CN111303556B - PVC decorative film - Google Patents
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- CN111303556B CN111303556B CN202010164278.8A CN202010164278A CN111303556B CN 111303556 B CN111303556 B CN 111303556B CN 202010164278 A CN202010164278 A CN 202010164278A CN 111303556 B CN111303556 B CN 111303556B
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
The invention relates to a PVC decorative film, which is prepared from PVC resin, polyurethane elastomer, plasticizer, stabilizer, pigment, titanium dioxide, light calcium carbonate and dicumyl peroxide.
Description
Technical Field
The invention relates to the field of PVC, in particular to a decorative PVC film.
Background
With the gradual improvement of the living standard of people and the rise of real estate industry, surface decoration materials enter a rapid development period, wherein thin film materials such as PVC thin films, PET thin films, composite thin films and the like occupy the leading position of the market of novel surface decoration materials due to simple production process, various surface decoration patterns and effects, simple use method and high cost performance. The PVC film has good wear resistance, good corrosion resistance, high quality and low price, is developed rapidly, and is widely applied to the fields of indoor and furniture decoration, decoration industry, airplane inner cabin film, ship cabin film and the like. The surface of the decorated object can obtain higher hardness, and the surface is prevented from being artificially scratched, scratched or collided, so that the decorated object is better protected, and the service life of the decorated object is prolonged; secondly, it can also make the ornamental have high temperature resistance characteristic, prevents the surface scald, in addition, PVC not only can show the colour of nature, can also show the colour in people's illusion.
Formaldehyde is one of the most serious indoor pollutants, is high on the priority control list of toxic chemicals in China at the 2 nd place, and is determined as a carcinogenic and teratogenic substance by the World Health Organization (WHO). If the PVC decorative film can have the functions of decoration and formaldehyde purification, the PVC decorative film has great significance.
Chinese patent CN105968633A discloses a formaldehyde-removing interior decoration film, which is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin powder, 40-60 parts of plasticizer, 1-5 parts of calcium-zinc stabilizer, 2-8 parts of formaldehyde absorbent, 1-4 parts of pigment, 5-11 parts of titanium dioxide and 2-8 parts of cold-resistant agent. According to the invention, a formaldehyde absorbent is added into the PVC film formula, so that the prepared indoor decoration film has the effect of purifying formaldehyde. The formaldehyde absorbent adopts one of nano silicon powder, 2-amino-2-methyl-1-propanol, isobutylene succinimide and N-hydroxysuccinimide, but the directly added micromolecule formaldehyde absorbent or inorganic powder is easy to migrate in use, so that the subsequent formaldehyde absorption effect is influenced.
In addition to migration problems associated with the addition of formaldehyde absorbers, the migration problems of plasticizers in PVC articles are well known and have been extensively studied in the past. The migration of the plasticizer reduces the physical properties of the article, makes the article hard and brittle, and significantly impairs the surface properties of the article, seriously affecting the performance and service life of the article. On the other hand, when the plasticizer in the PVC product migrates outward, it also poses a hazard to human health and ecological environment.
In conclusion, the plasticizer, formaldehyde absorbent and other substances added in the traditional PVC product are easy to migrate and have unstable performance, and the product can not maintain the mechanical performance for a long time.
Disclosure of Invention
The invention aims to overcome the defects in the existing PVC decorative film technology and provide a PVC decorative film which has less plasticizer migration, formaldehyde absorption effect and long-term and stable performance.
The PVC decorative film is realized by the following technical scheme:
the PVC decorative film is prepared from the following raw materials in parts by mass:
wherein the polyurethane elastomer is prepared from polyester polyol (with the number average molecular weight of 2000-3000), diisocyanate, glycol, methacrylamide and acetoacetic acid hydroxyethyl ester (CH)3COCH2COOCH2CH2OH) is prepared. The diisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate. Further, the polyurethane elastomer is prepared from 100 parts by mass of polyester polyol, 20-60 parts by mass of diisocyanate, 2-10 parts by mass of ethylene glycol, 2-10 parts by mass of methacrylamide and 2-10 parts by mass of hydroxyethyl acetoacetate.
