CN117903715B - PVC-PET composite board film and preparation method thereof - Google Patents
PVC-PET composite board film and preparation method thereof Download PDFInfo
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- CN117903715B CN117903715B CN202410084124.6A CN202410084124A CN117903715B CN 117903715 B CN117903715 B CN 117903715B CN 202410084124 A CN202410084124 A CN 202410084124A CN 117903715 B CN117903715 B CN 117903715B
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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
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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Abstract
The application discloses a PVC-PET composite board film and a preparation process thereof, and relates to the field of composite board films, wherein the PVC-PET composite board film comprises a substrate layer, a decorative layer, a bonding layer and a film coating layer; the decorative layer is bonded with the substrate layer; one side of the bonding layer is bonded with the film coating layer, and the other side of the bonding layer is bonded with one side of the decorative layer away from the substrate layer; the film coating layer is prepared from the following raw materials in parts by weight: 10-30 parts of polyethylene terephthalate; 8-16 parts of polysiloxane/polyester diol compound; 20-40 parts of polyisocyanate; 5-15 parts of modified nano silicon dioxide; 0.5-1.5 parts of catalyst; 1-3 parts of chain extender. The application has the effect of improving the wear resistance of the PVC-PET composite board film.
Description
Technical Field
The invention relates to the field of composite board films, in particular to a PVC-PET composite board film and a preparation method thereof.
Background
The polymer material has been widely used in various fields due to its good properties, wherein the protective film prepared from the polymer material is more visible in aspects of life.
At present, the PET-PVC composite film commonly used in furniture products is adhered to the surface of furniture, so that the furniture has a decoration effect, a certain protection effect on film-covered furniture, and the furniture has the effects of moisture resistance, corrosion resistance, surface decoration and the like.
However, the existing PET-PVC composite board film is poor in wear resistance, and if hard objects such as cutters and the like drop on the composite board carelessly, the PET-PVC composite board film is easy to have larger impact force, so that the PET-PVC composite board film is worn and scratched, and the using effect is affected.
Disclosure of Invention
The application provides a PVC-PET composite board film and a preparation method thereof in order to improve the wear resistance of the PVC-PET composite board film.
In a first aspect, the application provides a PVC-PET composite board film, which adopts the following technical scheme:
A PVC-PET composite board film comprises a substrate layer, a decorative layer, a bonding layer and a film coating layer; the decorative layer is bonded with the substrate layer; one side of the bonding layer is bonded with the film coating layer, and the other side of the bonding layer is bonded with one side of the decorative layer away from the substrate layer; the film coating layer is prepared from the following raw materials in parts by weight: 10-30 parts of polyethylene terephthalate; 8-16 parts of polysiloxane/polyester diol compound; 20-40 parts of polyisocyanate; 5-15 parts of modified nano silicon dioxide; 0.5-1.5 parts of catalyst; 1-3 parts of chain extender.
By adopting the technical scheme, the polysiloxane/polyester diol compound and polyisocyanate react and polymerize under the action of the catalyst and the chain extender to form polyurethane, the polysiloxane/polyester diol compound is incompatible with the polyethylene terephthalate, the polysiloxane can be separated out of the surface of the polyethylene terephthalate, the polysiloxane on the surface can improve the smoothness of the polyethylene terephthalate, further the abrasion of a coating layer is reduced, the abrasion resistance of the coating layer is improved, and the polyisocyanate reacts with the polysiloxane in the polysiloxane/polyester diol compound to form a polyurethane-siloxane copolymer; the wear resistance of polyethylene terephthalate is further improved by combining the advantages of polyurethane and siloxane.
Preferably, the preparation method of the nano silicon dioxide comprises the following steps: heating 10-20 parts by weight of simethicone, 5-15 parts by weight of methyl siloxane, 2-8 parts by weight of tetramethyl tetravinyl siloxane, 20-40 parts by weight of nano silicon dioxide and 1-3 parts by weight of stannous isooctanoate to 75-85 ℃ and uniformly stirring, heating to 155-165 ℃ and heating for 4-6 hours, and cooling to room temperature to obtain the modified nano silicon dioxide.
