CN110408249B - Preparation method of polymer composite film - Google Patents
Preparation method of polymer composite film Download PDFInfo
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- CN110408249B CN110408249B CN201910660010.0A CN201910660010A CN110408249B CN 110408249 B CN110408249 B CN 110408249B CN 201910660010 A CN201910660010 A CN 201910660010A CN 110408249 B CN110408249 B CN 110408249B
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Images
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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a preparation method of a polymer composite film, which comprises the following steps: (1) cleaning and drying the surface of the substrate; (2) performing antifouling protection on one surface of the cleaned and dried base material, wherein the surface is the back surface; (3) flatly coating the thermoplastic film on the front surface of the base material; (4) spraying thermosetting powder paint on the thermoplastic film on the front surface of the substrate; (5) curing the base material sprayed with the thermosetting powder coating, and cooling to normal temperature to form a composite film; (6) removing the antifouling protective material on the surface of the base material, and cleaning; (7) and (3) cooling the base material with the formed composite film to normal temperature, peeling the film from the surface of the base material, and rolling and packaging. The invention utilizes the coating strippable film-making technology to prepare the single-layer or multi-layer composite film, has simple method, greatly reduces the preparation cost of the composite film, has simple stripping process and does not use a release agent, an organic solvent and an acid-base solution.
Description
Technical Field
The invention relates to the technical field of film processing, in particular to a preparation method of a high-molecular composite film.
Background
Films made from polyvinyl chloride, polyethylene, polypropylene, polystyrene, and other resins are used for packaging, and as a film coating. Plastic packages and plastic package products occupy more and more share in the market, and particularly, composite plastic flexible packages are widely applied to the fields of food, medicine, chemical industry and the like. There are various methods for molding plastic films, such as calendering, casting, blowing, stretching, and the like. The production by the methods has the characteristics of high production efficiency and high yield.
For multilayer multifunctional composite films, the conventional preparation method comprises: 1. the manufactured thermoplastic films are laminated together, and the layers are bonded by an adhesive, 2, multilayer coextrusion molding is adopted, so that at present, the industrialized thermoplastic coextrusion molding of at most 7 layers is realized, and the thermoplastic multifunctional composite film has the defects of low surface hardness, poor dimensional thermal stability, large shrinkage rate, poor wear resistance, low strength, poor weather resistance, poor chemical resistance and the like. At the same time, these factories have a huge investment, often hundreds of millions of RMB.
On the other hand, the paint strippable film-making technology is to carry out multiple coating and film-coating on high-temperature resistant materials such as glass, vitrified polished ceramic chips, aluminum sheets, iron sheets and the like, and needs to completely and nondestructively strip a cured paint film to form a film, and faces great challenges in industrial application, at present, the main research and development direction in the paint industry is to improve the adhesive force of the paint on a substrate, and the damage to the adhesive force of the paint on the substrate is the industrial problem, and the strippable protective coating formed by a large number of water-based paints with poor adhesive force also needs to be removed by heated alkaline water, and most of paint films are stripped by dissolving acid-base and organic solvents in the solvent-based liquid coating, and meanwhile; in the powder coating industry, paint films are mostly removed by burning or soaking in strong solvent.
The mode of spraying the release agent to achieve stripping which is commonly used on the plastic mould has very little practicability on the technical scheme, because the thickness of the injection molding part is several orders of magnitude thicker than that of the thin film, the leveling of the release agent has limited influence on the surface of the injection molding part, but the flatness of the solvent-free environment-friendly coating is difficult to achieve the mirror surface effect on the premise of not grinding and polishing as limited by the prior art, therefore, the mirror surface highlight effect of the organic polymer composite film needs to be realized by the smoothness of the substrate surface, if the release agent is sprayed on a substrate with high smoothness, the leveling and high-temperature volatilization of the release agent can seriously affect the high-gloss mirror effect of the film, meanwhile, the release agent is attached to the surface of the composite film to seriously affect the use performance of the film, so that the environment-friendly stripping technology without the release agent, organic solvent and acid and alkali is required to be adopted for the highlight composite film with the widest application range.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a method for preparing a polymer composite film, which can prepare a single-layer or multi-layer composite film by using a coating strippable film-making technology, and has the advantages of simple method, greatly reduced preparation cost of the composite film, simple stripping process, and no use of a release agent, an organic solvent and an acid-base solution.
The second technical problem to be solved by the invention is to provide a preparation method of a polymer composite film, which greatly widens the raw material selection range of a multilayer composite functional film, has more abundant and various functions, and greatly improves the performance of the film.
The third technical problem to be solved by the invention is to provide a preparation method of the polymer composite film, which is environment-friendly, energy-saving, free of solvent pollution, 100% in film formation and low in energy consumption.