The preparation method of the polyurethane elastomer comprises the following steps: the polyester polyol, the diisocyanate, the ethylene glycol, the methacrylamide and the acetoacetic acid hydroxyethyl ester are put into a mixer and fully stirred for 10 to 30 minutes at the temperature of 100 ℃, and then fully plasticated in a high-temperature plastic machine or an internal mixer at the temperature of 140 ℃, and dried to obtain the polyurethane elastomer.
Further, the adding amount of the polyurethane elastomer is 20-30 parts.
The PVC resin is prepared by adopting an ethylene method, and the polymerization degree is 1400-1700.
The stabilizer is a mixture of a barium-zinc liquid stabilizer and an organic tin liquid stabilizer, and the mass ratio of the barium-zinc liquid stabilizer to the organic tin liquid stabilizer is 1: 2-2: 1.
The plasticizer is one or more of triethyl citrate, tributyl citrate and acetyl triethyl citrate. Further, the addition amount of the plasticizer is 50-60 parts.
The titanium dioxide is rutile titanium dioxide, and the particle size is 0.1-0.3 microns.
A preparation process of a PVC decorative film comprises the following steps:
(1) mixing materials: weighing and proportioning the raw materials in parts by weight, then mixing, and uniformly stirring;
(2) banburying: conveying the mixed material obtained in the step (1) to an internal mixer to fully mix and plasticate the material;
(3) scouring: conveying the materials in the step (2) to an open mill, wherein the temperature of the open mill is set to 190-210 ℃, and fully plasticating the materials;
(4) extrusion and filtration: the mesh number of the filter screen is 100-200 meshes, and impurities in the material in the step (3) are removed through a filter press;
(5) four-roll calendering: conveying the material in the step (4) to a four-roll calender for calendering, wherein the temperature of a 1# roll is controlled to be 160-170 ℃, the rotating speed is 10-11 m/min, the temperature of a 2# roll is controlled to be 160-170 ℃, the rotating speed is 13-14 m/min, the temperature of a 3# roll is 180-190 ℃, the rotating speed is 15-16 m/min, the temperature of a 4# roll is 160-170 ℃, and the rotating speed is 16-17 m/min;
(6) traction: after the film material is rolled in the step (5), the film material enters the next step at a speed of 19-20 m/min under the action of a traction wheel;
(7) embossing, cooling, trimming and coiling: and (4) embossing the film obtained in the step (6) through an embossing wheel, then cooling the film in a cooling roller, and then trimming and coiling the film.
Has the advantages that:
1. the addition of the polyurethane elastomer can reduce the migration of substances such as a plasticizer and the like, and the polyurethane elastomer has excellent mechanical properties, so that the stability of the product performance can be further ensured without brittleness. Dicumyl peroxide is used as a cross-linking agent, the addition of which can improve the compatibility of the polyurethane elastomer with PVC resin through cross-linking, and light calcium carbonate can make the dicumyl peroxide more uniformly dispersed in the matrix.
2. The polyurethane elastomer is synthesized by adopting special functional monomers of acrylamide and hydroxyethyl acetoacetate, the introduction of the monomers can endow the final formaldehyde absorption performance of the product, and the formaldehyde absorption performance is not realized by a micromolecule additive which is easy to migrate and exists in a macromolecular skeleton, so that the migration is not easy to occur.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that these embodiments are provided to illustrate the general principles, major features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Example 1
A PVC decorative film is prepared by the following steps:
(1) mixing materials: weighing and proportioning the raw materials in parts by weight, mixing, and uniformly stirring, wherein the raw materials are in the following ratio:
100 parts of PVC resin (with the polymerization degree of 1400), 20 parts of polyurethane elastomer, 60 parts of triethyl citrate, 3 parts of stabilizer (mixture of barium-zinc liquid stabilizer and organic tin liquid stabilizer in a mass ratio of 1:2), 2 parts of pigment, 20 parts of rutile titanium dioxide (with the particle size of 0.3 micrometer), 2 parts of light calcium carbonate and 10 parts of dicumyl peroxide;
the preparation method of the polyurethane elastomer comprises the following steps: 100 parts by mass of polyester polyol (number average molecular weight 2000), 40 parts by mass of MDI, 6 parts by mass of ethylene glycol, 4 parts by mass of methacrylamide and 6 parts by mass of acetoacetic acid hydroxyethyl ester are put in a mixer and fully stirred for 30 minutes at 100 ℃, then fully plasticated in a high-temperature internal mixer at 140 ℃, and dried to obtain the polyurethane elastomer.