Through adopting above-mentioned technical scheme, through dimethyl silicone oil, methyl siloxane, tetramethyl tetravinyl siloxane to the modification of nano silicon dioxide, dimethyl silicone oil, methyl siloxane, tetramethyl tetravinyl siloxane are organosilicon, can improve the compatibility of polysiloxane chain segment in the polyurethane, and the nano silicon dioxide after the modification promotes polysiloxane chain segment to surface migration as the filler in the course of working, makes polysiloxane chain segment distribute on the PET membrane surface, and the polysiloxane chain segment of inside distribution is less, further improves the wear resistance of composite board membrane.
Preferably, the weight ratio of the simethicone to the methyl siloxane to the tetramethyl tetravinyl siloxane to the nano silicon dioxide is (1.6-1.8): 1: (0.3-0.4): (2.8-3.2)
Through the adoption of the technical scheme, when the dimethyl silicone oil, the methyl siloxane, the tetramethyl tetravinyl siloxane and the nano silicon dioxide are in a specific weight ratio, the migration of the polysiloxane chain segment to the surface of the coating layer can be further promoted, and the wear resistance of the coating layer is greatly improved.
Preferably, the polyisocyanate includes one or more of 4,4' -diphenylmethane diisocyanate and triphenylmethane triisocyanate.
By adopting the technical scheme, isocyanate with a plurality of isocyanic acid groups is selected for reaction, polyurethane can be formed by the isocyanate with polyethylene terephthalate, and polyurethane-siloxane copolymer can be formed by the isocyanate with polysiloxane/polyester diol compound, so that the wear resistance and impact resistance of the coating layer are further improved.
Preferably, the weight ratio of the 4,4' -diphenylmethane diisocyanate to the triphenylmethane triisocyanate is (1-2): 1.
By adopting the technical scheme, when the 4,4 '-diphenylmethane diisocyanate and the triphenylmethane triisocyanate are in a specific weight ratio, the two are matched together, isocyanate groups in the 4,4' -diphenylmethane diisocyanate and the triphenylmethane triisocyanate react with hydroxyl groups in the polyethylene terephthalate to form polyurethane chain segments, and the wear resistance of the coating layer is improved.
Preferably, the polysiloxane/polyester diol complex is prepared by the following steps: 15-25 parts by weight of polysiloxane, 20-50 parts by weight of polyester diol and 10-20 parts by weight of silane coupling agent are mixed and heated to a molten state, and then are extruded and cooled to obtain the polysiloxane/polyester diol composite.
By adopting the technical scheme, the polysiloxane is modified, the polyester diol and the silane coupling agent are mixed with the polysiloxane to prepare the polysiloxane/polyester diol compound, so that a polyester chain segment and a polysiloxane chain segment exist in the polysiloxane/polyester diol compound, the compound reacts with a polyisocyanate monomer to form polyurethane, and a urethane bond in the polyurethane and the polyethylene terephthalate form a hydrogen bond to form a physical crosslinking structure, so that the strength and the wear resistance of the coating layer are improved.
Preferably, the weight ratio of the polyethylene terephthalate, the polysiloxane/polyester diol compound, the polyisocyanate and the modified nano silicon dioxide is (0.4-0.6): (0.4-0.5): 1: (0.4-0.44).
By adopting the technical scheme, when the polyethylene terephthalate, the polysiloxane/polyester diol compound, the polyisocyanate and the modified nano silicon dioxide are compounded together in a specific weight ratio, the wear resistance and the tearing strength of the coating layer can be further improved.
Preferably, the catalyst is dibutyl tin dilaurate.
Preferably, the chain extender is one of ethylenediamine and diethylenetriamine.
By adopting the technical scheme, the PET film with good wear resistance can be prepared by selecting a proper catalyst and a chain extender, so that the wear resistance of the film coating layer is improved.
In a second aspect, the preparation method of the PVC-PET composite board film provided by the application adopts the following technical scheme: the preparation method of the PVC-PET composite board film comprises the following steps: stirring and heating the polysiloxane/polyester diol compound and polyisocyanate to 40-50 ℃ under the condition of introducing nitrogen, adding a catalyst, heating to 70-80 ℃ and reacting to obtain a prepolymer; uniformly mixing the prepolymer, modified nano silicon dioxide and polyethylene terephthalate, performing melt coextrusion, and cooling to obtain a film coating;
Rolling and forming a decorative layer on the surface of the substrate layer;
Coating an adhesive on the surface of the film coating layer to form an adhesive layer;
and (3) attaching the decorative layer and the bonding layer, hot-pressing, and cooling to obtain the PVC-PET composite board film.
