CN112457694A - Environment-friendly ultraviolet-curing non-silicon release agent, release film and preparation method thereof - Google Patents
Environment-friendly ultraviolet-curing non-silicon release agent, release film and preparation method thereof Download PDFInfo
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- 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
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- 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
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The invention discloses an environment-friendly ultraviolet curing non-silicon release agent, a release film and a preparation method thereof, wherein the environment-friendly ultraviolet curing non-silicon release agent comprises the following raw materials in parts by weight: 30-40 parts of a fluorine-containing acrylic prepolymer, 60-70 parts of acrylate resin, 5-10 parts of polymethyl methacrylate, 4-8 parts of fumaric acid, 4-6 parts of ultra-high molecular weight polyethylene, 2-6 parts of ultra-high molecular weight polyacrylamide, 15-25 parts of polyvinyl alcohol, 2-10 parts of inorganic particles, 1.2-1.6 parts of a fluorine-containing additive, 3-5 parts of a leveling agent, 2-8 parts of a photoinitiator and 60-80 parts of an organic solvent. The release coating formed by coating the environment-friendly ultraviolet curing non-silicon release agent is environment-friendly and degradable, and has good corrosion resistance and adhesion, and is hydrophobic and oleophobic.
Description
Technical Field
The invention relates to the technical field of release materials, in particular to an environment-friendly ultraviolet curing non-silicon release agent, a release film prepared from the non-silicon release agent and a preparation method of the release film.
Background
The release material is a functional thin film material with low surface energy obtained by coating a special chemical coating on the surface of a base material and drying or ultraviolet curing. The organic silicone oil type release agent is a release material which is commonly applied at present, and is widely applied to pressure-sensitive adhesive tapes, waterproof materials, PCB manufacturing, automobile mould pressing material manufacturing and electronic communication industries, but along with the fact that the product requirements of the electronic industry are higher and higher, particularly in the field of FPC (flexible printed circuit), the release agent is extremely sensitive to silicon elements, and the silicon elements easily cause the risks of poor electronic products or short circuit. At present, the environment-friendly requirement of the electronic manufacturing industry on materials is higher and higher, most of the traditional organic silicon release materials take plastic films such as PET, PP, PE and the like as base materials, although the materials have excellent performance, a large amount of volatile solvents such as toluene and the like are required to be applied during the processing of the traditional oily release agent, and silicon element is not easy to degrade and can not meet the requirements of environment protection and degradation.
Disclosure of Invention
The invention aims to solve the technical problem of providing an environment-friendly ultraviolet curing non-silicon release agent.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides an environment-friendly ultraviolet curing non-silicon release agent, which comprises the following raw materials in parts by weight:
further, the monomer of the fluorine-containing acrylic prepolymer is at least one selected from fluorine-containing methyl acrylate, fluorine-containing ethyl acrylate, fluorine-containing n-butyl acrylate, fluorine-containing methyl methacrylate and fluorine-containing n-butyl methacrylate.
Further, the acrylate resin is obtained by free radical polymerization of methyl methacrylate and an acrylate functional monomer;
wherein the acrylate functional monomer is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, cyclohexyl methacrylate, 2-methoxyethyl acrylate, 3-ethoxyethyl acrylate and 2-phenoxyethyl acrylate.
Preferably, the mass ratio of the methyl methacrylate to the acrylate functional monomer is (0.8-0.9): 1.
further, the molecular weight of the ultra-high molecular weight polyethylene is preferably 100 to 150 ten thousand, and the molecular weight of the ultra-high molecular weight polyacrylamide is preferably 1800 to 2000 ten thousand.
Further, the polymerization degree of the polyvinyl alcohol is preferably 1700-1800, and the alcoholysis degree is preferably 85-89%.
Further, the inorganic particles are a mixture of barium titanate and at least one of nano alumina, nano silica and nano zinc oxide;
among them, it is preferable that the mass ratio of barium titanate in the inorganic particles is not more than 5%.
Further, the particle sizes of the nano aluminum oxide, the nano silicon dioxide and the nano zinc oxide are preferably 1-100 nm;
the particle size of the barium titanate is preferably 300-500 nm.
Further, the fluorine-containing auxiliary agent is at least one selected from tetrafluoroethylene polymer, hexafluoropropylene oxide polymer and vinylidene fluoride polymer.
