CN109776737B - Solvent-resistant resin, photosensitive composition containing resin and application of composition - Google Patents
Solvent-resistant resin, photosensitive composition containing resin and application of composition Download PDFInfo
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Abstract
The invention discloses a solvent-resistant resin, which is a copolymer of styrene, acrylic acid or methacrylic acid and polyethylene glycol acrylate or polyethylene glycol methacrylate. The weight average molecular weight of the solvent-resistant resin is 15000-100000. Compared with the prior art, the invention has the prominent characteristics that: the solvent-resistant resin is used in the composition, so that the solvent resistance and the printing resistance of the plate are obviously improved, the defects of poor solvent resistance and poor printing resistance of a thermosensitive plate in the existing thermosensitive plate technology are overcome, and particularly the plate has good UV ink resistance in UV ink printing and has the advantages of good film forming property, solvent resistance and high printing resistance.
Description
Technical Field
The invention belongs to the technical field of printing plates, and particularly relates to a solvent-resistant resin, a photosensitive composition containing the resin and an application of the composition.
Background
Computer To Plate (CTP) was started in 80 th 20 th century, and CTP technology is rapidly developed, wherein positive thermosensitive CTP plate-making technology is the most mature, stable and effective plate-making technology at present. With the stricter and stricter environmental requirements of various countries, the performance of the thermosensitive CTP plate is further improved, the environmental pollution is reduced, and especially the improvement of the solvent resistance and the printing resistance of the plate is the key point of the development of the thermosensitive CTP plate.
The solvent resistance of the printing plate refers to the corrosion resistance of the printing plate to organic solvents in various printing chemicals, such as washing oil, fountain solution, baking paste, printing plate preservative, printing plate cleaning agent and printing ink, particularly UV printing ink washing oil used in printing.
The plate material has a certain correlation between wear resistance and solvent resistance, generally speaking, the plate material with better solvent resistance generally has higher wear resistance, but the plate material with better wear resistance is not necessarily as good as the solvent resistance, and particularly the plate material resists the corrosion of UV ink.
Many methods for improving the solvent resistance and printing resistance of heat-sensitive CTP plates are available, one of the most important methods is the development of plate coating organic matters, especially functional film-forming resins, for example, kodak patent CN101321632A discloses the introduction of phosphoric acid side group or adamantane side group into the polymer to improve the chemical resistance of the plates.
The phenolic resin is an important film forming resin for the thermosensitive plate, and the solvent resistance and the printing resistance of the thermosensitive plate can be improved by modifying and modifying the phenolic resin.
The modification of the printing plate material with alkali-soluble phenolic resin is generally carried out by modifying phenolic hydroxyl telechelic groups, such as phenolic hydroxyl and sulfonic acid group or carboxyl part of phenolic resin esterification modification disclosed in EP-A0934822.
EP02102446.8, CN1688441A, by ikco, discloses a modification method of diazonium salt grafting of phenolic resin by phenolic hydroxyl telechelic group to improve chemical resistance of heat-sensitive plates. The method disclosed in Ackera is to perform diazonium salt graft modification on a phenolic resin to form azo-aryl groups (-N = N-Q group, Q is an aromatic group), which improve the chemical resistance of the coating.
Fuji film 2004.3.11 JP2004-069478 proposes that a thermosensitive plate resin having a phenol skeleton and a urea bond (-NHCONH-) in the main chain has solvent resistance.
WO2004/033206 by Kodak corporation suggests that introduction of barbituric acid groups into the side chains of polymeric resins can significantly improve the solvent resistance and abrasion resistance of plate coatings. Kodak discloses a method of grafting barbituric acid groups through phenolic hydroxyl groups of a phenolic resin.
Aceka DE60320436 (same family WO 2004035686) discloses polymers containing N-pyrazole groups which increase the chemical resistance of the printing plates.
Fuji film company CN201380011228.4 discloses a method for increasing chemical resistance and printing resistance of a printing plate by adding a polyvinyl acetal resin having one hydroxyl group.
Disclosure of Invention
The invention aims to solve the defects of poor solvent resistance and poor printing resistance of a thermosensitive plate in the prior thermosensitive plate technology, and provides a solvent-resistant resin, a photosensitive composition containing the resin and application of the composition.