By adopting the technical scheme, the components are added according to the steps, so that the PVC-PET composite board film with good wear resistance can be prepared.
In summary, the application has the following beneficial technical effects:
1. The polysiloxane/polyester diol compound reacts with polyisocyanate under the action of a catalyst and a chain extender to polymerize into polyurethane, the polysiloxane/polyester diol compound is incompatible with polyethylene terephthalate, the polysiloxane can separate out the surface of the polyethylene terephthalate, the polysiloxane on the surface can improve the smoothness of the polyethylene terephthalate, further reduce the abrasion of a coating layer, improve the abrasion resistance of the coating layer, and the polyisocyanate reacts with the polysiloxane in the polysiloxane/polyester diol compound to form a polyurethane-siloxane copolymer; the wear resistance of polyethylene terephthalate is further improved by combining the advantages of polyurethane and siloxane.
2. The nanometer silicon dioxide is modified by the dimethyl silicone oil, the methyl siloxane and the tetramethyl tetravinyl siloxane, and the dimethyl silicone oil, the methyl siloxane and the tetramethyl tetravinyl siloxane are all organic silicon, so that the compatibility of polysiloxane segments in polyurethane can be improved, the modified nanometer silicon dioxide is used as a filler to promote the migration of the polysiloxane segments to the surface in the processing process, the polysiloxane segments are distributed on the surface of the PET film, the number of internally distributed polysiloxane segments is small, and the wear resistance of the composite board film is further improved.
3. According to the application, polysiloxane is modified, polyester diol and a silane coupling agent are mixed with polysiloxane to prepare a polysiloxane/polyester diol compound, so that a polyester chain segment and a polysiloxane chain segment exist in the polysiloxane/polyester diol compound, the compound reacts with polyisocyanate monomers to form polyurethane, and a urethane bond in the polyurethane and polyethylene terephthalate have hydrogen bonds, so that a physical crosslinking structure is formed between the polyester chain segment and the polysiloxane chain segment, and the strength and the wear resistance of a coating layer are improved.
Drawings
Fig. 1 is a schematic overall structure of an embodiment of the present application.
Reference numerals illustrate:
1. a substrate layer; 2. a decorative layer; 3. a bonding layer; 4. and (5) coating a film layer.
Detailed Description
The present application will be described in further detail with reference to examples and comparative examples.
Examples
Example 1
Referring to fig. 1, a PVC-PET composite board film includes a base material layer 1, a decorative layer 2, an adhesive layer 3 and a film coating layer 4; the decorative layer 2 is bonded with the substrate layer 1; one side of the bonding layer 3 is bonded with the laminating layer 4, and the other side is bonded with one side of the decorative layer 2 away from the substrate layer 1; the substrate layer 1 is a PVC film.
A preparation method of a PVC-PET composite board film comprises the following steps:
Stirring and heating 8kg of polysiloxane/polyester diol compound and 20kg of 4,4' -diphenylmethane diisocyanate to 40 ℃ under the condition of introducing nitrogen, stirring for 20min, adding 0.5kg of dibutyltin dilaurate catalyst and 1kg of ethylenediamine chain extender, heating to 70 ℃ and reacting for 3h to obtain a prepolymer; putting the prepolymer, 5kg of modified nano silicon dioxide and 10kg of polyethylene terephthalate into a high-speed mixer, uniformly mixing for 10min, transferring into a screw extruder, melting and co-extruding under the condition that the screw rotating speed is 370r/min, and cooling to room temperature to obtain a film coating layer;
Wherein the 4,4' -diphenylmethane diisocyanate is Desmodur 44V20L; polyethylene terephthalate is DuPont RYNITE PET RE5329.
Rolling the surface of the substrate layer by adopting an embossing roller to form a decorative layer; the substrate layer is specifically a PVC film;
uniformly coating a silicone adhesive on the surface of the film coating layer by using a coating machine, wherein the coating speed is 70m/min, and drying in an oven at 80 ℃ to form a bonding layer;
and (3) attaching the decorative layer and the bonding layer, hot-pressing on a hot press with the temperature of 120 ℃, and cooling to room temperature to obtain the PVC-PET composite board film.
