CN101770170B - Photosensitive composition suitable for heat-sensitive positive computer to plate (CTP) and lithographic plate containing same - Google Patents
Photosensitive composition suitable for heat-sensitive positive computer to plate (CTP) and lithographic plate containing same Download PDFInfo
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- CN101770170B CN101770170B CN2008102315744A CN200810231574A CN101770170B CN 101770170 B CN101770170 B CN 101770170B CN 2008102315744 A CN2008102315744 A CN 2008102315744A CN 200810231574 A CN200810231574 A CN 200810231574A CN 101770170 B CN101770170 B CN 101770170B
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Abstract
The invention discloses a photosensitive composition suitable for heat-sensitive positive computer to plate (CTP) and a lithographic plate containing the same. The composition comprises the following components in part by weight: 30 to 80 parts of anti-solvent vinyl polymer, 3 to 20 parts of infrared absorbing dye, 5 to 35 parts of vinyl sulfonate polymer and 0.5 to 5 parts of cellulosic derivative. The lithographic plate consisting of the photosensitive composition has the characteristics of high photosensitivity, good storage stability, high development latitude, good abrasion resistance of plate coating, and high durability; besides, the plate coating has good chemical resistant performance and is suitable for UV ink printing. The durability of the plate using the photosensitive composition reaches over 200,000 printings by using the normal lithographic ink printing and 50,000 printings by using the UV oil printing; and pollution is avoided during printing.
Description
Technical field
The invention belongs to printing technology, be specifically related to a kind of flat stamping version that is suitable for the photosensitive composition of heat-sensitive positive-working CTP and contains said composition.
Background technology
The print principle of flat stamping version is the coated substance absorption printing ink through plate top, thereby the blank parts planar water reaches the purpose of repelling the water transfer ink.The preparation process of flat stamping version is known by the people in the industry in printing industry.The plate-making process of planographic printing plate material needed for two steps accomplished at least in the past: the one, go out a film (as: positive type and negative-type frisket) earlier, and comprised whole graph text informations on the film; The 2nd, the film (as: positive type and negative-type frisket) that top process obtains, under the situation that vacuumizes, to hold and on photosensitive lithoprint plate, carry out exposure-processed, plate becomes planographic printing plate material after flushing.The progress of Along with computer technology, it is more and more simpler and convenient that the plate-making processing of planographic printing plate material has become.The plate-making of planographic printing plate material has not needed film, and printing figure message information is directly transferred on the planographic printing plate material from computer, and this plate-making mode is called CTP plate-making.
Printing plate as the direct imaging of infrared laser scan exposure is a kind of of CTP plate, is called thermal CTP plate material.Thereby usually the structure of temperature-sensitive plate comprise one contain hydrophilic carrier and setting above that, can produce the sensible heat polymeric coating layer that heat causes that the plate coating changes through laser radiation.The sensible heat polymeric coating layer can be negative type or positive-working lithographic printing plate.Specifically; The present invention is the imaging layer that the convex-pattern type thermosensitive lithographic plate comprises a hydrophilic carrier and setting sense infrared laser above that; The imaging layer of this sense infrared laser has the infrared absorbent of ability absorbing IR ray; There is a kind of can the heat absorption release the vinyl sulfonic acid ester high molecular polymer of acid, a kind of anti-solvent vinyl polymer bonding agent that can be dissolved in the alkaline developer.This convex-pattern type thermosensitive lithographic plate has some good performances, like high resolving power, high press resistance rate, process simple etc., thereby make it become the possibility of desirable printing plate.
There is following defective in the thermal plastic phenolic resin who in lithographic plate, uses as film-forming resin: the cohesive to the version base is bad, and the top layer film is crisp, wears no resistance, and the pressrun when being used as the flat stamping version is low.And solvent resistance is poor, and the seal journey when especially using UV printing ink is lower etc.
In order to improve above-mentioned defective, the general employing baked version processing (heat treated behind the exposure imaging).But low molecular compound is prone to distil out from image area in the time of roasting edition, attached to non-image district, causes scumming.And roasting version causes the physical dimension of plate to deform easily, causes the register trouble problem in the polychrome printing.
For solving the problem that exists, the technician studies the various high molecular polymers as film forming matter.For example, the polycarboxylated styrene of putting down in writing in the special public clear 52-41050 communique has improved coating really, but still has the shortcoming of wearing quality, chemical-resistant difference.The spy opens in the clear 51-34711 communique macromolecular compound that proposes in molecular structure, to have the acrylic acid derivative unibody construction and is used as bonding agent.But this macromolecular compound still exists development latitude narrow, wear-resisting unfavorable problem.Open that flat 1-35436 communique, spy are opened flat 1-52139 communique, the spy opens in the flat 8-339082 communique and open clear 63-89864 communique, spy, propose macromolecular compound with the acrylic acid derivative that has band phenolic aldehyde property hydroxyl in the molecular structure as bonding agent the spy.Yet it is undesirable that the problem of existence is still mar proof, is easy to generate pollution during printing.
