CN118909538B - Low-warp-deformation scratch-resistant matte coating, low-warp-deformation scratch-resistant matte film and preparation method thereof - Google Patents
Low-warp-deformation scratch-resistant matte coating, low-warp-deformation scratch-resistant matte film and preparation method thereof Download PDFInfo
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Classifications
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- 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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- 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
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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
- C09D7/20—Diluents or solvents
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a low-warp-deformation scratch-resistant matte coating, a low-warp-deformation scratch-resistant matte film and a preparation method thereof, and belongs to the technical field of photo-curing coatings. The low-warp-deformation scratch-resistant matte coating comprises, by mass, 23-40% of an acrylate prepolymer, 0.6-12% of an acrylate active monomer, 8-23% of a multi-functional hyperbranched reactive diluent, 15-23% of a cationic photo-curing monomer, 3.5-7% of a modified matting agent, 0.7-2.3% of a free radical photoinitiator, 0.7-2.3% of a cationic photoinitiator, 0.5-1% of an organosilicon leveling agent and 10-20% of a solvent, wherein the multi-functional hyperbranched reactive diluent is formed by introducing acrylate functional groups into polyhydroxy hyperbranched polyethylene and methacrylic acid through a high-molecular esterification reaction. The low-warp-deformation scratch-resistant matte coating disclosed by the invention is coated on the surface of a BOPP film to form a low-warp-deformation scratch-resistant matte film after photo-curing, and the film has the advantages of low curing volume shrinkage, difficult warp deformation, good scratch resistance and wear resistance and excellent matte effect.
Description
Technical Field
The invention relates to the technical field of photo-curing coatings, in particular to a low-warp-deformation scratch-resistant matte coating, a low-warp-deformation scratch-resistant matte film and a preparation method thereof.
Background
BOPP matt films (with glossiness less than 5.0 at 60 degrees) are widely accepted by people due to soft and natural appearance, good visual effect and pleasant hand feeling, but the appearance, scratch resistance and wear resistance of the traditional BOPP matt films can not meet the use demands of customers.
BOPP matt film uses BOPP matt material to realize matt effect, BOPP matt material is the mixture of multiple polyolefin (mainly HDPE and PP), in the film making biaxial stretching process, because incompatible system crystallization rate and to tensile response's difference and produce coarse surface morphology, thereby shine the light of coarse surface and take place diffuse reflection and produce matt effect, but the matt layer that BOPP matt material formed does not possess and prevents scraping the nature, along with the development of material science and technology and the aesthetic change in film packaging printing field, use prevent scraping the matt coating to coat and prevent scraping the matt layer on BOPP film surface, realize BOPP film matt effect and give the surface and prevent scraping the performance, become the important development direction of BOPP matt film. Scratch-resistant matte coatings can be divided into aqueous and solvent-based coatings, and the scratch resistance of the aqueous scratch-resistant matte coatings is difficult to compare with that of solvent-based coatings at present, so that the aqueous scratch-resistant matte coatings are not applied in practice.
Conventional high performance solvent borne scratch resistant matte coatings typically have a large volume shrinkage because the photocuring process of the coating is a conversion process from small molecules to long chain or three dimensional network macromolecules, which have a greatly varying molecular structure. Before photo-curing, the anti-scratch matte coating has the advantages that the acting force between the components is Van der Waals force, the distance between molecules is Van der Waals distance (0.3-0.5 nm), after the chemical reaction is carried out and photo-curing is carried out, the original intermolecular distance is changed into covalent bond distance (average length of C-C bonds is 0.154 nm), the covalent bond distance is far smaller than the acting distance of Van der Waals force, the intermolecular distance is greatly changed, the volume shrinkage is generated in the curing process, and the phenomena such as buckling deformation of products are caused. Along with implementation of environmental protection policies such as plastic reduction, light weight and the like in BOPP industry, BOPP films are developing towards thinner directions, and the thickness of the BOPP film is below 12 mu m at present, so that the BOPP scratch-resistant film produced by the BOPP scratch-resistant film has the problem of larger and larger buckling deformation, is not easy to flatten when being compounded with other materials, is easy to generate flaws such as wrinkles and the like in the compounding use, and causes great inconvenience and loss in the use process.
Disclosure of Invention
Based on the above, the invention aims to provide a low-warp-deformation scratch-resistant matte coating, a low-warp-deformation scratch-resistant matte film and a preparation method thereof. The low-warp-deformation scratch-resistant matte coating disclosed by the invention is coated on the surface of a BOPP film to form a low-warp-deformation scratch-resistant matte film (also called a BOPP scratch-resistant matte film) after photo-curing, so that the problem of warp deformation of the existing BOPP scratch-resistant matte film can be solved, the scratch resistance of the surface of the film is improved, meanwhile, the matte appearance (the glossiness is less than 5.0 at 60 degrees) of the film is endowed, and the composite use requirement of the thinner BOPP scratch-resistant matte film is especially met.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention firstly provides a low-warp-deformation scratch-resistant matte coating which comprises, by mass, 23-40% of an acrylate prepolymer, 0.6-12% of an acrylate active monomer, 8-23% of a multi-functional hyperbranched active diluent, 15-23% of a cationic photo-curing monomer, 3.5-7% of a modified matting agent, 0.7-2.3% of a free radical photoinitiator, 0.7-2.3% of a cationic photoinitiator, 0.5-1% of an organosilicon leveling agent and 10-20% of a solvent, wherein the multi-functional hyperbranched active diluent is formed by introducing acrylate functional groups into polyhydroxy hyperbranched polyethylene and methacrylic acid through a macromolecular esterification reaction, the number average molecular weight of the multi-functional hyperbranched active diluent is 5000-20000g/mol, the branching degree is (85-110)/1000C, the functionality is 5-7, the cationic photo-curing monomer is an epoxy compound, and the modified matting agent contains epoxy groups.
