CN114574118A - Double-component polyurethane multilayer film and preparation method thereof - Google Patents
Double-component polyurethane multilayer film and preparation method thereof Download PDFInfo
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- CN114574118A CN114574118A CN202210200481.5A CN202210200481A CN114574118A CN 114574118 A CN114574118 A CN 114574118A CN 202210200481 A CN202210200481 A CN 202210200481A CN 114574118 A CN114574118 A CN 114574118A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
- C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a double-component polyurethane multilayer film and a preparation method thereof. The preparation method comprises the following steps: applying the flexible polyurethane coating liquid on the surface of a polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, and then carrying out plasma discharge treatment; coating the pressure-sensitive adhesive solution on the surface of the flexible polyurethane film coating to form a pressure-sensitive adhesive layer; applying a flexible polyurethane coating liquid on the surface of the other polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, carrying out plasma discharge treatment, and then compounding with the pressure-sensitive adhesive layer; after heating and curing, stripping off the two polyethylene glycol terephthalate lining films, coating a coating containing a heat-insulating nano material on the surface of the flexible polyurethane film coating on one surface, and baking and curing; and coating a pressure-sensitive adhesive solution on the surface of the other flexible polyurethane film coating. The sandwich structure can avoid the problem that the TPU base film prepared by a casting method has poor leveling property.
Description
Technical Field
The invention relates to the field of film preparation, in particular to a bi-component polyurethane multilayer film and a preparation method thereof.
Background
At present, the types of automobile paint protective films sold on the market are very many, and most of the automobile paint protective films are paved and adhered on the automobile paint by adopting common PVC (polyvinyl chloride) films so as to protect the automobile paint protective films from being abraded and damaged by the outside. The plasticizer in the PVC base film can slowly migrate to the surface along with the time, so that the PVC protective film can gradually become hard and brittle when used at the later stage, and meanwhile, the plasticizer migrates to the adhesive layer to reduce the adhesive force of the adhesive, so that the phenomena of scratching, bubbling, falling off and the like of the protective adhesive film occur, and the PVC protective film is very unsightly. Thermoplastic polyurethane elastomer-based films are therefore increasingly used at present as protective films for automotive finishes.
In addition, because the polyurethane elastomer base film has the function of buffering impact force, the polyurethane elastomer base film is used as an automobile paint protective film, and is also used for gradually replacing the existing PET automobile glass heat insulation adhesive film, and the polyurethane elastomer base film also has the functions of resisting impact and scratching while providing heat insulation function.
However, one problem of the existing TPU heat insulation film when applied to the front bumper of an automobile is that a general TPU (thermoplastic polyurethane elastomer rubber) base film is obtained by adopting a casting method to melt TPU particles, then casting and cooling the melted TPU particles under a high temperature condition (120-200 ℃). Since the viscosity of TPU melts is generally high, the leveling of TPU base films obtained by casting from TPU particles is poor, resulting in higher surface microroughness of the final TPU film. When it is used in a front bumper of an automobile, since a front glass is inclined, a human sight line is generally at an acute angle thereto, and the sight line is affected by light scattering due to surface roughness of a TPU film. Therefore, a self-healing heat insulating film having more excellent leveling property is required.
Disclosure of Invention
The invention relates to a double-component polyurethane multilayer film and a preparation method thereof.
The invention adopts a coating method, and uses a sandwich structure of a flexible PU coating/a pressure sensitive adhesive/a flexible PU coating to replace the traditional TPU base film, thereby avoiding the problem of poor leveling property of the TPU base film prepared by a casting method.
The inventor finds that the flexible polyurethane coating is formed by directly using the flexible polyurethane coating liquid, then the thin film layer is subjected to plasma discharge treatment, and the flexible polyurethane coating contains carboxylic silane modified nano silicon dioxide and 8-mercapto-1-octanol, so that the bonding strength of each layer of the thin film can be improved, adverse effects caused by light scattering of thin film particles can be effectively avoided, and the leveling performance of the thin film is more excellent.
