CN103881025A - Anti-solvent vinyl polymer with multilayer structure, synthetic method thereof and applications thereof - Google Patents
Anti-solvent vinyl polymer with multilayer structure, synthetic method thereof and applications thereof Download PDFInfo
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Abstract
The invention discloses anti-solvent vinyl polymer with a multilayer structure, a synthetic method thereof and applications thereof. The polymer is synthesized by adoption of a method of core-shell emulsion copolymerization. The polymer is vinyl multipolymer having structure units as follows: an amide type structure unit with alkaline solubility, a maleimide type structure unit with alkaline solubility, an acrylate type structure unit, an acrylonitrile type structure unit and an olefin acid type structure unit. The polymer is suitable for manufacturing thermosensitive positive-image CTP plates and can allow the plates to have characteristics of high sensitivity, good storage stability, large latitude of development, good wear resistance and high pressrun. In addition, coatings of the plates are high in resistance to chemicals, and the plates are suitable for UV printing ink printing.
Description
Technical field
The invention belongs to printing technology, be specifically related to a kind of anti-solvent vinyl polymer and preparation method and use thereof of multi-ply construction.
Background technology
The print principle of sensitive lithographic plate is the coated substance absorption ink by plate top, thereby blank parts planar water reaches the object of repelling water transfer ink.Lithography technique moves towards Computer To Plate technology (being called for short CTP technology) from traditional laser photo film copy PS platemaking technology comprehensively, and CTP plate is also universal gradually.CTP plate kind is a lot, relatively universal Silver Salt Diffusion Transfer CTP Plate material, UV-CTP version, purple laser polymerization CTP plate, the thermal CTP plate material etc. of comprising.Wherein, most popular is thermal CTP plate material.At present, further improving the performance of thermal CTP plate material, especially improve solvent resistance and the Nai Yin ability of plate, is the focus of thermal CTP plate material research and development.
The resistance to solvent of plate refers to the corrosion of the organic solvent in the resistance to various printing chemical of printing board material, as the washing composition, fountain solution, gummy solvent, forme preserving agent, forme sanitising agent, the particularly corrosion of UV ink washing oil of ink that use in printing.
The solvent resistance of raising heat-sensitive CTP plate plate and the method for Nai Yin ability are a lot, and wherein one of most important method is exactly the particularly exploitation of functional film-forming resin of printing board material organism.
For example, the polycarboxylated styrene of recording in examined patent publication 52-41050 communique has improved coating really, but still has wear resistance, the poor shortcoming of chemical-resistant.In JP 51-34711 communique, propose the macromolecular compound in molecular structure with acrylic acid derivative unibody construction to be used as tackiness agent.But this macromolecular compound still exists development latitude narrow, wear-resisting undesirable problem.And in JP 63-89864 communique, Unexamined Patent 1-35436 communique, Unexamined Patent 1-52139 communique, Unexamined Patent 8-339082 communique, propose the macromolecular compound in molecular structure with the acrylic acid derivative with phenolic aldehyde hydroxyl as tackiness agent.But it is undesirable that the problem of existence is still wearability, when printing, easily produce and pollute.
Summary of the invention
The object of the invention is to solve the shortcoming of the resistance to solvent ability of the temperature-sensitive version existing in existing temperature-sensitive platemaking technology and Nai Yin ability, particularly in the time using UV ink, a kind of brand-new anti-solvent vinyl polymer and the synthetic method thereof with multilayered structure are provided, it is high that this polymer application has light sensitivity in the time of heat-sensitive CTP plate, storage stability is good, development latitude is large, and especially resistance to abrasion is good, the feature that pressrun is high.
For achieving the above object, the present invention is by the following technical solutions:
The anti-solvent vinyl polymer of multi-ply construction of the present invention, is a kind of high molecular polymerization particle existing with emulsion discrete form, and it is the vinyl multiple copolymer that contains following structural unit:
A: have alkali-soluble amides structural unit, its structural formula is as follows:
R in formula
1expression-H Huo – CH
3, X
1what represent singly-bound or divalent has a switch base, expression-H or-CH
3, R
2expression can have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom.