The object of the invention is achieved in the following way:
solvent resistant resin, which is a copolymer of styrene, acrylic acid or methacrylic acid and polyethylene glycol acrylate or polyethylene glycol methacrylate. The weight average molecular weight of the solvent-resistant resin is 15000-100000.
Styrene accounts for 1-30% of the total mass of the solvent-resistant resin, acrylic acid or methacrylic acid accounts for 1-40% of the total mass of the solvent-resistant resin, and polyethylene glycol acrylate or polyethylene glycol methacrylate accounts for 58-98% of the total mass of the solvent-resistant resin.
The polymerization degree of polyethylene glycol in the acrylic acid polyethylene glycol ester or the methacrylic acid polyethylene glycol ester is 9-125.
A photosensitive composition containing the solvent-resistant resin comprises the solvent-resistant resin, alkali-soluble resin, a dissolution inhibitor, a development accelerator, an infrared absorption dye and a background dye.
The solvent-resistant resin accounts for 5-30% of the total mass of the photosensitive composition, the alkali-soluble resin accounts for 50-91% of the total mass of the photosensitive composition, the dissolution inhibitor accounts for 1-20% of the total mass of the photosensitive composition, the development accelerator accounts for 0.1-10% of the total mass of the photosensitive composition, the infrared absorption dye accounts for 1-5% of the total mass of the photosensitive composition, and the background dye accounts for 1-5% of the total mass of the photosensitive composition.
The solvent-resistant resin accounts for 10-15% of the total mass of the photosensitive composition, the alkali-soluble resin accounts for 60-85% of the total mass of the photosensitive composition, the dissolution inhibitor accounts for 1-20% of the total mass of the photosensitive composition, the development accelerator accounts for 0.1-10% of the total mass of the photosensitive composition, the infrared absorption dye accounts for 2.5-3.5% of the total mass of the photosensitive composition, and the background dye accounts for 2-3.5% of the total mass of the photosensitive composition.
The alkali soluble resin is phenolic resin or poly p-hydroxystyrene resin.
The phenolic resin is at least one of m-cresol-p-cresol phenolic resin, phenol-p-cresol phenolic resin, o-cresol-p-cresol phenolic resin and phenolic resin. The phenolic resin can be selected from m-cresol phenolic resin (Mw is 4000 to 8000, mw/Mn is 4 to 8), m-cresol-p-cresol phenolic resin (the molar ratio of m-cresol to p-cresol is 8: 2 to 6: 4, mw is 4000 to 10000, mw/Mn is 4 to 12), phenol-p-cresol phenolic resin (the molar ratio of phenol to p-cresol is 5: 5 to 3: 7, mw is 4000 to 6000, mw/Mn is 4 to 6), phenol-o-cresol-p-cresol phenolic resin (the molar ratio of phenol, o-cresol and p-cresol is 2: 1: 7, mw is 6000 to 9000, mw/Mn is 6 to 9), phenol-m-cresol-p-cresol phenolic resin (the molar ratio of phenol, m-cresol and p-cresol is 1: 6, mw is 7000 to 9000, mw/Mn is 7 to 10), and Mw/Mn is 12000, mw/Mn is 1208, and the like. The weight average molecular weight for synthesizing the phenolic novolac resin of the invention is preferably 1000-100000, more preferably 2000-50000, and most preferably 2500-14000.
The dissolution inhibitor is a quaternary ammonium salt nitrogen-containing compound, an imidazole compound, a quinolinium salt compound, a benzothiazole onium salt compound, an aromatic hydrocarbon carboxylic ester, a lactone ketone, an aromatic hydrocarbon disulfone, a polyalkoxy ether or polyethylene glycol.
The developing accelerator is organic acid, acid anhydride, phenols or sulfones. Such as sulfonic acid, phosphoric acid, alkylbenzene sulfonic acid, adipic acid benzoate, lauric acid, ascorbic acid, acetic anhydride, phthalic anhydride, maleic anhydride, chloromaleic anhydride, succinic anhydride, bisphenol a, p-nitrophenol, p-ethoxyphenol, 2,3, 4-trihydroxybenzophenone, 4-hydroxybenzophenone, and the like.