In order to achieve the technical effect, the invention provides a preparation method of a polymer composite film, which comprises the following steps:
(1) cleaning and drying the surface of the substrate;
(2) performing antifouling protection on one surface of the cleaned and dried base material, wherein the surface is the back surface;
(3) flatly coating the thermoplastic film on the front surface of the base material;
(4) spraying thermosetting powder paint on the thermoplastic film on the front surface of the substrate;
(5) curing the base material sprayed with the thermosetting powder coating, and cooling to normal temperature to form a composite film;
(6) and (3) cooling the base material with the formed composite film to normal temperature, peeling the film from the surface of the base material, and rolling and packaging.
As an improvement of the scheme, the base material is glass, ceramic or metal.
As an improvement of the scheme, the thermoplastic film is a PET film, a PE film, a PVC film, a PP film or an ABS film.
As an improvement of the scheme, the PET film is a transparent PET film, a PET heat transfer film or a PET aluminized film.
As an improvement of the scheme, the curing temperature of the thermosetting powder coating is more than or equal to the melting temperature of the thermoplastic film, and the thermoplastic film becomes an inseparable part of the composite film.
As an improvement of the scheme, the curing temperature of the thermosetting powder coating is less than the melting temperature of the thermoplastic film, and the thermoplastic film becomes a strippable protective film of the composite film.
As an improvement of the scheme, the D50 particle size of the thermosetting powder coating is 5-60 μm;
the thermosetting powder coating is one or more of pure epoxy powder coating, epoxy polyester powder coating, pure polyester powder coating, polyurethane powder coating, acrylic acid powder coating and fluorocarbon powder coating.
As an improvement of the scheme, the thermosetting powder coating is sprayed on the thermoplastic film on the front surface of the substrate by an electrostatic powder spraying device, and the thickness of the sprayed thermosetting powder coating is 20-300 mu m.
As an improvement of the scheme, in the step (4), after the thermosetting powder coating is sprayed on the thermoplastic film on the front surface of the substrate, a 3D texture effect is formed on the surface of the coating by using a mould pressing plate.
As a modification of the above scheme, the steps (4) and (5) are repeated for a plurality of times to form a multilayer composite film.
As an improvement of the above scheme, the method further comprises the following steps after the step (5) and before the step (6):
one or more layers of thermoplastic or metal films are provided on the film formed by the thermosetting powder coating by means of bonding to form a multilayer composite film.
As an improvement of the scheme, in the step (5), the curing treatment is infrared radiation curing, hot air baking or UV curing;
the hot air baking temperature is 60-200 ℃, and the baking time is 1-30 minutes.
As an improvement of the above scheme, the method further comprises the following steps after the step (5) and before the step (6):
printing a pattern on the film on the front surface of the base material to form a decorative pattern;
and spraying or coating a thermosetting coating on the film with the decorative pattern.
As an improvement of the scheme, the pattern is printed on the film on the front surface of the substrate in an ink printing, ink-jet printing or sticker printing mode;
the thermosetting coating is ultraviolet radiation curing coating or thermosetting powder coating.
The implementation of the invention has the following beneficial effects:
(1) the invention combines the thermoplastic and the thermosetting material by utilizing the paint stripping technology to manufacture the multilayer composite thermosetting film, the composite layer number, the type and the thickness of the coating can be flexibly adjusted, and the composite layer number is not limited by equipment and process. Moreover, the equipment investment is small, the method is simple, the preparation cost of the composite film is greatly reduced, the production organization is flexible, the types and functions of the film are rich, and the personalized customization can be realized.
(2) The invention combines the thermoplasticity and the thermosetting material by utilizing the paint strippable technology to manufacture the multilayer composite thermosetting film, greatly widens the raw material selection range of the multilayer composite functional film, has more abundant and various functions and greatly improves the performance of the film. The invention adopts thermosetting coating, and the network structure is formed due to intermolecular crosslinking in the curing process, so that the prepared macromolecular composite film has the advantages of higher rigidity, high hardness, high temperature resistance, nonflammability and good product dimensional stability.
(3) The invention coats the thermoplastic film on the front surface of the substrate, then selects the thermosetting powder coating with a certain compatibility with the thermoplastic film, and controls the curing conditions of each layer, the curing temperature of the thermosetting powder coating is set to be higher than or close to the melting temperature of the thermoplastic film, the thermosetting film and the thermoplastic film are melted and compounded into a whole after the thermosetting powder coating is completely cured, the composite film can be completely stripped on the substrate, the stripping process is simple, no release agent, organic solvent and acid-base solution are used, and the specular highlight effect can be realized on the surface of the film.
In the present invention, the curing temperature of the thermosetting powder coating material may be set to be lower than the melting temperature of the thermoplastic film, and the cured film may be easily peeled from the substrate, and in this case, the thermoplastic film becomes a peelable protective film of the surface layer of the composite film.