The low-warp-deformation scratch-resistant matte coating provided by the invention belongs to a hybrid type photocuring system, utilizes a synergistic action mechanism of two curing modes, and obtains a coating with an interpenetrating network structure (IPN) after ultraviolet light curing, so that the scratch-resistant performance of the coating is improved, and the curing volume shrinkage and warp deformation of the coating are inhibited.
The low-warp-deformation scratch-resistant matte coating is a hybrid type photocuring scratch-resistant coating, adopts the free radical photoinitiator and the cationic photoinitiator, provides two curing modes through the two photoinitiators, overcomes the problems of low cationic polymerization curing speed and difficult production by utilizing a synergistic mechanism, maintains the respective advantages of free radical polymerization and cationic polymerization, and has the advantages of high curing speed, small volume shrinkage and high mechanical strength. Under the irradiation of ultraviolet light, the free radical photoinitiator firstly generates a free radical active center to initiate free radical polymerization, and meanwhile, free radical fragments generated by the photolysis of the free radical photoinitiator can reduce the cationic photoinitiator to generate electron transfer, so that indirect photolysis is realized, a cation active center is generated, and a cation polymerization reaction is initiated. Besides the electron transfer function, the free radical photoinitiator can directly photosensitize the cationic photoinitiator to a certain extent, so that the long-wave ultraviolet light is fully utilized, and the cationic polymerization curing speed is improved.
The acrylate prepolymer has excellent flexibility and wear resistance, and can improve the mechanical properties of a coating formed by the low-warp-deformation scratch-resistant matte coating. However, the viscosity of the acrylate prepolymer is high (generally more than 2000 mPa.s), and meanwhile, the adhesive force with the BOPP film is low, and the viscosity of a coating system is reduced by adding the acrylate active monomer and the multifunctional hyperbranched reactive diluent into the low warp deformation scratch-resistant matte coating, and the acrylate prepolymer can be polymerized with the acrylate active monomer and the multifunctional hyperbranched reactive diluent to form a crosslinking system, so that the coating formed by polymerization has good scratch resistance, high adhesive force with the BOPP film, and the problems of poor production applicability and low adhesive force of the coating caused by the high viscosity of the acrylate prepolymer are solved.
The viscosity of the coating is increased rapidly along with the increase of the content of the prepolymer, the mechanical property is improved, but the coating with high viscosity is not suitable for coating processing of a film. The acrylic ester active monomer belongs to a free radical type active diluent (the viscosity is usually less than 50 mPa.s), can obviously reduce the viscosity of the coating, and simultaneously participates in a crosslinking reaction in the curing process to promote polymerization to form a crosslinking system. The addition amount of the acrylic ester active monomer in the low-warp-deformation scratch-resistant matte coating is 0.6-12wt%, and the acrylic ester active monomer is small in molecular weight and belongs to a small-molecule active diluent, so that if the addition amount of the acrylic ester active monomer is too large, the curing and crosslinking density of a coating formed by the low-warp-deformation scratch-resistant matte coating is too large, the volume shrinkage of the coating is increased, the problems of coating brittleness, adhesive force reduction and the like are caused, and the warp deformation of a product is difficult to control.
The multifunctional hyperbranched reactive diluent is functional hyperbranched polyethylene, and is formed by introducing acrylate functional groups into polyhydroxy hyperbranched polyethylene and methacrylic acid through a high molecular esterification reaction. The multifunctional hyperbranched reactive diluent is used as a polyethylene-based copolymer, can effectively wet the surface of the BOPP film, is in a non-crystalline state, can diffuse into the BOPP film after being attached to the surface of the BOPP film, is intertwined with molecular chain segments on the surface of the BOPP film, improves intermolecular acting force, and improves the adhesive force between a coating formed by the low-warp-deformation scratch-resistant matte coating and the BOPP film. The acrylate functional group at the molecular chain end of the multi-functional hyperbranched reactive diluent can participate in the free radical photo-curing reaction, and is crosslinked into the coating through chemical bonds, so that the problems of overlarge crosslinking density, large volume shrinkage, brittleness and insufficient adhesive force of the coating after free radical photo-curing can be effectively overcome, and an interpenetrating network structure (IPN) is formed by matching with cationic polymerization, so that the coating with extremely low warp deformation and high scratch resistance is obtained. The content of the multifunctional hyperbranched reactive diluent in the low-warp-deformation scratch-resistant matte paint is 8-23wt%, if the content of the multifunctional hyperbranched reactive diluent is too low, the effects of reducing the paint viscosity and preventing the paint from embrittling and the problem of low adhesion of the paint on the BOPP film surface cannot be effectively improved, and if the content of the multifunctional hyperbranched reactive diluent is too low, the cost is increased, the hardness of the paint is reduced, and the scratch resistance of the paint is affected.