Further, the leveling agent comprises an acrylate leveling agent and an organic silicon polyether leveling agent;
wherein, in the leveling agent, the mass ratio of the acrylate leveling agent is preferably not less than 25%.
Further, the photoinitiator is at least one selected from 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholinyl-1-acetone, 2,4, 6-trimethyl phenyl formyl-diphenyl phosphine oxide, tolidine and 2-hydroxy-2-methyl phenyl propane-1-ketone;
further, the organic solvent is a mixture of a ketone solvent and an ester solvent, wherein the volume ratio of the ketone solvent to the ester solvent is 1 (1.5-2.5).
The invention provides an environment-friendly ultraviolet light curing non-silicon release film, which comprises a base material and a release coating arranged on the base material, wherein the release coating is formed by coating the environment-friendly ultraviolet light curing non-silicon release agent of the first aspect on the base material.
Further, the substrate is a biaxially oriented polylactic acid (BOPLA) film. The BOPLA film is a film layer which is biaxially stretched by using polylactic acid (PLA) as a raw material, has good biocompatibility and degradability, and simultaneously has excellent optical characteristics, mechanical characteristics and stretchability.
Further, the preparation method of the BOPLA film comprises the following steps:
drying the polylactic acid resin at 80 ℃ for 5h under a vacuum condition, then mixing the polylactic acid resin with polybutylene carbonate, an antioxidant and an inorganic filler, putting the mixed block material into a double-screw extruder for processing, and stretching longitudinally and transversely to obtain the BOPLA film.
Further, the BOPLA is subjected to bidirectional stretching by the following steps:
the melting temperature of a die head of the main extruder is 220 ℃ and 230 ℃; longitudinal stretching is firstly carried out, the temperature of a preheating zone is 40-75 ℃, the temperature of a stretching zone is 60-80 ℃, the longitudinal stretching multiple is 2.5-3.5 times, and the temperature is cooled to 15-35 ℃; then transversely stretching, wherein the temperature of a preheating zone is 50-120 ℃, the temperature of a stretching zone is 60-130 ℃, the temperature of a setting zone is 100-; and (3) drawing the heat-set film to a thickness gauge through a drawing device, adding a dust adsorption device at an inlet of a drawing position to perform dust absorption treatment on the film, performing corona or flame treatment on the upper surface and the lower surface of the film to enable the surface tension to reach 38-42mN/m, and cooling to obtain the BOPLA film.
The third aspect of the invention provides a preparation method of an environment-friendly ultraviolet curing non-silicon release film, which comprises the following steps:
(1) mixing 60-70 parts by weight of acrylate resin, 30-40 parts by weight of a fluorine-containing acrylic prepolymer, 5-10 parts by weight of polymethyl methacrylate, 4-8 parts by weight of fumaric acid, 4-6 parts by weight of ultra-high molecular weight polyethylene, 2-6 parts by weight of ultra-high molecular weight polyacrylamide, 15-25 parts by weight of polyvinyl alcohol, 2-10 parts by weight of inorganic particles, 1.2-1.6 parts by weight of a fluorine-containing auxiliary agent, 3-5 parts by weight of a leveling agent and 60-80 parts by weight of an organic solvent, and stirring at 30-40 ℃ for 20-40 minutes to obtain a premix;
(2) cooling the premix prepared in the step (1) to 10-15 ℃, adding 2-8 parts by weight of a photoinitiator under the condition of isolating ultraviolet rays, heating to 23-25 ℃, and stirring for 20-40 minutes to obtain a coating composition;
(3) providing a base material, coating the coating composition prepared in the step (2) on the base material, and performing infrared leveling and ultraviolet irradiation curing to obtain the environment-friendly ultraviolet curing non-silicon release film.
Further, the coating composition is coated by adopting a mode of micro-gravure coating, three-roller/five-roller rotary coating, slit extrusion coating or mesh roller coating, and the wet coating amount is 5-10g/m2The baking temperature after coating is 80-130 ℃, the baking time is 30-60s, and the UV light energy is 300-2。
Further, the infrared leveling temperature is 45-55 ℃, and the infrared leveling time is 8-12 minutes.
