CN114905877B - Negative CTP plate with heat-resistant protective layer and preparation method thereof - Google Patents
Negative CTP plate with heat-resistant protective layer and preparation method thereof Download PDFInfo
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- CN114905877B CN114905877B CN202210530555.1A CN202210530555A CN114905877B CN 114905877 B CN114905877 B CN 114905877B CN 202210530555 A CN202210530555 A CN 202210530555A CN 114905877 B CN114905877 B CN 114905877B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a negative CTP plate with a heat-resistant protective layer and a preparation method thereof, which belong to the technical field of printing, wherein an aluminum substrate is cleaned and dried, eugenol modified resin is coated on one side of the aluminum substrate, the aluminum substrate is solidified for 2-3 hours at 60 ℃, a layer of composite resin is coated after the aluminum substrate is cooled to room temperature, and the aluminum substrate is solidified for 2-3 hours at 80 ℃ to finish the coating of the heat-resistant protective layer; mixing nanoscale styrene, CTP infrared dye, an initiator and an antioxidant in proportion to obtain a photosensitive layer coating, and then coating the photosensitive layer coating on the surface of the heat-resistant protective layer to form a negative image CTP plate with the heat-resistant protective layer; the heat-resistant protective layer is arranged between the aluminum substrate and the photosensitive layer, the heat-resistant protective coating has thermal stability, good form and performance are still kept under the condition of 200 ℃, and the part remained after the development of the photosensitive layer is firmly adhered to the surface of the heat-resistant protective layer, so that the movement of the photosensitive layer is reduced, and the stability and printing quality of the plate are kept.
Description
Technical Field
The invention belongs to the technical field of printing, and particularly relates to an negative CTP plate with a heat-resistant protective layer and a preparation method thereof.
Background
Green environmental protection is one of the ideas of enterprise production, and CTP printing also gradually develops to the environmental protection direction. The environment-friendly CTP plate comprises a non-processing CTP plate, a non-chemical processing CTP plate and a low-chemical processing CTP plate, wherein the non-processing CTP plate refers to a CTP plate which is directly printed on a machine without flushing after being scanned and imaged by a computer direct plate-making machine; the CTP plate without chemical treatment is a CTP plate which is printed on the upper machine after being scanned and imaged by a computer-to-plate machine and is firstly washed and processed by water without chemicals; the low chemical treatment CTP plate is a CTP plate which is formed by scanning and imaging with a computer-to-plate machine, then is rinsed with a developing solution containing less chemicals than a conventional CTP plate developing solution, and then is printed on the machine.
Compared with the conventional common CTP plate, the environment-friendly CTP plate has low consumption and low pollution, but has poor printing performance, can generate higher heat after a large amount of printing, and the printing part on the plate material has cracks at high temperature to seriously influence the printing quality.
Disclosure of Invention
The invention aims to provide an negative CTP plate with a heat-resistant protective layer and a preparation method thereof, which are used for solving the problems in the background technology.
The aim of the invention can be achieved by the following technical scheme:
an negative CTP plate with a heat-resistant protective layer comprises an aluminum substrate, the heat-resistant protective layer and a photosensitive layer; wherein the heat-resistant protective layer comprises eugenol modified resin and composite resin; the photosensitive layer comprises nano-scale styrene, CTP infrared dye, initiator and antioxidant.
The preparation method of the eugenol modified resin comprises the following steps: adding eugenol into a flask at room temperature, continuously heating under the condition of magnetic stirring, wherein the heating rate is 5 ℃/min, and adding diphenylmethane bismaleimide step by step at the temperature of 130 ℃, continuously stirring to enable propenyl in eugenol and maleimide groups in the diphenylmethane bismaleimide to react with each other, pouring reactants into a mold after the reaction is finished, cooling to the room temperature, then placing the mold in an oven, and prepolymerizing for 2-3h at the temperature of 120 ℃ to obtain the eugenol modified resin.