The monomer and the acrylamide monomers copolymerization that propose to contain sulfoamido in CN1292508, the JP286964 prospectus obtain bonding agent, be applied in the plate after, improved pressrun, the drug resistance of plate really.But the above-mentioned plate alkali resistance that contains the sulfonamides superpolymer is poor, poor storage stability.
Mention the solvent resistance that adopts the superpolymer that contains the maleimide class formation to improve plate in the WO99/63407 prospectus.But the plate solvent resistance of using this base polymer is undesirable.
The maleimide combination of monomers of the band phenolic hydroxyl group of using among sulfonamides monomer of using in CN1292508, JP286964 and the WO99/63407 is applied in the plate, can improve solvent resistance, storage stability, the wide dominance of plate.But the alkali resistant membrane left rate of plate is low, thereby influences the pressrun of plate.
Essential as existing of thermic acid-releasing agent in the composition of sensible heat type CTP plate, but traditional thermic acid-releasing agent is owing to being that micromolecular compound exists heat setting not high, so that have influence on the light sensitivity and the storage stability of plate.
The technician studies various high molecular polymers and thermic acid-releasing agent as film forming matter; But have following defective such as above-mentioned functional acrylic resin and thermic acid-releasing agent: the cohesive to the version base is bad; Coating is bad; Wear no resistance, poor storage stability, the seal journey when especially using UV printing ink is lower.
Summary of the invention
The object of the invention just is a kind of better effects if to be provided to the problems referred to above, be fit to the UV ink printing heat-sensitive positive-working CTP photosensitive composition and contain the flat stamping version of said composition.
The present invention seeks to through following technical scheme:
The strong polyvinyl of anti-solvent ability among the present invention; Be containing the monomer of sulfonamides group, the monomer copolymerization of phenolic hydroxy group class; Superpolymer contains N substituted acrylamide class formation and maleimide class formation simultaneously; Through the esterification ratio and the kind of control acidic-group, make that plate has simultaneously that alkali resistance is good, the development tolerance is big, wearing quality, drug resistance be good.
Specifically, the temperature-sensitive coating comprises a kind of water insoluble but dissolve in the polyvinyl of the alkaline WS, and polyvinyl contains the multipolymer of following (a) and (b), (c) three kinds of structural units:
Has alkali-soluble structural unit (a)
In the formula, X
1Expression-O-or-NR
3-, R
1Expression-H or-CH
3, R
2The organic group of expression singly-bound or divalent, Y
1The expression arylene, Z
1Expression-OH ,-COOH ,-SO
2NHR
4,-NHSO
2R
5, CONHSO
2R
6,-SO
2NHCOR
7,-NHCONHSO
2R
3,-SO
2NHCONHR
9,-CONHSO
2NHR
10, NHSO
2NHCOR
11,-SO
2NHSO
2R
12,-COCH
2COR
13,-OCONHSO
2R
14, SO
2NHCOOR
15N representes 0 or 1, R
2During for singly-bound and Z
1During for-OH, n is 1, and m representes 1～5 integer.R
3Expression can have alkyl, naphthenic base, the aryl or aralkyl of hydrogen atom or substituent 1～12 carbon atom.R
4, R
9, R
10Expression can have alkyl, naphthenic base, fragrance or the aralkyl of hydrogen atom or substituent 1～12 carbon atom.R
5, R
6, R
7, R
8, R
11, R
12, R
13, R
14, R
15Expression can have alkyl, naphthenic base, the aryl or aralkyl of substituent 1-12 carbon atom.
(2) has the structural unit of alkali-soluble maleimide
Z representes to have the group of acid hydrogen atom, as-OH ,-COOH ,-SO
2NHR
4,-NHSO
2R
5, CONHSO
2R
6,-SO
2NHCOR
7,-NHCONHSO
2R
3,-SO
2NHCONHR
9,-CONHSO
2NHR
10, NHSO
2NHCOR
11,-SO
2NHSO
2R
12,-COCH
2COR
13,-OCONHSO
2R
14, SO
2NHCOOR
15Deng.R
4, R
9, R
10Expression can have alkyl, naphthenic base, fragrance or the aralkyl of a hydrogen atom or a substituent 1-12 carbon atom.R
5, R
6, R
7, R
8, R
11, R
12, R
13, R
14, R
15Expression can have alkyl, naphthenic base, the aryl or aralkyl of substituent 1-12 carbon atom.
(3) has the carboxylic acid esters structure that acid causes phase transition property
R representes alkyl, naphthenic base, aralkyl.
This high molecular polymer; (a) quality of compound unit in high molecular polymer that has the alkali solubility group shown in is 1～70% than content; Be preferably 20～40%, the quality of compound unit in high molecular polymer that has the alkali solubility group shown in (b) is 1～70% than content, is preferably 20～40%; (c) quality of the compound unit shown in high molecular polymer is 1～50% than content, is preferably 20～40%.
Anti-solvent-borne type superpolymer weight average molecular weight among the present invention is 3000～200,000, is preferably 5000～120,000.Number-average molecular weight is 1500～20,000, is preferably 5000-1 ten thousand.Dispersion degree is 1.1～10, is preferably 2～6.Can contain unreacted monomer in the high molecular polymer, these monomers shared quality ratio in macromolecular compound is preferably in below 10%.