(2) Banburying: conveying the mixed material obtained in the step (1) to an internal mixer to fully mix and plasticate the material;
(3) scouring: conveying the materials in the step (2) to an open mill, and setting the temperature of the open mill to 190 ℃ to fully plasticate the materials;
(4) extrusion and filtration: the mesh number of the filter screens is 100 meshes, and impurities in the material in the step (3) are removed through a filter press;
(5) four-roll calendering: conveying the material in the step (4) to a four-roll calender for calendering, controlling the temperature of a 1# roll to be 160 ℃, the rotating speed to be 10m/min, the temperature of a 2# roll to be 160 ℃, the rotating speed to be 13m/min, the temperature of a 3# roll to be 180 ℃, the rotating speed to be 15m/min, the temperature of a 4# roll to be 160 ℃, and the rotating speed to be 16 m/min;
(6) traction: after the film material is rolled in the step (5), the film material enters the next step at the speed of 19m/min under the action of a traction wheel;
(7) embossing, cooling, trimming and coiling: and (4) embossing the film obtained in the step (6) through an embossing wheel, then cooling the film in a cooling roller, and then trimming and coiling the film.
Example 2
A PVC decorative film is prepared by the following steps:
(1) mixing materials: weighing and proportioning the raw materials in parts by weight, mixing, and uniformly stirring, wherein the raw materials are in the following ratio:
100 parts of PVC resin (with the polymerization degree of 1700), 30 parts of polyurethane elastomer, 50 parts of triethyl citrate, 3 parts of stabilizer (mixture of barium-zinc liquid stabilizer and organic tin liquid stabilizer in a mass ratio of 1:2), 2 parts of pigment, 20 parts of rutile titanium dioxide (with the particle size of 0.3 micrometer), 2 parts of light calcium carbonate and 8 parts of dicumyl peroxide;
the preparation method of the polyurethane elastomer comprises the following steps: 100 parts by mass of polyester polyol (with a number average molecular weight of 2000), 40 parts by mass of MDI, 6 parts by mass of ethylene glycol, 4 parts by mass of methacrylamide and 6 parts by mass of hydroxyethyl acetoacetate are put in a mixer and fully stirred for 30 minutes at 100 ℃, then fully plasticated in a high-temperature plastic machine or an internal mixer at 140 ℃, and dried to obtain the polyurethane elastomer.
(2) Banburying: conveying the mixed material obtained in the step (1) to an internal mixer to fully mix and plasticate the material;
(3) scouring: conveying the materials in the step (2) to an open mill, and setting the temperature of the open mill to 210 ℃ to fully plasticate the materials;
(4) extrusion and filtration: the mesh number of the filter screen is 200 meshes, and impurities in the material in the step (3) are removed through a filter press;
(5) four-roll calendering: conveying the material in the step (4) to a four-roll calender for calendering, controlling the temperature of a 1# roll to be 170 ℃, the rotating speed to be 11m/min, the temperature of a 2# roll to be 170 ℃, the rotating speed to be 14m/min, the temperature of a 3# roll to be 190 ℃, the rotating speed to be 16m/min, the temperature of a 4# roll to be 170 ℃ and the rotating speed to be 17 m/min;
(6) traction: after the film material is rolled in the step (5), the film material enters the next step at the speed of 20m/min under the action of a traction wheel;
(7) embossing, cooling, trimming and coiling: and (4) embossing the film obtained in the step (6) through an embossing wheel, then cooling the film in a cooling roller, and then trimming and coiling the film.