The multi-functionality hyperbranched reactive diluent disclosed by the invention is not a multi-functionality small molecular reactive diluent, but is different from a linear high polymer prepolymer. The linear polyethylene molecular chain structure has high regularity and is easy to crystallize, but the regularity of the polyethylene molecular chain structure is destroyed along with the increase of the branching degree, so that the crystallinity of the polyethylene is reduced, and the polyethylene molecular chain segment starts to be easy to thermally move. By utilizing the characteristics, the branching degree of the multi-functional hyperbranched reactive diluent is defined as (85-110)/1000 ℃, and the branching degree of the multi-functional hyperbranched reactive diluent forms a spherical topological structure at (85-110)/1000 ℃, is in a completely non-crystalline state at room temperature, has good flow permeability and has strong adhesive force to BOPP films. Compared with linear macromolecules of random coils, the spherical topological structure of the multi-functional hyperbranched reactive diluent has compact structure, small hydrodynamic radius, no intrachain entanglement and small intermolecular friction, achieves reactive dilution in a coating system, reduces viscosity, is not easy to entangle with an IPN system in a photocuring process, plays a role in reactive dilution and lubrication, is uniformly distributed in a coating, has complete photocuring crosslinking reaction, and improves the residual problem of unreacted free radicals. The invention limits the number average molecular weight of the multi-functional hyperbranched reactive diluent to be 5000-20000 g/mol, when the molecular weight of the multi-functional hyperbranched reactive diluent is too low, the topological structure of a polyethylene molecular chain segment in the structure is deviated to be linear, the multi-functional hyperbranched reactive diluent is easy to be entangled with the multi-functional hyperbranched reactive diluent and the acrylate prepolymer in a coating system, the multi-functional hyperbranched reactive diluent cannot play a role of the diluent, and when the molecular weight of the multi-functional hyperbranched reactive diluent is too high, the multi-functional hyperbranched reactive diluent is difficult to be mutually dissolved with the coating system, and phase separation and layering phenomena are easy to occur. The functionality of the multi-functionality hyperbranched reactive diluent is 5-7, so that the moderate crosslinking density can be ensured, and if the functionality is too large, the problems of too large crosslinking density, large volume shrinkage and insufficient adhesive force of the coating are easily caused.
When the cationic photocuring monomer, namely the epoxy compound, is subjected to photoinitiated cationic ring-opening polymerization, two C-O covalent bonds on the alicyclic ring are broken and intermolecular covalent bonds are generated simultaneously, and the intermolecular distance is not changed greatly, so that the epoxy compound has small volume shrinkage in the polymerization reaction process, the volume shrinkage of free radical polymerization is effectively controlled in the coating of an IPN system, and the warp deformation of the product is restrained. The addition amount of the cationic photo-curing monomer, namely the epoxy compound, in the low-warp-deformation scratch-resistant matte coating is 15-23wt%, so that the low-warp-deformation scratch-resistant matte coating can be ensured to have lower viscosity and good production applicability, and meanwhile, the problem of small coating curing volume shrinkage and product warp deformation is solved. If the addition amount of the cationic photo-curing monomer in the low-warp-deformation scratch-resistant matte coating is too high, the viscosity of the low-warp-deformation scratch-resistant matte coating is easily caused to be too high due to the fact that the viscosity of the cationic photo-curing monomer is relatively high (generally more than 200 mPa.s), and the coating with high viscosity is not suitable for coating processing of BOPP films.
The modified matting agent contains epoxy groups, has good compatibility with a coating system, and does not cause severe increase of the viscosity of the coating system. The epoxy groups on the modified matting agent are crosslinked into an interpenetrating network (IPN) structure of the coating by chemical bonds during photoinitiated cationic ring-opening polymerization, so that powder is not dropped after curing, the hardness is high, the scratch resistance and the wear resistance of the coating are greatly improved, and an excellent matte effect is given to the coating.
Further, the acrylate prepolymer is aliphatic polyurethane acrylate, the functionality of the aliphatic polyurethane acrylate is 2-4, and the molecular weight is 1000 g/mol. The invention adopts the aliphatic polyurethane acrylic ester with the functionality of 2-4, so that the coating formed by the low-warp-deformation scratch-resistant matte coating has good scratch resistance and good coating flexibility. If the functionality of the aliphatic polyurethane acrylate is too high, the coating formed by polymerization has high crosslinking density, high hardness and good scratch resistance, but the problem of brittleness and reduced flexibility of the coating can be caused by too high crosslinking density.
Further, the acrylic ester active monomer is a difunctional or trifunctional acrylic ester compound. Preferably, the acrylate-reactive monomer is one or more of EGDA (ethylene glycol diacrylate, viscosity: 8 mPa.s), NPGDA (neopentyl glycol diacrylate, viscosity: 10 mPa.s), TPGDA (tripropylene glycol diacrylate, viscosity: 13 mPa.s), ETPTA (ethoxylated trimethylolpropane triacrylate, viscosity: 25 mPa.s). The difunctional or trifunctional acrylate compound belongs to a free radical reactive diluent, has small molecular weight, can obviously reduce the viscosity of the coating, can prevent the excessive curing crosslinking density of a coating formed by the low warp deformation scratch-resistant matte coating, prevents the increase of the volume shrinkage of the coating, and improves the problems of brittleness, adhesive force reduction and the like of the coating.
The multi-functional hyperbranched reactive diluent is prepared by catalyzing ethylene and silane to protect hydroxyl acrylate monomers to carry out copolymerization reaction under the action of a post-transition metal palladium-diimine catalyst, precipitating the product by ethanol to obtain colorless transparent oily matter, and then treating the colorless transparent oily matter by using tetra-n-butyl ammonium fluoride solution to remove the protection of hydroxyl groups to obtain multi-hydroxyl-group-containing polyhydroxy hyperbranched polyethylene, wherein the polyhydroxy hyperbranched polyethylene and methacrylic acid introduce acrylate functional groups through high molecular esterification reaction to form the multi-functional hyperbranched reactive diluent. The hyperbranched reactive diluent with the polyfunctional degree (the functionality is 5-7) obtained by catalytic polymerization of the late transition metal palladium-diimine has a spherical topological structure, is in a completely non-crystalline state at room temperature, has good flow permeability and has strong adhesive force to BOPP films.