(4) The thermoplastic film is introduced in the process of manufacturing the multilayer composite thermosetting film by the coating strippable technology, patterns are formed in various modes, decorative patterns can be formed by printing the patterns on the composite film on the front surface of the base material, the thermoplastic film can also be used as a strippable protective film of the composite film, so that the thermal transfer patterns on the thermoplastic film are completely transferred to the composite film to form high-definition patterns, and the matte or mirror surface highlight effect can be realized on the surface of the film.
(5) The invention selects the thermosetting powder coating, spontaneously generates interconnection during reaction, has no solvent participation, is environment-friendly and energy-saving, has high utilization rate of the coating, 100 percent film forming and low energy consumption.
Drawings
FIG. 1 is a flow chart of an embodiment of a method for preparing a polymer composite film according to the present invention.
FIG. 2 is a flow chart of another embodiment of the method for preparing a polymer composite film according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
The traditional film is produced by using thermoplastic plastics through blow molding, calendering, tape casting, multilayer coextrusion and other methods, but the invention uses the material and construction principle of thermosetting coating to prepare single-layer or multilayer polymer composite films with different functions, and then the films are peeled from a base material. The number of the composite layers is not limited by equipment, and the thickness can be flexibly adjusted; because the coating is various, the composite film can realize more functions by coating various functional coatings. Specifically, as shown in fig. 1, the preparation method of the polymer composite film of the present invention comprises:
s101, cleaning and drying the surface of the base material.
The base material is glass, ceramic or metal; the metal may be aluminum sheet, iron sheet, stainless steel sheet, etc., the ceramic may be vitrified tile, and the substrate may be smooth or sanded, but is not limited thereto.
And S102, performing antifouling protection on one surface of the cleaned and dried base material, wherein the surface is the back surface.
In order to prevent the surface or bottom surface of the pattern layer from forming defects, the substrate is cleaned to remove impurities on the surface, and the cleaning method generally adopts clean water or any water-based cleaning agent or organic solvent with surfactant. Drying is carried out in an oven or baking equipment thereof, the baking time is 1-30 minutes, and the temperature is 50-200 ℃.
S103, flatly coating the thermoplastic film on the front surface of the base material;
any thermoplastic film can be selected for use in the present invention, and preferably, the thermoplastic film is one of a PET film, a PE film, a PVC film, a PP film and an ABS film, but is not limited thereto.
Preferably, the thermoplastic film is a PET film, and the PET film is one of thermoplastic films, so that the PET film has good transparency and luster; the air tightness and the fragrance retention are good; the moisture resistance is moderate, and the moisture permeability is reduced at low temperature; the mechanical property is excellent, the toughness is the best of all thermoplastic plastics, and the tensile strength and the impact strength are much higher than those of common films; the steel has good stiffness and stable size, and is suitable for secondary processing; in addition, the rubber composition has excellent heat resistance and cold resistance and good chemical resistance and oil resistance.
The PET film may or may not be provided with a pattern. Preferably, the PET film is a transparent PET film, a PET heat transfer film or a PET aluminized film.
S104, spraying thermosetting powder coating on the thermoplastic film on the front surface of the base material;
the thermosetting coating is a coating which is gradually hardened and molded after a chemical reaction of the coating and is not softened even after being heated. The powder coating is a solid powder synthetic resin coating composed of solid resin, pigment, filler, auxiliary agent and the like. Unlike common solvent-based and water-based coatings, it does not contain solvent and water. Thermosetting powder paint takes thermosetting synthetic resin as a film forming substance, and the resin is firstly melted in the drying process and then solidified into a flat and hard coating after chemical crosslinking. It has the characteristics of no solvent pollution, 100 percent film forming and low energy consumption.
The thermosetting powder coating is selected to form a film, and the thermosetting powder coating forms a network structure due to intermolecular crosslinking, so that the thermosetting powder coating has the advantages of higher rigidity, high hardness, high temperature resistance, non-flammability and good product size stability.
The invention can select the common thermosetting powder coating on the market, and particularly can select one or more of pure epoxy powder coating, epoxy polyester powder coating, pure polyester powder coating, polyurethane powder coating, acrylic powder coating and fluorocarbon powder coating, but is not limited to the above. The powder coating of the thermosetting powder coating commonly used in the market basically has certain compatibility with the thermoplastic film, but the epoxy polyester powder coating and the pure polyester powder coating have better compatibility with the thermoplastic film due to the polyester component, so the epoxy polyester powder coating and the pure polyester powder coating are better choices.
The invention selects the thermosetting powder coating with certain compatibility with the thermoplastic film, controls the curing conditions of each layer, and when the curing temperature of the thermosetting powder coating is more than or equal to the melting temperature of the thermoplastic film, the thermoplastic film becomes an inseparable part of the composite film; when the curing temperature of the thermosetting powder coating is less than the melting temperature of the thermoplastic film, the thermoplastic film becomes a strippable protective film of the composite film.