The infrared absorption dye is cyanine infrared absorption dye. Namely, the infrared absorption dye with an absorption peak value at 790-830nm, and the infrared dye is cyanine series infrared absorption dye. Generally, cyanine infrared absorption dyes sold at home and abroad, such as LC-01 of Honywell company, NK-2014, NK-2268 and HCD-21 of forest source company, PS-101 and PS-102 of Japanese chemical drugs, S0094 of FEW CHEMICALS company, NIRD of Liaoning Huahai blue sail and the like, are selected, and the invention mainly selects the 830nm infrared sensitizing dye in chemical competition. The absorption peak wavelength of these infrared absorption dyes is generally 810 to 830nm, the absorption peak measured in ethanol solvent is generally 815 to 820nm, and the absorption peak in the heat-sensitive CTP coating liquid is generally about 815 nm. The amount is 1 to 5%, preferably 2.5 to 3.5% by weight based on the total weight of the photosensitive composition. Since the infrared dye is an alkali insoluble substance and has a dissolution inhibiting effect, development is difficult when the infrared dye is used in an excessively high amount. When the dosage is too low, the heat is too low, the decomposition is not thorough under the specified scanning energy, especially at the position close to the aluminum plate base, and the development is easy to leave.
The background dye is oil soluble blue, basic brilliant blue, victoria pure blue, phthalocyanine blue, malachite green, dark green, phthalocyanine green, crystal violet, methyl violet, ethyl violet, dimethyl yellow or fluorescein.
The use of the photosensitive composition as defined above in a positive thermosensitive CTP plate.
The solid content of the positive thermosensitive CTP coating liquid prepared from the photosensitive composition is 7-20%.
The photosensitive composition is prepared into a thermosensitive CTP coating liquid, and a solvent system with good solubility to the components, moderate evaporation speed and a boiling point of 70-150 ℃ is selected, wherein the boiling point of a main solvent is preferably 100-140 ℃. The solvent can be at least one selected from ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, cyclohexanone, butanone, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, gamma-butyrolactone, dioxane, etc. The solvent amount depends on the viscosity of the coating liquid required by the coating machine, and the solid content of the photosensitive composition solution is 10-15% and the viscosity is 3-5 mm 2 ·s -1 In between. Certain high speed production lines require coating fluids with viscosities below 3mm 2 ·s -1 Therefore, the solid content is less than 10%.
When the thermosensitive CTP coating liquid is prepared, a plurality of components are dissolved in the following sequence, generally, infrared dye which is difficult to dissolve is dissolved firstly, after the infrared dye is completely dissolved, film-forming resin, a dissolution inhibitor and a development accelerator are added, and finally background dye is added.
The developer used in the present invention is mainly composed of an aqueous alkaline solution.
The alkaline developer is an alkaline solution and mainly comprises a developer, a protective agent, a wetting agent and the like. The developer is used for dissolving the exposed photosensitive layer of the positive image CTP plate, and a strong alkaline substance is commonly used, and can be selected from the following components: the concentration of the strongly basic substance is preferably 0.5 to 30% (wt) in the case of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, disodium hydrogen phosphate, or trisodium phosphate. The protective agent and wetting agent in the developer are anionic surfactant and nonionic surfactant.
The innovation points of the invention are as follows: 1. the solvent-resistant resin contains an external suspension carboxyl group and a polyether hydrophilic group, a polymeric chain is a hydrophobic group, and the structure of the solvent-resistant resin has the characteristics of a surfactant with a polar group and a nonpolar group, so that the surface tension of the solution is improved, and the coating adaptability is increased; 2. designed as high molecular solvent resistant resin, improves the miscibility of the resin and other components in the thermosensitive composition, reduces the phenomenon of phase separation and improves the overall mechanical property of high polymer; 3. the invention provides a solvent-resistant resin photosensitive composition and application thereof in a positive thermosensitive CTP plate, wherein the solvent-resistant resin photosensitive composition used for the thermosensitive CTP plate has the advantages of good film forming property, solvent resistance and high pressrun.
Compared with the prior art, the invention has the prominent characteristics that: the solvent-resistant resin is used in the composition, so that the solvent resistance and the printing resistance of the plate are obviously improved, the defects of poor solvent resistance and poor printing resistance of the thermosensitive plate in the existing thermosensitive plate technology are overcome, particularly the plate has good UV ink resistance in UV ink printing, and the plate has the advantages of good film forming property, solvent resistance and high printing resistance.