Further, the cationic photo-curing monomer is one or two of EEC (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate) and BEA (bis (3, 4-epoxycyclohexylmethyl) adipate). EEC (3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate) and BEA (bis (3, 4-epoxycyclohexylmethyl) adipate) are epoxy compounds, and can simultaneously break two C-O covalent bonds on alicyclic rings and generate intermolecular covalent bonds during photoinitiated cationic ring-opening polymerization, and the change range of the intermolecular distance is small, so that the volume shrinkage is small during the polymerization process, and the properties of inhibiting the volume shrinkage and warp deformation of the cured coating are good in the hybrid type photocuring coating system.
Further, the modified matting agent is a silane coupling agent modified silica particle, wherein in the silane coupling agent modified silica particle, the silane coupling agent is a silane coupling agent containing an epoxy group, the dosage of the silane coupling agent is 0.5-3wt% of the silica particle, and the particle size of the modified matting agent is 1-2 mu m. Preferably, the modified flatting agent is modified silica particles of a silane coupling agent KH-560, and the modified flatting agent is a specific modification mode, wherein the silane coupling agent KH-560 is added into ethanol, the pH is adjusted to 7-9, the silica particles are added, the ultrasonic treatment is carried out for 30 minutes, stirring is carried out for 10 minutes (the rotating speed is less than 200 r/min), the temperature is raised to 120 ℃ after full wetting, the high-speed shearing and the dispersing are carried out for 30 minutes, (the rotating speed is more than 5000 r/min), the cooling is carried out, the filtration is carried out, the ethanol is used for flushing, the vacuum drying is carried out for 4 hours, and the ball mill grinding and the dispersing are carried out, thus obtaining the modified silica particles of the silane coupling agent KH-560. The invention adopts the silane coupling agent modified silica particles as the modified matting agent, has good compatibility with a coating system, and does not cause severe increase of the viscosity of the coating system. The tail end of the silane coupling agent KH-560 contains an epoxy group, and the modified silica particles of the silane coupling agent KH-560 are used as a modified matting agent, so that chemical bonds are crosslinked into an interpenetrating network (IPN) structure of the coating during photoinitiated cationic ring-opening polymerization, powder is not dropped after curing, the hardness is high, and the scratch resistance and the wear resistance of the coating are greatly improved.
Further, the free radical photoinitiator is one or more of benzoin, benzoin ethers, acetophenones and acetophenone ketals. Preferably, the free radical photoinitiator is one or more of photoinitiator 184, photoinitiator 1173, photoinitiator TPO and photoinitiator 907. These radical photoinitiators are capable of efficiently generating radicals during the photocuring process, promoting rapid curing of the coating.
Further, the cationic photoinitiator is one or more of diaryl iodonium salt, triarylsulfonium salt and alkyl sulfonium salt compounds. Preferably, the cationic photoinitiator is one or more of photoinitiator PAG208, photoinitiator PAG202, photoinitiator UVI6976 and photoinitiator UVI 6974. These cationic photoinitiators are capable of efficiently generating cations under irradiation of ultraviolet light, thereby initiating and accelerating cationic polymerization reactions.
Further, the solvent is one or more of butanone, ethyl acetate and butyl acetate. The solvent can uniformly disperse the components of the coating, adjust the viscosity and the coating property of the coating, has low boiling point, is favorable for drying the coating after coating to remove the solvent, and forms the coating through photo-curing.
The invention also provides a low-warp-deformation scratch-resistant matte film (also called as BOPP scratch-resistant matte film), which comprises a coating and a BOPP film layer, wherein the coating is formed by coating any of the low-warp-deformation scratch-resistant matte paint on the surface of the BOPP film layer, and the BOPP film layer is a BOPP film.
The low-warp-deformation scratch-resistant film solves the problem that the existing BOPP scratch-resistant film is insufficient in warp deformation and adhesion of a coating on the surface of the BOPP film. The low-warp-deformation anti-scratch-dumb film improves the anti-scratch/wear resistance of the coating, has high adhesive force with the BOPP film, is not easy to generate warp deformation, and meets the high-end compound requirement of the BOPP anti-scratch-dumb film.
Further, the dry weight of the coating is 1-4g/m 2, and the thickness of the BOPP film layer is 8-12 mu m. Coating a coating with the dry weight of 1-4g/m 2 on the surface of a thinner BOPP film (with the thickness of 8-12 mu m), so that the obtained low-warp-deformation scratch-resistant film (BOPP scratch-resistant film) is not easy to generate warp deformation, is easy to flatten when being compounded with other materials, improves defects such as wrinkles and the like in the compounding use, and particularly meets the compounding use requirement of the thinner BOPP scratch-resistant film.
The invention also provides a preparation method of the low warp deformation scratch-resistant dumb film, which comprises the following steps:
s1, preparing any one of the low warp deformation scratch-resistant matte paint;
And S2, coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film, drying the solvent, and performing ultraviolet light curing to obtain the low-warp-deformation scratch-resistant matte film.
Further, the solvent is dried by heating for 40-60s at 70-80 ℃ in an oven, and then is cured into the matte scratch-resistant layer by ultraviolet irradiation for 40-60 s. If the drying temperature is too low, the drying efficiency is affected, and if the drying temperature is too high, the quality of the low warp deformation scratch-resistant dumb film is adversely affected, such as discoloration, oxidization and the like of a product.