Contain the anti-solvent polyvinyl of above-mentioned (a) and (b), (c) three kinds of structural units, the mass ratio in the plate coating is 30～80%, is preferably 40～50%.
In sensible heat type flat stamping version of the present invention, contain have above-mentioned (a) and (b), (c) expression structural unit multipolymer; Make that thus flat stamping version of the present invention has strong adhesion, coating is tough and tensile, the superpolymer dissolubility is good, and pressrun is high; The advantage that solvent resistance is strong is fit to the UV ink printing.
The superpolymer that the present invention uses is the multipolymer of (a) and (b), (c) three kinds of structural units.It also can be the multipolymer that contains the polymerizable compound of one or more other different with (a) and (b), (c) structure.With (a) and (b), the different polymerizable compound of (c) structure is the compound that from acrylic compounds, esters of acrylic acid, phenylethylene, vinyl cyanide, screens.
Esters of acrylic acid: like methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid pentyl ester, α-Jia Jibingxisuan-beta-hydroxy ethyl ester, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid pentyl ester, epihydric alcohol methylpropenoic acid ester, pentaerythrite monomethacrylates or the like.
Phenylethylene: methyl styrene, styrene, 4-hydroxy styrenes or the like.
Acrylic compounds: methacrylic acid, acrylic acid or the like.
Vinyl cyanide: vinyl cyanide, methacrylonitrile or the like.
Preferred monomers is in the above monomer: methacrylic acid, acrylic acid, methyl methacrylate, acrylic acid pentyl ester, vinyl cyanide, methacrylonitrile or the like.
The solvent that uses as synthetic this superpolymer has: acetone, MEK, cyclohexanone, N-Methyl pyrrolidone, N, dinethylformamide, DMAC N,N, dioxane, ethyl acetate, dimethyl sulfoxide (DMSO) etc.
These solvents can use separately or two or more mixing is used.
Vinyl sulfonic acid ester polymer among the present invention is a monomer that contains the sulfonic acid esters group, contains the monomer copolymerization of carboxyl, ester group class, through the ratio and the kind of control acidic-group, makes plate have simultaneously that alkali resistance is good, the development tolerance is big, storage stability is high.
Specifically, the temperature-sensitive coating comprises a kind of vinyl sulfonic acid ester polymer, and vinyl sulfonic acid ester group polymkeric substance contains the multipolymer of following (d), (e), (f) three kinds of structural units:
Structural unit (d) with sulphonic acid ester is:
CH
2=CH-R
1-SO
3-R
2Or CH
2=CH-SO
3-R
2(d)
R wherein
1Expression benzene R
2Expression normal-butyl, isopropyl, methyl or cyclohexyl.
Having alkali-soluble structural unit (e) is:
R
3-CH＝CH-CO
2-H (e)
R wherein
3Expression hydrogen or methyl.
Having structural unit (f) is:
R
3-CH＝CH-CO
2-R
4 (f)
R wherein
3Expression hydrogen or methyl R
4Expression butyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, the tert-butyl group or amyl group.
In this high molecular polymer: the quality percentage composition of the sulfonate ester group shown in (d) in the vinyl sulfonic acid ester polymer is 20～70%, is preferably 30～55%.The quality percentage composition of the compound unit with alkali solubility group shown in the structural formula (e) in the vinyl sulfonic acid ester polymer is 1～20%, is preferably 2～10%.Vinyl sulfonic acid ester superpolymer weight average molecular weight among the present invention is preferably 3000-3 ten thousand more than 1000.Number-average molecular weight is preferably 1000-1 ten thousand more than 500.Dispersion degree is more than 2.Can contain unreacted monomer in the high molecular polymer, these monomers shared quality ratio in macromolecular compound is preferably in below 5%.
The solvent that uses as synthetic this superpolymer has: acetone, MEK, cyclohexanone, N-Methyl pyrrolidone, N, dinethylformamide, DMAC N,N, dioxane, ethyl acetate, dimethyl sulfoxide (DMSO) etc.
These solvents can use separately or two or more mixing is used.
Contain at vinyl sulfonic acid ester polymer of the present invention have above-mentioned (d), the vinyl sulfonic acid ester copolymer of (e), (f) expression structural unit, mass ratio is 5～35% in the sensitization of heat-sensitive positive picture CTP plate material is formed, and is preferably 10～20%.Make flat stamping version of the present invention have advantages such as the plate light sensitivity is high, the development tolerance is big, storage stability is good thus.
Can absorbing IR among the present invention the infrared absorbent (A) of ray, the infrared absorbent of this IR ray contains a kind of of dyestuff that the absorption maximum scope is 760-1200nm and pigment.