The preparation method of the modified nano silicon dioxide comprises the following steps:
10kg of simethicone, 5kg of methyl siloxane, 2kg of tetramethyl tetravinyl siloxane, 20kg of nano silicon dioxide and 1kg of stannous isooctanoate are put into a high-speed stirrer to be heated to 75 ℃ and stirred uniformly for 10min, then the temperature is raised to 155 ℃ and heated for 4h, and the mixture is cooled to room temperature, so that the modified nano silicon dioxide is obtained.
The preparation method of the polysiloxane/polyester diol compound comprises the following steps:
15kg of polysiloxane, 20kg of polyester diol and 10kgKH kg of silane coupling agent were put into an extruder, extruded after being heated to a molten state, and cooled to room temperature to obtain a polysiloxane/polyester diol composite.
Wherein the polysiloxane is Dow Corning 200Fluid 100cst; the polyester diol is selected from China petrochemical group Lutropur.
Example 2
A preparation method of a PVC-PET composite board film comprises the following steps:
Stirring and heating 16kg of polysiloxane/polyester diol compound and 40kg of 4,4' -diphenylmethane diisocyanate to 50 ℃ under the condition of introducing nitrogen, stirring for 20min, adding 1.5kg of dibutyltin dilaurate catalyst and 3kg of ethylenediamine chain extender, heating to 80 ℃ and reacting for 3h to obtain a prepolymer; putting the prepolymer, 15kg of modified nano silicon dioxide and 30kg of polyethylene terephthalate into a high-speed mixer, uniformly mixing for 10min, transferring into a screw extruder, melting and co-extruding under the condition that the screw rotating speed is 370r/min, and cooling to room temperature to obtain a film coating layer; wherein the 4,4' -diphenylmethane diisocyanate is Desmodur 44V20L; polyethylene terephthalate is DuPont RYNITE PET RE5329.
Rolling the surface of the substrate layer by adopting an embossing roller to form a decorative layer; the substrate layer is specifically a PVC film;
uniformly coating a silicone adhesive on the surface of the film coating layer by using a coating machine, wherein the coating speed is 70m/min, and drying in an oven at 80 ℃ to form a bonding layer;
and (3) attaching the decorative layer and the bonding layer, hot-pressing on a hot press with the temperature of 120 ℃, and cooling to room temperature to obtain the PVC-PET composite board film.
The preparation method of the modified nano silicon dioxide comprises the following steps:
10kg of simethicone, 5kg of methyl siloxane, 2kg of tetramethyl tetravinyl siloxane, 20kg of nano silicon dioxide and 1kg of stannous isooctanoate are put into a high-speed stirrer to be heated to 75 ℃ and stirred uniformly for 10min, then the temperature is raised to 155 ℃ and heated for 4h, and the mixture is cooled to room temperature, so that the modified nano silicon dioxide is obtained.
The preparation method of the polysiloxane/polyester diol compound comprises the following steps:
15kg of polysiloxane, 20kg of polyester diol and 10kgKH kg of silane coupling agent were put into an extruder, extruded after being heated to a molten state, and cooled to room temperature to obtain a polysiloxane/polyester diol composite. Wherein the polysiloxane is Dow Corning200Fluid 100cst; the polyester diol is selected from China petrochemical group Lutropur.
Example 3
A preparation method of a PVC-PET composite board film comprises the following steps:
Stirring and heating 12kg of polysiloxane/polyester diol compound and 30kg of 4,4' -diphenylmethane diisocyanate to 45 ℃ under the condition of introducing nitrogen, stirring for 20min, adding 1kg of dibutyltin dilaurate catalyst and 2kg of ethylenediamine chain extender, heating to 75 ℃ and reacting for 3h to obtain a prepolymer; putting the prepolymer, 10kg of modified nano silicon dioxide and 20kg of polyethylene terephthalate into a high-speed mixer, uniformly mixing for 10min, transferring into a screw extruder, melting and co-extruding under the condition that the screw rotating speed is 370r/min, and cooling to room temperature to obtain a film coating layer; wherein the 4,4' -diphenylmethane diisocyanate is Desmodur 44V20L; polyethylene terephthalate is DuPont RYNITE PET RE5329.
Rolling the surface of the substrate layer by adopting an embossing roller to form a decorative layer; the substrate layer is specifically a PVC film;
uniformly coating a silicone adhesive on the surface of the film coating layer by using a coating machine, wherein the coating speed is 70m/min, and drying in an oven at 80 ℃ to form a bonding layer;
and (3) attaching the decorative layer and the bonding layer, hot-pressing on a hot press with the temperature of 120 ℃, and cooling to room temperature to obtain the PVC-PET composite board film.