The invention has the beneficial effects that:
1. the environment-friendly ultraviolet curing non-silicon release agent provided by the invention comprises fluorine-containing acrylic prepolymer, acrylate resin, polymethyl methacrylate, fumaric acid, ultra-high molecular weight polyethylene, ultra-high molecular weight polyacrylamide, polyvinyl alcohol, inorganic particles, a fluorine-containing assistant, a leveling agent and a photoinitiator, wherein the acrylate resin has better transparency and weather resistance, and forms a non-silicon release coating substrate after photocuring, the acrylate resin is taken as a main molecule, the polymethyl methacrylate, the ultra-high molecular weight polyethylene and the ultra-high molecular weight polyacrylamide are added, the polymethyl methacrylate and the ultra-high molecular weight polyacrylamide form hydrogen bonds, the crosslinking density of the non-silicon release coating is greatly increased, the corrosion resistance of the non-silicon release coating to acid, alkali and salt is improved, and the non-silicon release coating has good adhesion performance (the release force is more than 400g), the defects that the conventional non-silicon release coating prepared only by acrylate resin has insufficient toughness, poor adhesion performance, large volume shrinkage rate in the photocuring process, coating curling and the like are avoided; under the action of polyvinyl alcohol, inorganic particles are uniformly distributed in the non-silicon release coating and are matched with polymethyl methacrylate, so that the thermal stability of the non-silicon release coating is improved; the fumaric acid contains more double bonds, and is matched with polymethyl methacrylate, ultra-high molecular weight polyethylene and ultra-high molecular weight polyacrylamide, so that the heat resistance of the non-silicon release coating is enhanced.
Meanwhile, the fluorine-containing acrylic prepolymer is polymerized under the action of a photoinitiator, fluorine floats on the surface of the environment-friendly ultraviolet-curing non-silicon release material coating, and a fluorine-containing auxiliary agent is added, so that the environment-friendly ultraviolet-curing non-silicon release material coating has super-strong and lasting hydrophobic and oleophobic properties, and can keep stable high water drop contact angle (larger than or equal to 105 ℃) and release effect even after being scraped.
2. The environment-friendly ultraviolet curing non-silicon release agent provided by the invention adopts the acrylate leveling agent and the organic silicon polyether leveling agent to be compounded, so that the leveling property of the coating composition in the preparation of the non-silicon release coating is improved, the smoothness and the wear resistance of the surface of the non-silicon release coating can be improved, and the hydrophobicity can be further improved.
3. The preparation method of the environment-friendly ultraviolet curing non-silicon release film adopts a coating production mode, reduces the using amount of the coating composition and reduces the cost of raw materials; the production efficiency is improved and the production cost is reduced by adopting photocuring.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
The embodiment provides an environment-friendly ultraviolet curing non-silicon release film, which comprises a substrate and a non-silicon release coating which is arranged on the substrate and formed by coating an environment-friendly ultraviolet curing non-silicon release agent.
The environment-friendly ultraviolet curing non-silicon release agent comprises the following raw materials in parts by weight:
the substrate is a BOPLA film.
The monomer of the fluorine-containing acrylic prepolymer is a mixture of fluorine-containing methyl acrylate and fluorine-containing ethyl acrylate, wherein the mass ratio of the fluorine-containing methyl acrylate to the fluorine-containing ethyl acrylate is 1:1.
The acrylate resin is obtained by free radical polymerization of methyl methacrylate and an acrylate functional monomer according to the mass ratio of 0.85: 1; wherein the selected acrylate functional monomer is acrylic acid and methacrylic acid, and the mass ratio of the acrylic acid to the methacrylic acid is 1:1.
The molecular weight of the ultra-high molecular weight polyethylene is 120-130 ten thousand; the molecular weight of the ultrahigh molecular weight polyacrylamide is 1875-1925 ten thousand.
The polymerization degree of the polyvinyl alcohol was 1750 and the alcoholysis degree was 87%.
The inorganic particles are a mixture of nano aluminum oxide and barium titanate; wherein the particle size of the nano alumina is 1nm, the particle size of the barium titanate is 300nm, and the mass ratio of the nano alumina to the barium titanate is 97: 3.
The fluorine-containing auxiliary agent is tetrafluoroethylene polymer.
The leveling agent is a commercially available acrylate leveling agent and an organic silicon polyether leveling agent; wherein the mass ratio of the acrylate leveling agent to the organic silicon leveling agent is 30: 70. The water drop contact angle of the prepared environment-friendly ultraviolet curing type non-silicon release material film is smaller without adding an acrylate leveling agent; when the addition amount of the acrylate leveling agent is less than 25%, the leveling effect is not obvious.
The photoinitiator is 1-hydroxycyclohexyl phenyl ketone.
