CN107602761B - Film-forming resin for lithographic printing plate and preparation method thereof - Google Patents
Film-forming resin for lithographic printing plate and preparation method thereof Download PDFInfo
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- CN107602761B CN107602761B CN201610541687.9A CN201610541687A CN107602761B CN 107602761 B CN107602761 B CN 107602761B CN 201610541687 A CN201610541687 A CN 201610541687A CN 107602761 B CN107602761 B CN 107602761B
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Abstract
The invention discloses a film-forming resin for lithographic printing plates, which is an acrylic resin composition and is prepared by polymerizing three or more monomers including 6-10 parts of methacrylic acid, 15-35 parts of methyl methacrylate, 6-10 parts of acrylic acid, 20-40 parts of β -hydroxyethyl acrylate, 20-40 parts of β -hydroxyethyl methacrylate, 12-20 parts of acrylonitrile, 2-10 parts of acrylamide, 15-35 parts of ethyl methacrylate and 15-35 parts of butyl methacrylate.
Description
Technical Field
The invention belongs to the technical field of photosensitive materials for lithographic printing plates, and particularly relates to a film-forming resin for lithographic printing plates and a preparation method of the film-forming resin for lithographic printing plates.
Background
The photosensitive material of the lithographic printing plate is one of the core components of the plate, the material is coated on an aluminum plate which is chemically and electrochemically treated, when the photosensitive material is used, the scanning exposure treatment is carried out on the aluminum plate through a plate-making light source, the coating generates a photochemical reaction, then the photochemical reaction is carried out through alkaline water development and cleaning, the pictures and texts required by printing are remained on the plate, and a blank hydrophilic layer is exposed, so that the manufacturing of the lithographic printing plate which is designed based on the 'water and ink incompatibility' principle is completed. The left image-text part bears the generation of the image-text in the printing process, so that the coating is required to have good lipophilicity, wear resistance, chemical resistance and stability; in addition, in order to ensure the hydrophilicity of the space portions, the coating material of the photosensitive composition must have excellent alkali solubility and easy cleanability after the photochemical reaction.
The photosensitive composition basically comprises two main components: one is non-silver high molecular photosensitizer, and the other is high molecular film forming resin; the film-forming resin is an important composition in the plate coating, and the composition determines the lipophilicity, the wear resistance and the chemical resistance of the image-text part of the plate and also determines whether the blank part of the plate can be developed cleanly.
Novolac resins including m-cresol novolac, p-cresol novolac and t-butyl phenol novolac are used as film-forming resins in the prior art photosensitive compositions. With the continuous improvement of printing technology, especially entering the era of digital CTP printing, the original composition can not meet the requirements of market technology. 1. The contradiction between alkali solubility and abrasion resistance results in a decrease in the press life of the plate in order to ensure alkali solubility. 2. The use of various novel environmentally friendly printing auxiliary materials, such as alcohol-free fountain solution, gasoline-free cleaning agent, strong acid-free plate cleaning solution, etc., results in insufficient chemical resistance of the original photosensitive layer, resulting in decreased oleophilicity and press resistance of the plate. 3. With environmentally friendly printing inks: the UV curing printing ink is widely popularized and used, and the phenomenon that phenolic resin is dissolved in printing ink monomers becomes a barrier which cannot be exceeded by the original lithographic printing plate.
Disclosure of Invention
The invention solves the defects of the prior art and provides the film-forming resin for the lithographic printing plate, which has good alkali solubility and keeps better lipophilicity, wear resistance and chemical resistance.
The invention also provides a preparation method of the film-forming resin for the lithographic printing plate, and the film-forming resin prepared by the method can be used as an additive component of the film-forming resin for a common lithographic printing plate and can also be used as a base coating material of a double-layer coating plate for UV curing ink.
The technical scheme includes that the film-forming resin for the lithographic printing plate is an acrylic resin composition, and the acrylic resin composition is formed by polymerization reaction of 6-10 parts of methacrylic acid, 15-35 parts of methyl methacrylate, 6-10 parts of acrylic acid, 20-40 parts of acrylic acid- β -hydroxyethyl ester, 20-40 parts of methacrylic acid- β -hydroxyethyl ester, 12-20 parts of acrylonitrile, 2-10 parts of acrylamide, 15-35 parts of ethyl methacrylate and 15-35 parts of butyl methacrylate.
In a preferred embodiment of the present invention, the solvent for the polymerization reaction of the acrylic resin composition is one or a combination of any several of dioxane, ethylene glycol monoethyl ether, and dimethylformamide, and the amount of the solvent is 1 to 3 times of the total amount of the monomers.