Detailed Description
The following are specific examples of the invention, but the content of the invention is not limited thereto. In an embodiment, the styrene is from yanshan petrochemical; (meth) acrylic acid is from Mitsubishi yang Japan; the polyethylene glycol meth) acrylates are all from British-Sigma; benzoyl peroxide, azobisisobutyronitrile, comes from fossen chemistry; n, N-dimethylformamide, N-dimethylacetamide is from the chemistry of dicarbon; tetrahydrofuran was from exxonmobil (china); acetone and butanone are from Tianjin chemical reagent factory.
Solvent resistant resin, which is a copolymer of styrene, acrylic acid or methacrylic acid and polyethylene glycol acrylate or polyethylene glycol methacrylate.
Styrene accounts for 1-30% of the total mass of the solvent-resistant resin, acrylic acid or methacrylic acid accounts for 1-40% of the total mass of the solvent-resistant resin, and polyethylene glycol acrylate or polyethylene glycol methacrylate accounts for 58-98% of the total mass of the solvent-resistant resin.
The polymerization degree of polyethylene glycol in the acrylic acid polyethylene glycol ester or the methacrylic acid polyethylene glycol ester is 9-125.
A photosensitive composition containing the solvent-resistant resin comprises the solvent-resistant resin, alkali-soluble resin, a dissolution inhibitor, a development accelerator, an infrared absorption dye and a background dye.
The solvent-resistant resin accounts for 5-30% of the total mass of the photosensitive composition, the alkali-soluble resin accounts for 50-91% of the total mass of the photosensitive composition, the dissolution inhibitor accounts for 1-20% of the total mass of the photosensitive composition, the development accelerator accounts for 0.1-10% of the total mass of the photosensitive composition, the infrared absorption dye accounts for 1-5% of the total mass of the photosensitive composition, and the background dye accounts for 1-5% of the total mass of the photosensitive composition.
The solvent-resistant resin accounts for 10-15% of the total mass of the photosensitive composition, the alkali-soluble resin accounts for 60-85% of the total mass of the photosensitive composition, the dissolution inhibitor accounts for 1-20% of the total mass of the photosensitive composition, the development accelerator accounts for 0.1-10% of the total mass of the photosensitive composition, the infrared absorption dye accounts for 2.5-3.5% of the total mass of the photosensitive composition, and the background dye accounts for 2-3.5% of the total mass of the photosensitive composition.
The alkali-soluble resin is phenolic resin or poly-p-hydroxystyrene resin.
The dissolution inhibitor is a quaternary ammonium salt nitrogen-containing compound, an imidazole compound, a quinolinium salt compound, a benzothiazole onium salt compound, an aromatic hydrocarbon carboxylic ester, a lactone ketone, an aromatic hydrocarbon disulfone, a polyalkoxy ether or polyethylene glycol.
The developing accelerator is organic acid, acid anhydride, phenols or sulfones.
The infrared absorption dye is cyanine infrared absorption dye.
The background dye is oil soluble blue, basic brilliant blue, victoria pure blue, phthalocyanine blue, malachite green, dark green, phthalocyanine green, crystal violet, methyl violet, ethyl violet, dimethyl yellow or fluorescein.
The use of the photosensitive composition as defined above in a positive thermosensitive CTP plate.
Example 1
Preparation of lithographic printing plates
(1) Preparing an aluminum plate base:
an aluminum plate having a thickness of 0.28mm was degreased in a 7wt% aqueous solution of sodium hydroxide at a temperature of 55 ℃ for 40 seconds, and subjected to electrolysis at a temperature of 25 ℃ by a sine wave alternating current in a 10wt% aqueous solution of hydrochloric acid with a 50Hz alternating current and a 50A/dm current 2 The electrolysis time is 60 seconds, and Ra =0.3-0.6um, preferably 0.4-0.6 μm. Then, the resultant was subjected to a slag-removing treatment in a 50wt% aqueous solution of sodium hydroxide at a temperature of 60 ℃ for 10 seconds, and then, at a temperature of 25 ℃, the current density was 5A/dm 2 Treating in 20wt% sulfuric acid solution for 40s, and controlling oxide film =2.5-3.5g/m 2 . Finally, naH was used at 60 ℃ 2 PO 4 And carrying out hole sealing treatment on the NaF solution for 30 seconds to obtain the aluminum plate base suitable for the lithographic printing plate.
