical drug company or PS-102, the main body solvent should be selected ethylene glycol monoethyl ether or dihydroxypropane single-ether for use, and ketones solvent, esters solvent or organic chloride can be used as secondary solvent.The consumption of solvent in image forming composition decided according to viscosity, the solid content of preparation thermolabile imaging liquid, the solid content of general imaging liquid is 10-30%, so the content of solvent in imaging liquid should be 70-90%, wherein the addition of secondary solvent generally is the 10-15% of main body solvent.
The present invention also provides a cover to utilize aforementioned image forming composition to cooperate different mask-making technologies to obtain the method for dissimilar thermosensitive CTP formes, they comprise: (1) preparation negative heat cross-linking type (has been often referred to preheating, the method of thermosensitive CTP forme down together), comprise on the aluminum substrate of handling, being coated with and make the thermosensitive CTP master with induced thermal imaging composition of the present invention, carry out infrared laser scanning by the complete victory 3244 thermosensitive CTP platemaking machine of Creo Co., Ltd (Canadian Ottawa), then about 1 minute, in being housed, the lithographic plate developing machine of liquid alkali developing liquid develops 120-130 ℃ of preheating.Available thermosensitive CTP platemaking machine also can be the platemaking machine that infrared laser that any other producer provides is output as 830nm in this process.(2) preparing the method for negative without preheating heat cross-linking type thermosensitive CTP forme, comprise being coated with aforementioned image forming composition and make the thermosensitive CTP master, is the near ultraviolet light source blanket exposure of 320-450nm with output wavelength at first then, and exposure is controlled at 150-250mJ/cm
2, carry out infrared laser scanning through the heat-sensitive plate-making machine again, and directly enter in the above-mentioned developing machine without warm and to develop.The maximum characteristics of this method are to utilize fast and convenient near ultraviolet pre-exposure to replace preheating and process for cooling in the method (1) to make thermosensitive CTP negative forme.(3) prepare the method for positive without preheating thermosensitive CTP forme, comprise that (wherein producing acid source selects for use the photo-thermal of general formula 3 to produce acid source and select maximum amount for use with image forming composition of the present invention, and crosslinking chemical is selected the lower limit consumption for use and select the high film forming line style phenol resin of acid-decomposed activity as far as possible for use) be coated with and make the thermosensitive CTP master, after carrying out infrared laser scanning by the heat-sensitive plate-making machine, directly enter the developer solution more weak and develop than aforementioned developer solution.
In addition, can the polyphenolic substance that have high crosslinking active in preheating or the without preheating CTP image forming composition shown in the adding following formula 4-6 be arranged at the negative heat cross-linking.These compounds can improve the cross-linked speed and the efficient of HMMM under the effect of acid, thereby improve the sensitivity of induced thermal imaging composition.It is the developing powder and the imaging contrast that can improve the image forming composition rete that another of these polyphenolic substances mainly acts on, and avoids residual dirty keeping on file.Its Chinese style 4 is the resorcinol acetone (the RA condensation product that sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce) that contracts; Formula 5 is benzil acid resorcinol condensation product (the BZR condensation product that sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce); Formula 6 is rosin resorcinol addition product (the RR addition product that sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce).Tung oil resorcinol addition product (TOR addition product), eleostearic acid resorcinol addition product (TAR addition product) and the resorcinol that also has sky, economic and technological development zone, Weihai, Shandong to become chemical company to produce the in addition cyclohexanone (RCH condensation product) etc. that contracts.