The invention provides a preparation method of a double-component polyurethane multilayer film, which comprises the following steps:
(1) applying the flexible polyurethane coating liquid on the surface of a polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, and then carrying out plasma discharge treatment;
(2) coating the pressure-sensitive adhesive solution on the surface of the flexible polyurethane film coating in the step (1) to form a pressure-sensitive adhesive layer;
(3) applying a flexible polyurethane coating liquid on the surface of the other polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, carrying out plasma discharge treatment, and then compounding with the pressure-sensitive adhesive layer in the step (2);
(4) after heating and curing, stripping off the two polyethylene glycol terephthalate lining films, coating a coating containing a heat-insulating nano material on the surface of the flexible polyurethane film coating on one surface, and baking and curing; coating a pressure-sensitive adhesive solution on the surface of the other flexible polyurethane film coating;
in the step (1) and the step (3), the raw material formula of the flexible polyurethane coating liquid comprises: hydroxyl-terminated waterborne acrylate resin, waterborne isocyanate, carboxylic silane modified nano-silica, metal oxide nanoparticles, 8-mercapto-1-octanol, a wetting agent, a defoaming agent and deionized water.
Among them, the hydroxyl-terminated water-based acrylate resin is preferably Bayhydrol A series, Bayhydrol UH series or Bayhydrol U series. The aqueous isocyanate may be any of various isocyanates conventionally used in the art.
The flexible polyurethane coating liquid uses a double-component polyurethane raw material, a low-temperature curing step is added in the step (4), and a flexible polyurethane film layer obtained by the double-component polyurethane is a cross-linked polyurethane film layer.
The pressure-sensitive adhesive solution is preferably an acrylic pressure-sensitive adhesive solution.
In the invention, 8-sulfydryl-1-octanol can effectively improve the dispersibility of particles, and sulfydryl at the tail end of a molecular chain can modify nano silicon dioxide and metal oxide nano particles, thereby being beneficial to the dispersion of the particles; hydroxyl at the other end of the molecular chain can participate in the curing reaction of the waterborne polyurethane resin to form a space network structure, so that the particles are dispersed more uniformly in the polyurethane coating liquid on one hand, and the bonding property and the mechanical property of the flexible polyurethane coating can be improved on the other hand.
Wherein, the metal oxide nano-particles are preferably one or more of nano titanium dioxide, nano aluminum oxide and nano zinc oxide.
Among them, the wetting agent is preferably SN-5040 as a dispersant.
Wherein, the defoaming agent is preferably defoaming agent CF-16.
The gas used in the plasma discharge treatment is preferably nitrogen.
Among them, the carboxylic silane is preferably tetrakis (4-carboxyphenyl) silane.
The carboxylic silane modified nano-silica is preferably prepared by the following method: mixing the silica sol and carboxylic silane in a solvent DMF, and heating and reacting under a vacuum sealing condition to obtain the silica sol-gel resin. The heating reaction temperature is preferably 90-100 ℃; the heating reaction time is preferably 20 to 30 hours.
In the step (4), the heating and curing conditions are preferably 95-105 ℃ for 2-3 minutes, and then 40-69 ℃ for 48-144 hours.
In the step (4), the baking and curing temperature is preferably 70-120 ℃, and the time is preferably 1-8 minutes.
The invention also provides a bi-component polyurethane multilayer film prepared by the preparation method.
The double-component polyurethane multilayer film is formed by laminating and compounding a pressure-sensitive adhesive layer, a flexible polyurethane coating, a pressure-sensitive adhesive layer, a flexible polyurethane coating and a heat-insulating nano material layer from bottom to top in sequence.
Preferably, the thickness of the pressure-sensitive adhesive layer is 10-20 micrometers.
Preferably, the thickness of the flexible polyurethane coating is 20-50 microns.
Preferably, the thickness of the heat insulation nanometer material layer is 5-15 micrometers.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effect achieved by the invention is as follows: the sandwich structure of the flexible PU coating/the pressure-sensitive adhesive/the flexible PU coating is used for replacing the traditional TPU base film, so that the problem of poor leveling property of the TPU base film prepared by a casting method is solved.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Solvent resistance test method: 1ml of xylene is sprayed onto the surface of the material to be tested and after 30 seconds is wiped dry with a wipe. If the appearance of the material has no obvious change (such as swelling deformation, coating falling off and the like), the solvent resistance test is qualified.
The self-repairing test method comprises the following steps: after brushing the surface of the film with a straight wire steel brush, it was observed whether the brush marks automatically disappeared within 1 hour or in the case of a heat source (e.g., hot water casting). If the material can disappear, the material is considered to have a self-repairing function.