(2) Preparing a photosensitive composition into a thermosensitive CTP coating liquid with the solid content of 10 percent, coating the thermosensitive CTP coating liquid on an aluminum plate substrate prepared by the method by a bar coating method, drying the aluminum plate substrate for 2 minutes at 130 ℃, then placing the plate in an oven, and curing the plate for 24 hours at 50 ℃ to obtain a thermosensitive lithographic plate, wherein the film thickness of the photosensitive layer is 1.5g/m 2 。
(3) The optimal exposure laser amount detection method comprises the following steps:
on a SCREEN8600E plate making machine, a self-contained test strip was used, an image was formed by screening 175lpi, a resolution of 2400dpi was outputted, scanning plate making was performed on a master at different laser energies under the following exposure conditions (see Table 1) and development conditions (see Table 2), and then the exposure laser amount determined by the following method was used as the sensitivity.
The 50% open mesh value at different exposure energies was measured with a densitometer IC-Plate2 of X-rite until a display value was found in the range of 49.5% to 50.4% for 50% of the open mesh area in the ladder bar, which is the sensitivity of the Plate.
And recording the sensitivity of the printing plate material.
(4) Detecting the development tolerance:
exposing on a SCREEN8600E plate making machine according to the exposure amount which is 1.1 time of the obtained sensitivity value, performing scanning plate making on a sample by using a self-contained test strip, and performing development processing on the sample under the conditions of different development time (20 s, 30s and 40s are selected), wherein the difference between the highest value and the lowest value of the development time of the plate material can meet the use requirement (no blank remains, the density OD value is less than 0.29, the coating is not reduced on the spot, the density loss is less than or equal to 4 percent, and the dot reduction is 2-99 percent) is the development latitude of the plate material.
The photosensitive compositions are shown in table 3:
the synthesis method of the solvent-resistant resin I in the table comprises the following steps: 30g of styrene, 10.0g of methacrylic acid, 60.0g of polyethylene glycol methacrylate (n = 25), 1.0g of azodiisobutyronitrile and 240g of acetone are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃, after 7 hours of reaction, 1.0g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then vacuum drying is carried out. Weight average molecular weight 15000.
Example 2
Preparation of the master
The photosensitive compositions are shown in table 4:
the synthesis method of the solvent-resistant resin II in the table comprises the following steps: 5g of styrene, 10.0g of acrylic acid, 85.0g of polyethylene glycol acrylate (n = 9), 1.0g of azodiisobutyronitrile and 250g of tetrahydrofuran are added into a 500ml flask, stirred for 200r/min under the protection of nitrogen, heated to 80 ℃, reacted for 7 hours, added with 1g of hydroquinone to terminate the reaction, decompressed to remove the solvent, and then dried in vacuum. Weight average molecular weight 48000.
Example 3
Preparation of the master
The photosensitive compositions are shown in table 5:
the synthesis method of the solvent-resistant resin III in the table comprises the following steps: 1g of styrene, 40.0g of methacrylic acid, 59.0g of polyethylene glycol methacrylate (N = 42), 1.0g of benzoyl peroxide and 250g of N, N-dimethylformamide are added into a 500ml flask, nitrogen protection is carried out, stirring is carried out for 200r/min, the temperature is increased to 85 ℃, after 7 hours of reaction, 1g of hydroquinone is added to terminate the reaction, the solvent is removed under reduced pressure, and then vacuum drying is carried out. The weight average molecular weight is 100000.
Example 4
Preparation of the master
The photosensitive compositions are shown in table 6:
in the table, the synthesis method of the solvent-resistant resin IV comprises the following steps: 10g of styrene, 20.0g of acrylic acid, 70.0g of polyethylene glycol methacrylate (n = 75), 1.0g of azobisisobutyronitrile and 280g of butanone are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 80 ℃, after 7 hours of reaction, 1g of hydroquinone is added to terminate the reaction, the solvent is removed under reduced pressure, and then the mixture is dried in vacuum. Weight average molecular weight 30000
Example 5
Preparation of the master
The photosensitive compositions are shown in table 7:
synthesis of solvent resistant resin V in Table: 20g of styrene, 1.0g of methacrylic acid, 79.0g of polyethylene glycol methacrylate (N = 125), 1.0g of benzoyl peroxide and 200g of N, N-dimethylacetamide are added into a 500ml flask, nitrogen protection is carried out, stirring is carried out for 200r/min, the temperature is increased to 90 ℃, after 8 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then vacuum drying is carried out. Weight average molecular weight 72000.