Resorcinol acetone (RA condensation product) the benzil acid resorcinol condensation product (BZR condensation product) that contracts
(4)????????????????????????????????????????????????????(5)
Rosin resorcinol addition product (RR addition product)
(6)
In order to improve the sensitivity of negative without preheating heat cross-linking type CTP version, can also in image forming composition of the present invention, add a small amount of nitrine compounds.These nitrine compounds can be the condensation products of azido pyrene, azidobenzoic acid, phenylazide formaldehyde, nitrine chalcone, two-fold nitrogen stilbene and sulphonic acid ester thereof, two-fold nitrogen benzal cyclohexanone, two-fold nitrogen benzal methyl cyclohexanone, phenylazide formaldehyde and polyvinyl alcohol (PVA) etc.2 shown in following formula 7 and the formula 8 wherein, the two-fold nitrogen benzal of 6-cyclohexanone (BAC-H of Japanese Japan compound probability company) and 2, therefore the compound that the two-fold nitrogen benzal of 6-methyl cyclohexanone (BAC-M of Japanese Japan compound probability company) is two kinds of photo-thermal decomposition efficiency height, crosslinking active is big preferably uses in the present invention.Particularly they and aforementioned active phenolic compound are used and can obtain gratifying color development (orange red) cross-linking effect.
2, the two-fold nitrogen benzal of 6-cyclohexanone 2, the two-fold nitrogen benzal of 6-methyl cyclohexanone
(7)??????????????????????????????????????????????????????(8)
Embodiment
Describe the present invention in detail below with reference to embodiment.
Following preparation embodiment 1-3 illustrates the synthetic method that novel light produces acid source shown in key component-general formula 1 of the present invention, general formula 2, the general formula 3.
Preparation embodiment 1
N-hydroxyphthalimide and 2,1,4-diazo naphthoquinone sulfonic acid chloride Synthetic 2,1, the method for 4-diazo naphthoquinone sulphonyl oxygen phthalimide ester
Get N-hydroxyphthalimide 8.15g (0.05mol), 2,1,4-diazo naphthoquinone sulfonic acid chloride 13.4g (0.05mol) adds 50ml N, dinethylformamide and 60ml acetone, stirring and dissolving.System temperature is raised to 30 ℃, in system, splashes into one 5% dilute sulfuric acid, in 30 minutes to 60 minutes, slowly drip then than 2,1, the triethylamine of 4-diazo naphthoquinone sulfonic acid chloride excessive 5% when the pH value that is reacted to system is 7 left and right sides, is poured reactant liquor in the distilled water of its 10 times amount volumes, separate out product, after soaking a few hours, suction filtration, dry about 40 ℃ then, get the yellow powder solid, productive rate is 84%.
Preparation embodiment 2
By the condensation product and 2,1 of resorcinol and acetone, 4-diazo naphthoquinone sulfonic acid chloride Synthetic 2,1, the method for 4-diazonium naphthoquinone sulphonate
Get resorcinol that sky, economic and technological development zone, Weihai, 15g Shandong becomes chemical company the to produce acetone (0.05mol) that contracts, 26.8g (0.1mol) 2,1,4-diazo naphthoquinone sulfonic acid chloride is dissolved in the 300ml acetone stirring and dissolving.System temperature is raised to 35 ℃, in 1 hour, splashes into 10% Na through tap funnel
2CO
3Aqueous solution 58.3g (quite containing 0.055mol).Drip the back and between 35-40 ℃, keep reaction 1 hour, then reactant liquor is poured in the distilled water of its 10 times of amounts, adjust pH value to 6.5 with rare HCl, separate out product, filter, and with distilled water drip washing 3 times, dry under 40-50 ℃, get the yellow powder solid product, productive rate 91%.
Preparation embodiment 3
By linear phenol-aldehyde resin and 2,1,4-diazo naphthoquinone sulfonic acid chloride Synthetic 2,1,4-diazonium naphthoquinone sulphonate
Line taking type bakelite B TB-24 (sky, Cheng Hai economic and technological development zone, Shandong becomes chemical company) 15g, 2,1,4-diazo naphthoquinone sulfonic acid chloride 10g adds 130ml acetone, stirring and dissolving.System temperature is raised to 35 ℃, in system, splash into one 5% dilute sulfuric acid, in 30 minutes, slowly drip than 2,1 the triethylamine of 4-diazo naphthoquinone sulfonic acid chloride excessive 5% then, when the pH value that is reacted to system is 7 left and right sides, reactant liquor is poured in the distilled water of its 10 times amount volumes, soak a few hours after, suction filtration, dry about 40 ℃, get the yellow powder solid.Productive rate is 98%.