Gloss evaluation method: the flexible polymer substrate coated with the self-repairing coating is adhered to a ferrous metal plate, and the gloss of the surface of the material is observed from the front side and the side (45 degrees). The surface is smooth and reflective, the reverse image is clear and sharp, the gloss is considered to be excellent, otherwise, the gloss is considered to be poor.
Stain resistance evaluation method: marking the surface of the coating by using a 6881 black oily marking pen, placing for 1 day after the mark is dried, directly wiping by using a piece of mirror wiping paper or wiping by dipping the mirror wiping paper in absolute alcohol, and observing the clearing condition of the mark. The stain resistance is considered to be excellent if the mark can be completely wiped off without leaving a mark. If the mark is not erasable, the stain resistance is considered poor. Stain resistance is considered good if the mark can be wiped off, but there is a small amount of marking.
Elongation at break test method: cutting the material to be measured into sample strips with the specification of 5 cm (length) and 2 cm (width), marking the length of the middle 2 cm, forcibly stretching the sample strips to two sides until cracks appear, measuring the length L1 of the marked part at the moment, and then calculating the elongation at break according to the following formula.
Elongation at break (%) - (L1-2)/2
The weather resistance test method is as follows: weather resistance tests were performed using Eye Super UV Tester W-151, Iwasaki Electric co. One cycle consists of keeping the temperature at 63 deg.C, relative humidity at 50%, and illumination at 50Mw/cm2And a rain shower for 5 hours at 10 seconds/hour, and a relative humidity of 95% at 30 ℃ for 1 hour. After repeating the above weathering cycle 300 times, the coating was observed with the naked eye and under a microscope (x 250), and if no cracks or partial peeling were observed, the coating surface was good and the weathering performance was good.
The components in the formula are calculated by weight parts.
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive formula conventionally used in the field, and specifically comprises the following components: acrylic acid, methyl acrylate, myrcene,
Butadiene, toluene.
The coating of the heat insulation nano material adopts a heat insulation coating which is conventional in the field; the parts in the following examples are all parts by weight.
Example 1
The steps for preparing the polyurethane multilayer film are as follows:
(1) applying the flexible polyurethane coating liquid on the surface of a polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, and then carrying out plasma discharge treatment; the gas used for the plasma discharge treatment is nitrogen for 10 minutes;
(2) coating acrylic pressure-sensitive adhesive liquid on the surface of the flexible polyurethane film coating in the step (1) to form a pressure-sensitive adhesive layer;
(3) applying a flexible polyurethane coating liquid on the surface of the other polyethylene terephthalate lining film, drying to form a flexible polyurethane film coating, carrying out plasma discharge treatment (the gas used for the plasma discharge treatment is nitrogen, and the time is 10 minutes), and then compounding with the pressure-sensitive adhesive layer in the step (2);
(4) heating at 100 deg.C for 2 min, aging at 50 deg.C for 60 hr, peeling off two polyethylene terephthalate lining films, coating a polyurethane film coating layer containing heat insulating nanometer material on one surface, baking and curing (at 70 deg.C for 8 min); coating acrylic pressure-sensitive glue solution on the surface of the polyurethane film coating on the other surface;
in this embodiment, the raw material formula of the flexible polyurethane coating liquid includes the following components in parts by weight: 20 parts of hydroxyl-terminated waterborne acrylate resin (Bayhydrol A series), 10 parts of waterborne isocyanate, 10 parts of carboxylic silane modified nano silicon dioxide, 5 parts of metal oxide nanoparticles, 3 parts of 8-mercapto-1-octanol, 1 part of wetting agent, 1 part of defoaming agent and 20 parts of deionized water.
In this embodiment, the metal oxide nanoparticles are nano titanium dioxide, the wetting agent is dispersant SN-5040, and the defoaming agent is defoaming agent CF-16.
The carboxylic silane modified nano silicon dioxide is prepared by the following method: mixing the silica sol and tetra (4-carboxyphenyl) silane in a solvent DMF, and heating and reacting under the vacuum sealing condition to obtain the silica sol. The temperature of the heating reaction is 90 ℃; the reaction time was 30 hours.