Compared with the prior art:
The low-warp-deformation scratch-resistant coating has good fluidity, meets the requirements of the traditional mature industrial coating processes such as roller coating, spraying, scratch coating and the like, has a simple and easy use method, and has strong practicability and commercial prospect. The low-warp-deformation scratch-resistant matte coating disclosed by the invention is coated on the surface of a BOPP film to form a low-warp-deformation scratch-resistant matte film (also called as a BOPP scratch-resistant matte film) after photo-curing, and the film has the advantages of low cured volume shrinkage, difficult warp deformation, good scratch resistance and excellent matte effect.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
The invention provides a low-warp-deformation scratch-resistant matte coating which comprises, by mass, 23-40% of an acrylate prepolymer, 0.6-12% of an acrylate active monomer, 8-23% of a multi-functional hyperbranched active diluent, 15-23% of a cationic photo-curing monomer, 3.5-7% of a modified matting agent, 0.7-2.3% of a free radical photoinitiator, 0.7-2.3% of a cationic photoinitiator, 0.5-1% of an organosilicon leveling agent and 10-20% of a solvent, wherein the multi-functional hyperbranched active diluent is formed by introducing acrylate functional groups into polyhydroxy hyperbranched polyethylene and methacrylic acid through a high-molecular esterification reaction, the number average molecular weight of the multi-functional hyperbranched active diluent is 5000-20000, the branching degree is (85-110)/1000C, the functionality is 5-7, and the cationic photo-curing monomer is an epoxy compound.
The preparation method of the multi-functional hyperbranched reactive diluent comprises the following steps of catalyzing ethylene and silane to protect hydroxyl acrylate monomers to carry out copolymerization reaction under the action of a post-transition metal palladium-diimine catalyst, precipitating a product by ethanol to obtain colorless transparent oily matter, and then treating the colorless transparent oily matter by using tetra-n-butyl ammonium fluoride solution to remove the protection of hydroxyl groups to obtain polyhydroxy hyperbranched polyethylene containing a plurality of hydroxyl groups, wherein the polyhydroxy hyperbranched polyethylene and methacrylic acid introduce acrylate functional groups through high molecular esterification reaction to form the multi-functional hyperbranched reactive diluent.
Taking a multi-functionality hyperbranched reactive diluent with the number average molecular weight of 20000g/mol, the branching degree of 100/1000 ℃ and the functionality of 7 as an example, the specific operation process comprises the steps of connecting a low-pressure glass reaction kettle with a circulating vacuum pump, drying for more than 3 hours at high temperature under the irradiation of an infrared lamp, pumping for 1 hour, and keeping the absolute dryness in the glass reaction kettle. The method comprises the steps of dissolving a post-transition metal palladium-diimine catalyst in an amount of 100 mmol in anhydrous dichloromethane, adding a dichloromethane solution in which the catalyst is dissolved and a trimethylsilane-protected hydroxyethyl acrylate (HEA-TMS) monomer solution in an amount of 0.02-mol into a dry and airtight glass reaction kettle under the protection of nitrogen, introducing ethylene to control the pressure to be 0.1-5 atm, and setting the temperature to be 0-5 ℃. After 24 h of reaction in a constant temperature water bath, a small amount of ethanol was added to terminate the reaction, thereby obtaining a mixture of the copolymer containing ethylene and HEA-TMS. After the above mixture was dissolved with an appropriate amount of dichloromethane, it was poured into absolute ethanol containing cold water to precipitate, and left to stand until the precipitation was completed to remove the catalyst and comonomer, to give a colorless transparent oil. Dissolving the colorless transparent oily matter in 100 ml tetrahydrofuran for 2-3 hr, adding tetrahydrofuran solution of tetra-n-butyl ammonium fluoride, adding concentrated hydrochloric acid after lh for 0.5 hr, stopping reaction, separating product, adding excessive methanol to precipitate polymer, washing with methanol for several times, stoving in vacuum oven to obtain polyhydroxy hyperbranched polyethylene, and introducing acrylate functional group into the prepared polyhydroxy hyperbranched polyethylene and methacrylic acid via high molecular esterification reaction to obtain the multifunctional hyperbranched reactive diluent with average number molecular weight of 20000g/mol, branching degree of 100/1000 deg.c and functionality of 7. The preparation of other number average molecular weight, branching degree and functionality of the multi-functional hyperbranched reactive diluents can be controlled by adjusting and controlling the polymerization time, ethylene pressure and polymerization temperature, and can be adjusted conventionally by a person skilled in the art according to the preparation method, and the details are not repeated here.
The modified matting agents used in the following examples or comparative examples were modified silica particles of a silane coupling agent KH-560, the amount of the silane coupling agent KH-560 used was 2% by weight of the silica particles, and the average particle diameter of the modified matting agent was 2. Mu.m.
The specific modification mode of the silane coupling agent KH-560 modified silica particles comprises the steps of adding the silane coupling agent KH-560 into ethanol, regulating the pH value to 7-9, adding the silica particles, carrying out ultrasonic treatment for 30 minutes, stirring for 10 minutes (the rotating speed is less than 200 r/min), heating to 120 ℃ after full wetting, carrying out high-speed shearing and dispersing for 30 minutes (the rotating speed is more than 5000 r/min), cooling, filtering, flushing with ethanol, drying for 4 hours under vacuum, and carrying out grinding and dispersing by a ball mill to obtain the silane coupling agent KH-560 modified silica particles.
Example 1
The embodiment provides a low-warp-deformation scratch-resistant matte coating, which comprises the following components, by mass, of 40% of acrylate prepolymer (aliphatic polyurethane acrylate, the molecular weight of which is 1000 g/mol), 12% of acrylate active monomer (EGDA), 8% of multi-functional hyperbranched reactive diluent (number average molecular weight Mn:20000g/mol, branching degree: 100/1000C, functionality: 7), 23% of cationic photo-curing monomer (EEC), 4.3% of modified matting agent, 0.7% of free radical photoinitiator (photoinitiator 184), 1.5% of cationic photoinitiator (photoinitiator UVI 6974), 0.5% of organosilicon leveling agent and 10% of solvent (butyl acetate).