Example 6
Preparation of the master
Photosensitive compositions are as in table 8:
in the table, the synthesis method of the solvent-resistant resin VI comprises the following steps: 1g of styrene, 1.0g of acrylic acid, 98.0g of polyethylene glycol methacrylate (N = 100), 1.0g of azodiisobutyronitrile and 250g of N, N-dimethylformamide are added into a 500ml flask, nitrogen is protected, stirring is started for 200r/min, the temperature is increased to 70 ℃, after 7 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then vacuum drying is carried out. Weight average molecular weight 60000.
Example 7
The preparation of the master was the same as in example 1.
The photosensitive compositions are shown in table 9:
the synthesis method of the solvent-resistant resin VII in the table comprises the following steps: 30g of styrene, 12g of acrylic acid, 58.0g of polyethylene glycol methacrylate (N = 9), 1.0g of azobisisobutyronitrile and 250g of N, N-dimethylformamide are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃, after 7 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then the mixture is dried in vacuum.
Example 8
The preparation of the master was the same as in example 1.
Photosensitive compositions are as in table 10:
the synthesis method of the solvent-resistant resin VIII in the table comprises the following steps: 25g of styrene, 5g of acrylic acid, 70.0g of polyethylene glycol methacrylate (N = 40), 1.0g of azobisisobutyronitrile and 250g of N, N-dimethylformamide are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃, after 7 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then the mixture is dried in vacuum.
Example 9
The preparation of the master was the same as in example 1.
Photosensitive compositions are as in table 11:
synthesis method of solvent-resistant resin IX in Table: 5g of styrene, 30g of acrylic acid, 65.0g of polyethylene glycol methacrylate (N = 60), 1.0g of azodiisobutyronitrile and 250g of N, N-dimethylformamide are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃, after 7 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then vacuum drying is carried out.
Example 10
The preparation of the master was the same as in example 1.
Photosensitive compositions are as in table 12:
method for synthesizing solvent-resistant resin X in Table: 15g of styrene, 15g of acrylic acid, 70.0g of polyethylene glycol methacrylate (N = 80), 1.0g of azodiisobutyronitrile and 250g of N, N-dimethylformamide are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃, after 7 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then vacuum drying is carried out.
Example 11
The preparation of the master was the same as in example 1.
Photosensitive compositions are as in table 13:
the synthesis method of the solvent-resistant resin XI in the table comprises the following steps: 5g of styrene, 5g of acrylic acid, 90.0g of polyethylene glycol methacrylate (N = 100), 1.0g of azobisisobutyronitrile and 250g of N, N-dimethylformamide are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃, after 7 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then the mixture is dried in vacuum.
Example 12
The preparation of the master was the same as in example 1.
Photosensitive compositions are as in table 14:
method for synthesizing solvent-resistant resin XII in Table: 10g of styrene, 10g of acrylic acid, 80.0g of polyethylene glycol methacrylate (N = 125), 1.0g of azobisisobutyronitrile and 250g of N, N-dimethylformamide are added into a 500ml flask, the mixture is stirred for 200r/min under the protection of nitrogen, the temperature is raised to 70 ℃, after 7 hours of reaction, 1g of hydroquinone is added to stop the reaction, the solvent is removed under reduced pressure, and then the mixture is dried in vacuum.
Comparative examples 1 to 12
Similarly, a positive working heat-sensitive lithographic printing plate was prepared by replacing the solvent-resistant resin with the alkali-soluble resin in the formulation as described in the above examples.
Solvent resistance performance investigation: the plate samples were immersed in a solution of isopropanol and water (mass ratio 1) at 23 ℃ for 30 minutes, rinsed with deionized water, and plate coating loss was measured.
Investigating printing endurance: the plate samples were printed normally on a press (northern four-color quarto high-speed rotary press) and their press resistance was examined.
The plate properties are shown in the attached Table 15.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the overall concept of the present invention, and these should also be considered as the protection scope of the present invention.