The organic solvent is a mixture of a ketone solvent and an ester solvent, wherein the ketone solvent is butanone, the ester solvent is ethyl acetate, and the mass ratio of the butanone to the ethyl acetate is 1: 1.5.
The invention also provides a method for preparing the environment-friendly ultraviolet curing non-silicon release film by adopting the raw materials, which comprises the following steps:
(1) mixing methyl methacrylate, acrylic acid and methacrylic acid according to the mass ratio of 0.85:0.075:0.075, and polymerizing to obtain acrylate resin;
(2) mixing 65 parts by weight of acrylate resin prepared in the step (1), 17.5 parts by weight of fluorine-containing methyl acrylate, 17.5 parts by weight of fluorine-containing ethyl acrylate, 7.5 parts by weight of polymethyl methacrylate, 6 parts by weight of fumaric acid, 5 parts by weight of ultra-high molecular weight polyethylene, 4 parts by weight of ultra-high molecular weight polyacrylamide, 20 parts by weight of polyvinyl alcohol, 5.82 parts by weight of nano alumina, 0.18 part by weight of barium titanate, 1.4 parts by weight of tetrafluoroethylene polymer, 1.2 parts by weight of acrylate leveling agent, 2.8 parts by weight of organic silicon polyether leveling agent, 25.5 parts by weight of butanone and 44.5 parts by weight of ethyl acetate, and stirring for 30 minutes at 35 ℃ to obtain a premix;
(3) cooling the premix prepared in the step (2) to 12 ℃, adding 6 parts by weight of 1-hydroxycyclohexyl phenyl ketone under the condition of isolating ultraviolet rays, heating to 24 ℃, and stirring for 30 minutes to obtain a coating composition;
(4) providing a BOPLA film, coating the coating composition prepared in the step (3) on a base material PET film, leveling for 10 minutes at 50 ℃ in an infrared mode, and then placing the PET film under ultraviolet light for irradiation and curing, wherein the dosage is 340mj/cm2Obtaining the environment-friendly ultraviolet curing non-silicon release film;
wherein the coating amount of the coating composition on the PET film is 4.0g/m2。
Through detection, the contact angle of a water drop of the environment-friendly ultraviolet curing non-silicon release film is 112 degrees, and the release force is 18 g.
Example 2
The embodiment provides an environment-friendly ultraviolet curing non-silicon release film, which comprises a substrate and a non-silicon release coating which is arranged on the substrate and formed by coating an environment-friendly ultraviolet curing non-silicon release agent.
The environment-friendly ultraviolet curing non-silicon release agent comprises the following raw materials in parts by weight:
the substrate is a BOPLA film.
The monomer of the fluorine-containing acrylic prepolymer is fluorine-containing n-butyl acrylate.
The acrylate resin is obtained by free radical polymerization of methyl methacrylate and an acrylate functional monomer according to the mass ratio of 0.8: 1; wherein the selected acrylate functional monomer is hydroxyethyl acrylate, hydroxypropyl acrylate, cyclohexyl methacrylate, 2-methoxyethyl acrylate and 3-ethoxy ethyl acrylate, and the mass ratio of the hydroxyethyl acrylate, the hydroxypropyl acrylate, the cyclohexyl methacrylate, the 2-methoxyethyl acrylate and the 3-ethoxy ethyl acrylate is 1:1:1: 1.
The molecular weight of the ultra-high molecular weight polyethylene is 100-120 ten thousand; the molecular weight of the ultrahigh molecular weight polyacrylamide is 1800-1875 ten thousand.
The polyvinyl alcohol had a degree of polymerization of 1700 and a degree of alcoholysis of 89%.
The inorganic particles are a mixture of nano-alumina, nano-silica and barium titanate; wherein the particle size of the nano aluminum oxide is 50nm, the particle size of the nano silicon dioxide is 50nm, the particle size of the barium titanate is 400nm, and the mass ratio of the nano aluminum dioxide to the nano silicon dioxide to the barium titanate is 49:49: 2.
The fluorine-containing assistant is hexafluoropropylene polymer and hexafluoropropylene oxide polymer, wherein the mass ratio of the hexafluoropropylene polymer to the hexafluoropropylene oxide polymer is 1:1.