The embodiment also provides a low-warp-deformation scratch-resistant matte film, which comprises a coating and a BOPP film layer, wherein the coating is formed by coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film layer, and the BOPP film layer is a BOPP film.
The embodiment also provides a preparation method of the low warp deformation scratch-resistant dumb film, which comprises the following steps:
s1, adding raw materials of the components into a constant-temperature sealing high-speed stirring cylinder in sequence to stir according to the mass percent of the low-warp-deformation scratch-resistant matte coating to obtain the low-warp-deformation scratch-resistant matte coating, wherein the stirring speed is 1500 revolutions per minute, the temperature is controlled at 30 ℃, and the stirring time is 4 hours;
S2, coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film with the thickness of 12 mu m by using a coating machine by adopting a micro-concave roller coating method, heating a drying solvent for 50S by using an oven at 70 ℃, and irradiating ultraviolet light for 40S for curing to form the BOPP scratch-resistant matte film, namely the low-warp-deformation scratch-resistant matte film.
In the low warp deformation scratch-resistant film of this embodiment, the dry weight of the coating layer was 1.5 g/m 2.
Example 2
The embodiment provides a low-warp-deformation scratch-resistant matte coating, which comprises the following components, by mass, of 30% of acrylate prepolymer (aliphatic polyurethane acrylate, the molecular weight of which is 1000 g/mol), 0.6% of acrylate active monomer (ETPTA), 23% of multi-functionality hyperbranched reactive diluent (number average molecular weight Mn:5500g/mol, branching degree: 86/1000C, functionality: 5), 20% of cationic photo-curing monomer (BEA), 4% of modified matting agent, 1.2% of free radical photoinitiator (photoinitiator TPO), 0.7% of cationic photoinitiator (photoinitiator UVI 6976), 0.5% of organosilicon leveling agent and 20% of solvent (ethyl acetate).
The embodiment also provides a low-warp-deformation scratch-resistant matte film, which comprises a coating and a BOPP film layer, wherein the coating is formed by coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film layer, and the BOPP film layer is a BOPP film.
The embodiment also provides a preparation method of the low warp deformation scratch-resistant dumb film, which comprises the following steps:
s1, adding raw materials of the components into a constant-temperature sealing high-speed stirring cylinder in sequence to stir according to the mass percent of the low-warp-deformation scratch-resistant matte coating to obtain the low-warp-deformation scratch-resistant matte coating, wherein the stirring speed is 1500 revolutions per minute, the temperature is controlled at 30 ℃, and the stirring time is 3 hours;
s2, coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film with the thickness of 10 mu m by using a coating machine by adopting a micro-concave roller coating method, heating the solvent for 60S by an oven at 80 ℃, and irradiating ultraviolet light for 60S for curing to form the BOPP scratch-resistant matte film, namely the low-warp-deformation scratch-resistant matte film.
In the low warp distortion scratch-resistant film of this embodiment, the dry weight of the coating is 3.5 g/m 2.
Example 3
The embodiment provides a low-warp-deformation scratch-resistant matte coating, which comprises the following components, by mass, of 23% of acrylate prepolymer (aliphatic polyurethane acrylate, the molecular weight of which is 1000 g/mol), 10% of acrylate active monomer (ETPTA), 15% of multi-functional hyperbranched reactive diluent (number average molecular weight Mn:10000g/mol, branching degree: 95/1000C, functionality: 6), 22% of cationic photo-curing monomer (BEA), 7% of modified matting agent, 2.3% of free radical photoinitiator (photoinitiator TPO), 2.3% of cationic photoinitiator (photoinitiator UVI 6976), 1% of organosilicon leveling agent and 17.4% of solvent (butanone).
The embodiment also provides a low-warp-deformation scratch-resistant matte film, which comprises a coating and a BOPP film layer, wherein the coating is formed by coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film layer, and the BOPP film layer is a BOPP film.
The embodiment also provides a preparation method of the low warp deformation scratch-resistant dumb film, which comprises the following steps:
s1, adding raw materials of the components into a constant-temperature sealing high-speed stirring cylinder in sequence to stir according to the mass percent of the low-warp-deformation scratch-resistant matte coating to obtain the low-warp-deformation scratch-resistant matte coating, wherein the stirring speed is 1500 revolutions per minute, the temperature is controlled at 30 ℃, and the stirring time is 3 hours;
S2, coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film with the thickness of 10 mu m by using a coating machine by adopting a micro-concave roller coating method, heating a drying solvent for 50S at 80 ℃ by using an oven, and irradiating ultraviolet light for 50S for curing to form the BOPP scratch-resistant matte film, namely the low-warp-deformation scratch-resistant matte film.
In the low warp deformation scratch-resistant film of this embodiment, the dry weight of the coating layer was 2.5 g/m 2.
Comparative example 1
The comparative example provides a photo-curing matte coating which comprises, by mass, 40% of an acrylate prepolymer (aliphatic polyurethane acrylate with a molecular weight of 1000 g/mol), 35% of an acrylate reactive monomer (EGDA), 8% of a multi-functional hyperbranched reactive diluent (number average molecular weight Mn:20000g/mol, branching degree: 100/1000C, functionality: 7), 4.3% of a modified matting agent, 2.2% of a free radical photoinitiator (photoinitiator 184), 0.5% of an organosilicon leveling agent, and 10% of a solvent (butyl acetate).