Wherein each X can be S, O, NR or C (alkyl) independently
2
Each R
1Can be alkyl, alkyl azochlorosulfonate or alkyl ammonium group independently;
R
2Can be hydrogen, halogen, SR, SO
2R, OR or NR
2
Each R
3Can be hydrogen, alkyl, COOR, OR, SR, SO independently
3 -, NR
2, halogen and not necessarily substituted fused benzo ring;
A
-The expression negative ion;
---expression nonessential five yuan or six-membered carbon ring;
Wherein each R can be hydrogen, alkyl and aryl independently; With
Wherein each n can be 0,1,2 or 3 independently.
If R
1Be alkyl azochlorosulfonate, then owing to having formed inner salt, so A
-Can not exist and alkali metal cation will be essential as gegenion.If R
1Be alkyl ammonium group, then need second kind of negative ion as gegenion.Second kind of negative ion can with A
-Identical maybe can be different negative ion.
The photosensitive composition infrared Absorption dyestuff that is suitable for heat-sensitive positive-working CTP among the present invention is the cyanine dye that contains kation and anion salt structure as stated, and the mass ratio in the plate coating is 3～20%, is preferably 5～10%.
The photosensitive composition that is suitable for heat-sensitive positive-working CTP among the present invention contains the plain analog derivative of dimension, and tieing up plain analog derivative is acetylbutyrylcellulose, and acetylbutyrylcellulose mass ratio in the sensitization of heat-sensitive positive picture CTP plate material is formed is 0.5～5%, is preferably 1～3%.
Be coated with hydrophilic layer under the coating of sensible heat flat stamping version of the present invention, Main Ingredients and Appearance is a polyacrylic acid sodium salt in the hydrophilic layer, and its mass ratio is 0.01～1% in hydrophilic layer, is preferably 0.03～0.1%.
Beneficial effect of the present invention: in photosensitive lithoprint plate sensitization component of the present invention, contain have above-mentioned (a) and (b), the anti-solvent-borne type ethylenic copolymer of (c) expression structural unit with contain have above-mentioned (d), the vinyl sulfonic acid ester polymer multipolymer of (e), (f) expression structural unit; And unique each component proportioning, make thus that flat stamping version of the present invention has strong adhesion, coating is tough and tensile, light sensitivity is high, good printing-force-resistence, the development tolerance is big, the alkali resistant membrane left rate is high, storage stability is good, solvent resistance is strong.The lithographic plate that obtains thus uses common litho printing ink pressrun can reach more than 200,000 seals, is fit to the UV ink printing, uses UV printing ink pressrun can reach 50,000 seals, and does not produce pollution during printing.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated, but also limit protection scope of the present invention never in any form.
(1) the concrete of anti-solvent vinyl polymer for example synthesized down
Synthetic example 1
In the 500ml there-necked flask that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 2.2g benzoyl peroxide.Utilize hot bath to be heated to 78 ℃ on one side, on one side logical nitrogen protection.Dropping is by 20gN, and the mixed solution that dinethylformamide, 70g N-(4-hydroxy benzenes) Methacrylamide, 29g N-(4-sulfoamido benzene) maleimide, 1gN-(4-acetyl oxygen phenyl) maleimide are formed dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 90.66g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 40000.
Synthetic example 2
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 2.2g benzoyl peroxide.Utilize hot bath to be heated to 78 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N; The mixed solution that dinethylformamide, 1g N-(4-hydroxy benzenes) Methacrylamide, 1g N-(4-sulfoamido benzene) maleimide, 50g N-(4-acetyl oxygen phenyl) maleimide, 48g methyl methacrylate are formed dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 90.68g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 50000.
Synthetic example 3
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 2.2g benzoyl peroxide.Utilize hot bath to be heated to 78 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N; The mixed solution that dinethylformamide, 70g N-(4-hydroxy benzenes) Methacrylamide, 20g N-(4-sulfoamido benzene) maleimide, 1g N-(4-acetyl oxygen phenyl) maleimide, 9g methyl methacrylate are formed dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 89.00g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 60000.
Synthetic example 4
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 2.2g benzoyl peroxide.Utilize hot bath to be heated to 78 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N, dinethylformamide, 20g N-(4-sulfoamido benzene) acrylic amide,, the mixed solution formed of 70g N-(4-hydroxy benzenes) maleimide, 10g N-(4-acetyl oxygen phenyl) maleimide, dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 91.69g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 45000.
Synthetic example 5
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 2.2g benzoyl peroxide.Utilize hot bath to be heated to 78 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N, and the mixed solution that dinethylformamide, 40g N-(4-sulfoamido benzene) acrylic amide, 40g N-(4-hydroxy benzenes) maleimide, 20g N-(4-acetyl oxygen phenyl) maleimide are formed dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 200g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 88.05g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 52000.
Synthetic example 6
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 2.2g benzoyl peroxide.Utilize hot bath to be heated to 78 ℃ on one side, on one side logical nitrogen protection.Dropping is by 130g N; The mixed solution that dinethylformamide, 15g N-(4-sulfoamido benzene) acrylic amide, 70g N-(4-hydroxy benzenes) maleimide, 10g N-(4-acetyl oxygen phenyl) maleimide, 5g methacrylic acid are formed dropwised in 2 hours.Constant temperature reacted 10 hours down.Reaction finishes the back and adds 250g methyl alcohol, and cooling joins in the 2L water under stirring, and stirs filtration drying after 1 hour, obtains the 92.56g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 65000.