The preparation method of the modified nano silicon dioxide comprises the following steps:
10kg of simethicone, 5kg of methyl siloxane, 2kg of tetramethyl tetravinyl siloxane, 20kg of nano silicon dioxide and 1kg of stannous isooctanoate are put into a high-speed stirrer to be heated to 75 ℃ and stirred uniformly for 10min, then the temperature is raised to 155 ℃ and heated for 4h, and the mixture is cooled to room temperature, so that the modified nano silicon dioxide is obtained.
The preparation method of the polysiloxane/polyester diol compound comprises the following steps:
15kg of polysiloxane, 20kg of polyester diol and 10kgKH kg of silane coupling agent were put into an extruder, extruded after being heated to a molten state, and cooled to room temperature to obtain a polysiloxane/polyester diol composite. Wherein the polysiloxane is Dow Corning200Fluid 100cst; the polyester diol is selected from China petrochemical group Lutropur.
Example 4
The preparation method of the PVC-PET composite board film is different from that of the embodiment 3 in that the preparation method of the modified nano silicon dioxide is as follows: 20kg of simethicone, 15kg of methyl siloxane, 8kg of tetramethyl tetravinyl siloxane, 40kg of nano silicon dioxide and 3kg of stannous isooctanoate are put into a high-speed stirrer to be heated to 85 ℃ and stirred uniformly for 10min, then the temperature is raised to 165 ℃ and heated for 6h, and the mixture is cooled to room temperature, so that the modified nano silicon dioxide is obtained.
Example 5
The preparation method of the PVC-PET composite board film is different from example 3 in that in the preparation method of the modified nano silicon dioxide, the input amount of the simethicone is 16kg, the input amount of the methyl siloxane is 10kg, the input amount of the tetramethyl tetravinyl siloxane is 3kg, and the input amount of the nano silicon dioxide is 28kg.
Example 6
The preparation method of the PVC-PET composite board film is different from example 3 in that in the preparation method of the modified nano silicon dioxide, the input amount of the simethicone is 18kg, the input amount of the methyl siloxane is 10kg, the input amount of the tetramethyl tetravinyl siloxane is 4kg, and the input amount of the nano silicon dioxide is 32kg.
Example 7
A method for preparing a PVC-PET composite board film is different from example 6 in that the input amount of 4,4' -diphenylmethane diisocyanate is 15kg, and triphenylmethane triisocyanate is also 15 kg.
Example 8
A method for preparing a PVC-PET composite board film is different from example 6 in that the input amount of 4,4' -diphenylmethane diisocyanate is 20kg, and 10kg of triphenylmethane triisocyanate is also input.
Example 9
A method for preparing a PVC-PET composite board film is different from that of example 8 in that,
The preparation method of the polysiloxane/polyester diol compound comprises the following steps:
25kg of polysiloxane, 50kg of polyester diol and 20kgKH g of silane coupling agent were put into an extruder, extruded after being heated to a molten state, and cooled to room temperature to obtain a polysiloxane/polyester diol composite.
Example 10
A method for producing a PVC-PET composite sheet film was different from example 8 in that the amount of polyethylene terephthalate added was 12kg, the amount of polysiloxane/polyester diol composite added was 12kg, the amount of polyisocyanate (4, 4' -diphenylmethane diisocyanate 20kg, triphenylmethane triisocyanate 10 kg) added was 30kg, and the amount of modified nano silica added was 12kg.
Example 11
A method for producing a PVC-PET composite sheet film was different from example 8 in that the amount of polyethylene terephthalate added was 18kg, the amount of polysiloxane/polyester diol composite added was 15kg, the amount of polyisocyanate (4, 4' -diphenylmethane diisocyanate 20kg, triphenylmethane triisocyanate 10 kg) added was 30kg, and the amount of modified nano silica added was 13.2kg.
Comparative example
Comparative example 1
A method for preparing a PVC-PET composite board film, which is different from example 3 in that the modified nano silicon dioxide is replaced by nano silicon dioxide in an equivalent amount.
Comparative example 2
The preparation method of the PVC-PET composite board film is different from that of the embodiment 3 in that the modified nano silicon dioxide is replaced by nano titanium dioxide in an equivalent amount.