The composite resin is prepared by the following steps:
step one: adding nano silicon dioxide powder into a flask, adding deionized water, dropwise adding ammonia water to adjust the pH value to 10, then performing ultrasonic dispersion for 15-20min, adding methyltriethoxysilane, continuing ultrasonic dispersion for 15-20min, drying in a constant temperature drying oven at 80 ℃, crushing, and sieving with a 300-mesh sieve to obtain hydrophobic nano silicon dioxide;
step two: dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl triethoxy silane, tetraethoxy silane, concentration of 1X 10 -3 Adding mol/L hydrochloric acid and isopropanol into a flask, and hydrolyzing and condensing for 12-16h at 30 ℃ to obtain a prepolymer;
step three: dissolving zirconium n-butoxide in isopropanol, adding acetylacetone as a chelating agent, stirring for reaction for 1-1.5h, then dripping into a prepolymer, and reacting for 6-8h at 30 ℃ to form a stable metal ligand with larger steric hindrance, thereby inhibiting self-hydrolytic condensation of zirconium n-butoxide; adding triethylamine to adjust the pH value to 7, and removing water and isopropanol by rotary evaporation at 50 ℃ to obtain zirconium silicon resin;
step four: adding hydrophobic nano silicon dioxide and butyl acetate into a flask, stirring for 15-20min at 1500-2000r/min, adding zirconium silicon resin and fluorocarbon resin, continuously stirring for 10min, and then adding hexamethylene diisocyanate, and stirring for 5min to obtain the composite resin.
The preparation method of the negative CTP plate with the heat-resistant protective layer comprises the following steps: soaking an aluminum substrate in an ethanol solution with the mass fraction of 75%, ultrasonically cleaning for 5-10min, and drying the aluminum substrate; coating a layer of eugenol modified resin on the surface of one side of an aluminum substrate, solidifying for 2-3 hours at 60 ℃, cooling to room temperature, coating a layer of composite resin, solidifying for 2-3 hours at 80 ℃, and finishing the coating of a heat-resistant protective layer; nanoscale styrene, CTP infrared dye, initiator and antioxidant were mixed according to 40g:20-24g:8-10g: mixing 6-8g of the materials in proportion to obtain a photosensitive layer coating, and then coating the photosensitive layer coating on the surface of the heat-resistant protective layer to form a negative pattern CTP plate with the heat-resistant protective layer.
Further, the ratio of eugenol to diphenylmethane bismaleimide was 9g:10g.
Further, the usage ratio of the silicon dioxide powder, the deionized water and the methyltriethoxysilane in the first step is 30g:100mL:5-7mL.
Further, the ratio of the amounts of dimethyldiethoxysilane, methylphenyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane, hydrochloric acid and isopropyl alcohol in step two was 44.7g:9.12g:14.9g:2.1g:333mL:100mL.
Further, the ratio of the amount of zirconium n-butoxide, isopropyl alcohol, acetylacetone and prepolymer used in the third step was 5.76g:25mL:3.5g:100g.
Further, the dosage ratio of the hydrophobic nano silicon dioxide, the butyl acetate, the zirconium silicone resin, the fluorocarbon resin and the hexamethylene diisocyanate in the fourth step is 5g:30g:8g:8g:4g.
Further, the initiator is potassium persulfate and triazine compound according to the following formula 1:2 mass ratio and mixing.
Further, the antioxidant is any one of butylated hydroxytoluene, dibutylhydroxytoluene and butylated hydroxyanisole.
The invention has the beneficial effects that:
the negative CTP plate of the invention is coated with a heat-resistant protective layer, and the heat-resistant protective layer comprises eugenol modified resin and composite resin; in the raw materials of the eugenol modified resin, the diphenylmethane bismaleimide has good heat resistance, and after the eugenol is modified, the crosslinking density and toughness are increased, so that the eugenol modified resin still has good adhesion effect at high temperature, the adhesive force between the eugenol modified resin and an aluminum substrate is increased, and the strength of the plate is increased; the composite resin contains hydrophobic nano silicon dioxide, zirconium silicon resin and fluorocarbon resin; the hydrophobic effect of the nano silicon dioxide is increased by the treatment of methyltriethoxysilane, and the hydrophobic property of the nano silicon dioxide can avoid the problem of unclear printing caused by the adsorption of water-based ink by the heat-resistant protective layer after the composite resin is coated on the surface of eugenol modified resin; the zirconium silicon resin and the fluorocarbon resin can increase the heat resistance and the bonding effect of the composite resin, and the addition of zirconium can increase the infrared refraction and the heat transfer, thereby being beneficial to improving the plate making rate.