Claims (10)
1. A solvent-resistant resin characterized by: the resin is a copolymer of styrene, acrylic acid or methacrylic acid and polyethylene glycol acrylate or polyethylene glycol methacrylate;
styrene accounts for 1-30% of the total mass of the solvent-resistant resin, acrylic acid or methacrylic acid accounts for 1-40% of the total mass of the solvent-resistant resin, and polyethylene glycol acrylate or polyethylene glycol methacrylate accounts for 58-98% of the total mass of the solvent-resistant resin;
the polymerization degree of polyethylene glycol in the acrylic acid polyethylene glycol ester or the methacrylic acid polyethylene glycol ester is 9-125.
2. A photosensitive composition comprising the solvent-resistant resin of claim 1, wherein: including solvent resistant resins, alkali soluble resins, dissolution inhibitors, development promoters, infrared absorbing dyes, and background dyes.
3. The photosensitive composition of claim 2, wherein: the solvent-resistant resin accounts for 5-30% of the total mass of the photosensitive composition, the alkali-soluble resin accounts for 50-91% of the total mass of the photosensitive composition, the dissolution inhibitor accounts for 1-20% of the total mass of the photosensitive composition, the development accelerator accounts for 0.1-10% of the total mass of the photosensitive composition, the infrared absorption dye accounts for 1-5% of the total mass of the photosensitive composition, and the background dye accounts for 1-5% of the total mass of the photosensitive composition.
4. The photosensitive composition of claim 3, wherein: the solvent-resistant resin accounts for 10-15% of the total mass of the photosensitive composition, the alkali-soluble resin accounts for 60-85% of the total mass of the photosensitive composition, the dissolution inhibitor accounts for 1-20% of the total mass of the photosensitive composition, the development accelerator accounts for 0.1-10% of the total mass of the photosensitive composition, the infrared absorption dye accounts for 2.5-3.5% of the total mass of the photosensitive composition, and the background dye accounts for 2-3.5% of the total mass of the photosensitive composition.
5. The photosensitive composition of claim 2, wherein: the alkali-soluble resin is phenolic resin or poly-p-hydroxystyrene resin.
6. The photosensitive composition of claim 2, wherein: the dissolution inhibitor is a quaternary ammonium salt nitrogen-containing compound, an imidazole compound, a quinolinium salt compound, a benzothiazole onium salt compound, an aromatic hydrocarbon carboxylic ester, a lactone ketone, an aromatic hydrocarbon disulfone, a polyalkoxy ether or polyethylene glycol.
7. The photosensitive composition of claim 2, wherein: the developing accelerator is organic acid, acid anhydride, phenols or sulfones.
8. The photosensitive composition of claim 2, wherein: the infrared absorption dye is cyanine infrared absorption dye.
9. The photosensitive composition of claim 2, wherein: the background dye is oil soluble blue, basic brilliant blue, victoria pure blue, phthalocyanine blue, malachite green, dark green, phthalocyanine green, crystal violet, methyl violet, ethyl violet, dimethyl yellow or fluorescein.
10. The use of the photosensitive composition of claim 2 in positive thermosensitive CTP plates.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11212263A (en) * | 1997-10-02 | 1999-08-06 | Dainippon Printing Co Ltd | Photosensitive resin composition |
| US6184268B1 (en) * | 1999-08-30 | 2001-02-06 | Xerox Corporation | Ink jet ink compositions and processes thereof |
| CN1445608A (en) * | 2002-03-20 | 2003-10-01 | 富士胶片株式会社 | Photosensitive composition of infrared sensitive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7261998B2 (en) * | 2001-04-04 | 2007-08-28 | Eastman Kodak Company | Imageable element with solvent-resistant polymeric binder |
| JP2007079153A (en) * | 2005-09-14 | 2007-03-29 | Nippon Paint Co Ltd | Photosensitive resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11212263A (en) * | 1997-10-02 | 1999-08-06 | Dainippon Printing Co Ltd | Photosensitive resin composition |
| US6184268B1 (en) * | 1999-08-30 | 2001-02-06 | Xerox Corporation | Ink jet ink compositions and processes thereof |
| CN1445608A (en) * | 2002-03-20 | 2003-10-01 | 富士胶片株式会社 | Photosensitive composition of infrared sensitive |
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