Example 3
A PVC decorative film is prepared by the following steps:
(1) mixing materials: weighing and proportioning the raw materials in parts by weight, mixing, and uniformly stirring, wherein the raw materials are in the following ratio:
100 parts of PVC resin (with the polymerization degree of 1600), 30 parts of polyurethane elastomer, 60 parts of triethyl citrate, 3 parts of stabilizer (mixture of barium-zinc liquid stabilizer and organic tin liquid stabilizer in a mass ratio of 1:2), 2 parts of pigment, 20 parts of rutile titanium dioxide (with the particle size of 0.3 micrometer), 2 parts of light calcium carbonate and 10 parts of dicumyl peroxide;
the preparation method of the polyurethane elastomer comprises the following steps: 100 parts by mass of polyester polyol (with a number average molecular weight of 3000), 30 parts by mass of MDI, 6 parts by mass of ethylene glycol, 4 parts by mass of methacrylamide and 6 parts by mass of hydroxyethyl acetoacetate are put in a mixer and fully stirred for 30 minutes at 100 ℃, then fully plasticated in a high-temperature plastic machine or an internal mixer at 140 ℃, and dried to obtain the polyurethane elastomer.
(2) Banburying: conveying the mixed material obtained in the step (1) to an internal mixer to fully mix and plasticate the material;
(3) scouring: conveying the materials in the step (2) to an open mill, and setting the temperature of the open mill to be 200 ℃ to fully plasticate the materials;
(4) extrusion and filtration: the mesh number of the filter screens is 150 meshes, and impurities in the material in the step (3) are removed through a filter press;
(5) four-roll calendering: conveying the material in the step (4) to a four-roll calender for calendering, controlling the temperature of a 1# roll to be 170 ℃, the rotating speed to be 11m/min, the temperature of a 2# roll to be 170 ℃, the rotating speed to be 14m/min, the temperature of a 3# roll to be 190 ℃, the rotating speed to be 16m/min, the temperature of a 4# roll to be 170 ℃ and the rotating speed to be 17 m/min;
(6) traction: after the film material is rolled in the step (5), the film material enters the next step at the speed of 20m/min under the action of a traction wheel;
(7) embossing, cooling, trimming and coiling: and (4) embossing the film obtained in the step (6) through an embossing wheel, then cooling the film in a cooling roller, and then trimming and coiling the film.
Comparative example 1
A PVC decorative film is prepared by the following steps:
(1) mixing materials: weighing and proportioning the raw materials in parts by weight, mixing, and uniformly stirring, wherein the raw materials are in the following ratio:
100 parts of PVC resin (with the polymerization degree of 1400), 60 parts of triethyl citrate, 3 parts of stabilizer (a mixture of barium-zinc liquid stabilizer and organic tin liquid stabilizer with the mass ratio of 1:2), 2 parts of pigment, 20 parts of rutile titanium dioxide (with the particle size of 0.3 micron), 2 parts of light calcium carbonate and 10 parts of dicumyl peroxide;
(2) banburying: conveying the mixed material obtained in the step (1) to an internal mixer to fully mix and plasticate the material;
(3) scouring: conveying the materials in the step (2) to an open mill, and setting the temperature of the open mill to 190 ℃ to fully plasticate the materials;
(4) extrusion and filtration: the mesh number of the filter screens is 100 meshes, and impurities in the material in the step (3) are removed through a filter press;
(5) four-roll calendering: conveying the material in the step (4) to a four-roll calender for calendering, controlling the temperature of a 1# roll to be 160 ℃, the rotating speed to be 10m/min, the temperature of a 2# roll to be 160 ℃, the rotating speed to be 13m/min, the temperature of a 3# roll to be 180 ℃, the rotating speed to be 15m/min, the temperature of a 4# roll to be 160 ℃, and the rotating speed to be 16 m/min;
(6) traction: after the film material is rolled in the step (5), the film material enters the next step at the speed of 19m/min under the action of a traction wheel;
(7) embossing, cooling, trimming and coiling: and (4) embossing the film obtained in the step (6) through an embossing wheel, then cooling the film in a cooling roller, and then trimming and coiling the film.