The heat-resistant protective layer is arranged between the aluminum substrate and the photosensitive layer, the heat-resistant protective coating has thermal stability, good form and performance are still kept under the condition of 200 ℃, the part remained after the development of the photosensitive layer is firmly adhered to the surface of the heat-resistant protective layer, the movement of the photosensitive layer is reduced under the condition of high temperature, and the stability of the CTP plate and the definition of a printed product are kept.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the eugenol modified resin comprises the following steps:
900g of eugenol is added into a flask at room temperature, the temperature is continuously raised under the condition of magnetic stirring, the heating rate is 5 ℃/min, 1kg of diphenylmethane bismaleimide is added step by step at the temperature of 130 ℃, the stirring is continuously carried out to enable propenyl in the eugenol and maleimide groups in the diphenylmethane bismaleimide to react with each other, after the reaction is finished, the reactant is poured into a mould and cooled to the room temperature, and then the mould is placed into an oven to be prepolymerized for 2 hours under the condition of 120 ℃, so as to obtain the eugenol modified resin.
Example 2
The preparation method of the eugenol modified resin comprises the following steps:
900g of eugenol is added into a flask at room temperature, the temperature is continuously raised under the condition of magnetic stirring, the heating rate is 5 ℃/min, 1kg of diphenylmethane bismaleimide is added step by step at the temperature of 130 ℃, the stirring is continuously carried out to enable propenyl in the eugenol and maleimide groups in the diphenylmethane bismaleimide to react with each other, after the reaction is finished, the reactant is poured into a mould and cooled to the room temperature, and then the mould is placed into an oven to be prepolymerized for 2.5h under the condition of 120 ℃ to obtain the eugenol modified resin.
Example 3
The preparation method of the eugenol modified resin comprises the following steps:
900g of eugenol is added into a flask at room temperature, the temperature is continuously raised under the condition of magnetic stirring, the heating rate is 5 ℃/min, 1kg of diphenylmethane bismaleimide is added step by step at the temperature of 130 ℃, the stirring is continuously carried out to enable propenyl in the eugenol and maleimide groups in the diphenylmethane bismaleimide to react with each other, after the reaction is finished, the reactant is poured into a mould and cooled to the room temperature, and then the mould is placed into an oven to be prepolymerized for 3 hours under the condition of 120 ℃, so as to obtain the eugenol modified resin.
Example 4
Preparing composite resin, which comprises the following steps:
step one: adding 30g of nano silicon dioxide powder into a flask, then adding 100mL of deionized water, dropwise adding ammonia water to adjust the pH value to 10, then performing ultrasonic dispersion for 15min, adding 5mL of methyltriethoxysilane, continuing ultrasonic dispersion for 15min, drying in a constant temperature drying oven at 80 ℃, crushing, and sieving with a 300-mesh sieve to obtain hydrophobic nano silicon dioxide;
step two: 44.7g of dimethyldiethoxysilane, 9.12g of methylphenyldimethoxysilane, 14.9g of methyltriethoxysilane, 2.1g of tetraethoxysilane, 333mL of 1X 10 concentration -3 Adding mol/L hydrochloric acid and 100mL isopropanol into a flask, and hydrolyzing and condensing for 12 hours at 30 ℃ to obtain a prepolymer;
step three: dissolving 5.76g of zirconium n-butoxide in 25mL of isopropanol, adding 3.5 acetylacetone as a chelating agent, stirring and reacting for 1h, then dripping into 100g of prepolymer, and reacting for 6h at 30 ℃ to form a stable metal ligand with larger steric hindrance, and inhibiting self-hydrolytic condensation of zirconium n-butoxide; adding triethylamine to adjust the pH value to 7, and removing water and isopropanol by rotary evaporation at 50 ℃ to obtain zirconium silicon resin;
step four: 30g of hydrophobic nano silica and 180g of butyl acetate are added into a flask, stirring is carried out for 15min at 1500r/min, 48g of zirconium silicone resin and 48g of fluorocarbon resin are added, stirring is continued for 10min, and then 24g of hexamethylene diisocyanate is added, stirring is carried out for 5min, so that the composite resin is obtained.