By synthetic example 1～6, synthesize 1～No. 6 anti-solvent-borne type vinyl polymer in the table one, application result is seen table two.
(2) the concrete synthetic example of vinyl sulfonic acid ester polymer
The synthetic example of following basis illustrates in greater detail vinyl sulfonic acid ester polymer of the present invention, but these do not limit protection scope of the present invention.
Synthetic example 7
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 1.66g azoisobutyronitrile.Utilize hot bath to be heated to 60 ℃ on one side, on one side logical nitrogen protection.Dropping is by 80g N, and the mixed solution that dinethylformamide, the positive butyl ester of 70g p-vinylbenzenesulfonic acid, 1g methacrylic acid, 29g methyl methacrylate are formed dropwised in 2 hours.Constant temperature reacted 8 hours down.After reaction finished, cooling was separated out flocky precipitate with the 200g sherwood oil, washed 50 ℃ of vacuum drying 5 hours.Obtain the 80.22g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 15000.
Synthetic example 8
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 1.66g azoisobutyronitrile.Utilize hot bath to be heated to 60 ℃ on one side, on one side logical nitrogen protection.Dropping is by 80g N, and the mixed solution that dinethylformamide, the positive butyl ester of 55g p-vinylbenzenesulfonic acid, 20g methacrylic acid, 25g methyl methacrylate are formed dropwised in 2 hours.Constant temperature reacted 8 hours down.After reaction finished, cooling was separated out flocky precipitate with the 200g sherwood oil, washed 50 ℃ of vacuum drying 5 hours.Obtain the 81.25g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 16000.
Synthetic example 9
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 1.66g azoisobutyronitrile.Utilize hot bath to be heated to 60 ℃ on one side, on one side logical nitrogen protection.Dropping is by 80g N, and the mixed solution that dinethylformamide, the positive butyl ester of 55g p-vinylbenzenesulfonic acid, 15g methacrylic acid, 30g methyl methacrylate are formed dropwised in 2 hours.Constant temperature reacted 8 hours down.After reaction finished, cooling was separated out flocky precipitate with the 200g sherwood oil, washed 50 ℃ of vacuum drying 5 hours.Obtain the 79.25g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 12000.
Synthetic example 10
In the 500ml four-hole bottle that has stirrer, recirculatory pipe, tap funnel, add 20gN, dinethylformamide, 1.66g azoisobutyronitrile.Utilize hot bath to be heated to 60 ℃ on one side, on one side logical nitrogen protection.Dropping is by 80g N, and the mixed solution that dinethylformamide, the positive butyl ester of 50g p-vinylbenzenesulfonic acid, 20g methacrylic acid, 30g methyl methacrylate are formed dropwised in 2 hours.Constant temperature reacted 8 hours down.After reaction finished, cooling was separated out flocky precipitate with the 200g sherwood oil, washed 50 ℃ of vacuum drying 5 hours.Obtain the 79.25g white solid.The weight average molecular weight (polystyrene standard) of utilizing the silica gel permeation chromatography to measure this high molecular polymer is 12000.
By synthetic example 7～10, synthesize 7～No. 10 vinyl sulfonic acid ester polymers in the table three, application result is seen table four.
The photosensitive composition that contains anti-solvent vinyl polymer and vinyl sulfonic acid ester polymer of the present invention is applied to can produce the photosensitive lithographic plate that contains these two kinds of polyvinyls in the temperature-sensitive coating in the sensible heat type positive lithographic plate.
With embodiment the present invention is carried out below bright more specifically, but the present invention is not limited to this.
Make the base version:
Using No. 8 nylon brusses and 800 purpose float stone aqueous suspensions, is that water cleaned fully after the surface of aluminum plate of 0.3mm was carried out graining to thickness.In 10% NaOH, after 70 ℃ dipping carried out etching in 60 seconds down, clean, use 20%HNO afterwards with flowing water
3Washing, washing neutralize.Use under the condition of V=12.7V sinusoidal wave alternately waveform electric current in 1% aqueous solution of nitric acid with 300 coulombs/dm
2Anode the time electric weight it is carried out the processing of electrolysis asperities.Measure its surperficial Grains situation, O.45um the result for (representing with Ra).Then be immersed in 30% H
2SO
4In the WS, 55 ℃ of following decontaminations after 2 minutes, at 33 ℃, 20%H
2SO
4In the WS, on the face that has carried out graining, disposing negative electrode, is 5A/dm in current density
2Condition under carry out 50 seconds of anodizing, thickness is 3.0g/m as a result
2
The formation in middle layer:
On the base version through above-mentioned processing, be coated with the primary coat liquid of following composition, in 80 ℃ of following dry 30 seconds, dried amount of coating is 0.1g/m
2
Primary coat liquid:
Sodium polyacrylate 0.11g
Paratoluenesulfonic acid sodium salt 0.05g
Methyl alcohol 100g
Water 10g
Then, on this base version, apply following sensitization liquid with getting rid of an edition method, 110 ℃ were descended dry 1 minute, and obtained thermosensitive positive-type CTP flat stamping version.Dried coating weight is about 1.6g/m
2
The concrete proportioning of the photosensitive composition that is suitable for heat-sensitive positive-working CTP of the present invention is following:
Embodiment 1
Photosensitive composition of the present invention is concrete to be formed as follows:
Phenolics (weight-average molecular weight is 8000, number-average molecular weight 2000) 3.93g
Anti-solvent vinyl polymer 5.18g of the present invention
Vinyl sulfonic acid ester polymer 1.50g of the present invention
2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine 0.3g of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethyl one 2H-indoline-2-subunit)-ethylidene]-1 one cyclohexene-1-yl]-vinyl]-1,3,3-
Trimethyl-3H-indoles chloride 0.64g
Acetylbutyrylcellulose 0.15g
Tetrahydrophthalic anhydride 0.03g
Alkaline bright blue 0.3g
Fluorochemical surfactant 0.02g.