B: have the structural unit of alkali-soluble maleimide, its structural formula is as follows:
In formula, Y represents to have the group of acid hydrogen atom
C: have the structural unit of esters of acrylic acid, its structural formula is as follows:
R in formula
3, R
4expression can have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom, and R5 represents to have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom;
D: alkene nitrile structural unit, its structural formula is as follows:
R in formula
6, R
7expression can have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom.
E: structural acrylic unit, its structural formula is as follows:
R in formula
3, R
4expression can have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom.
The weight average molecular weight of the anti-solvent vinyl polymer of multilayer of the present invention is 3000-20 ten thousand, and number-average molecular weight is 1500-2 ten thousand, and dispersity is 1.1-10.The quality percentage composition of structural unit shown in structural formula A in vinyl polymer is 0.5-50%; The quality percentage composition of structural unit shown in structural formula B in vinyl polymer is 10-80%; The quality percentage composition of structural unit shown in structural formula C in vinyl polymer is 0.5-40%; The quality percentage composition of the structural unit of the esters of acrylic acid shown in structural formula D in vinyl polymer is 10-50%; The quality percentage composition of the structural unit of the acrylic acid or the like shown in structural formula E in vinyl polymer is 0.5-30%.
The weight average molecular weight of the anti-solvent vinyl polymer of multilayer of the present invention is preferably 2-4 ten thousand, and number-average molecular weight is preferably 1700-4000, and dispersity is preferably 1.1-10.The quality percentage composition of structural unit shown in structural formula A in vinyl polymer is preferably 20-30%; The quality percentage composition of structural unit shown in structural formula B in vinyl polymer is preferably 20-40%; The quality percentage composition of structural unit shown in structural formula C in vinyl polymer is preferably 10-20%; The quality percentage composition of structural unit shown in structural formula D in vinyl polymer is preferably 20-30%; The quality percentage composition of structural unit shown in structural formula E in vinyl polymer is preferably 4-10%.
The anti-solvent vinyl polymer that the present invention has multilayered structure adopts the method for core-shell emulsion copolymerization synthetic, and core-shell emulsion copolymerization is the method that adopts segmentation letex polymerization, i.e. " seed " letex polymerization.First synthetic kernel emulsion, forms the polymkeric substance of core as seed, then carries out subordinate phase polymerization with " seed ", thereon additional heterogeneous polymkeric substance.Core-shell emulsion copolymerization, in the situation that not changing monomer composition, can significantly change the performance of polymkeric substance.Use the plate of this polymkeric substance to have that good solubility-resistence is good, development latitude is large, wear resistance good, pressrun is high simultaneously.
Specifically, the reaction solvent of building-up process of the present invention adopts one or more mixture of the alcohols such as water and methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols.
Catalysts of the present invention is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, tertbutyl peroxide, one or more in the azos such as peroxidized t-butyl perbenzoate or organo-peroxide.
Emulsifying agent of the present invention is that dioctyl succsinic acid is received other emulsifying agents.
Core-shell emulsion copolymerization of the present invention is stage feeding polymerization, first partial monosomy is dissolved in solvent, add emulsifying agent, form emulsion, heated and stirred, carries out polymerization and forms seed, then all or part of residue monomer is dissolved in solvent, all or in batches drip in emulsion, carry out polymerization, thereby form the high molecular polymerization particle existing with emulsion discrete form of multilayered structure.
The anti-solvent vinyl polymer of multi-ply construction of the present invention can be applicable in heat-sensitive positive picture CTP plate, as a part for heat-sensitive positive picture CTP plate photosensitive composition.
Beneficial effect of the present invention is as follows: the anti-solvent vinyl polymer of multi-ply construction of the present invention adopts the method for core-shell emulsion copolymerization synthetic, the method is not in the situation that changing monomer composition, can significantly change the performance of polymkeric substance, improve the good solubility-resistence and the wear resistance that use this polymkeric substance CTP version, thereby raising press resistance rate, the press resistance rate while especially using UV ink; Esters of acrylic acid structural unit in the anti-solvent vinyl polymer of multi-ply construction of the present invention and alkene nitrile structural unit can improve solvent resistance and the hardness of this polymkeric substance, thereby significantly improve good solubility-resistence and the resistance to marring of CTP version; There is the developing performance that alkali-soluble amides structural unit, the structural unit with alkali-soluble maleimide and olefin(e) acid class formation unit can improve CTP version.The advantage such as therefore, use the heat-sensitive positive picture CTP plate of the anti-solvent vinyl polymer of this multi-ply construction to there is strong adhesion, coating is tough and tensile, light sensitivity is high, good printing-force-resistence, development latitude large, alkali resistant film-remaining ratio is high, storage stability good, good solubility-resistence is strong.