Example 5
Preparing composite resin, which comprises the following steps:
step one: adding 30g of nano silicon dioxide powder into a flask, then adding 100mL of deionized water, dropwise adding ammonia water to adjust the pH value to 10, then performing ultrasonic dispersion for 18min, adding 6mL of methyltriethoxysilane, continuing ultrasonic dispersion for 18min, drying in a constant temperature drying oven at 80 ℃, crushing, and sieving with a 300-mesh sieve to obtain hydrophobic nano silicon dioxide;
step two: 44.7g of dimethyldiethoxysilane, 9.12g of methylphenyldimethoxysilane, 14.9g of methyltriethoxysilane, 2.1g of tetraethoxysilane, 333mL of 1X 10 concentration -3 Adding mol/L hydrochloric acid and 100mL isopropanol into a flask, and hydrolyzing and condensing for 14h at 30 ℃ to obtain a prepolymer;
step three: dissolving 5.76g of zirconium n-butoxide in 25mL of isopropanol, adding 3.5 acetylacetone as a chelating agent, stirring and reacting for 1.2h, then dripping into 100g of prepolymer, and reacting for 7h at 30 ℃ to form a stable metal ligand with larger steric hindrance and inhibit the autohydrolytic condensation of zirconium n-butoxide; adding triethylamine to adjust the pH value to 7, and removing water and isopropanol by rotary evaporation at 50 ℃ to obtain zirconium silicon resin;
step four: 30g of hydrophobic nano silica and 180g of butyl acetate are added into a flask, stirring is carried out for 18min under the condition of 1800r/min, 48g of zirconium silicon resin and 48g of fluorocarbon resin are added, stirring is continued for 10min, and then 24g of hexamethylene diisocyanate is added, stirring is carried out for 5min, so that the composite resin is obtained.
Example 6
Preparing composite resin, which comprises the following steps:
step one: adding 30g of nano silicon dioxide powder into a flask, then adding 100mL of deionized water, dropwise adding ammonia water to adjust the pH value to 10, then performing ultrasonic dispersion for 20min, adding 7mL of methyltriethoxysilane, continuing ultrasonic dispersion for 20min, drying in a constant temperature drying oven at 80 ℃, crushing, and sieving with a 300-mesh sieve to obtain hydrophobic nano silicon dioxide;
step two: 44.7g of dimethyldiethoxysilane, 9.12g of methylphenyldimethoxysilane, 14.9g of methyltriethoxysilane, 2.1g of tetraethoxysilane, 333mL of 1X 10 concentration -3 Adding mol/L hydrochloric acid and 100mL isopropanol into a flask, and hydrolyzing and condensing for 16h at 30 ℃ to obtain a prepolymer;
step three: dissolving 5.76g of zirconium n-butoxide in 25mL of isopropanol, adding 3.5 acetylacetone as a chelating agent, stirring and reacting for 1.5h, then dripping into 100g of prepolymer, and reacting for 8h at 30 ℃ to form a stable metal ligand with larger steric hindrance and inhibit the autohydrolytic condensation of zirconium n-butoxide; adding triethylamine to adjust the pH value to 7, and removing water and isopropanol by rotary evaporation at 50 ℃ to obtain zirconium silicon resin;
step four: 30g of hydrophobic nano silica and 180g of butyl acetate are added into a flask, stirring is carried out for 20min at 2000r/min, 48g of zirconium silicone resin and 48g of fluorocarbon resin are added, stirring is continued for 10min, and then 24g of hexamethylene diisocyanate is added, stirring is carried out for 5min, so that the composite resin is obtained.