The polyurethane multilayer film prepared by the embodiment comprises a pressure-sensitive adhesive layer, a flexible polyurethane coating, a pressure-sensitive adhesive layer, a flexible polyurethane coating and a heat-insulating nano material layer which are laminated and compounded from bottom to top in sequence. The thickness of the pressure-sensitive adhesive layer is 10 micrometers. The thickness of the flexible polyurethane coating is 20 microns. The thickness of the heat insulation nanometer material layer is 5 micrometers.
The detection effect is as follows:
(1) the polyurethane coating has good adhesion fastness and is not easy to fall off, and the hundred-grid test reaches 5B;
(2) the elongation at break reaches 400 percent, and the breaking strength reaches 45 MPa;
(3) the scratch resistance is good, and the No. 0000 steel wire is loaded with 1kg and rubbed back and forth for more than 1000 times without scars;
(4) the weather resistance is good, and after the weather resistance cycle is repeated for 300 times, no crack or local peeling is still observed on the surface of the coating;
(5) the film is flat, the leveling property is excellent, and the 20-degree gloss is 97.
Example 2
The steps for preparing the polyurethane multilayer film are as follows:
(1) applying the flexible polyurethane coating liquid on the surface of a polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, and then carrying out plasma discharge treatment; the gas used for the plasma discharge treatment is nitrogen for 15 minutes;
(2) coating acrylic pressure-sensitive adhesive liquid on the surface of the flexible polyurethane film coating in the step (1) to form a pressure-sensitive adhesive layer;
(3) applying a flexible polyurethane coating liquid on the surface of the other polyethylene terephthalate lining film, drying to form a flexible polyurethane film coating, carrying out plasma discharge treatment (the gas used for the plasma discharge treatment is nitrogen, and the time is 15 minutes), and then compounding with the pressure-sensitive adhesive layer in the step (2);
(4) heating at 100 deg.C for 2 min, aging at 60 deg.C for 100 hr, peeling off two polyethylene terephthalate lining films, coating a polyurethane film coating layer containing heat insulating nanometer material on one surface, baking and curing (at 95 deg.C for 5 min); coating acrylic pressure-sensitive glue solution on the surface of the polyurethane film coating on the other surface;
in this embodiment, the raw material formula of the flexible polyurethane coating liquid includes the following components in parts by weight: 20 parts of hydroxyl-terminated waterborne acrylate resin (Bayhydrol U series), 10 parts of waterborne isocyanate, 14 parts of carboxylic silane modified nano silicon dioxide, 7 parts of metal oxide nanoparticles, 3 parts of 8-mercapto-1-octanol, 1 part of wetting agent, 1 part of defoaming agent and 20 parts of deionized water.
In this embodiment, the metal oxide nanoparticles are nano alumina, the wetting agent is dispersant SN-5040, and the defoaming agent is defoaming agent CF-16.
The carboxylic silane modified nano silicon dioxide is prepared by the following method: mixing the silica sol and tetra (4-carboxyphenyl) silane in a solvent DMF, and heating and reacting under the vacuum sealing condition to obtain the silica sol. The temperature of the heating reaction is 100 ℃; the reaction time was 20 hours.
The polyurethane multilayer film prepared by the embodiment comprises a pressure-sensitive adhesive layer, a flexible polyurethane coating, a pressure-sensitive adhesive layer, a flexible polyurethane coating and a heat-insulating nano material layer which are laminated and compounded from bottom to top in sequence. The thickness of the pressure-sensitive adhesive layer is 20 micrometers. The thickness of the flexible polyurethane coating is 50 microns. The thickness of the heat insulation nanometer material layer is 15 micrometers.
The detection effect is as follows:
(1) the polyurethane coating has good adhesion fastness and is not easy to fall off, and the hundred-grid test reaches 5B;
(2) the elongation at break reaches 400 percent, and the breaking strength reaches 46 MPa;
(3) the scratch resistance is good, and the No. 0000 steel wire is loaded with 1kg and rubbed back and forth for more than 1000 times without scars;
(4) the weather resistance is good, and after the weather resistance cycle is repeated for 300 times, no crack or local peeling is still observed on the surface of the coating;
(5) the film is flat, the leveling property is excellent, and the 20-degree gloss is 99.