In a preferred embodiment of the present invention, the acrylic resin composition further comprises an initiator and a chain transfer agent.
In a preferred embodiment of the present invention, the initiator is benzoyl peroxide, and the amount of the benzoyl peroxide is 0.5 to 1.5% of the total amount of the monomers.
In a preferred embodiment of the present invention, the chain transfer agent is dodecanethiol, and the amount of the dodecanethiol is 0.1 to 0.5% of the total amount of the monomers.
In a preferred embodiment of the invention, methacrylic acid- β -hydroxyethyl ester is used in place of acrylic acid- β -hydroxyethyl ester.
According to another technical scheme, the preparation method of the film-forming resin for the lithographic printing plate comprises the steps of mixing and dropwise adding monomers at a polymerization reaction temperature of 90-95 ℃, uniformly stirring at a rotating speed of more than 1000 rpm, reacting for 8-24 hours under the protection of nitrogen, cooling, pouring into water, separating out, and drying in vacuum.
The acid value of the acrylic resin composition is controlled to be 44-47.
The invention has the following beneficial effects: the film-forming resin has good alkali solubility and keeps better lipophilicity, wear resistance and chemical resistance. The film-forming resin prepared by the method can be used as an additive component of the film-forming resin for common lithographic printing plates and can also be used as a primer material of a double-layer coating plate for UV curing ink.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The film-forming resin for the lithographic printing plate is an acrylic resin composition, and is formed by polymerization reaction of three or more monomers, namely 6-10 parts of methacrylic acid, 15-35 parts of methyl methacrylate, 6-10 parts of acrylic acid, 20-40 parts of β -hydroxyethyl acrylate, 20-40 parts of β -hydroxyethyl methacrylate, 12-20 parts of acrylonitrile, 2-10 parts of acrylamide, 15-35 parts of ethyl methacrylate and 15-35 parts of butyl methacrylate.
The solvent for the polymerization reaction of the acrylic resin composition is one or a combination of any more of dioxane, ethylene glycol monoethyl ether and dimethylformamide, and the dosage of the solvent is 1-3 times of the total amount of the monomers.
The acrylic resin composition is also added with an initiator and a chain transfer agent. Selecting benzoyl peroxide as an initiator, wherein the dosage of the benzoyl peroxide is 0.5-1.5% of the total amount of the monomers; dodecyl mercaptan is selected as a chain transfer agent, and the using amount of the dodecyl mercaptan is 0.1-0.5% of the total amount of the monomers.
Methacrylic acid- β -hydroxyethyl ester is adopted to replace acrylic acid- β -hydroxyethyl ester, so that the impact resistance and chemical resistance of the resin can be improved, and the printing plate material is favorable for improving the printing resistance.
A preparation method of film-forming resin for lithographic printing plates comprises the steps of mixing and dropwise adding monomers at a polymerization reaction temperature of 90-95 ℃, uniformly stirring at a rotating speed of more than 1000 rpm, adopting nitrogen protection, reacting for 8-24 hours, cooling, pouring into water, separating out, and drying in vacuum. The obtained acrylic resin composition is titrated by potassium hydroxide-methanol standard solution, and the acid value is controlled to be 44-47.
The method comprises the steps of mixing and cleaning 5-10% of sodium hydroxide aqueous solution and a monomer in a ratio of 1: 1, standing, layering and separating, and then using the mixture.
Example one
Methacrylic acid: 20-30 g
Methyl methacrylate (alkaline wash): 100-110 g
120 g of acrylic acid- β -hydroxyethyl ester
Acrylonitrile: 40-60 g
Benzoyl peroxide: 1.5 g
Dodecyl mercaptan: 0.2-0.5 g
Dioxane: 400 g
Ethylene glycol monoethyl ether: 200 g
Adding 400 g of dioxane into a reactor, stirring, refluxing, heating and protecting with nitrogen, slowly dropwise adding a mixture of a monomer, an initiator, mercaptan and ethylene glycol monoethyl ether into the reactor at 90 ℃, wherein the time is 1.5-2 hours, and after dropwise adding, controlling the temperature to be 90-95 ℃ and reacting for 6 hours; stopping the reaction, cooling to room temperature, pouring the reaction solution into 10 liters of water under stirring, separating out a solid, filtering, washing with water, and drying at 40-45 ℃ in vacuum to obtain the film-forming resin.