The following example is used for illustrating the preparation of image forming composition of the present invention, wherein embodiment 1-6 is the embodiment of negative heat cross-linking type thermal CTP plate material imaging liquid, embodiment 7-12 is the embodiment of negative without preheating heat cross-linking type CTP plate imaging liquid, and embodiment 13-16 is a positive without preheating thermosensitive CTP
The embodiment of plate imaging liquid.
Embodiment 1
Get BTB-26 metacresol-formaldehyde resin that sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce
70g, the PAG-1 4g of preparation embodiment 3 gained, 3, two trichloromethyl-the 1-of 5-are to methoxy styryl triazine (the S-triazine that Inst. of Applied chemistry, Beijing Normal Univ. produces) 5g, hexakis-methoxy methylated melamine (the methoxylation percent is more than the 95%) 15g that Inst. of Applied chemistry, Beijing Normal Univ. produces, Japan Lin Yuan company produces infrared absorbing dye NK-2014 5g, Japanese hodogaya chemical product Victoria of company pure blue B OH 1g, cyclohexanone 900g.
At first infrared absorbing dye NK-2014 is dissolved in the cyclohexanone, adds triaizine compounds again, after treating thoroughly to dissolve, add phenolics and other components again, be heated to 30-40 ℃ in case of necessity and make its thorough dissolving.Filter core with 10 μ m, 5 μ m and 0.5 μ m aperture carries out three-stage filtration then, gets heat-sensitive CTP heat-sensible image-forming liquid TCL-1.
Embodiment 2
Get the Japanese Cao Da product poly(4-hydroxystyrene) VP-8000 of company
70g, the RA condensation product 4g that sky, Cheng Hai economic and technological development zone, Shandong becomes chemical company to produce, 1-is to methoxy-naphthyl-3, the two trichloromethyl triazines of 5-(Beijing Normal University produces the S-triazine in the experiment chemical plant) 4g, the PAG-1 1g of preparation embodiment 1 gained, the サ イ メ of Mitsui amino resins company Le-300 (methoxyl etherificate rate 〉=95%) 12.5g, the NK-2014 infrared absorbing dye 7.5g of embodiment 1, Victoria's ethereal blue 0.5g of embodiment 1, dimethyl yellow (Beijing chemical reagent factory) 0.5g, cyclohexanone 900g is with the dissolving of embodiment 1, preparation obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-2 with filter method.
Embodiment 3
Get Benxi, Liaoning light industry research institute and produce metacresol-formaldehyde resin (softening point 110-115 ℃) 65g, the PAG-24g of preparation embodiment 2 gained, 3 of embodiment 1, two trichloromethyl-the 1-of 5-are to methoxyl-styrene triazine 5g, BTC-101 (hexakis-methoxy methylated melamine) 12.5g and RCH condensation product 5g that sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce, the S 0094 infrared absorbing dye 7.5g of Germany FEW CHEMICALS company, alkaline bright blue (Beijing chemical reagent factory) 0.5g, the dimethyl yellow 0.5g of embodiment 2, cyclohexanone 900g is with the dissolving of embodiment 1, preparation obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-3 with filter method.
Embodiment 4
(sky, economic and technological development zone, Weihai, Shandong becomes chemical company to get BTB-26 phenolics, softening point 110-115 ℃) 70g, the PAG-3 4g of preparation embodiment 3 gained, 3 of embodiment 1, the two trichloromethyl-1-of 5-be to methoxyl-styrene triazine 5g, the BTC-101 12.5g of embodiment 3, the S 0094 infrared absorbing dye 7.5g of embodiment 3, the alkaline bright blue 1g of embodiment 3, cyclohexanone 900g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-4 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 5
Getting sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce BTB-134 phenolics (terpolymer) 70g, the PAG-2 5g of preparation embodiment 2 gained, trisbromomethyl phenyl sulfone (Chiba, Japan university provides) 4g, Inst. of Applied chemistry, Beijing Normal Univ. produces 1,1,2, the methoxymethylation compound of 2-four phenylol ethane (four methoxyl methyls are arranged on the per molecule) 15g, Japan chemical drug company produces PS-101 (being CY10) infrared absorbing dye 5g, solvent blue (Beijing chemical reagent factory) 1g, ethylene glycol monoethyl ether 800g, cyclohexanone 100g is with the dissolving of embodiment 1, preparation obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-5 with filter method.