Embodiment
Be synthetic example of the present invention below, but the present invention is not limited to following example:
Embodiment 1(emulsion particle 01)
To having in the 1000ml there-necked flask of agitator, return line, dropping funnel, add 250 g Virahols, 150g deionized water, 25gN, dinethylformamide, 15g methyl acrylate, 5g dioctyl succsinic acid are received, 1.2 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip and be dissolved in by 29g N-(4-acetyl oxygen phenyl) maleimide, 25g3-crotononitrile, 6g methacrylic acid, 0.8g AIBN (Diisopropyl azodicarboxylate) mixing solutions that 250g Virahol forms, within 2 hours, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 18.3%, and weight average molecular weight is 25000, and number-average molecular weight is 2500.
Embodiment 2(emulsion particle 02)
To having in the 1000ml there-necked flask of agitator, return line, dropping funnel, add 250 g Virahols, 150g deionized water, 15gN, dinethylformamide, 20g methyl acrylate, 5g dioctyl succsinic acid are received, 1.2 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip and be dissolved in by 31g N-(4-sulfoamido benzene) maleimide, 30g3-crotononitrile, 4g methacrylic acid, 0.8g AIBN (Diisopropyl azodicarboxylate) mixing solutions that 250g Virahol forms, within 1.5 hours, dropwise.Under constant temperature, react after 9 hours and finish.
Solid content is 16.1%, and weight-average molecular weight is 32000, and number-average molecular weight is 2300.
Embodiment 3(emulsion particle 03)
To having agitator, return line, in the 1000ml there-necked flask of dropping funnel, add 250 g Virahols, 150g deionized water, 30g N-(4-hydroxybenzene) Methacrylamide, 10g methyl acrylate, 5g dioctyl succsinic acid is received, 1.2 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip by 25g N-(4-acetyl oxygen phenyl) maleimide, 30g vinyl cyanide, 5g methacrylic acid, 0.8g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 250g Virahol composition, within 2 hours, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 14.2%, and weight average molecular weight is 30000, and number-average molecular weight is 2100.
Embodiment 4(emulsion particle 04)
To having in the 1000ml there-necked flask of agitator, return line, dropping funnel, add 250 g Virahols, 150g deionized water, 25gN, dinethylformamide, 10g methyl acrylate, 5g dioctyl succsinic acid are received, 1.2 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip and be dissolved in by 32g N-(4-acetyl oxygen phenyl) maleimide, 23g3-crotononitrile, 10g methacrylic acid, 0.8g AIBN (Diisopropyl azodicarboxylate) mixing solutions that 250g Virahol forms, within 2 hours, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 15.7%, and weight average molecular weight is 33000, and number-average molecular weight is 1900.
Embodiment 5(emulsion particle 05)
To having in the 1000ml there-necked flask of agitator, return line, dropping funnel, add 250 g Virahols, 150g deionized water, 23gN, dinethylformamide, 15g methyl methacrylate, 5g dioctyl succsinic acid are received, 1.2 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip and be dissolved in by 30g N-(4-acetyl oxygen phenyl) maleimide, 27g vinyl cyanide, 5g vinylformic acid, 0.8g AIBN (Diisopropyl azodicarboxylate) mixing solutions that 250g Virahol forms, within 2 hours, dropwise.Under constant temperature, react after 9 hours and finish.
Solid content is 15.1%, and weight average molecular weight is 31000, and number-average molecular weight is 2100.
Embodiment 6(emulsion particle 06)
To having in the 1000ml there-necked flask of agitator, return line, dropping funnel, add 250 g Virahols, 150g deionized water, 30gN, dinethylformamide, 10g vinylformic acid pentyl ester, 5g dioctyl succsinic acid are received, 1.2 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip and be dissolved in by 26g N-(4-acetyl oxygen phenyl) maleimide, 27g vinyl cyanide, 7g vinylformic acid, 0.8g AIBN (Diisopropyl azodicarboxylate) mixing solutions that 250g Virahol forms, within 1.5 hours, dropwise.Under constant temperature, react after 8 hours and finish.