Above-mentioned photosensitive composition is dissolved in 40g MEK and the 95g1-methoxyl-2-propyl alcohol solvent obtains sensitization liquid.
Embodiment 2
Phenolics (weight-average molecular weight is 8000, number-average molecular weight 2000) 2.37g
Anti-solvent vinyl polymer 5.18g of the present invention
Vinyl sulfonic acid ester polymer 2.40g of the present invention
2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine 0.3g of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethyl one 2H-indoline-2-subunit)-ethylidene]-1 one cyclohexene-1-yl]-vinyl]-1,3,3-
Trimethyl-3H-indoles chloride 1.20g
Acetylbutyrylcellulose 0.25g
Tetrahydrophthalic anhydride 0.03g
Alkaline bright blue 0.3g
Fluorochemical surfactant 0.02g.
Above-mentioned photosensitive composition is dissolved in 40g MEK and the 95g1-methoxyl-2-propyl alcohol solvent obtains sensitization liquid.
Embodiment 3
Phenolics (weight-average molecular weight is 8000, number-average molecular weight 2000) 0.52g
Anti-solvent vinyl polymer 5.18g of the present invention
Vinyl sulfonic acid ester polymer 3.56g of the present invention
2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine 0.3g of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethyl one 2H-indoline-2-subunit)-ethylidene]-1 one cyclohexene-1-yl]-vinyl]-1,3,3-
Trimethyl-3H-indoles chloride 1.68g
Acetylbutyrylcellulose 0.46g
Tetrahydrophthalic anhydride 0.03g
Alkaline bright blue 0.3g
Fluorochemical surfactant 0.02g.
Above-mentioned photosensitive composition is dissolved in 40g MEK and the 95g1-methoxyl-2-propyl alcohol solvent obtains sensitization liquid.
Embodiment 4
Phenolics (weight-average molecular weight is 8000, number-average molecular weight 2000) 3.40g
Anti-solvent vinyl polymer 5.18g of the present invention
Vinyl sulfonic acid ester polymer 1.68g of the present invention
2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine 0.3g of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethyl one 2H-indoline-2-subunit)-ethylidene]-1 one cyclohexene-1-yl]-vinyl]-1,3,3-
Trimethyl-3H-indoles chloride 0.96g
Acetylbutyrylcellulose 0.18g
Tetrahydrophthalic anhydride 0.03g
Alkaline bright blue 0.3g
Fluorochemical surfactant 0.02g
MEK 40g
1-methoxyl-2-propyl alcohol 95g
To sensitization liquid 1
Phenolics (weight-average molecular weight is 8000, number-average molecular weight 2000) 8.06g
The non-sour thing 1.20g that releases of the present invention
2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine 0.3g of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethyl one 2H-indoline-2-subunit)-ethylidene]-1 one cyclohexene-1-yl]-vinyl]-1,3,3-
Trimethyl-3H-indoles chloride 1.68g
Acetylbutyrylcellulose 0.46g
Tetrahydrophthalic anhydride 0.03g
Alkaline bright blue 0.3g
Fluorochemical surfactant 0.02g.
Above-mentioned photosensitive composition is dissolved in 40g MEK and the 95g1-methoxyl-2-propyl alcohol solvent obtains sensitization liquid.
To sensitization liquid 2
Phenolics (weight-average molecular weight is 8000, number-average molecular weight 2000) 3.58g
Anti-solvent vinyl polymer 5.18g of the present invention
Vinyl sulfonic acid ester polymer 1.68g of the present invention
2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine 0.3g of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethyl one 2H-indoline-2-subunit)-ethylidene]-1 one cyclohexene-1-yl]-vinyl]-1,3,3-
Trimethyl-3H-indoles chloride 0.96g
Tetrahydrophthalic anhydride 0.03g
Alkaline bright blue 0.3g
Fluorochemical surfactant 0.02g
MEK 40g
1-methoxyl-2-propyl alcohol 95g
Except containing macromolecular compound of the present invention; Can also contain the phenolic resinoid that is described below in the photographic layer of photosensitive lithoprint plate of the present invention, like phenol-formaldehyde resin, cresol-formaldehyde resin, metacresol phenolics, mixture cresol phenolics, metacresol-tert-butyl phenol copolycondensation phenolic resin, bisphenol-A methylal resin etc.