Preferably, the D50 particle size of the thermosetting powder coating is 5-60 μm, the thermosetting powder coating has specific morphology and particle size, has the advantages of low curing temperature, good leveling property, short-time curing film forming and good stability, forms a thermosetting coating after being sprayed with the powder coating, and is printed with patterns by thermal transfer printing, ink printing or ink jet printing, so that the patterns are bright, vivid, clear and fine in color.
Preferably, the thermosetting powder coating is sprayed on the thermoplastic film on the front surface of the substrate by an electrostatic powder spraying device, and the thickness of the sprayed thermosetting powder coating is 20-300 μm. The thickness of the powder spray is of great importance, and the coating thickness can affect the clear effect of surface grains besides the requirement of physical and chemical properties. If the thickness of the powder coating sprayed is more than 300 mu m, the adhesion of the coating is poor, and the physical properties are not up to standard. If the thickness of the powder coating sprayed is less than 20 μm, the orange peel on the surface of the coating is serious, the transfer effect is poor, and the integral pattern definition is affected.
For the composite film with 3D texture requirement, after the thermosetting powder coating is sprayed on the thermoplastic film on the front surface of the base material, a 3D texture effect can be formed on the surface of the coating by using a mould pressing plate, so that the pattern is abundant and vivid, and the decorative property is strong.
For a single-layer composite film, the step (4) and the step (5) can be operated once.
And for the multilayer composite film, the step (4) and the step (5) need to be repeated for multiple times to form the multilayer composite film. In this case, the multilayer composite film is made of thermosetting powder coating.
In the process of preparing the multilayer composite film, the coating with the same or different chemical composition, different color and different functions can be sprayed for multiple times to prepare the multilayer composite film. The adhesion force formed by various chemical bonds between layers of the multilayer composite film or the adhesion force formed by the chemical reaction among functional groups such as hydroxyl, isocyanic acid, carboxyl, amino, unsaturated bonds and the like between the layers does not influence the appearance gloss and the smoothness of the film.
In addition, one or more layers of functional films such as plastic are sometimes added, but the bonding of the upper and lower layers of the plastic film is realized by chemical bonds formed by the coating and the plastic, and not by adhesives. The composite film is manufactured by adopting the coating stripping technology, although the composite film is manufactured by multiple layers, the manufactured finished product is an integral body, the problem of falling off of thermoplastic composite film layers caused by adhesives or interlayer shrinkage can not occur in a severe environment, and the size stability is good.
In another embodiment of the multilayer composite film, one or more layers of thermoplastic films or metal films are further provided on the film formed by the thermosetting coating material by means of adhesion to form a multilayer composite film, and different functions are realized by compounding different films, such as: high abrasion resistance film, high hardness film, strong weather resistance film, heat insulation film, radiation protection film, antibacterial layer film or conductive film.
S105, curing the base material sprayed with the thermosetting powder coating, and cooling to normal temperature to form a composite film;
the curing treatment is preferably infrared radiation curing, hot air baking or UV curing; the curing equipment is preferably a natural gas combustion hot air oven, an electric heating infrared baking oven, a natural gas low-temperature catalytic combustion infrared baking oven or an ultraviolet mercury lamp, a potassium lamp and an LED lamp. The hot air baking temperature is 60-200 ℃, the baking time is 1-30 minutes, preferably 90-200 ℃, and the baking time is 2-20 minutes.
According to the invention, thermosetting coatings are selectively coated on a base material, and firm cross-linking adhesion among multiple layers of composite coating layers is realized by matching different curing processes according to thermosetting coatings with different chemical compositions and different functions.
And S106, removing the antifouling protective material on the surface of the base material, and cleaning.
It should be noted that step S106 may not be provided in the present invention.
And S107, cooling the base material with the formed composite film to normal temperature, peeling the film from the surface of the base material, and rolling and packaging.
Because the thermoplastic film is flatly coated on the front surface of the base material at first, the thermoplastic film is directly connected with the base material, the stripping condition of the thermoplastic film is determined by the deformation temperature of the thermoplastic film, and the stripping can be realized when the temperature is lower than the glass transition temperature of the thermoplastic film.
The invention coats the thermoplastic film on the front surface of the substrate, then selects the thermosetting powder coating with a certain compatibility with the thermoplastic film, and controls the curing conditions of each layer, the curing temperature of the thermosetting powder coating is set to be higher than or close to the melting temperature of the thermoplastic film, the thermosetting film and the thermoplastic film are melted and compounded into a whole after the thermosetting powder coating is completely cured, the composite film can be completely stripped on the substrate, the stripping process is simple, no release agent, organic solvent and acid-base solution are used, and the specular highlight effect can be realized on the surface of the film.