Embodiment 6
Getting sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce bakelite B TB-22 (B) 70g and BZR condensation product 4g, Chiba, Japan university provide to phenoxy group dichloroacetophenone 3g, the PAG-22g of preparation embodiment 2 gained, sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce methoxymethylation bakelite B TB-4215g, Japan chemical drug company produces PS-102 infrared absorbing dye 5g, the solvent blue 1g of embodiment 5, the alkaline bright blue 1g of embodiment 3, ethylene glycol monoethyl ether 800g, cyclohexanone 100g is with the dissolving of embodiment 1, preparation obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-6 with filter method.
Embodiment 7
Get the BTB-26 phenolics 70g of embodiment 4, the PAG-15g of preparation embodiment 1 gained, the BTC-101 12.5g of embodiment 3 and RCH condensation product 4g, the S 0094 infrared absorbing dye 7.5g of embodiment 3, Victoria's pure blue B OH 1g of embodiment 1, cyclohexanone 900g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-7 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 8
Get the BTB-26 phenolics 40g of embodiment 4, used BTB-24 phenolics 30g among the preparation embodiment 3, the RA condensation product 5g that sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce, the PAG-2 5g of preparation embodiment 2 gained, the BTC-101 10g of embodiment 3, the BAC-M 2.5g of Japan Japan compound probability company, the S 0094 infrared absorbing dye 6.5g of embodiment 3, Victoria's pure blue B OH 0.75g of embodiment 1, crystal violet 0.25g, cyclohexanone 900g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-8 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 9
Get the poly(4-hydroxystyrene) VP-8000 70g of embodiment 2, sky, Cheng Hai economic and technological development zone, Shandong becomes chemical company to produce tung oil resorcinol resin TOR addition product 5g, the PAG-1 5g of preparation embodiment 1 gained, the BTB-101 8.5g of embodiment 3, the BAC-H 4g that Japan Japan compound probability company produces, the NK-2014 infrared absorbing dye 6g of embodiment 1, the alkaline bright blue 1g of embodiment 3, the dimethyl yellow 0.5g of embodiment 2, cyclohexanone 900g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-9 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 10
Get the BTB-26 resin 70g of embodiment 1, RR addition product 5g, the PAG-1 5g of preparation embodiment 1 gained, サ イ メ Le-300 10g of embodiment 2, the BAC-H 3g of embodiment 9, the NK-2014 infrared absorbing dye 6g of embodiment 1, the solvent blue 0.5g of embodiment 5, the dimethyl yellow 0.25g of embodiment 2, crystal violet 0.25g, cyclohexanone 900g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-10 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 11
Get BTB-22 (B) the phenolics 30g of embodiment 6, the BTB-26 phenolics 40g of embodiment 4, RA condensation product 5g, the PAG-3 5g of preparation embodiment 3 gained, 1-anisyl-3, the two trichloromethyl triazines of 5-(Beijing Normal University experiment chemical plant) 1.5g, the BTC-101 10g of embodiment 3, the NK-2268 infrared absorbing dye 7.5g of Japan Lin Yuan company, the alkaline bright blue 0.5g of embodiment 3, the dimethyl yellow 0.5g of embodiment 2, cyclohexanone 900g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-11 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 12
Get the BTB-134 phenolics 50g of embodiment 5, the BTB-22 of embodiment 6 (B) phenolics 20g, BZR condensation product 5g, the PAG-1 5g of preparation embodiment 1 gained, the BTC-101 9g of embodiment 3, the BAC-M 5g of embodiment 8, the NK-2014 infrared absorbing dye 5g of embodiment 1, Victoria's pure blue B OH 1g of embodiment 1, cyclohexanone 900g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-12 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 13
Get sky, economic and technological development zone, Weihai, Shandong and become the main chain of chemical company's production or the linear phenol-aldehyde resin BTB-31 7g of the high etherificate rate of end group, the PAG-3 0.7g of preparation embodiment 3 gained, the PAG-1 0.5g of preparation embodiment 1 gained, 3 of embodiment 1, two trichloromethyl-the 1-of 5-are to methoxy styryl triazine 0.5g, サ イ メ Le-300 0.5g of embodiment 2, the NK-2014 infrared absorbing dye 0.7g of embodiment 2, Victoria's pure blue B OH 0.1g of embodiment 1, cyclohexanone 90g is with the dissolving of embodiment 1, preparation obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-13 with filter method.