The leveling agent is a commercially available acrylate leveling agent and an organic silicon polyether leveling agent; wherein the mass ratio of the acrylate leveling agent to the organic silicon leveling agent is 50: 50. The water drop contact angle of the prepared environment-friendly ultraviolet curing type non-silicon release material film is smaller without adding an acrylate leveling agent; when the addition amount of the acrylate leveling agent is less than 25%, the leveling effect is not obvious.
The photoinitiator is 2-methyl-1- (4-methylmercaptophenyl) -2-morpholinyl-1-acetone, 2,4, 6-trimethylphenylformyl-diphenylphosphine oxide and 2-hydroxy-2-methylphenylpropane-1-ketone, wherein the mass ratio of the 2-methyl-1- (4-methylmercaptophenyl) -2-morpholinyl-1-acetone, the 2,4, 6-trimethylphenylformyl-diphenylphosphine oxide and the 2-hydroxy-2-methylphenylpropane-1-ketone is 3:3: 4.
The organic solvent is a mixture of a ketone solvent and an ester solvent, wherein the ketone solvent is methyl ethyl ketone, the ester solvent is butyl acetate, and the mass ratio of the methyl ethyl ketone to the butyl acetate is 1:2.
The invention also provides a method for preparing the environment-friendly ultraviolet curing non-silicon release film by adopting the raw materials, which comprises the following steps:
(1) mixing methyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, cyclohexyl methacrylate, 2-methoxyethyl acrylate and 3-ethoxyethyl acrylate according to the mass ratio of 0.8:0.02:0.02:0.02:0.02:0.02 to 0.02, and polymerizing to obtain acrylate resin;
(2) mixing 60 parts by weight of acrylate resin prepared in the step (1), 40 parts by weight of fluorine-containing n-butyl acrylate, 5 parts by weight of polymethyl methacrylate, 4 parts by weight of fumaric acid, 4 parts by weight of ultra-high molecular weight polyethylene, 2 parts by weight of ultra-high molecular weight polyacrylamide, 25 parts by weight of polyvinyl alcohol, 4.9 parts by weight of nano alumina, 4.9 parts by weight of nano silica, 0.2 part by weight of barium titanate, 0.8 part by weight of hexafluoropropylene polymer, 0.8 part by weight of hexafluoropropylene oxide polymer, 2.5 parts by weight of acrylate leveling agent, 2.5 parts by weight of organic silicon polyether leveling agent, 20 parts by weight of methyl ethyl ketone and 40 parts by weight of butyl acetate, and stirring at 30 ℃ for 40 minutes to obtain a premix;
(3) cooling the premix prepared in the step (2) to 10 ℃, adding 0.6 part by weight of 2-methyl-1- (4-methylmercaptophenyl) -2-morpholinyl-1-acetone, 0.6 part by weight of 2,4, 6-trimethylphenylformyl-diphenylphosphine oxide and 0.8 part by weight of 2-hydroxy-2-methylphenylpropane-1-one under the condition of isolating ultraviolet rays, heating to 23 ℃, and stirring for 40 minutes to obtain a coating composition;
(4) providing a PE film, coating the coating composition prepared in the step (3) on a BOPLA film as a base material, leveling for 12 minutes at 55 ℃ in an infrared mode, and then placing the BOPLA film under ultraviolet light for irradiation and curing, wherein the dosage is 350mj/cm2Obtaining the environment-friendly ultraviolet curing non-silicon release film;
wherein the coating amount of the coating composition on the PE film is 4.5g/m2。
Through detection, the contact angle of a water drop of the environment-friendly ultraviolet curing non-silicon release film is 115 degrees, and the release force is 15 g.
Example 3
The embodiment provides an environment-friendly ultraviolet curing non-silicon release film, which comprises a substrate and a non-silicon release coating which is arranged on the substrate and formed by coating an environment-friendly ultraviolet curing non-silicon release agent.
The environment-friendly ultraviolet curing non-silicon release agent comprises the following raw materials in parts by weight:
the substrate is a BOPLA film.
The monomer of the fluorine-containing acrylic prepolymer is a mixture of fluorine-containing methyl methacrylate and fluorine-containing n-butyl methacrylate, wherein the mass ratio of the fluorine-containing methyl methacrylate to the fluorine-containing n-butyl methacrylate is 1:1.
The acrylate resin is obtained by free radical polymerization of methyl methacrylate and an acrylate functional monomer according to the mass ratio of 0.9: 1; wherein the selected acrylate functional monomer is 2-phenoxyethyl acrylate.