Example two
Methacrylic acid: 20 g
Methyl methacrylate (alkaline wash): 100-120 g
Methacrylic acid β -hydroxyethyl ester 135-150 g
Acrylonitrile: 40-60 g
Benzoyl peroxide: 3.0 g
Dodecyl mercaptan: 0.2-0.5 g
Dioxane: 600 g
Adding 400 g of dioxane into a reactor, stirring, refluxing, heating and protecting with nitrogen, slowly dropwise adding a mixture of a monomer, an initiator, mercaptan and 200 g of dioxane into the reactor at 90 ℃, wherein the time is 1.5-2 hours, and after dropwise adding, controlling the temperature to be 90-95 ℃ and reacting for 6 hours; stopping the reaction, cooling to room temperature, pouring the reaction solution into 10 liters of water under stirring, separating out a solid, filtering, washing with water, and drying at 40-45 ℃ in vacuum to obtain the film-forming resin.
Example three
Methacrylic acid: 20-40 g
Ethyl methacrylate (alkaline wash): 100 g
40-70 g of methacrylic acid- β -hydroxyethyl ester
30-60 g of acrylic acid- β -hydroxyethyl ester
Acrylonitrile: 60 g
Benzoyl peroxide: 2.5 g
Dodecyl mercaptan: 0.2-0.5 g
Dioxane: 600 g
Adding 400 g of dioxane into a reactor, stirring, refluxing, heating and protecting with nitrogen, slowly dropwise adding a mixture of a monomer, an initiator, mercaptan and 200 g of dioxane into the reactor at 90 ℃, wherein the time is 1.5-2 hours, and after dropwise adding, controlling the temperature to be 90-95 ℃ and reacting for 8 hours; stopping the reaction, cooling to room temperature, pouring the reaction solution into 10 liters of water under stirring, separating out a solid, filtering, washing with water, and drying at 40-45 ℃ in vacuum to obtain the film-forming resin.
Example four
Ethyl methacrylate (alkaline wash): 40-50 g
Methyl methacrylate (alkaline wash): 50-60 g
135 g of methacrylic acid β hydroxyethyl ester
Acrylonitrile: 30-60 g
Acrylic acid: 5-10 g
Benzoyl peroxide: 3.5 g
Dodecyl mercaptan: 0.2-0.5 g
Dioxane: 600 g
Ethylene glycol monoethyl ether: 400 g
Adding 600 g of dioxane into a reactor, stirring, refluxing, heating and protecting with nitrogen, slowly dropwise adding a mixture of a monomer, an initiator, mercaptan and ethylene glycol monoethyl ether into the reactor at 90 ℃, wherein the time is 1.5-2 hours, and after dropwise adding, controlling the temperature to be 92-95 ℃ and reacting for 10 hours; stopping the reaction, cooling to room temperature, pouring the reaction solution into 10 liters of water under stirring, separating out a solid, filtering, washing with water, and drying at 40-45 ℃ in vacuum to obtain the film-forming resin.
Example five
Methacrylic acid: 40 g
Butyl methacrylate (alkaline wash): 150 g
30-50 g of methacrylic acid- β -hydroxyethyl ester
Acrylonitrile: 20 g
Acrylamide: 60-80 g
Benzoyl peroxide: 2.7 g
Dodecyl mercaptan: 0.2-0.5 g
Dimethylformamide (DMF): 800 g
Adding 600 g of Dimethylformamide (DMF) into a reactor, stirring, refluxing, heating and protecting with nitrogen, slowly dropwise adding a mixture of a monomer, an initiator, mercaptan and 200 g of DMF (DMF) into the reactor at 90 ℃, wherein the time is 1.5-2 hours, and after dropwise adding, the temperature is controlled to be 90-93 ℃ and the reaction is carried out for 8 hours; stopping the reaction, cooling to room temperature, pouring the reaction solution into 10 liters of water under stirring, separating out a solid, filtering, washing with water, and drying at 40-45 ℃ in vacuum to obtain the film-forming resin.
The reaction products were dissolved in Dimethylformamide (DMF) to prepare 10% solutions, and a small amount of dye, for example: crystal violet, alkali brilliant blue BO, etc. are filtered, coated on chemically and electrochemically treated aluminum plate base, stoved at 110 deg.c for 5 min and coated in 1.0 g/sq m. Alkali solubility, isopropanol resistance (50%), etc. were tested. The results are as follows:
note: the wear resistance test adopts special sealed rotating equipment, chemical and mechanical abrasive materials are added in the equipment, the wear resistance is judged according to the wear degree at fixed temperature and time, and A, A-, B +, B, B-and + C, C are respectively used for representing the wear resistance
The above-mentioned embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the scope of the invention, and therefore all equivalent variations made by the following claims should be included in the scope of the invention.