In the present invention, the curing temperature of the thermosetting powder coating material may be set to be lower than the melting temperature of the thermoplastic film, and the cured film may be easily peeled from the substrate, and in this case, the thermoplastic film becomes a peelable protective film of the surface layer of the composite film.
Thus, the thermoplastic film is introduced in the process of manufacturing the multilayer composite thermosetting film by the coating strippable technology, patterns are formed in various modes, the patterns can be printed on the composite film on the front surface of the base material to form decorative patterns, the thermoplastic film can also be used as a strippable protective film of the composite film, so that the thermal transfer patterns on the thermoplastic film are completely transferred to the composite film to form high-definition patterns, and the surface of the film can realize a matte or mirror high-gloss effect.
The embodiment method of printing a pattern on the composite film on the front surface of the substrate to form a decorative pattern can be seen in fig. 2, and fig. 2 also provides a preparation method of another embodiment of the polymer composite film of the present invention, which comprises:
s201, cleaning and drying the surface of a base material;
s202, performing antifouling protection on one surface of the cleaned and dried base material, wherein the surface is a back surface;
s203, flatly coating the thermoplastic film on the front surface of the base material;
s204, spraying thermosetting powder coating on the thermoplastic film on the front surface of the base material;
s205, curing the base material sprayed with the thermosetting powder coating, and cooling to normal temperature to form a composite film;
s206, printing a pattern on the film on the front surface of the base material to form a decorative pattern;
s207, spraying or coating thermosetting paint on the film with the decorative pattern;
s208, removing the antifouling protective material on the surface of the base material, and cleaning;
and S209, cooling the base material with the formed composite film to normal temperature, peeling the film from the surface of the base material, and rolling and packaging.
Different from the method for preparing the polymer composite film shown in fig. 1, the method for preparing shown in fig. 2 additionally prints a pattern on the film on the front surface of the substrate after the step S205 to form a decorative pattern; and spraying or applying a thermosetting coating to the film on which the decorative pattern is formed.
The pattern can be printed on the film on the front surface of the substrate in various ways, and specifically, the pattern can be printed on the film on the front surface of the substrate in an ink printing way, an ink-jet printing way or a decal printing way.
Preferably, in step S207, the thermosetting coating is an ultraviolet radiation curable coating or a thermosetting powder coating. The technical details of the thermosetting powder coating are the same as those described above and are not described herein again.
As a more preferred embodiment of the present invention, step S206 is followed by:
and coating a base coating matched with the decorative pattern on the front surface of the base material with the decorative pattern.
After the decorative pattern is formed, a UV or electrostatic powder spraying base coat matched with the pattern can be roll-coated according to the needs of a user, and the mirror surface effect is more plump and real after the pattern is provided with a base color; the transparent coating can also be roll-coated or electrostatic sprayed, so that a user can conveniently stick various colored polymer composite films in a DIY manner to form favorite color register effect.
In conclusion, the functional multilayer composite film can be manufactured by selecting high polymer materials in the plastic and paint fields in a cross-boundary way by adopting the paint stripping technology, so that the raw material selection range of the multilayer composite functional film is greatly widened, the performance of the film is greatly improved, and the functions are more abundant and diversified. For example: the development trend in the building field is towards the development of green, environment-friendly, low-carbon and energy-saving, the ultra-weather-resistant film is very consistent with the trend, and the film meeting the requirement at present is mostly made of fluorine-containing materials, so that the film is expensive and difficult to popularize and use on a large scale. The coating strippable film-making technology can be applied to super weather-resistant films or multi-layer composite films compounded with fluorine-containing materials, the weather-resistant grade and the performance of the film-making technology are completely equivalent to those of pure fluorine-containing material films, and the cost is only 30 percent. In the field of conductive films, carbon nanotubes and coatings can be compounded to form a carbon nanotube composite film, the surface resistance of the film reaches 30 ohms per square meter, and the cost is only 10% of the process of adding carbon nanomaterials into high polymer materials and plating noble metals. In the aspect of high hardness and flexibility, the problem of the film is more outstanding, the high hardness can cause the film to have poor bending resistance and folding resistance, the problem is solved by adopting metal ion sputtering, the coating strippable film-making technology can make a very hard coating film into a very thin film of 1-5 mu m, then a coating with good flexibility is coated on the very hard coating film for composite film-making, the hard film and the film with good flexibility are combined into a whole after the coating film is stripped, the hardness and the flexibility are well considered, and the cost is greatly reduced.