Comparative example 1
In this example, a polyurethane multilayer film was prepared by using the same conditions as in example 1 except that the formulation of the raw material of the flexible polyurethane coating liquid contained no carboxylic acid silane-modified nano-silica. The film was tested for its performance by eye observation for surface irregularities and a 20 degree gloss of 83.
Comparative example 2
In this example, the raw material formulation of the flexible polyurethane coating liquid was changed to 8-mercapto-1-octanol with n-octanol, and the conditions of other parameters were the same as those in example 1, to obtain a polyurethane multilayer film. The film was tested for performance by eye observation for surface irregularities and a 20 degree gloss of 80.
Claims (10)
1. A method of making a two-component polyurethane multilayer film comprising the steps of:
(1) applying the flexible polyurethane coating liquid on the surface of a polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, and then carrying out plasma discharge treatment;
(2) coating the pressure-sensitive adhesive solution on the surface of the flexible polyurethane film coating in the step (1) to form a pressure-sensitive adhesive layer;
(3) applying a flexible polyurethane coating liquid on the surface of the other polyethylene glycol terephthalate lining film, drying to form a flexible polyurethane film coating, carrying out plasma discharge treatment, and then compounding with the pressure-sensitive adhesive layer in the step (2);
(4) after heating and curing, stripping off the two polyethylene terephthalate lining films, coating a coating containing a heat-insulating nano material on the surface of the flexible polyurethane film coating on one surface, and baking and curing; coating a pressure-sensitive adhesive solution on the surface of the other flexible polyurethane film coating;
in the step (1) and the step (3), the raw material formula of the flexible polyurethane coating liquid comprises: hydroxyl-terminated waterborne acrylate resin, waterborne isocyanate, carboxylic silane modified nano-silica, metal oxide nanoparticles, 8-mercapto-1-octanol, a wetting agent, a defoaming agent and deionized water.
2. The method according to claim 1, wherein the pressure-sensitive adhesive solution is an acrylic pressure-sensitive adhesive solution.
3. The method of claim 1, wherein the metal oxide nanoparticles are one or more of nano titanium dioxide, nano aluminum oxide and nano zinc oxide.
4. The process according to claim 1, wherein the wetting agent is dispersant SN-5040;
the defoaming agent is a defoaming agent CF-16;
the gas used for the plasma discharge treatment is nitrogen.
5. The method of claim 1, wherein the carboxylic silane is tetrakis (4-carboxyphenyl) silane.
6. The preparation method of claim 1, wherein the carboxylic silane modified nano-silica is prepared by the following method: mixing silica sol and carboxylic silane in a solvent DMF, and heating and reacting under a vacuum sealing condition to obtain the modified silicon dioxide sol; the temperature of the heating reaction is 90-100 ℃; the heating reaction time is preferably 20 to 30 hours.
7. The method according to claim 1, wherein in the step (4), the heating and curing conditions are 95-105 ℃ for 2-3 minutes, and then 40-69 ℃ for 48-144 hours.
8. The method according to claim 1, wherein in the step (4), the temperature for baking and curing is 70-120 ℃ for 1-8 minutes.
9. A two-component polyurethane multilayer film prepared by the preparation method of any one of claims 1 to 8.
10. The double-component polyurethane multilayer film of claim 1, wherein the double-component polyurethane multilayer film is formed by laminating and compounding a pressure-sensitive adhesive layer, a flexible polyurethane coating, a pressure-sensitive adhesive layer, a flexible polyurethane coating and a heat-insulating nano material layer from bottom to top in sequence;
preferably, the thickness of the pressure-sensitive adhesive layer is 10-20 micrometers;
preferably, the thickness of the flexible polyurethane coating is 20-50 micrometers;
preferably, the thickness of the heat insulation nano material layer is 5-15 micrometers.
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| CN202210200481.5A CN114574118B (en) | 2022-02-26 | 2022-02-26 | Polyurethane multilayer film and preparation method thereof |
| PCT/CN2022/093702 WO2023159780A1 (en) | 2022-02-26 | 2022-05-18 | Bicomponent polyurethane multilayer film and preparation method therefor |
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| CN202210200481.5A CN114574118B (en) | 2022-02-26 | 2022-02-26 | Polyurethane multilayer film and preparation method thereof |
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| CN114574118B (en) | 2023-04-28 |
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