The comparative example also provides a photo-curing matte film which comprises a coating and a BOPP film layer, wherein the coating is formed by coating the photo-curing matte paint on the surface of the BOPP film layer, and the BOPP film layer is a BOPP film.
The comparative example also provides a method for preparing a photo-cured dummy film, comprising the following steps:
s1, sequentially adding raw materials of the components into a constant-temperature sealing high-speed stirring cylinder for stirring according to the mass percent of the photo-curing matte coating of the comparative example to obtain the photo-curing matte coating, wherein the stirring speed is 1500 rpm, the temperature is controlled at 30 ℃, and the stirring time is 4 hours;
s2, coating the photo-curing matte coating on the surface of the BOPP film with the thickness of 12 mu m by using a coating machine by adopting a micro-gravure coating method, heating the BOPP film for 50S by using an oven at 70 ℃, and curing the BOPP film by irradiating ultraviolet light for 40S to form the photo-curing matte film.
In the photo-curable dummy film of this comparative example, the dry weight of the coating layer was 1.5 g/m 2.
Comparative example 2
The comparative example provides a photo-curing matte coating comprising, by mass, 40% of an acrylate prepolymer (aliphatic urethane acrylate with a molecular weight of 1000 g/mol), 20% of an acrylate reactive monomer (EGDA), 23% of a cationic photo-curing monomer (EEC), 4.3% of a modified matting agent, 0.7% of a free radical photoinitiator (photoinitiator 184), 1.5% of a free radical photoinitiator (photoinitiator UVI 6974), 0.5% of an organosilicon leveling agent, and 10% of a solvent (butyl acetate).
The comparative example also provides a photo-curing matte film which comprises a coating and a BOPP film layer, wherein the coating is formed by coating the photo-curing matte paint on the surface of the BOPP film layer, and the BOPP film layer is a BOPP film.
The comparative example also provides a method for preparing a photo-cured dummy film, comprising the following steps:
s1, sequentially adding raw materials of the components into a constant-temperature sealing high-speed stirring cylinder for stirring according to the mass percent of the photo-curing matte coating of the comparative example to obtain the photo-curing matte coating, wherein the stirring speed is 1500 rpm, the temperature is controlled at 30 ℃, and the stirring time is 4 hours;
s2, coating the photo-curing matte coating on the surface of the BOPP film with the thickness of 12 mu m by using a coating machine by adopting a micro-gravure coating method, heating the BOPP film for 50S by using an oven at 70 ℃, and curing the BOPP film by irradiating ultraviolet light for 40S to form the photo-curing matte film.
In the photo-curable dummy film of this comparative example, the dry weight of the coating layer was 1.5 g/m 2.
Performance testing
The following performance tests were conducted on the matte paints and matte films of examples 1-3 and comparative examples 1-2, respectively, with reference to tables 1 and 2.
Pencil hardness the pencil hardness of the coating was measured according to the standard of JISK5400-1990 determination of adhesion Properties of powder coating film.
Gloss is measured according to GB/T9754-2007 using a 60o gloss meter.
Adhesion of the coating the adhesion of the coating was tested according to the standard of GB1720-1979 paint film adhesion assay, where 100/100 means no stripping and 90/100 means 10% stripping.
Scratch/abrasion resistance test, namely testing the abrasion resistance of a coating according to HG/T4303-2012 surface hardening polyester film abrasion resistance determination method, wherein 0000# steel wool and 1000gf/cm 2 are adopted to bear load, and the abrasion resistance effect of the film is judged by detecting the abrasion resistance limit of no scratch on the surface of the film.
Volume shrinkage test the test was performed according to the relevant specifications in international standard ISO 3521.
Table 1 matte coating test of examples 1-3 and comparative examples 1-2
Table 2 examples 1-3 and comparative examples 1-2 matte film test
As known by the person skilled in the art, the volume shrinkage rate of the conventional low-warp-deformation scratch-resistant matte paint is generally more than 5%, and the high-warp-deformation problem exists when the low-warp-deformation scratch-resistant matte paint is coated on the BOPP scratch-resistant matte film prepared by coating the low-warp-deformation scratch-resistant matte paint on the surface of a thin BOPP film.
As can be seen from the test data in tables 1 and 2, the low warp deformation scratch-resistant matte paint of the embodiments 1-3 has good fluidity, the viscosity is less than or equal to 450 mPa.s (30 ℃), the curing volume shrinkage is low, the curing volume shrinkage is less than or equal to 3%, the low warp deformation scratch-resistant matte film (BOPP scratch-resistant matte film) produced in the embodiments 1-3 effectively improves the warp deformation problem, and meanwhile, the adhesive force of the coating to the BOPP film is qualified, the appearance glossiness is low, and the scratch/wear resistance is excellent.
In the photo-curing matte coating of comparative example 1, no cationic photo-curing monomer and cationic photoinitiator are added, which is a pure free radical photo-curing scratch-resistant matte coating, the produced photo-curing matte film has serious warp deformation, and meanwhile, the scratch resistance of the photo-curing matte film of comparative example 1 is reduced due to the interpenetrating network structure (IPN) which is generated by the lack of cations and simultaneous polymerization.
In the photo-curing matte coating of comparative example 2, the coating formed by the photo-curing matte coating of comparative example 2 lacks an adhesion promoting component with the BOPP film, the coating is tested to be partially peeled off by using an adhesive tape, and the adhesion to the BOPP film is not qualified, meanwhile, since the photo-curing coating of comparative example 2 uses a large amount of small molecular reactive diluent (namely acrylic ester reactive monomer) for maintaining the low viscosity state of the coating, the volume shrinkage after curing is difficult to be inhibited by an IPN system, the solid volume shrinkage rate is slightly high, and the degree of warp deformation of the film is larger than that of examples 1-3.