Therefore, the invention utilizes the material and the construction principle of the thermosetting coating to prepare the single-layer or multi-layer polymer composite film with different functions, and then the film is peeled from the base material, so the equipment investment is small, the production organization is flexible, the types and the functions of the film are rich, and the personalized customization can be realized. The number of the composite layers is not limited by equipment, and the thickness can be flexibly adjusted; because the coating is various, the composite film can realize more functions by coating various functional coatings.
Moreover, the coating film prepared by the invention is prepared by the thermosetting coating, so that the performances of thermal stability, solvent resistance, hardness, elongation and the like are greatly improved. When the temperature is increased from room temperature to 40 ℃, the elongation of the PVC film with the film thickness of 20um is 300 percent higher than that of the PVC film prepared by the common method under the same external force action. For another example: the hardness of the pencil is B, the PVC film prepared by the common method, and the film prepared by the invention can reach HB-6H according to different coatings.
The invention is further illustrated by the following specific examples
Example 1:
1) selecting a base material: selecting a piece of ordinary white glass with the thickness of 400 x 600 x 5mm, cleaning the surface of the glass by using clean water, and drying the glass at the drying temperature of 120 ℃ for 5 minutes;
2) performing antifouling protection on one surface of the cleaned and dried glass, wherein the surface is the back surface;
3) the front surface of the glass is reversely pasted with a PET film (the using surface is pasted to the glass), and the back surface of the glass is fixed by back glue of sodium carboxymethyl cellulose glue;
4) adding 0.5% of flatting agent, 0.5% of degassing agent and 1% of carbon black into 96% of epoxy resin BE503 produced by national chemical company and 2% of dicyandiamide curing agent produced by Ningxia Darong company to prepare powder coating, spraying the powder coating on the PET film obtained in the step 3) by adopting electrostatic powder spraying equipment, baking the powder coating at high temperature of 180 ℃ for 15min by using a hot air oven to form a black coating with the thickness of 30 mu m, and melting the black coating and the PET film to form a complete composite film;
5) cooling the workpiece after the step 4) to room temperature;
6) peeling the composite film from the glass;
7) and protecting the front surface of the clean and dried composite film, and making the composite film into a roll, wherein the composite film is a black matte composite film.
Example 2:
1) selecting a base material: selecting a piece of ordinary white glass with the thickness of 400 x 600 x 5mm, cleaning the surface of the glass by using clean water, and drying the glass at the drying temperature of 120 ℃ for 5 minutes;
2) performing antifouling protection on one surface of the cleaned and dried glass, wherein the surface is the back surface;
3) one side of the PET film is provided with a wood grain pattern, the front side of the glass is reversely pasted with the PET film (the surface of the wood grain pattern is pasted to the glass), and the back side of the glass is fixed by back glue of sodium carboxymethyl cellulose;
4) taking 95% of epoxy resin NPES903 produced by south Asia company and 2% of dicyandiamide produced by Ningxia Darong company as curing agents, adding 1% of flatting agent, 1% of degassing agent and 1% of white pigment to prepare powder coating, spraying the powder coating on the PET film obtained in the step 3) by adopting electrostatic powder spraying equipment, baking the powder coating at high temperature of a hot air oven for 15min at the baking temperature of 190 ℃ to form a white coating with the thickness of 50 mu m, and melting the white coating and the PET film to form a complete composite film;
5) cooling the workpiece after the step 4) to room temperature;
6) peeling the composite film from the glass;
7) and protecting the front surface of the clean and dried composite film, and making the composite film into a roll, wherein the composite film is a wood grain texture matte composite film.
Example 3:
1) selecting a base material: selecting a piece of ordinary white glass with the thickness of 400 x 600 x 5mm, cleaning the surface of the glass by using clean water, and drying the glass at the drying temperature of 120 ℃ for 5 minutes;
2) performing antifouling protection on one surface of the cleaned and dried glass, wherein the surface is the back surface;
3) adhering a PET transparent high-light film on the front surface of the glass, and fixing the back surface of the glass by using sodium carboxymethylcellulose glue as a back glue;
4) adding 1% of flatting agent and 1% of degassing agent into 49% of polyester resin SJ6200 produced by Anhui Shenjian company and 49% of epoxy resin KD-213 produced by Country company to prepare powder coating, spraying the powder coating on the PET film obtained in the step 3) by adopting electrostatic powder spraying equipment, and baking the PET film at the high temperature of 150 ℃ for 15min by using a hot air oven to form a transparent powder coating with the thickness of 60 mu m;
5) cooling the workpiece after the step 4) to room temperature;
6) pattern printing on the transparent powder coating layer by using a UV printer;
7) adding 1% of carbon black, 2% of a leveling agent, 1% of a degassing agent and other auxiliaries into 48% of polyester resin SJ6200 produced by Anhui Shenjian company and 48% of epoxy resin KD-213 produced by Country company to prepare a powder coating, spraying the powder coating on the printing coating obtained in the step 6) by adopting an electrostatic powder spraying device, and baking the powder coating at a high temperature of 150 ℃ for 15min by using a hot air oven to form a black coating with the thickness of 50 microns;
8) peeling a composite film from the glass, wherein the composite film is a black highlight composite film with DIY printing effect;
9) the PET film on the front surface of the composite film does not need to be peeled off, the PET film is used as front surface protection and is made into a roll, and the PET film on the surface is torn off when the PET film is to be used.