Solid content is 17.1%, and weight average molecular weight is 28000, and number-average molecular weight is 2100.
Embodiment 7(emulsion particle 07)
To having agitator, return line, in the 1000ml there-necked flask of dropping funnel, add 250 g Virahols, 150g deionized water, 23g N-(4-hydroxybenzene) Methacrylamide, 16g methyl acrylate, 5g dioctyl succsinic acid is received, 1 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip by 27g3-crotononitrile, 6g methacrylic acid, 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 150g Virahol composition, within 1 hour, dropwise, react 1 hour, drip again the maleimide by 28g N-(4-acetyl oxygen phenyl), 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 100g Virahol composition, within 1 hour, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 16.3%, and weight average molecular weight is 30000, and number-average molecular weight is 2100.
Embodiment 8(emulsion particle 08)
To having agitator, return line, in the 1000ml there-necked flask of dropping funnel, add 250 g Virahols, 150g deionized water, 23gN, dinethylformamide, 8g methyl acrylate, 5g dioctyl succsinic acid is received, 1 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip by 15g3-crotononitrile, 9g methacrylic acid, 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 100g Virahol composition, within 1 hour, dropwise, react 1 hour, drip again the maleimide by 45g N-(4-sulfoamido benzene), 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 150g Virahol composition, within 1 hour, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 21.2%, and weight average molecular weight is 35000, and number-average molecular weight is 2000.
Embodiment 9(emulsion particle 09)
To having agitator, return line, in the 1000ml there-necked flask of dropping funnel, add 250 g Virahols, 150g deionized water, 18g N-(4-hydroxybenzene) Methacrylamide, 17g methyl acrylate, 5g dioctyl succsinic acid is received, 1 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip by 27g3-crotononitrile, 4g methacrylic acid, 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 150g Virahol composition, within 1 hour, dropwise, react 1 hour, drip again the maleimide by 34g N-(4-acetyl oxygen phenyl), 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 100g Virahol composition, within 1 hour, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 18.7%, and weight average molecular weight is 31000, and number-average molecular weight is 2200.
Embodiment 10(emulsion particle 10)
To having agitator, return line, in the 1000ml there-necked flask of dropping funnel, add 250 g Virahols, 150g deionized water, 23gN, dinethylformamide, 15g β-dimethyl-aminoethylmethacrylate, 5g dioctyl succsinic acid is received, 1 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip by 27g vinyl cyanide, 6g vinylformic acid, 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 150g Virahol composition, within 1 hour, dropwise, react 1 hour, drip again the maleimide by 29g N-(4-acetyl oxygen phenyl), 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 100g Virahol composition, within 1 hour, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 19.4%, and weight average molecular weight is 32000, and number-average molecular weight is 2000.
Embodiment 11(emulsion particle 11)
To having agitator, return line, in the 1000ml there-necked flask of dropping funnel, add 250 g Virahols, 150g deionized water, 24gN, dinethylformamide, 34g methyl acrylate, 5g dioctyl succsinic acid is received, 1 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip by 27g vinyl cyanide, 5g methacrylic acid, 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 150g Virahol composition, within 1 hour, dropwise, react 1 hour, drip again the maleimide by 10g N-(4-sulfoamido benzene), 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 100g Virahol composition, within 1 hour, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 18.9%, and weight average molecular weight is 29000, and number-average molecular weight is 2700.
Embodiment 12(emulsion particle 12)
To having agitator, return line, in the 1000ml there-necked flask of dropping funnel, add 250 g Virahols, 150g deionized water, 16gN, dinethylformamide, 11g vinylformic acid pentyl ester, 5g dioctyl succsinic acid is received, 1 g AIBN (Diisopropyl azodicarboxylate), stir, and utilize hot water bath to be heated to 80 DEG C, drip by 25g vinyl cyanide, 6g methacrylic acid, 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 150g Virahol composition, within 1 hour, dropwise, react 1 hour, drip again the maleimide by 42g N-(4-sulfoamido benzene), 0.5g AIBN (Diisopropyl azodicarboxylate) is dissolved in the mixing solutions of 100g Virahol composition, within 1 hour, dropwise.Under constant temperature, react after 10 hours and finish.