Embodiment 14
Get the BTB-32 phenolics 8g that sky, economic and technological development zone, Weihai, Shandong becomes chemical company to produce, the PAG-2 0.7g of preparation embodiment 2 gained, the 1-of embodiment 2 is to methoxy-naphthyl-3, the two trichloromethyl triazine 0.2g of 5-, the BTC-101 0.5g of embodiment 3, the PS-101 infrared absorbing dye 0.5g of embodiment 5, Victoria's pure blue B OH 0.1g of embodiment 1, ethylene glycol monoethyl ether 80g, cyclohexanone 10g obtains heat-sensitive CTP heat-sensible image-forming liquid TCI-14 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 15
Get the BTB-32 8g of embodiment 14, the PAG-3 1g of preparation embodiment 3 gained, 3 of embodiment 1, two trichloromethyl-the 1-of 5-are to methoxy styryl triazine 0.1g, the BTC-101 0.3g of embodiment 3, the PS-102 infrared absorbing dye 0.5g of embodiment 6, the alkaline bright blue 0.1g of embodiment 3, ethylene glycol monoethyl ether 90g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-15 with dissolving, preparation and the filter method of embodiment 1.
Embodiment 16
Get the BTB-32 8g of embodiment 14; the VRR that sky, Cheng Hai economic and technological development zone, Shandong becomes chemical company to produce hinders molten chaotropic agent (rosin-resorcinol resin that has protecting group) 0.3g; the BTC-101 0.2g of embodiment 3; the PAG-1 0.5g of preparation embodiment 1 gained; the 1-of embodiment 2 is to methoxy-naphthyl-3; the two trichloromethyl triazine 0.4g of 5-; the NK-2268 infrared absorbing dye 0.5g of embodiment 11; the solvent blue 0.1g of embodiment 5; cyclohexanone 90g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-16 with dissolving, preparation and the filter method of embodiment 1.
As a comparison case, reference example in the patent (spy opens flat 11-119428) of selecting Mitsubishi Chemical Ind for use and being applied for and two embodiment as a comparison case 1, Comparative Examples 2 and Comparative Examples 3.
Comparative Examples 1
Get the condensation resin of phenol-metacresol-paracresol (mol ratio is 5: 3: 2) and formaldehyde
50g, P-F phenolics
50g, サ イ メ Le-300 20g of embodiment 2, Japan chemical drug company produces cy10 infrared absorbing dye 5g, 3 of embodiment 1, the two trichloromethyls of 5--1-methoxy styryl triazine 5g, Victoria's pure blue B OH 1g of embodiment 1, cyclohexanone 1000g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-1 (contrast) with dissolving, preparation and the filter method of embodiment 1.
Comparative Examples 2
On the batching basis of Comparative Examples 1, add wherein 20% hydroxyl by 2,1, the condensation resin of pyrogallol acetone resin of 5-diazo naphthoquinone sulfonic acid chloride esterification
10g obtains heat-sensitive CTP heat-sensible image-forming liquid TCL-2 (contrast) with dissolving, preparation and the filter method of embodiment 1.