Compared with the prior art, the low-warp-deformation scratch-resistant matte coating disclosed by the invention is coated on the surface of the BOPP film by using a general coating process for one time, and the low-warp-deformation scratch-resistant matte film is formed after photo-curing, so that the problems of serious warp deformation of the existing BOPP scratch-resistant matte film and insufficient adhesive force of the coating on the surface of the BOPP film can be solved, the scratch/wear resistance of the coating is improved, meanwhile, the excellent matte effect is given to the film, and the high-end composite requirement of the BOPP scratch-resistant matte film is met. The low-warp-deformation scratch-resistant matte coating has good fluidity, the viscosity is less than or equal to 450 mPa.s, the volume shrinkage rate after curing is less than or equal to 3%, and the low-warp-deformation scratch-resistant matte coating can be suitable for thinner BOPP films and is used for preparing low-warp-deformation BOPP scratch-resistant matte films.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and the invention is intended to encompass such modifications and improvements.
Claims (10)
1. The low warp deformation scratch-resistant matte coating is characterized by comprising, by mass, 23-40% of an acrylate prepolymer, 0.6-12% of an acrylate active monomer, 8-23% of a multi-functional hyperbranched reactive diluent, 15-23% of a cationic photocuring monomer, 3.5-7% of a modified matting agent, 0.7-2.3% of a free radical photoinitiator, 0.7-2.3% of a cationic photoinitiator, 0.5-1% of an organosilicon leveling agent and 10-20% of a solvent;
the multifunctional hyperbranched reactive diluent is formed by introducing acrylate functional groups into polyhydroxy hyperbranched polyethylene and methacrylic acid through a high molecular esterification reaction, the number average molecular weight of the multifunctional hyperbranched reactive diluent is 5000-20000g/mol, the branching degree is (85-110)/1000 ℃ and the functionality is 5-7, the cationic photo-curing monomer is an epoxy compound, and the modified matting agent contains epoxy groups.
2. The low warp deformation scratch-resistant matte coating of claim 1 wherein the acrylate prepolymer is aliphatic polyurethane acrylate, the functionality of the aliphatic polyurethane acrylate is 2-4, and the molecular weight of the aliphatic polyurethane acrylate is 1000 g/mol.
3. The low warp deformation scratch-resistant matte coating of claim 1 wherein the acrylate-reactive monomer is one or more of ethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate.
4. The low warp deformation scratch-resistant matte coating is characterized in that the multi-functional hyperbranched reactive diluent is prepared by catalyzing ethylene and silane to protect hydroxyl acrylate monomers to carry out copolymerization reaction under the action of a post-transition metal palladium-diimine catalyst, precipitating the product by ethanol to obtain colorless transparent oily matter, then treating the colorless transparent oily matter by using tetra-n-butyl ammonium fluoride solution to remove the protection of hydroxyl groups to obtain polyhydroxy hyperbranched polyethylene containing a plurality of hydroxyl groups, and introducing acrylate functional groups into the polyhydroxy hyperbranched polyethylene and methacrylic acid through high molecular esterification reaction to form the multi-functional hyperbranched reactive diluent.
5. The low warp deformation scratch-resistant matte coating of claim 1 wherein the cationic photo-curing monomer is one or two of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate and bis (3, 4-epoxycyclohexylmethyl) adipate.
6. The low warp deformation scratch-resistant matte coating is characterized in that the modified matting agent is silane coupling agent modified silica particles, wherein the silane coupling agent is silane coupling agent containing epoxy groups, the amount of the silane coupling agent is 0.5-3wt% of the silica particles, and the particle size of the modified matting agent is 1-2 mu m.
7. The low warp deformation scratch-resistant matte coating of claim 1, wherein the free radical photoinitiator is one or more of benzoin, benzoin ethers, acetophenones and acetophenone ketals, and the cationic photoinitiator is one or more of diaryl iodonium salt, triarylsulfonium salt and alkyl sulfonium salt compounds.
8. A low-warp-deformation scratch-resistant matte film is characterized by comprising a coating and a film layer, wherein the coating is formed by coating the low-warp-deformation scratch-resistant matte paint according to any one of claims 1-7 on the surface of the film layer, and the film layer is a BOPP film layer.
9. The low warp distortion scratch resistant dumb film of claim 8, wherein the dry weight of the coating is 1-4g/m 2, and the thickness of the BOPP film layer is 8-12 μm.
10. The method for preparing the low warp deformation scratch-resistant dumb film according to claim 8 or 9, comprising the following steps:
s1, preparing the low warp deformation scratch-resistant matte paint as claimed in any one of claims 1 to 7;
And S2, coating the low-warp-deformation scratch-resistant matte coating on the surface of the BOPP film, drying the solvent, and performing ultraviolet light curing to obtain the low-warp-deformation scratch-resistant matte film.
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| CN102206307A (en) * | 2011-04-11 | 2011-10-05 | 中山大学 | Functional branched polyolefin copolymer and preparation method thereof |
| CN106281174A (en) * | 2016-09-22 | 2017-01-04 | 株洲时代新材料科技股份有限公司 | A kind of high tenacity, impact resistance, high flexibility epoxy pouring sealant and preparation method thereof |
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| CN102206307A (en) * | 2011-04-11 | 2011-10-05 | 中山大学 | Functional branched polyolefin copolymer and preparation method thereof |
| CN106281174A (en) * | 2016-09-22 | 2017-01-04 | 株洲时代新材料科技股份有限公司 | A kind of high tenacity, impact resistance, high flexibility epoxy pouring sealant and preparation method thereof |
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