Solid content is 23.6%, and weight average molecular weight is 36000, and number-average molecular weight is 2300.
By embodiment 1 ~ 12, synthesize anti-solvent-borne type vinyl emulsion particle 1 ~ No. 12, its performance is in table one.
Below with plate-making example the present invention is carried out more specifically bright, but the present invention is not limited to this.
Make base version:
Use No. 8 nylon brushes and 800 object float stone aqueous suspensions, the surface of aluminum plate that is 0.3mm to thickness is carried out after graining, and water cleans fully.In 10% sodium hydroxide, at 70 DEG C, flood and within 60 seconds, carry out after etching, with flowing water cleaning, use afterwards 20%HNO
3neutralize washing, washing.Under the condition of V=12.7V, use sinusoidal wave alternately waveform electric current in 1% aqueous nitric acid with 300 coulombs/dm
2anode time electric weight it is carried out to the roughened processing of electrolysis.Measure its surperficial Grains situation, result is u m O.45 (representing with Ra).Then be immersed in 30% H
2s0
4in the aqueous solution, at 55 DEG C, decontamination is after 2 minutes, at 33 DEG C, 20%H
2s0
4in the aqueous solution, on the face that has carried out graining, configuring negative electrode, is 5A/dm in current density
2condition under carry out 50 seconds of anodizing, result thickness is 3.0g/m
2.
The formation in middle layer:
At the primary coat liquid through being coated with following composition in the base version of above-mentioned processing, in dry 30 seconds at 80 DEG C, 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, in this base version, apply following sensitization liquid with getting rid of an edition method, at 110 DEG C dry 1 minute, obtain thermosensitive positive-type CTP sensitive lithographic plate.Dried glue spread 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 as follows:
Photosensitive composition of the present invention is specifically composed as follows:
Resol (weight-average molecular weight is 8000, number-average molecular weight 2000) 3.93 g
Anti-solvent vinyl polymer 5.18 g of multi-ply construction of the present invention
Vinyl sulfonic acid ester polymer 1.50 g
2-(4-p-methoxy-phenyl)-4, two (trichloromethyl)-s-triazine 0.3 g of 6-
2-[2-[2-thiophenyl-3-[2-(1,3-dihydro-1,3,3-trimethylammonium, one 2H-indoline-2-subunit)-ethylidene]-1 one tetrahydrobenzene-1-yl]-vinyl]-1,3,3-trimethylammonium-3H-indoles muriate 0.64 g
Cellulose acetate butyrate 0.15 g
Tetrahydronaphthalic anhydride 0.03 g
Alkaline bright blue 0.3 g
Fluorochemical surfactant 0.02 g.
Above-mentioned photosensitive composition is dissolved in 40 g methylethylketones and 95 g1-methoxy-2-propanol solvents and obtains sensitization liquid.
Except containing macromolecular compound of the present invention, in the sensitive layer of photosensitive lithoprint plate of the present invention, can also contain phenolic resinoid as described below, as phenol-formaldehyde resin, cresol-formaldehyde resin, meta-cresol resol, mixture cresol resol, meta-cresol-tert-butyl phenol copolycondensation phenolic resin, dihydroxyphenyl propane methylal resin etc.
Dyestuff applicable in the present invention has: oil orchid 603, the gorgeous blue BO of alkalescence, Victoria's ethereal blue, malachite green, methylene blue etc.
What in photosensitive lithoprint plate sensitive layer of the present invention, contained development promoter was suitable for has: Tetra hydro Phthalic anhydride, tetrahydronaphthalic anhydride, tosic acid, Witco 1298 Soft Acid, to toluenesulfinic acid, phosphenylic acid, M-nitro benzoic acid, lauric acid and xitix etc.
What in photosensitive lithoprint plate sensitive layer of the present invention, contained tensio-active agent was suitable for has: fluorine-containing nonionogenic tenside F-171, F-173, FC-430, FC-431, FC-4430.The suitable proportion of these tensio-active agents in sensitive layer is 0.01-0.1%, is preferably between 0.01-0.05%.