Comparative Examples 3
On the batching basis of Comparative Examples 1, add Comparative Examples 2 described resin 20g, obtain heat-sensitive CTP heat-sensible image-forming liquid TCL-3 (contrast) with dissolving, preparation and the filter method of embodiment 1.
Performance test
Be coated in the thermographic liquid of embodiment 1-16 and Comparative Examples 1-3 on the PS version aluminum substrate of anticipating and satisfy following condition with centrifugal coating machine:
Aluminum substrate size: 1030mm * 800mm
Aluminum substrate thickness: 0.28-0.30mm
Grains specification: Ra=0.5-0.6 μ m
Rh＝0.3-0.35μm
Anode oxide film weight: 3-3.5g/m
2
Control the rotating speed of centrifugal coating machine, making the coating weight (in solid content) that is coated on the aluminum substrate is 1.8-2.2g/m
2Behind preliminarily dried on the centrifugal coating machine, transfer in 100 ℃ the blast drier dry 3 minutes, get thermosensitive CTP master TPS-1 to TPS-16 and TPS-1 (contrast) to TPS-3 (contrast), wherein TPS-1 to TPS-6 and TPS-1 (contrast) estimate with comparing result and list in table 1, wherein TPS-7 to TPS-12 and TPS-2 (contrast) estimate with comparing result and list in table 2, and TPS-13 to TPS-16 and TPS-3 (contrast) estimate with comparing result and list in table 3.
The evaluation and the comparing result of table 1 negative heat cross-linking type heat-sensitive CTP plate
| The plate sequence number | Coating weight (g/m 2) | Dissolvent residual rate (%) | Temperature-sensitive sensitivity (mJ/cm 2) | Resolution (dpi) | Dot reproduction (%) | Press resistance rate (ten thousand seals) |
| ??TPS-1 | ??2.10 | ????4.2 | ????150 | ≥200 | ??1-98 | ??≥12 |
| ??TPS-2 | ??2.01 | ????4.8 | ????100 | ≥250 | ??1-98 | ??≥15 |
| ??TPS-3 | ??1.95 | ????4.4 | ????125 | ≥250 | ??1-98 | ??≥12 |
| ??TPS-4 | ??2.05 | ????4.0 | ????125 | ≥250 | ??1-99 | ??≥10 |
| ??TPS-5 | ??2.15 | ????3.94 | ????160 | ≥200 | ??2-99 | ??≥10 |
| ??TPS-6 | ??2.06 | ????3.2 | ????200 | ≥200 | ??2-98 | ??7.5 |
| TPS-1 (contrast) | ??2.20 | ????4.9 | ????400 | 200 | ??2-98 | ??7 |
The evaluation and the comparing result of table 2 negative without preheating heat cross-linking type heat-sensitive CTP plate
| The plate sequence number | Coating weight (g/m 2) | Dissolvent residual rate (%) | Temperature-sensitive sensitivity (mJ/cm 2) | Resolution (dpi) | Dot reproduction (%) | The developer solution dilution ratio |
| ???TPS-7 | ??2.15 | ????4.8 | ????200 | ????200 | ????2-98 | ????1∶5 |
| ???TPS-8 | ??2.06 | ????4.4 | ????160 | ????200 | ????1-98 | ????1∶5 |
| ???TPS-9 | ??2.01 | ????4.0 | ????175 | ????250 | ????1-98 | ????15 |
| ???TPS-10 | ??2.05 | ????4.2 | ????175 | ????200 | ????1-98 | ????1.5 |
| ???TPS-11 | ??2.10 | ????3.9 | ????175 | ????200 | ????2-98 | ????1∶5 |
| ???TPS-12 | ??1.90 | ????3.4 | ????150 | ????250 | ????1-98 | ????1∶6 |
| TPS-2 (contrast) | ??2.20 | ????4.8 | Can't imaging | ????1∶6 |
The evaluation and the comparing result of table 3 positive without preheating heat-sensitive CTP plate
| The plate sequence number | Coating weight (g/m 2) | Dissolvent residual rate (%) | Temperature-sensitive sensitivity (mJ/cm 2) | Resolution (dpi) | Dot reproduction (%) | The developer solution dilution ratio | Press resistance rate (ten thousand seals) |
| ??TPS-13 | ??1.96 | ??3.9 | ??175 | ???200 | ??2-98 | ??1∶3 | ??≥7.5 |
| ??TPS-14 | ??1.90 | ??3.6 | ??200 | ???200 | ??2-98 | ??1∶4 | |
| ??TPS-15 | ??1.92 | ??3.2 | ??200 | ???200 | ??2-98 | ??1∶4 | |
| ??TPS-16 | ??1.95 | ??3.8 | ??175 | ???200 | ??2-98 | ??1∶5 | ??＞7 |