The dyestuff that is suitable among the present invention has: oil orchid 603, the gorgeous blue BO of alkalescence, Victoria's ethereal blue, malachite green, methylene blue etc.
What contained development promoter was suitable in the photosensitive lithoprint plate photographic layer of the present invention has: phthalic anhydride, tetrahydrophthalic anhydride, p-toluenesulfonic acid, dodecylbenzene sulfonic acid, to toluenesulfinic acid, phosphenylic acid, benzoic acid, lauric acid and ascorbic acid etc.
What contained surfactant was suitable in the photosensitive lithoprint plate photographic layer of the present invention has: fluorine-containing non-ionic surfactant F-171, F-173, FC-430, FC-431, FC-4430.The proper proportion of these surfactants in photographic layer is 0.01-0.1%, is preferably between the 0.01-0.05%.
Plate coating solid constituent of the present invention is dissolved in the appropriate solvent and is applied to subsequently on the support and can obtains.The solvent that is suitable for has: ethylene glycol monoemethyl ether, cyclohexanone, hexone, butanone, ethylene glycol monomethyl ether, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), dioxane, tetrahydrofuran, furans furfural, normal butyl alcohol, ethyl acetate, butyl acetate, methyl lactate.These solvents can use separately or two or more mixing is used.The suitable coated weight of heat-sensitive ingredients of the present invention is 0.5g/m
2-2.0g/m
2, preferred 1.4g/m
2-1.8g/m
2
The support of flat stamping version of the present invention can be aluminium plate or other metallographs, also can be polyester film base and scribble high molecular paper substrate.Best support is the aluminium plate of anode electrolysis, oxidation, sealing of hole processing.
The plate that makes as stated makes public on the direct platemaking machine of the TRENDSETTER 800III of Kodak temperature-sensitive, and rotating speed is 150 commentaries on classics, and this serial plate sensitivity is 100-120mJ/cm2.Then, known by one of skill in the art method makes forme develop in moisture developer composition.Afterwards, handle the forme that has developed with protection glue.The concrete performance application result of plate is seen table five.
Application result by table two, table four, table five shows; In photosensitive lithoprint plate sensitization component of the present invention, contain have above-mentioned (a) and (b), the anti-solvent-borne type ethylenic copolymer of (c) expression structural unit with contain have above-mentioned (d), the vinyl sulfonic acid ester polymer multipolymer of (e), (f) expression structural unit; And unique each component proportioning, make thus that flat stamping version of the present invention has strong adhesion, coating is tough and tensile, light sensitivity is high, good printing-force-resistence, the development tolerance is big, the alkali resistant membrane left rate is high, storage stability is good, solvent resistance is strong.The lithographic plate that obtains thus uses common litho printing ink pressrun can reach more than 200,000 seals, is fit to the UV ink printing, uses UV printing ink pressrun can reach 50,000 seals, and does not produce pollution during printing.
Claims (5)
1. photosensitive composition that is suitable for heat-sensitive positive-working CTP, it is characterized in that: said composition comprises following component:
Described anti-solvent vinyl polymer is the multipolymer that contains following (a) and (b), (c) three kinds of structural units:
(1) has alkali-soluble structural unit (a)
X in the formula
1Expression-O-or-NR
3-, R
1Expression-H or-CH
3, R
2Expression singly-bound or divalent switch base, Y arranged
1The expression arylene, n representes 0 or 1, R
3Alkyl, naphthenic base, the aryl or aralkyl of 1-12 carbon atom of expression, Z
1Expression has the group of acid hydrogen atom, and m representes 1～5 integer;
(2) has the structural unit (b) of alkali-soluble maleimide
Z representes to have the group of acid hydrogen atom;
(3) has the carboxylic acid esters structure (c) that acid causes phase transition property
R representes alkyl, naphthenic base, aralkyl.
In the described anti-solvent vinyl polymer, the quality percentage composition of the compound unit with alkali solubility group shown in the structural formula (a) in polyvinyl is 1～70%; The quality percentage composition of the compound unit with alkali solubility group shown in the structural formula (b) in polyvinyl is 1～70%; The quality percentage composition of compound unit shown in the structural formula (c) in polyvinyl is 1～50%;
The weight average molecular weight of described anti-solvent vinyl polymer is 3000-20 ten thousand, and number-average molecular weight is 1500-2 ten thousand, and dispersion degree is 1.1～10;
It is the multipolymer that contains following (d), (e), (f) three kinds of structural units for described vinyl sulfonic acid ester polymer:
(1) containing sulfonate ester group structural unit (d) is:
CH
2=CH-R
1-SO
3-R
2, or CH
2=CH-SO
3-R
2(d)
R wherein
1Expression benzene, R
2Expression normal-butyl, isopropyl, methyl, cyclohexyl;
(2) having alkali-soluble structural unit (e) is:
R
3-CH＝CH-CO
2-H (e)
R wherein
3Expression hydrogen or methyl;
(3) having structural unit (f) is:
R
3-CH＝CH-CO
2-R
4 (f)
R wherein
3Expression hydrogen or methyl, R
4Expression butyl, methyl, ethyl, hydroxyethyl, hydroxypropyl, the tert-butyl group, amyl group;
In the described vinyl sulfonic acid ester polymer; The quality percentage composition of sulfonate ester group shown in the structural formula (d) in the vinyl sulfonic acid ester polymer is 20～70%, and the quality percentage composition of the compound unit with alkali solubility group shown in the structural formula (e) in the vinyl sulfonic acid ester polymer is 1～20%.