Claims (3)
1. The film-forming resin for the lithographic printing plate is characterized by being an acrylic resin composition, wherein the acrylic resin composition is prepared by polymerizing monomers of methacrylic acid, methyl methacrylate, β -hydroxyethyl acrylate and acrylonitrile, or methacrylic acid, methyl methacrylate, β -hydroxyethyl methacrylate and acrylonitrile, or methacrylic acid, ethyl methacrylate, β -hydroxyethyl methacrylate, β -hydroxyethyl acrylate and acrylonitrile, or ethyl methacrylate, methyl methacrylate, β -hydroxyethyl methacrylate, acrylonitrile and acrylic acid, or methacrylic acid, butyl methacrylate, β -hydroxyethyl methacrylate, acrylonitrile and acrylamide;
wherein, 6 to 10 parts of methacrylic acid, 15 to 35 parts of methyl methacrylate, 6 to 10 parts of acrylic acid, 20 to 40 parts of acrylic acid- β -hydroxyethyl ester, 20 to 40 parts of methacrylic acid- β -hydroxyethyl ester, 12 to 20 parts of acrylonitrile, 2 to 10 parts of acrylamide, 15 to 35 parts of ethyl methacrylate and 15 to 35 parts of butyl methacrylate;
wherein when the methyl methacrylate, the ethyl methacrylate and the butyl methacrylate are used, alkali water treatment is needed, a 5-10% sodium hydroxide aqueous solution and a monomer are mixed and cleaned in a ratio of 1: 1, and then the mixture is used after standing, layering and liquid separation;
wherein the solvent for the polymerization reaction of the acrylic resin composition is one or a combination of any more of dioxane, ethylene glycol monoethyl ether and dimethylformamide, and the dosage of the solvent is 1-3 times of the total amount of the monomers;
wherein, the acrylic resin composition is also added with an initiator and a chain transfer agent;
wherein the initiator is benzoyl peroxide, and the dosage of the initiator is 0.5-1.5% of the total amount of the monomers;
wherein the chain transfer agent is dodecyl mercaptan, and the dosage of the dodecyl mercaptan is 0.1-0.5% of the total amount of the monomers.
2. The method for preparing the film-forming resin for the lithographic printing plate as claimed in claim 1, wherein the method comprises the steps of mixing and dripping monomers at a polymerization reaction temperature of 90-95 ℃, uniformly stirring at a rotation speed of more than 1000 rpm, reacting for 8-24 hours under the protection of nitrogen, cooling, pouring into water, separating out, and drying in vacuum.
3. The method of claim 2, wherein the acrylic resin composition has an acid value of 44 to 47.
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| CN201610541687.9A CN107602761B (en) | 2016-07-11 | 2016-07-11 | Film-forming resin for lithographic printing plate and preparation method thereof |
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| CN201610541687.9A CN107602761B (en) | 2016-07-11 | 2016-07-11 | Film-forming resin for lithographic printing plate and preparation method thereof |
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| CN107602761B true CN107602761B (en) | 2020-05-29 |
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| US4025037A (en) * | 1973-11-10 | 1977-05-24 | Mitsubishi Denki Kabushiki Kaisha | Process for soldering an electrocoated substrate |
| CN101851316B (en) * | 2010-06-13 | 2012-06-13 | 东莞市英科水墨有限公司 | Alkali-soluble emulsion, preparation method thereof and application thereof in water-based ink |
| CN104861109B (en) * | 2014-02-24 | 2017-06-13 | 中国科学院理化技术研究所 | Have water-soluble and oil-soluble film-forming resin and its preparation method and application concurrently |
| CN104231148A (en) * | 2014-09-28 | 2014-12-24 | 张家港康得新光电材料有限公司 | Hydroxyl acrylic resin and preparation method thereof |
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Address after: 710077 No. 62 Hancheng South Road, Xijiao, Lianhu District, Xi'an City, Shaanxi Province Patentee after: Shaanxi Institute of Printing Science and Technology Co.,Ltd. Address before: 710077 No. 62 Hancheng South Road, Xijiao, Lianhu District, Xi'an City, Shaanxi Province Patentee before: SHAANXI ACADEMY OF PRINTING TECHNOLOGY |