| TPS-3 (contrast) | ??2.18 | ??4.9 | ??＞200 | ???200 | ??2-97 | ??1∶5 |
The thermosensitive CTP plate-making testing machine that the temperature-sensitive sensitometry adopts Creo Co., Ltd to provide is measured.Resolving power determination adopts two kinds of methods: a kind of is to utilize the PS version to cooperate near ultraviolet light source exposure carrying out simulated determination with signal strips; Another kind is directly to measure with designated software on all-victorious 3244 heat-sensitive plate-making machines.Developer solution is commercial with negative heat-sensitive CTP plate developer solution (temperature-sensitive 830 negative developer solutions (preheating is arranged)) and positive thermosensitive CTP version developer solution (Horsell Premium Positive Developer) with KPG respectively.
Conclusion: utilize basic composition of the present invention suitably to adjust, under different mask-making technology conditions, obtained sensitivity height, good resolution, higher negative heat cross-linking type thermal CTP plate material, negative without preheating heat cross-linking type thermal CTP plate material and the positive without preheating thermal CTP plate material of pressrun respectively.
Claims (14)
1. thermal CTP plate material image forming composition comprises following component:
1) 1-20% weight, the photo-thermal of preferred 2-10% weight produces acid source;
2) 50-90% weight, the film-forming resin of preferred 60-80% weight;
3) 1-20% weight, the crosslinking chemical of preferred 5-15% weight;
4) 1-10% weight, the photo-thermal conversion material of preferred 4-8% weight;
5) 0.2-2% weight, the coloring background dye of preferred 0.5-1.5% weight; With
6) making the solid content of described composition is the solvent of 10-30% weight,
Wherein said percent by weight is based on the solid gross mass of described composition.
2. according to the image forming composition of claim 1, wherein photo-thermal product acid source is the compound shown in the following general formula:
General formula 1 general formula 2 general formulas 3
Wherein R is
Or
R
1Be H or C
1-C
4Alkyl, n is 2-5,2n=m+p, m 〉=p, and p is not equal to 0.
3. according to the image forming composition of claim 2, wherein photo-thermal product acid source also comprises compound in triazine class, as 1-to methoxy styryl-3, the two trichloromethyl triazines of 5-, 1-anisyl-3, the two trichloromethyl triazines of 5-, or diphenyl iodnium or other conventional light product acid sources, its consumption is a 1-10% weight based on the solid gross mass of described composition.
4. according to the image forming composition of claim 1, wherein said crosslinking chemical is selected from one or more in methoxymethylation melamine, methoxymethylation phenol resin or the methoxymethylation polyphenolic substance.
5. according to the image forming composition of claim 1, wherein said film-forming resin is to be selected from following line style phenol resin: weight-average molecular weight M
wBe the poly(4-hydroxystyrene) of 5000-20000, poly-o-hydroxy ethene or their modified product; Weight-average molecular weight M
wBe 3000-8000, M
w/ M
nPhenol-formaldehyde resin, metacresol-formaldehyde resin, orthoresol-formaldehyde resin, phenol-metacresol-formaldehyde resin, phenol-orthoresol-formaldehyde resin, phenol-paracresol-formaldehyde resin, phenol-tert-butyl group resinox, phenol-metacresol-paracresol-formaldehyde resin, metacresol-paracresol-formaldehyde resin and metacresol-tert-butyl group resinox etc. for 3-10.