Comparative example 3
A method for preparing a PVC-PET composite board film is different from example 3 in that 4,4' -diphenylmethane diisocyanate is replaced by ethyl isocyanate in equal amount.
Comparative example 4
A method for preparing a PVC-PET composite sheet film, which differs from example 3 in that the polysiloxane/polyester diol complex is replaced by an equivalent amount of polysiloxane.
Comparative example 5
A method for preparing a PVC-PET composite board film is different from example 3 in that polysiloxane/polyester diol complex is replaced by polyoxypropylene diol (selected from neomycin 25322-69-4) in equal amount.
Performance test:
According to the wear resistance measuring method, with reference to GB1768-79 (89), the weight loss of the film is less than 10%, so that the wear resistance reaches the standard, otherwise, the wear resistance does not reach the standard. The film layers obtained in examples 1 to 11 and comparative examples 1 to 5 were adhered to a sample plate (diameter: 200mm, center hole diameter: 9 mm), and after drying, ground for 50 revolutions, and tested for abrasion resistance.
Tear strength: the tear strength of the coating layers produced in examples 1-11 and comparative examples 1-5 was tested with reference to GB/T529-2008.
Transmittance: the light transmittance of the coating layers prepared in examples 1 to 11 and comparative examples 1 to 5 was measured using a light transmittance-haze detector.
According to the data comparison of examples 1-3 and comparative examples 1-5, polyethylene terephthalate and polyisocyanate react and polymerize under the action of a catalyst and a chain extender to form polyurethane, a polysiloxane/polyester diol compound is incompatible with the polyethylene terephthalate, polysiloxane can be separated out of the surface of the polyethylene terephthalate, the polysiloxane on the surface can improve the smoothness of the polyethylene terephthalate, further the abrasion of a coating layer is reduced, the abrasion resistance of the coating layer is improved, and the polyisocyanate reacts with the polysiloxane in the polysiloxane/polyester diol compound to form a polyurethane-siloxane copolymer; the wear resistance of polyethylene terephthalate is further improved by combining the advantages of polyurethane and siloxane.
According to the data comparison of the examples 3-6, the nano silicon dioxide is modified by the dimethyl silicone oil, the methyl siloxane and the tetramethyl tetravinyl siloxane, and the dimethyl silicone oil, the methyl siloxane and the tetramethyl tetravinyl siloxane are all organic silicon, so that the compatibility of polysiloxane chain segments in polyurethane can be improved, the modified nano silicon dioxide is used as a filler to promote the migration of the polysiloxane chain segments to the surface in the processing process, the polysiloxane chain segments are distributed on the surface of the PET film, the polysiloxane chain segments distributed in the interior are fewer, and the wear resistance of the composite board film is further improved.
According to the data comparison of examples 6-8, when the 4,4 '-diphenylmethane diisocyanate and triphenylmethane triisocyanate are mixed together in a specific weight ratio, isocyanate groups in the 4,4' -diphenylmethane diisocyanate and triphenylmethane triisocyanate react with hydroxyl groups in polyethylene terephthalate to form polyurethane chain segments, so that the blending of polyurethane and PET is realized, and the wear resistance of the coating layer is improved.
According to the data comparison of examples 8-9, the polysiloxane is modified, the polyester diol and the silane coupling agent are mixed with the polysiloxane to prepare a polysiloxane/polyester diol compound, the polyester chain segment and the polysiloxane chain segment exist in the polysiloxane/polyester diol compound, the compound reacts with polyisocyanate monomers to form polyurethane, and a urethane bond in the polyurethane and the polyethylene terephthalate exist hydrogen bonds to form a physical crosslinking structure, so that the strength and the wear resistance of the coating layer are improved.
According to the data comparison of the embodiment 8 and the embodiment 10-11, when the polyethylene terephthalate, the polysiloxane/polyester diol compound, the polyisocyanate and the modified nano silicon dioxide are compounded together in a specific weight ratio, the wear resistance and the tearing strength of the coating layer can be further improved.