Comparative example 2
A PVC decorative film is prepared by the following steps:
(1) mixing materials: weighing and proportioning the raw materials in parts by weight, mixing, and uniformly stirring, wherein the raw materials are in the following ratio:
100 parts of PVC resin (with the polymerization degree of 1400), 20 parts of polyurethane elastomer, 60 parts of triethyl citrate, 3 parts of stabilizer (mixture of barium-zinc liquid stabilizer and organic tin liquid stabilizer in a mass ratio of 1:2), 2 parts of pigment, 20 parts of rutile titanium dioxide (with the particle size of 0.3 micrometer), 2 parts of light calcium carbonate and 10 parts of dicumyl peroxide;
the preparation method of the polyurethane elastomer comprises the following steps: 100 parts by mass of polyester polyol (with a number average molecular weight of 2000), 40 parts by mass of MDI and 6 parts by mass of ethylene glycol are placed in a mixer and fully stirred for 30 minutes at 100 ℃, then fully plasticated in a high-temperature plasticator internal mixer at 140 ℃, and dried to obtain the polyurethane elastomer.
(2) Banburying: conveying the mixed material obtained in the step (1) to an internal mixer to fully mix and plasticate the material;
(3) scouring: conveying the materials in the step (2) to an open mill, and setting the temperature of the open mill to 190 ℃ to fully plasticate the materials;
(4) extrusion and filtration: the mesh number of the filter screens is 100 meshes, and impurities in the material in the step (3) are removed through a filter press;
(5) four-roll calendering: conveying the material in the step (4) to a four-roll calender for calendering, controlling the temperature of a 1# roll to be 160 ℃, the rotating speed to be 10m/min, the temperature of a 2# roll to be 160 ℃, the rotating speed to be 13m/min, the temperature of a 3# roll to be 180 ℃, the rotating speed to be 15m/min, the temperature of a 4# roll to be 160 ℃, and the rotating speed to be 16 m/min;
(6) traction: after the film material is rolled in the step (5), the film material enters the next step at the speed of 19m/min under the action of a traction wheel;
(7) embossing, cooling, trimming and coiling: and (4) embossing the film obtained in the step (6) through an embossing wheel, then cooling the film in a cooling roller, and then trimming and coiling the film.
Testing of plasticizer migration
A120 mm by 120mm sample was prepared and weighed (weight d 1). Subsequently, these test samples were placed on a body made of expanded polystyrene rigid foam having dimensions of 120mm × 120mm and a thickness of about 40-50 mm. A glass plate having a size of 100mm X100 mm was also placed on the test piece, and a weight of 2kg was placed thereon. The formulation was stored at 70 ℃ at 50. + -. 5% relative humidity for 28 days. Thereafter, the test sample is weighed again (weight d2) and the weight difference is determined as a percentage of the weight d 1.
Test of Formaldehyde scavenging Effect
The test was performed based on JC/T1074-2008 test standards.
The properties of all examples and comparative examples are reported in table 1.
TABLE 1PVC decorative film Performance test results
| Performance testing | Mobility (%) | Formaldehyde purification efficiency (%) |
| Example 1 | 0.42 | 71 |
| Example 2 | 0.31 | 78 |
| Example 3 | 0.37 | 75 |
| Comparative example 1 | 3.87 | 5 |
| Comparative example 2 | 0.43 | 7 |
The present invention has been described in detail, and the embodiments are only used for understanding the method and the core idea of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and to implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. The PVC decorative film is prepared from the following raw materials in parts by mass:
100 portions of PVC resin
10-30 parts of polyurethane elastomer
40-70 parts of plasticizer
1-5 parts of stabilizer
1-2 parts of pigment
10-20 parts of titanium dioxide
1-2 parts of light calcium carbonate
1-10 parts of dicumyl peroxide;
the polyurethane elastomer is prepared from 100 parts by mass of polyester polyol, 20-60 parts by mass of diisocyanate, 2-10 parts by mass of ethylene glycol, 2-10 parts by mass of methacrylamide and 2-10 parts by mass of acetoacetic acid hydroxyethyl ester; the number average molecular weight of the polyester polyol is 2000-3000;
the preparation method of the polyurethane elastomer comprises the following steps: the polyester polyol, the diisocyanate, the ethylene glycol, the methacrylamide and the acetoacetic acid hydroxyethyl ester are put into a mixer and fully stirred for 10 to 30 minutes at the temperature of 100 ℃, and then fully plasticated in a high-temperature plastic machine or an internal mixer at the temperature of 140 ℃, and dried to obtain the polyurethane elastomer.