The molecular weight of the ultra-high molecular weight polyethylene is 130-150 ten thousand; the molecular weight of the ultra-high molecular weight polyacrylamide is 1925-2000 ten thousand.
The polyvinyl alcohol had a polymerization degree of 1800 and an alcoholysis degree of 85%.
The inorganic particles are a mixture of nano zinc oxide and barium titanate; wherein the particle size of the nano zinc oxide is 100nm, the particle size of the barium titanate is 500nm, and the mass ratio of the nano zinc oxide to the barium titanate is 99: 1.
The fluorine-containing auxiliary agent is a difluoroethylene polymer.
The leveling agent is a commercially available acrylate leveling agent and an organic silicon polyether leveling agent; wherein the mass ratio of the acrylate leveling agent to the organic silicon leveling agent is 25: 75. The water drop contact angle of the prepared environment-friendly ultraviolet curing type non-silicon release material film is smaller without adding an acrylate leveling agent; when the addition amount of the acrylate leveling agent is less than 25%, the leveling effect is not obvious.
The photoinitiator is xylene ketone.
The organic solvent is a mixture of a ketone solvent and an ester solvent, wherein the ketone solvent is cyclohexanone, the ester solvent is ethyl acetate, and the mass ratio of the cyclohexanone to the ethyl acetate is 1: 2.5.
The invention also provides a method for preparing the environment-friendly ultraviolet curing non-silicon release film by adopting the raw materials, which comprises the following steps:
(1) mixing methyl methacrylate and 2-phenoxyethyl acrylate according to the mass ratio of 0.9:0.1, and polymerizing to obtain acrylate resin;
(2) mixing 70 parts by weight of acrylate resin prepared in the step (1), 15 parts by weight of fluorine-containing methyl methacrylate, 15 parts by weight of fluorine-containing n-butyl methacrylate, 10 parts by weight of polymethyl methacrylate, 8 parts by weight of fumaric acid, 6 parts by weight of ultra-high molecular weight polyethylene, 6 parts by weight of ultra-high molecular weight polyacrylamide, 15 parts by weight of polyvinyl alcohol, 1.98 parts by weight of nano zinc oxide, 0.02 part by weight of barium titanate, 1.2 parts by weight of a difluoroethylene polymer, 0.75 part by weight of an acrylate leveling agent, 2.25 parts by weight of an organic silicon polyether leveling agent, 24.6 parts by weight of cyclohexanone and 61.4 parts by weight of ethyl acetate, and stirring at 40 ℃ for 20 minutes to obtain a premix;
(3) cooling the premix prepared in the step (2) to 15 ℃, adding 8 parts by weight of tolidine under the condition of isolating ultraviolet rays, heating to 25 ℃, and stirring for 30 minutes to obtain a coating composition;
(4) providing a BOPLA film, coating the coating composition prepared in the step (3) on a substrate BOPLA film, leveling for 8 minutes at 45 ℃ in an infrared mode, and then placing the BOPLA film under ultraviolet light for irradiation and curing, wherein the dosage is 330mj/cm2Obtaining the environment-friendly ultraviolet curing non-silicon release film;
wherein the coating weight of the coating composition on the BOPLA film is 3.5g/m2。
Through detection, the contact angle of a water drop of the environment-friendly ultraviolet curing non-silicon release film is 110 degrees, and the release force is 20 g.
Comparative example 1
The comparative example provides an environment-friendly ultraviolet-curable non-silicon release film, which is different from example 1 in that the raw materials of the prepared non-silicon release agent coating composition do not comprise polymethyl methacrylate, ultra-high molecular weight polyethylene and ultra-high molecular weight polyacrylamide.
Through detection, the contact angle of a water drop of the environment-friendly ultraviolet curing non-silicon release film is 120 degrees, and the release force is 10 g.
Comparative example 2
The comparative example provides an environment-friendly ultraviolet-curable non-silicon release film, which is different from example 1 in that the raw materials of the prepared non-silicon release agent coating composition do not comprise fluorine-containing acrylic prepolymer, fluorine-containing auxiliary agent and leveling agent.
Through detection, the contact angle of a water drop of the environment-friendly ultraviolet curing non-silicon release film is 93 degrees, and the release force is 50 g.