Example 4:
1) selecting a base material: selecting a piece of ordinary white glass with the thickness of 400 x 600 x 5mm, cleaning the surface of the glass by using clean water, and drying the glass at the drying temperature of 120 ℃ for 5 minutes;
2) performing antifouling protection on one surface of the cleaned and dried glass, wherein the surface is the back surface;
3) adhering a PET transparent high-light film on the front surface of the glass, and fixing the back surface of the glass by using sodium carboxymethylcellulose glue as a back glue;
4) adding 1% of flatting agent and 1% of degassing agent into 49% of polyester resin Uralac P5127 produced by DSM company and 49% of polyester resin NPES903 produced by Taiwan south Asia company to prepare powder coating, spraying the powder coating on the PET film obtained in the step 3) by adopting electrostatic powder spraying equipment, and baking the PET film at high temperature of 160 ℃ for 15min by a hot air oven to form a transparent powder coating with the thickness of 80 mu m;
5) cooling the workpiece after the step 4) to room temperature;
6) pattern printing on the transparent powder coating layer by using a UV printer;
7) using UV roller coating equipment to coat a UV coating on the printing coating in the step 6) to play a role in protection and color register;
8) peeling a composite film from glass, wherein the composite film is a composite film with DIY printing effect;
9) the PET film on the front surface of the coating does not need to be peeled off, the PET film is used as front surface protection and is made into a roll, and the PET film on the surface is torn off when the PET film is to be used.
Example 5: UV printing is carried out after PET matte transparent film is sprayed with fluorocarbon transparent powder coating
1) Selecting a base material: selecting a piece of ordinary white glass with the thickness of 400 x 600 x 5mm, cleaning the surface of the glass by using clean water, and drying the glass at the drying temperature of 120 ℃ for 5 minutes;
2) performing antifouling protection on one surface of the cleaned and dried glass, wherein the surface is the back surface;
3) pasting a PET matte transparent film on the front surface of the glass, and fixing the back surface of the glass by using sodium carboxymethylcellulose glue as a back glue;
4) preparing 83% of fluorocarbon resin Lumiflon710LF produced by Asahi glass company in Japan, and 15% of isocyanate curing agent B1530 produced by Yingchuang company, 1% of leveling agent and 1% of degassing agent into powder coating, spraying the powder coating on the PET film obtained in the step 3) by adopting electrostatic powder spraying equipment, baking the PET film at a high temperature of 200 ℃ for 20min by using a hot air oven to form a transparent powder coating with the thickness of 100 mu m, and melting the transparent powder coating and the PET thermoplastic film to form a complete composite film;
5) cooling the workpiece after the step 4) to room temperature;
6) pattern printing on the transparent powder coating layer by using a UV printer;
7) using UV roller coating equipment to coat a UV coating on the printing coating in the step 6) to play a role in protection and color register;
8) and peeling the composite film from the glass, performing front protection, and manufacturing into a roll, wherein the composite film is a composite film with a DIY printing effect.
The technical tests of the embodiment 1-5 are as follows:
the gloss was measured according to ISO 2813; the pencil hardness is measured according to ISO 15184; weather resistance was measured according to the method of ASTM-G53; MEK (methyl ethyl ketone) resistance is detected according to the method of ISO 2812-1; the detergent resistance was measured according to ASTM2248-01 a.
It should be noted that, in the examples, the raw materials of the thermosetting powder coating are selected and the preparation method is as follows.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (13)
1. A method for preparing a polymer composite film is characterized by comprising the following steps:
(1) cleaning and drying the surface of a substrate, wherein the substrate is made of glass, ceramic or metal;
(2) performing antifouling protection on one surface of the cleaned and dried base material, wherein the surface is the back surface;
(3) flatly coating the thermoplastic film on the front surface of the base material;
(4) spraying thermosetting powder coating on the thermoplastic film on the front surface of the substrate, wherein the thermosetting powder coating and the thermoplastic film have compatibility, and the curing temperature of the thermosetting powder coating is more than or equal to the melting temperature of the thermoplastic film, or the curing temperature of the thermosetting powder coating is less than the melting temperature of the thermoplastic film;
(5) curing the base material sprayed with the thermosetting powder coating, and cooling to normal temperature to form a composite film;
(6) and (3) cooling the base material with the formed composite film to normal temperature, peeling the film from the surface of the base material, and rolling and packaging.