Example 7
Preparing an negative CTP plate with a heat-resistant protective layer, which comprises the following steps:
mixing 10g of potassium persulfate and 20g of triazine compound to prepare an initiator; soaking an aluminum substrate in an ethanol solution with the mass fraction of 75%, ultrasonically cleaning for 5min, and drying the aluminum substrate; coating a layer of eugenol modified resin on the surface of one side of an aluminum substrate, curing for 2 hours at 60 ℃, cooling to room temperature, coating a layer of composite resin, and curing for 2 hours at 80 ℃ to finish the coating of a heat-resistant protective layer; nanoscale styrene, CTP infrared dye, initiator and butylhydroxytoluene were mixed according to 40g:20g:8g:6g of the materials are mixed according to the dosage ratio to obtain a photosensitive layer coating, and then the photosensitive layer coating is coated on the surface of the heat-resistant protective layer to form a negative pattern CTP plate with the heat-resistant protective layer.
Example 8
Preparing an negative CTP plate with a heat-resistant protective layer, which comprises the following steps:
mixing 10g of potassium persulfate and 20g of triazine compound to prepare an initiator; soaking an aluminum substrate in an ethanol solution with the mass fraction of 75%, ultrasonically cleaning for 8min, and drying the aluminum substrate; coating a layer of eugenol modified resin on the surface of one side of an aluminum substrate, curing for 2.5 hours at 60 ℃, cooling to room temperature, coating a layer of composite resin, curing for 2.5 hours at 80 ℃, and finishing the coating of a heat-resistant protective layer; nanoscale styrene, CTP infrared dye, initiator and dibutylhydroxytoluene were mixed according to 40g:22g:9g: and mixing the materials in an amount ratio of 7g to obtain a photosensitive layer coating, and then coating the photosensitive layer coating on the surface of the heat-resistant protective layer to form a negative pattern CTP plate with the heat-resistant protective layer.
Example 9
Preparing an negative CTP plate with a heat-resistant protective layer, which comprises the following steps:
mixing 10g of potassium persulfate and 20g of triazine compound to prepare an initiator; soaking an aluminum substrate in an ethanol solution with the mass fraction of 75%, ultrasonically cleaning for 10min, and drying the aluminum substrate; coating a layer of eugenol modified resin on the surface of one side of an aluminum substrate, curing for 3 hours at 60 ℃, cooling to room temperature, coating a layer of composite resin, and curing for 3 hours at 80 ℃ to finish the coating of a heat-resistant protective layer; nanoscale styrene, CTP infrared dye, initiator and butyl hydroxy anisole according to 40g:24g:10g:8g of the materials are mixed according to the dosage ratio to obtain a photosensitive layer coating, and then the photosensitive layer coating is coated on the surface of the heat-resistant protective layer to form a negative pattern CTP plate with the heat-resistant protective layer.
Comparative example 1: on the basis of example 9, the negative CTP plate was prepared without applying eugenol modified resin, with the remaining steps unchanged.
Comparative example 2: on the basis of example 9, the negative CTP plate was prepared without coating the composite resin, with the remaining steps remaining unchanged.
Comparative example 3: on the basis of example 9, the negative CTP plate was prepared without coating a heat-resistant protective layer, with the remaining steps remaining unchanged.
Performance tests were performed on the CTP plates prepared in examples 7 to 9 and comparative examples 1 to 3, and CTP plates prepared in examples 7 to 9 and comparative examples 1 to 3 were placed in an oven at 100 ℃, 200 ℃, 300 ℃ and 400 ℃ and the morphology of the CTP plates was observed at 10min, 30min and 60min, and the results are shown in table 1:
TABLE 1
As can be seen from table 1, CTP plates coated with the heat-resistant protective layer in examples 7 to 9 still have good morphology at 300 ℃ and have good heat-resistant effect.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. An negative CTP plate with a heat-resistant protective layer is characterized by comprising an aluminum substrate, the heat-resistant protective layer and a photosensitive layer; the heat-resistant protective layer comprises eugenol modified resin and composite resin; the photosensitive layer comprises nanoscale styrene, CTP infrared dye, an initiator and an antioxidant;
the composite resin is prepared by the following steps:
step one: adding dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl triethoxy silane, tetraethoxy silane, hydrochloric acid and isopropanol into a flask, and hydrolyzing and condensing for 12-16h at 30 ℃ to obtain a prepolymer;
step two: dissolving zirconium n-butoxide in isopropanol, adding acetylacetone, stirring for reacting for 1-1.5h, dripping into the prepolymer, and reacting at 30 ℃ for 6-8h; adding triethylamine to adjust the pH value to 7, and removing water and isopropanol by rotary evaporation at 50 ℃ to obtain zirconium silicon resin;
step three: adding hydrophobic nano silicon dioxide and butyl acetate into a flask, stirring for 15-20min at 1500-2000r/min, adding zirconium silicon resin and fluorocarbon resin, stirring for 10min, and then adding hexamethylene diisocyanate, stirring for 5min to obtain composite resin;
the preparation method of the eugenol modified resin comprises the following steps: adding eugenol into a flask at room temperature, magnetically stirring, heating at a speed of 5 ℃/min, adding diphenylmethane bismaleimide at a temperature of 130 ℃ for reaction, pouring into a mold for cooling after the reaction is finished, and then prepolymerizing for 2-3h at 120 ℃ to obtain the eugenol modified resin.