The test data of the environmentally friendly uv-curable non-silicon release material film prepared in examples 1 to 3 and comparative examples 1 to 2 are listed as follows:
TABLE 1 Performance parameters of non-silicon release films prepared in examples 1-3 and comparative examples 1-2
| Contact angle of water drop | Force of separation | |
| Example 1 | 112° | 18g |
| Example 2 | 115° | 15g |
| Example 3 | 110° | 20g |
| Comparative example 1 | 120° | 10g |
| Comparative example 2 | 93° | 50g |
As shown in table 1, the ratio of the raw materials of polymethyl methacrylate, ultra-high molecular weight polyethylene, and ultra-high molecular weight polyacrylamide in example 3 is greater than the ratio of the raw materials of polymethyl methacrylate, ultra-high molecular weight polyethylene, and ultra-high molecular weight polyacrylamide in examples 1 and 2, and therefore, the non-silicon release film prepared by using the method has better adhesion performance and larger release force; in comparative example 1, no polymethyl methacrylate, ultra-high molecular weight polyethylene, or ultra-high molecular weight polyacrylamide was added, and the adhesion property was the worst, and the release force was rapidly decreased. Therefore, the polymethyl methacrylate, the ultra-high molecular weight polyethylene and the ultra-high molecular weight polyacrylamide are beneficial to improving the adhesion performance of the non-silicon release film and adjusting the release force.
As can be seen from table 1, the ratio of the raw materials of the fluorine-containing acrylic prepolymer, the fluorine-containing auxiliary agent and the leveling agent in example 2 is greater than the ratio of the raw materials of the fluorine-containing acrylic prepolymer, the fluorine-containing auxiliary agent and the leveling agent in examples 1 and 3, and therefore, the contact angle of the non-silicon release film prepared by using the method is larger; in comparative example 2, the contact angle of water drops was the smallest without adding a fluorine-containing acrylic prepolymer, a fluorine-containing auxiliary agent, and a leveling agent. Therefore, the fluorine-containing acrylic prepolymer, the fluorine-containing auxiliary agent and the leveling agent are beneficial to improving the hydrophobic property of the non-silicon release film and increasing the contact angle of water drops.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The environment-friendly ultraviolet curing non-silicon release agent is characterized by comprising the following raw materials in parts by weight:
2. the environment-friendly ultraviolet-curable non-silicon release agent as claimed in claim 1, wherein the monomer of the fluorine-containing acrylic prepolymer is at least one selected from fluorine-containing methyl acrylate, fluorine-containing ethyl acrylate, fluorine-containing n-butyl acrylate, fluorine-containing methyl methacrylate and fluorine-containing n-butyl methacrylate.
3. The environment-friendly ultraviolet-curing non-silicon release agent as claimed in claim 1, wherein the acrylate resin is obtained by free radical polymerization of methyl methacrylate and acrylate functional monomers;
wherein the acrylate functional monomer is at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, cyclohexyl methacrylate, 2-methoxyethyl acrylate, 3-ethoxyethyl acrylate and 2-phenoxyethyl acrylate;
the mass ratio of the methyl methacrylate to the acrylate functional monomer is (0.8-0.9): 1.
4. the environment-friendly ultraviolet-curing non-silicon release agent as claimed in claim 1, wherein the molecular weight of the ultra-high molecular weight polyethylene is 100 to 150 ten thousand; the molecular weight of the ultrahigh molecular weight polyacrylamide is 1800-2000 ten thousand; the polymerization degree of the polyvinyl alcohol is 1700-1800, and the alcoholysis degree of the polyvinyl alcohol is 85-89%.
5. The environment-friendly ultraviolet-curing non-silicon release agent as claimed in claim 1, wherein the inorganic particles are a mixture of barium titanate and at least one of nano alumina, nano silica and nano zinc oxide; wherein, in the inorganic particles, the mass ratio of barium titanate is not more than 5%;
the particle sizes of the nano aluminum oxide, the nano silicon dioxide and the nano zinc oxide are all 1-100 nm; the particle size of the barium titanate is 300-500 nm.
6. The environment-friendly ultraviolet-curable non-silicon release agent according to claim 1, wherein the fluorine-containing auxiliary agent is at least one selected from tetrafluoroethylene polymer, hexafluoropropylene oxide polymer, and vinylidene fluoride polymer;
the leveling agent comprises an acrylate leveling agent and an organic silicon polyether leveling agent; wherein, in the leveling agent, the mass ratio of the acrylate leveling agent is not less than 25%.