The above embodiments are not intended to limit the scope of the present application, so: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (8)
1. The utility model provides a PVC-PET composite board membrane which characterized in that: comprises a base material layer (1), a decorative layer (2), an adhesive layer (3) and a film coating layer (4); the decorative layer (2) is bonded with the substrate layer (1); one side of the bonding layer (3) is bonded with the film covering layer (4), and the other side is bonded with one side of the decorative layer (2) away from the substrate layer (1); the coating layer (4) is prepared from the following raw materials in parts by weight: 10-30 parts of polyethylene terephthalate; 8-16 parts of polysiloxane/polyester diol compound; 20-40 parts of polyisocyanate; 5-15 parts of modified nano silicon dioxide; 0.5-1.5 parts of catalyst; 1-3 parts of chain extender; the preparation method of the modified nano silicon dioxide comprises the following steps: heating 10-20 parts by weight of simethicone, 5-15 parts by weight of methyl siloxane, 2-8 parts by weight of tetramethyl tetravinyl siloxane, 20-40 parts by weight of nano silicon dioxide and 1-3 parts by weight of stannous isooctanoate to 75-85 ℃ and uniformly stirring, heating to 155-165 ℃ and heating for 4-6 hours, and cooling to room temperature to obtain the modified nano silicon dioxide; the preparation method of the polysiloxane/polyester diol compound comprises the following steps: 15-25 parts by weight of polysiloxane, 20-50 parts by weight of polyester diol and 10-20 parts by weight of silane coupling agent are mixed and heated to a molten state, and then are extruded and cooled to obtain the polysiloxane/polyester diol composite.
2. A PVC-PET composite sheet film according to claim 1, wherein: the weight ratio of the simethicone, the methyl siloxane, the tetramethyl tetravinyl siloxane and the nano silicon dioxide is (1.6-1.8): 1: (0.3-0.4): (2.8-3.2).
3. A PVC-PET composite sheet film according to claim 1, wherein: the polyisocyanate includes one or more of 4,4' -diphenylmethane diisocyanate or triphenylmethane triisocyanate.
4. A PVC-PET composite sheet film according to claim 3, wherein: the weight ratio of the 4,4' -diphenylmethane diisocyanate to the triphenylmethane triisocyanate is (1-2): 1.
5. A PVC-PET composite sheet film according to claim 1, wherein: the weight ratio of the polyethylene terephthalate, the polysiloxane/polyester diol compound, the polyisocyanate and the modified nano silicon dioxide is (0.4-0.6): (0.4-0.5): 1: (0.4-0.44).
6. A PVC-PET composite sheet film according to claim 1, wherein: the catalyst is dibutyl tin dilaurate.
7. A PVC-PET composite sheet film according to claim 1, wherein: the chain extender is one of ethylenediamine and diethylenetriamine.
8. A preparation method of a PVC-PET composite board film is characterized by comprising the following steps: a process for preparing the PVC-PET composite sheet film of any of claims 1 to 7, comprising the steps of: stirring and heating the polysiloxane/polyester diol compound and polyisocyanate to 40-50 ℃ under the condition of introducing nitrogen, adding a catalyst, heating to 70-80 ℃ and reacting to obtain a prepolymer; uniformly mixing the prepolymer, modified nano silicon dioxide and polyethylene terephthalate, performing melt coextrusion, and cooling to obtain a film coating; rolling and forming a decorative layer on the surface of the substrate layer; coating an adhesive on the surface of the film coating layer to form an adhesive layer; and (3) attaching the decorative layer and the bonding layer, hot-pressing, and cooling to obtain the PVC-PET composite board film.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0664109A (en) * | 1992-08-20 | 1994-03-08 | Bando Chem Ind Ltd | Decorative material and manufacture thereof |
| CN112029296A (en) * | 2020-09-17 | 2020-12-04 | 成都思立可科技有限公司 | Organic carrier-free polysiloxane particles and preparation method thereof |
| CN116141799A (en) * | 2022-12-21 | 2023-05-23 | 东莞市雄林新材料科技股份有限公司 | TPU composite decorative film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398565A (en) * | 2016-08-30 | 2017-02-15 | 浙江华江科技股份有限公司 | Novel PVC composite veneer and preparation method thereof |
| DE102019104311B4 (en) * | 2019-02-20 | 2023-09-21 | Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V. | Wear protection layer and process for its production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0664109A (en) * | 1992-08-20 | 1994-03-08 | Bando Chem Ind Ltd | Decorative material and manufacture thereof |
| CN112029296A (en) * | 2020-09-17 | 2020-12-04 | 成都思立可科技有限公司 | Organic carrier-free polysiloxane particles and preparation method thereof |
| CN116141799A (en) * | 2022-12-21 | 2023-05-23 | 东莞市雄林新材料科技股份有限公司 | TPU composite decorative film |
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