6. according to the image forming composition of claim 1, wherein photo-thermal conversion material is to be selected from following one or more: benzindole is cyanine dyes, step cyanine dye and variously is tied to form λ in the picture composition at phenol resin
MaxThe infrared absorbing dye of=825-840nm.
7. according to the image forming composition of claim 1, wherein coloring background dye is just to be selected from following one or more: solvent blue, alkaline bright blue, Victoria's ethereal blue, indigo, methyl violet, crystal violet, malachite green, sudan black, methyl orange, eosin, dimethyl yellow, fluorescein.
8. according to the image forming composition of claim 1, wherein said solvent is selected from cyclohexanone, MEK, ethylene glycol monoethyl ether, dihydroxypropane single-ether, gamma-butyrolacton, ethyl lactate, butyl acetate, dioxane, tetrahydrofuran, triclene, methenyl choloride, methylene chloride, and their consumption accounts for 70-90% in the gross mass of imaging liquid.
9. the photo-thermal shown in following general formula 1, general formula 2 and the general formula 3 produces acid source:
General formula 1 general formula 2 general formulas 3
Wherein R is
Or
R
1Be H or C
1-C
4Alkyl, n are 2-5,2n=m+p, and m 〉=p, and p is not equal to 0.
10. one kind prepares the method for producing acid source as the desired photo-thermal of claim 9, comprise 2,1,4-diazo naphthoquinone sulfonic acid chloride or paratoluensulfonyl chloride and be selected from the esterification of linear phenolic resin or reaction of grafting parent and the separating obtained product that N-hydroxyl acid imide material, polyhydroxy phenol compounds and weight-average molecular weight are 2000-4000.
11. method for preparing negative heat cross-linking type thermosensitive CTP forme, comprise the described image forming composition of claim 1 is coated with on the aluminum substrate of handling and make the thermosensitive CTP master, carry out infrared laser scanning by the thermosensitive CTP platemaking machine, then about 1 minute, in being housed, the lithographic plate developing machine of liquid alkali developing liquid develops then 120-130 ℃ of preheating.
12. method for preparing negative without preheating heat cross-linking type thermosensitive CTP forme, comprise being coated with and make the thermosensitive CTP master with the described image forming composition of claim 1, be the near ultraviolet light source blanket exposure of 320-450nm with output wavelength at first then, exposure is controlled at 150-250mJ/cm
2, carry out infrared laser scanning through the heat-sensitive plate-making machine again, and directly enter in the lithographic plate developing machine that liquid alkali developing liquid is housed without warm and to develop.
13. method for preparing positive without preheating thermosensitive CTP forme, comprise being coated with and make the thermosensitive CTP master with the described image forming composition of claim 1, after carrying out infrared laser scanning by the heat-sensitive plate-making machine, directly enter in the weak base water development liquid and develop, wherein said product acid source selects for use the photo-thermal of the described general formula 3 of claim 2 to produce acid source and select the described maximum amount of claim 1 for use, and crosslinking chemical is selected the described lower limit consumption of claim 1 for use and select the high film forming line style phenol resin of acid-decomposed activity for use.
14. thermosensitive CTP forme by each method preparation among the claim 11-13.
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Family Cites Families (4)
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2003
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| WO2016169425A1 (en) * | 2015-04-21 | 2016-10-27 | 青岛蓝帆新材料有限公司 | Positive-image thermosensitive lithographic printing plate |
| CN106933034A (en) * | 2015-12-01 | 2017-07-07 | 东京应化工业株式会社 | Positive light anti-etching agent composition |
| CN108227384A (en) * | 2016-12-14 | 2018-06-29 | 乐凯华光印刷科技有限公司 | Negative type heat-sensitive CTP plate precursor with double-layer structure |
| CN110563950A (en) * | 2019-09-23 | 2019-12-13 | 西北工业大学 | UV/near-infrared light dual-triggering curing sulfydryl-alkene system and preparation method thereof |
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| CN1297853C (en) | 2007-01-31 |
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