2. The negative CTP plate having a heat resistant protective layer according to claim 1, wherein the ratio of the amounts of dimethyldiethoxysilane, methylphenyldimethoxysilane, methyltriethoxysilane, tetraethoxysilane, hydrochloric acid and isopropyl alcohol used in step one is 44.7g:9.12g:14.9g:2.1g:333mL:100mL.
3. The negative CTP plate having a heat resistant protective layer according to claim 1, wherein the ratio of n-butoxyzirconium, isopropyl alcohol, acetylacetone and prepolymer in step two is 5.76g:25mL:3.5g:100g.
4. The negative CTP plate with heat-resistant protective layer according to claim 1, wherein the usage ratio of hydrophobic nano silica, butyl acetate, zirconium silicone resin, fluorocarbon resin and hexamethylene diisocyanate in step three is 5g:30g:8g:8g:4g.
5. The negative CTP plate with heat-resistant protective layer according to claim 1, wherein the preparation method of the nano silicon dioxide is as follows: adding nano silicon dioxide powder and deionized water into a flask, dropwise adding ammonia water to adjust the pH value to 10, performing ultrasonic dispersion for 15-20min, adding methyltriethoxysilane, continuing ultrasonic dispersion for 15-20min, drying, crushing, and sieving with a 300-mesh sieve to obtain the hydrophobic nano silicon dioxide.
6. The negative CTP plate with heat-resistant protective layer according to claim 1, wherein the ratio of eugenol to diphenylmethane bismaleimide is 9g:10g.
7. The negative CTP plate with heat resistant protective layer according to claim 1, wherein the initiator is potassium persulfate and triazine compound according to 1:2 mass ratio and mixing.
8. The negative CTP plate having a heat-resistant protective layer according to claim 1, wherein the antioxidant is any one of butylated hydroxytoluene, dibutylhydroxytoluene, butylated hydroxyanisole.
9. The method for preparing an negative CTP plate having a heat-resistant protective layer according to any one of claims 1 to 8, comprising the steps of:
cleaning and drying an aluminum substrate, coating eugenol modified resin on one side of the aluminum substrate, solidifying for 2-3 hours at 60 ℃, cooling to room temperature, coating a layer of composite resin, solidifying for 2-3 hours at 80 ℃, and finishing the coating of a heat-resistant protective layer; nanoscale styrene, CTP infrared dye, initiator and antioxidant were mixed according to 40g:20-24g:8-10g: mixing 6-8g of the materials in proportion to obtain a photosensitive layer coating, and then coating the photosensitive layer coating on the surface of the heat-resistant protective layer to form a negative pattern CTP plate with the heat-resistant protective layer.
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| CN113126437A (en) * | 2021-02-26 | 2021-07-16 | 上海宝士嘉印刷器材有限公司 | UV-resistant ink CTP imaging coating, UV-resistant ink CTP and preparation method thereof |
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| US4968762A (en) * | 1988-11-28 | 1990-11-06 | Mitsui Toatsu Chemicals, Inc. | Thermosetting-resin-forming composition from bis-maleimide and diallyl bis phenol |
| JP2007069560A (en) * | 2005-09-09 | 2007-03-22 | Konica Minolta Medical & Graphic Inc | Correction method and correction liquid for lithographic printing plate |
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