Plate coating solids component of the present invention is dissolved in suitable solvent and is applied to subsequently on support and can obtains.Applicable solvent has: ethylene glycol monoemethyl ether, pimelinketone, hexone, butanone, ethylene glycol monomethyl ether, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), dioxane, tetrahydrofuran (THF), furans furfural, propyl carbinol, ethyl acetate, butylacetate, 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, preferably 1.4g/m
2-1.8g/m
2.
The support of sensitive lithographic plate of the present invention can be aluminium plate or other metallographs, can be also polyester film base and scribbles high molecular paper substrate.Best support is the aluminium plate of anode electrolysis, oxidation, sealing of hole processing.
The plate making as mentioned above exposes on the TRENDSETTER of Kodak 800 III thermal CTP machines, and rotating speed is 150 to turn.Then,, by method known to those skilled in the art, in moisture developer composition, make forme develop.Afterwards, process with protection glue the forme having developed.Plate specific performance application result is in table two.
Table one emulsion particle performance table
| ? | Comonomer | Quality compares per-cent | Solid content | The polymkeric substance number of plies | Molecular weight |
| Emulsion particle 1 | DMF, methyl acrylate, N-(4-acetyl oxygen phenyl) maleimide, 3-crotononitrile, methacrylic acid | 25:29:15:25:6 | 18.3 | 2 | 25000 |
| Emulsion particle 2 | DMF, methyl acrylate, N-(4-sulfoamido benzene) maleimide, 3-crotononitrile, methacrylic acid | 15:31:20:30:4 | 16.1 | 2 | 32000 |
| Emulsion particle 3 | N-(4-hydroxybenzene) Methacrylamide, methyl acrylate, N-(4-acetyl oxygen phenyl) maleimide, vinyl cyanide, methacrylic acid | 30:25:10:30:5 | 14.2 | 2 | 30000 |
| Emulsion particle 4 | DMF, methyl acrylate, N-(4-acetyl oxygen phenyl) maleimide, 3-crotononitrile, methacrylic acid | 25:32:10:23:10 | 15.7 | 2 | 33000 |
| Emulsion particle 5 | DMF, methyl methacrylate, N-(4-acetyl oxygen phenyl) maleimide, vinyl cyanide, vinylformic acid | 23:30:15:27:5 | 15.1 | 2 | 31000 |
| Emulsion particle 6 | DMF, vinylformic acid pentyl ester, N-(4-acetyl oxygen phenyl) maleimide, vinyl cyanide, vinylformic acid | 30:26:10:27:7 | 17.1 | 2 | 28000 |
| Emulsion particle 7 | N-(4-hydroxybenzene) Methacrylamide, methyl acrylate, N-(4-acetyl oxygen phenyl) maleimide, 3-crotononitrile, methacrylic acid | 23:28:16:27:6 | 16.3 | 3 | 30000 |
| Emulsion particle 8 | DMF, methyl acrylate, N-(4-sulfoamido benzene) maleimide, 3-crotononitrile, methacrylic acid | 23:45:8:15:9 | 21.2 | 3 | 35000 |
| Emulsion particle 9 | N-(4-hydroxybenzene) Methacrylamide, methyl acrylate, N-(4-acetyl oxygen phenyl) maleimide, 3-crotononitrile, methacrylic acid | 18:34:17:27:4 | 18.7 | 3 | 31000 |
| Emulsion particle 10 | DMF, β-dimethyl-aminoethylmethacrylate, N-(4-acetyl oxygen phenyl) maleimide, vinyl cyanide, vinylformic acid | 23:29:15:27:6 | 19.4 | 3 | 32000 |
| Emulsion particle 11 | DMF, methyl acrylate, N-(4-sulfoamido benzene) maleimide, vinyl cyanide, methacrylic acid | 24:10:34:27:5 | 18.9 | 3 | 29000 |
| Emulsion particle 12 | DMF, vinylformic acid pentyl ester, N-(4-sulfoamido benzene) maleimide, vinyl cyanide, methacrylic acid | 16:42:11:25:6 | 23.6 | 3 | 36000 |
Table two plate application performance table
Claims (10)
1. an anti-solvent vinyl polymer for multi-ply construction, is characterized in that, it is the vinyl multiple copolymer that contains following structural unit:
A: have alkali-soluble amides structural unit, its structural formula is as follows:
Represent-H of R1 or – CH3 in formula, what X1 represented singly-bound or divalent has a switch base, expression-H or-CH3, R2 represents to have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom.