7. The environment-friendly UV-curable non-silicon release agent according to claim 1, wherein the photoinitiator is at least one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylmercapto phenyl) -2-morpholinyl-1-propanone, 2,4, 6-trimethylphenyl formyl-diphenyl phosphine oxide, tolidine ketone, 2-hydroxy-2-methylphenyl propane-1-one;
the organic solvent is a mixture of a ketone solvent and an ester solvent, wherein the volume ratio of the ketone solvent to the ester solvent is 1 (1.5-2.5).
8. An environment-friendly ultraviolet-curable non-silicon release film, which is characterized by comprising a substrate and a release coating arranged on the substrate, wherein the release coating is formed by coating the environment-friendly ultraviolet-curable non-silicon release agent as defined in any one of claims 1 to 10 on the substrate.
9. The method for preparing the environment-friendly ultraviolet curing non-silicon release film according to claim 8, characterized by comprising the following steps:
(1) mixing 60-70 parts by weight of acrylate resin, 30-40 parts by weight of a fluorine-containing acrylic prepolymer, 5-10 parts by weight of polymethyl methacrylate, 4-8 parts by weight of fumaric acid, 4-6 parts by weight of ultra-high molecular weight polyethylene, 2-6 parts by weight of ultra-high molecular weight polyacrylamide, 15-25 parts by weight of polyvinyl alcohol, 2-10 parts by weight of inorganic particles, 1.2-1.6 parts by weight of a fluorine-containing auxiliary agent, 3-5 parts by weight of a leveling agent and 60-80 parts by weight of an organic solvent, and stirring at 30-40 ℃ for 20-40 minutes to obtain a premix;
(2) cooling the premix prepared in the step (1) to 10-15 ℃, adding 2-8 parts by weight of a photoinitiator under the condition of isolating ultraviolet rays, heating to 23-25 ℃, and stirring for 20-40 minutes to obtain a coating composition;
(3) providing a base material, coating the coating composition prepared in the step (2) on the base material, and performing infrared leveling and ultraviolet irradiation curing to obtain the environment-friendly ultraviolet curing non-silicon release film.
10. The method for preparing the environment-friendly ultraviolet-curable non-silicon release film according to claim 9, wherein the coating composition is coated by micro-gravure coating, three-roll/five-roll transfer coating, slot extrusion coating or mesh roll coating, and the wet coating amount is 5-10g/m2The baking temperature after coating is 80-130 ℃, the baking time is 30-60s, and the UV light energy is 300-2。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265199A (en) * | 2021-05-12 | 2021-08-17 | 南京君弘新材料有限公司 | Hydrophobic light release type fluorine material coating |
| CN113637208A (en) * | 2021-09-24 | 2021-11-12 | 深圳泰得思科技有限公司 | PET recycling environment-friendly release film |
| CN113717655A (en) * | 2021-09-27 | 2021-11-30 | 深圳泰得思科技有限公司 | Grid release film |
| CN114350266A (en) * | 2022-01-12 | 2022-04-15 | 深圳日高胶带新材料有限公司 | Liquid optical cement and preparation method and application method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109929130A (en) * | 2019-03-11 | 2019-06-25 | 江苏斯迪克新材料科技股份有限公司 | High water droplet contact angle, cured film easily then and preparation method thereof |
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2020
- 2020-11-18 CN CN202011295473.0A patent/CN112457694A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109929130A (en) * | 2019-03-11 | 2019-06-25 | 江苏斯迪克新材料科技股份有限公司 | High water droplet contact angle, cured film easily then and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265199A (en) * | 2021-05-12 | 2021-08-17 | 南京君弘新材料有限公司 | Hydrophobic light release type fluorine material coating |
| CN113637208A (en) * | 2021-09-24 | 2021-11-12 | 深圳泰得思科技有限公司 | PET recycling environment-friendly release film |
| CN113637208B (en) * | 2021-09-24 | 2022-04-29 | 深圳泰得思科技有限公司 | PET recycling environment-friendly release film |
| CN113717655A (en) * | 2021-09-27 | 2021-11-30 | 深圳泰得思科技有限公司 | Grid release film |
| CN113717655B (en) * | 2021-09-27 | 2023-01-03 | 深圳泰得思科技有限公司 | Grid release film |
| CN114350266A (en) * | 2022-01-12 | 2022-04-15 | 深圳日高胶带新材料有限公司 | Liquid optical cement and preparation method and application method thereof |
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