2. The PVC decorative film of claim 1, wherein:
the preparation process of the PVC decorative film comprises the following steps:
(1) mixing materials: weighing and proportioning the raw materials in parts by weight, then mixing, and uniformly stirring;
(2) banburying: conveying the mixed material obtained in the step (1) to an internal mixer to fully mix and plasticate the material;
(3) scouring: conveying the materials in the step (2) to an open mill, wherein the temperature of the open mill is set to 190-210 ℃, and fully plasticating the materials;
(4) extrusion and filtration: the mesh number of the filter screen is 100-200 meshes, and impurities in the material in the step (3) are removed through a filter press;
(5) four-roll calendering: conveying the material in the step (4) to a four-roll calender for calendering, wherein the temperature of a 1# roll is controlled to be 160-170 ℃, the rotating speed is 10-11 m/min, the temperature of a 2# roll is controlled to be 160-170 ℃, the rotating speed is 13-14 m/min, the temperature of a 3# roll is 180-190 ℃, the rotating speed is 15-16 m/min, the temperature of a 4# roll is 160-170 ℃, and the rotating speed is 16-17 m/min;
(6) traction: after the film material is rolled in the step (5), the film material enters the next step at a speed of 19-20 m/min under the action of a traction wheel;
(7) embossing, cooling, trimming and coiling: and (4) embossing the film obtained in the step (6) through an embossing wheel, then cooling the film in a cooling roller, and then trimming and coiling the film.
3. The PVC decorative film of claim 1, wherein: the PVC resin is prepared by adopting an ethylene method, and the polymerization degree is 1400-1700.
4. The PVC decorative film of claim 1, wherein: the stabilizer is a mixture of a barium-zinc liquid stabilizer and an organic tin liquid stabilizer, and the mass ratio of the barium-zinc liquid stabilizer to the organic tin liquid stabilizer is 1: 2-2: 1.
5. The PVC decorative film of claim 1, wherein: the plasticizer is one or more of triethyl citrate, tributyl citrate and acetyl triethyl citrate.
6. The PVC decorative film of claim 1, wherein: the titanium dioxide is rutile type titanium dioxide.
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| CN201810015717.1A CN107841071B (en) | 2018-01-08 | 2018-01-08 | PVC decorative film |
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| CN110655731B (en) * | 2018-06-29 | 2022-03-04 | 3M创新有限公司 | Polyvinyl chloride composition for removing formaldehyde and product for removing formaldehyde |
| CN109280289A (en) * | 2018-09-03 | 2019-01-29 | 李永平 | One kind zero shrinks decorating film |
| CN109401127A (en) * | 2018-11-02 | 2019-03-01 | 九江赛璐珞实业有限公司 | A kind of preparation method of fancy PVC decorative Film |
| CN111808305A (en) * | 2019-11-21 | 2020-10-23 | 苏州欧邦塑胶有限公司 | Preparation method of composite decorative film base film |
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| JPS6153316A (en) * | 1984-08-22 | 1986-03-17 | Sumitomo Chem Co Ltd | Urethane resin composition |
| US20070138671A1 (en) * | 2005-12-15 | 2007-06-21 | Anastasiou Theodore J | Encapsulated active material with reduced formaldehyde potential |
| GB0613425D0 (en) * | 2006-07-06 | 2006-08-16 | H B Fuller Coatings Ltd | Floor covering and films for use therewith |
| CN102540714A (en) * | 2010-12-23 | 2012-07-04 | 上海印刷技术研究所 | High-elasticity photosensitive resin composition for flexible plate printing |
| CN102807664B (en) * | 2012-08-20 | 2014-01-29 | 陕西科技大学 | Method for preparing acrylate modified water-based polyurethane |
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| CN111154203B (en) | 2022-01-18 |
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