2.B: have the structural unit of alkali-soluble maleimide, its structural formula is as follows:
In formula, Y represents to have the group of acid hydrogen atom
C: have the structural unit of esters of acrylic acid, its structural formula is as follows:
Represent-H of R3 Huo – CH3 in formula, R4 represents to have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom, and R5 represents to have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom;
D: alkene nitrile structural unit, its structural formula is as follows:
R in formula
6expression-H Huo – CH
3, R
7expression can have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom;
E: structural acrylic unit, its structural formula is as follows:
R in formula
3expression-H Huo – CH
3, R
4expression can have alkyl, cycloalkyl, the aryl or aralkyl of hydrogen atom or substituent 1 ~ 12 carbon atom.
3. the anti-solvent vinyl polymer of multi-ply construction according to claim 1, it is characterized in that: the weight average molecular weight of the described anti-solvent vinyl polymer of multi-ply construction is 3000-20 ten thousand, number-average molecular weight is 1500-2 ten thousand, and dispersity is 1.1-10; The quality percentage composition of structural unit shown in structural formula A in vinyl polymer is 0.5-50%; The quality percentage composition of structural unit shown in structural formula B in vinyl polymer is 10-80%; The quality percentage composition of structural unit shown in structural formula C in vinyl polymer is 0.5-40%; The quality percentage composition of the structural unit of the esters of acrylic acid shown in structural formula D in vinyl polymer is 10-50%; The quality percentage composition of the structural unit of the acrylic acid or the like shown in structural formula E in vinyl polymer is 0.5-30%.
4. the anti-solvent vinyl polymer of multi-ply construction according to claim 2, is characterized in that: the weight average molecular weight of the described anti-solvent vinyl polymer of multilayer is 2-4 ten thousand, and number-average molecular weight is 1500-4000, and dispersity is 1.1-10; The quality percentage composition of structural unit shown in structural formula A in vinyl polymer is 20-30%; The quality percentage composition of structural unit shown in structural formula B in vinyl polymer is 20-40%; The quality percentage composition of structural unit shown in structural formula C in vinyl polymer is 10-20%; The quality percentage composition of structural unit shown in structural formula D in vinyl polymer is 20-30%; The quality percentage composition of structural unit shown in structural formula E in vinyl polymer is 4-10%.
5. the synthetic method of the anti-solvent vinyl polymer of multi-ply construction according to claim 1, is characterized in that: this polymkeric substance adopts the method for core-shell emulsion copolymerization synthetic, and particle exists with discrete emulsion particle form.
6. the synthetic method of the anti-solvent vinyl polymer of multi-ply construction according to claim 4, is characterized in that: the mixture of one or more of the alcohols such as reaction solvent employing water and methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols.
7. the synthetic method of the anti-solvent vinyl polymer of multi-ply construction according to claim 4, it is characterized in that: catalysts is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, tertbutyl peroxide, one or more in the azos such as peroxidized t-butyl perbenzoate or organo-peroxide.
8. the synthetic method of the anti-solvent vinyl polymer of multi-ply construction according to claim 4, is characterized in that: reaction emulsifier is the emulsifying agents such as dioctyl succsinic acid is received, sodium alkyl benzene sulfonate.
9. the synthetic method of the anti-solvent vinyl polymer of multi-ply construction according to claim 4, it is characterized in that: this is polymerized to stage feeding polymerization, first one or more monomers are dissolved in solvent, add emulsifying agent, form emulsion, heated and stirred, carry out polymerization and form seed, then by residue, whole or several monomers are dissolved in solvent, all or several times drip in emulsion, carry out polymerization, thereby form the high molecular polymerization particle existing with emulsion discrete form of multilayered structure.
10. the application of the anti-solvent vinyl polymer of multi-ply construction according to claim 4 in heat-sensitive positive picture CTP plate, it is characterized in that: the heat-sensitive positive picture CTP plate that contains this vinyl polymer, can significantly improve solvent resistance, wear resistance, resistance to marring and the press resistance rate of CTP version, especially, while using UV ink, can significantly improve its press resistance rate.
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| CN109774334A (en) * | 2017-11-11 | 2019-05-21 | 乐凯华光印刷科技有限公司 | A kind of positive heat-sensitive ink of resistance to UV CTP plate |
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