2. The method for preparing a polymer composite film according to claim 1, wherein the thermoplastic film is a PET film, a PE film, a PVC film, a PP film or an ABS film.
3. The method for preparing the polymer composite film according to claim 2, wherein the PET film is a transparent PET film, a PET heat transfer film or a PET aluminized film.
4. The method of claim 1, wherein the thermosetting powder coating has a curing temperature not lower than a melting temperature of the thermoplastic film, and the thermoplastic film becomes an inseparable part of the composite film.
5. The method of claim 1, wherein the thermosetting powder coating has a curing temperature < the melting temperature of the thermoplastic film, and the thermoplastic film becomes a peelable protective film of the composite film.
6. The method for preparing a polymer composite film according to claim 1, wherein the thermosetting powder coating has a D50 particle size of 5 μm to 60 μm;
the thermosetting powder coating is one or more of pure epoxy powder coating, epoxy polyester powder coating, pure polyester powder coating, polyurethane powder coating, acrylic acid powder coating and fluorocarbon powder coating.
7. The method of claim 1, wherein the thermosetting powder coating is sprayed onto the thermoplastic film on the front surface of the substrate by an electrostatic powder spraying device, and the thickness of the thermosetting powder coating is 20 μm to 300 μm.
8. The method of preparing a polymer composite film according to claim 1, wherein in the step (4), after the thermosetting powder coating is sprayed on the thermoplastic film on the front surface of the substrate, a 3D texture effect is formed on the surface of the coating by using a molded plate.
9. The method of producing a polymer composite film according to claim 1, wherein the steps (4) and (5) are repeated a plurality of times to form a multilayer composite film.
10. The method for preparing a polymer composite film according to claim 1, further comprising, after the step (5) and before the step (6):
one or more layers of thermoplastic or metal films are provided on the film formed by the thermosetting powder coating by means of bonding to form a multilayer composite film.
11. The method for preparing a polymer composite film according to claim 1, wherein in the step (5), the curing treatment is infrared radiation curing, hot air baking or UV curing;
the hot air baking temperature is 60-200 ℃, and the baking time is 1-30 minutes.
12. The method for preparing a polymer composite film according to claim 1, further comprising, after the step (5) and before the step (6):
printing a pattern on the film on the front surface of the base material to form a decorative pattern;
and coating the film with the decorative pattern with a thermosetting coating.
13. The method for preparing a polymer composite film according to claim 12, wherein the pattern is printed on the film on the front surface of the substrate by means of ink printing, ink jet printing or decal printing;
the thermosetting coating is ultraviolet radiation curing coating or thermosetting powder coating.
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| CN112223876B (en) * | 2020-09-03 | 2023-06-06 | 青岛中集创赢复合材料科技有限公司 | Composite sheet and composite sheet production system |
| CN112172372B (en) * | 2020-09-29 | 2021-07-02 | 中星中大印刷（深圳）有限公司 | Plastic-free coating laminating process and plastic-free coating laminating paper |
| CN112251161B (en) * | 2020-11-01 | 2022-05-31 | 浙江世窗光学薄膜制造有限公司 | Elastomer protective film with patterns and preparation method thereof |
| CN112795268B (en) * | 2021-02-01 | 2022-06-28 | 汕头市亮彩新材料科技有限公司 | High-temperature-resistant molecular release layer coating and method for preparing broken drill powder by using same |
| CN113527741A (en) * | 2021-07-19 | 2021-10-22 | 湖北高正新材料科技有限公司 | Preparation method of polymer composite film |
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| AU2001292823A1 (en) * | 2000-09-20 | 2002-04-02 | World Properties Inc. | Electrostatic deposition of high temperature, high performance thermoplastics |
| CN1330689C (en) * | 2002-11-13 | 2007-08-08 | 伊斯曼柯达公司 | Optical switch microfilms |
| WO2004050748A1 (en) * | 2002-11-29 | 2004-06-17 | Eamex Corporation | Process for producing high-strength polypyrrole film |
| CN101037300A (en) * | 2007-03-16 | 2007-09-19 | 李守进 | Production method of color-based glass with solid pattern |
| EP2253466A4 (en) * | 2008-03-09 | 2012-08-01 | Mitsubishi Plastics Inc | MOVING FILM |
| CN103448344A (en) * | 2013-08-09 | 2013-12-18 | 辉旭微粉技术（上海）有限公司 | Preparation method of PVDF (Polyvinylidene Fluoride) composite film |
| CN107473601B (en) * | 2017-09-12 | 2020-04-10 | 浙江新迪在龙涂料科技有限公司 | Decorative glass and preparation method thereof |
| CN208682263U (en) * | 2018-08-15 | 2019-04-02 | 深圳永昌和科技有限公司 | A kind of ventilative release film of 3D printing |
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