2. the photosensitive composition that is suitable for heat-sensitive positive-working CTP according to claim 1; It is characterized in that: in the described vinyl sulfonic acid ester polymer; The quality percentage composition of sulfonate ester group shown in the structural formula (d) in the vinyl sulfonic acid ester polymer is 30～55%, and the quality percentage composition of the compound unit with alkali solubility group shown in the structural formula (e) in the vinyl sulfonic acid ester polymer is 2～10%.
3. according to the said photosensitive composition that is suitable for heat-sensitive positive-working CTP of claim 1; It is characterized in that: described infrared Absorption dyestuff is the cyanine dye that contains cationic salts and anion salt structure, and the quality percentage composition of infrared Absorption dyestuff in photosensitive composition is 3～20%.
4. according to the said photosensitive composition that is suitable for heat-sensitive positive-working CTP of claim 1, it is characterized in that: described cellulose derivative is an acetylbutyrylcellulose, and the quality percentage composition of acetylbutyrylcellulose in photosensitive composition is 0.5～5%.
5. one kind contains any described photosensitive composition lithographic plate that is suitable for heat-sensitive positive-working CTP in the claim 1～4; Comprise support and sense infrared laser coating, it is characterized in that: sense infrared laser coating is formed by the photosensitive composition coating that is suitable for heat-sensitive positive-working CTP.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102315744A CN101770170B (en) | 2008-12-30 | 2008-12-30 | Photosensitive composition suitable for heat-sensitive positive computer to plate (CTP) and lithographic plate containing same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102315744A CN101770170B (en) | 2008-12-30 | 2008-12-30 | Photosensitive composition suitable for heat-sensitive positive computer to plate (CTP) and lithographic plate containing same |
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| CN102314087A (en) * | 2011-05-10 | 2012-01-11 | 刘华礼 | Diazo naphthoquinone type CTCP (Client-to-Client Protocol) coating solution and preparation method thereof |
| CN106950799B (en) * | 2017-03-28 | 2020-10-30 | 广东潮新科数字科技有限公司 | Photosensitive emulsion composition and application thereof in electrochemical-free treatment of thermosensitive CTP (computer to plate) |
| CN109774334B (en) * | 2017-11-11 | 2021-11-30 | 乐凯华光印刷科技有限公司 | Positive thermosensitive UV-resistant ink CTP plate |
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| JP2001133965A (en) * | 1998-11-16 | 2001-05-18 | Mitsubishi Chemicals Corp | Positive photosensitive planographic printing plate, its producing method and positive image forming method |
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| JP2005157246A (en) * | 2003-03-20 | 2005-06-16 | Fuji Photo Film Co Ltd | Lithographic printing original plate |
| WO2007087162A2 (en) * | 2006-01-23 | 2007-08-02 | Eastman Kodak Company | Multilayer imageable element containing sulfonamido resin |
| CN101063832A (en) * | 2006-04-28 | 2007-10-31 | 乐凯集团第二胶片厂 | Preparation method for light sensitive planographic printing plate material |
| CN101174090A (en) * | 2006-11-02 | 2008-05-07 | 乐凯集团第二胶片厂 | Photo-polymerization type lithographic printing plate |
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2008
- 2008-12-30 CN CN2008102315744A patent/CN101770170B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001133965A (en) * | 1998-11-16 | 2001-05-18 | Mitsubishi Chemicals Corp | Positive photosensitive planographic printing plate, its producing method and positive image forming method |
| 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 |
| CN1512271A (en) * | 2002-12-31 | 2004-07-14 | 北京师范大学 | Non-diazo naphthaquinone type positive map PS plate photosensitive composition and positive map thermosensitive CTP plate image forming composition |
| JP2005157246A (en) * | 2003-03-20 | 2005-06-16 | Fuji Photo Film Co Ltd | Lithographic printing original plate |
| WO2007087162A2 (en) * | 2006-01-23 | 2007-08-02 | Eastman Kodak Company | Multilayer imageable element containing sulfonamido resin |
| CN101063832A (en) * | 2006-04-28 | 2007-10-31 | 乐凯集团第二胶片厂 | Preparation method for light sensitive planographic printing plate material |
| CN101174090A (en) * | 2006-11-02 | 2008-05-07 | 乐凯集团第二胶片厂 | Photo-polymerization type lithographic printing plate |
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