Color migration prevention polyurethane composite film as well as preparation method and application thereof

Abstract

The color migration prevention polyurethane composite film is prepared from the following raw materials in parts by weight: 40 to 50 parts of crystalline modified polyurethane, 30 to 40 parts of waterborne polyurethane, 10 to 15 parts of vinyltriethoxysilane, 5 to 8 parts of graphene, 5 to 8 parts of color fixing agent, 6 to 8 parts of toner and 1 to 3 parts of silicon dioxide. According to the color migration prevention polyurethane composite film and the preparation method thereof, the obtained polyurethane composite film has excellent color migration prevention and washing resistance effects.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyurethane films, in particular to a color migration resistant polyurethane composite film and a preparation method and application thereof. BACKGROUND

[0002] With more and more people joining outdoor sports, the functional requirements of outdoor products are also getting higher and higher, and the products need to have good mechanical properties and environmental resistance, especially some sports products, which need to have high elasticity and high color stability at the same time, to provide better quality experience and color effect for sports groups.

[0003] At present, the defect of structural color film is that the color of the structural color film comes from its microstructure, but under the action of external force, the microstructure is easy to change irreversibly, resulting in the loss of color or functional characteristics of the structural color film, and the use durability of the structural color film needs to be improved. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a color migration resistant polyurethane composite film and a preparation method thereof, and the obtained polyurethane composite film has excellent color migration resistance and washing resistance.

[0005] In order to achieve the above purpose, the present application provides the following technical scheme: A color migration resistant polyurethane composite film comprises the following raw materials by weight: 40-50 parts of crystalline modified polyurethane, 30-40 parts of water-based polyurethane, 10-15 parts of vinyl triethoxysilane, 5-8 parts of graphene, 5-8 parts of color fixing agent, 6-8 parts of toner and 1-3 parts of silicon dioxide.

[0006] A preparation method of a color migration resistant polyurethane composite film comprises the following steps: S1: mixing crystalline modified polyurethane, water-based polyurethane, vinyl triethoxysilane, graphene, color fixing agent, toner and silicon dioxide to obtain a coating liquid; S2: placing the coating liquid in a mold, and performing ultraviolet curing treatment after annealing to obtain a color migration resistant polyurethane composite film.

[0007] Preferably, the preparation method of the crystalline modified polyurethane is: S11: preparing a crystalline material; S12: mixing polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid and dibutyl tin dilaurate, and reacting at 80-90℃ for 2-4h, then adding 1,4-butanediol and the crystalline material, continuing to react for 1-2h, adding deionized water, and performing emulsification treatment at a temperature of 35℃ and a speed of 1200r / s, and cooling to room temperature to obtain the crystalline modified polyurethane.

[0008] Preferably, the weight ratio of the polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid, dibutyltin dilaurate, 1,4-butanediol and the crystalline material is 2:1:1:2:3:3.

[0009] Preferably, the preparation method of the crystalline material is specifically as follows: Zirconium oxide hydroxide octahydrate, 1,4-benzenedicarboxylic acid, N,N-dimethylformamide and glacial acetic acid are mixed in a weight ratio of 1:1:1:2, reacted at 80-90℃ for 10-12h, centrifuged, dried, and the crystalline material is obtained.

[0010] Preferably, the preparation method of the water-based polyurethane is as follows: polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate and dimethylol butyric acid are mixed, reacted at 80-90℃ for 2-4h, triethylamine, 2,2'-diaminodi-phenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide are added, and the reaction is continued for 1-2h, deionized water is added, and emulsification treatment is carried out at a temperature of 35℃ and a speed of 1200r / s, and the water-based polyurethane is obtained after cooling to room temperature.

[0011] Preferably, the weight ratio of the polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate, dimethylol butyric acid, triethylamine, 2,2'-diaminodi-phenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide is 2:1:1:2:3:1:1:3.

[0012] Preferably, the preparation method of the fixing agent is as follows: isopropyl alcohol, isomeric tridecanol polyoxyethylene ether, methacrylic acid and ammonium persulfate are mixed, reacted at 100-120℃ for 12-18h in a nitrogen environment, filtered and dried, and the fixing agent is obtained.

[0013] Preferably, the weight ratio of the isopropyl alcohol, isomeric tridecanol polyoxyethylene ether, methacrylic acid and ammonium persulfate is 3:2:3:1.

[0014] An application of a color migration resistant polyurethane composite film in shoe materials.

[0015] The crystalline modified polyurethane can dissociate ions and organic complexes with slow-release effect, contains a large number of hydroxyl and carboxyl groups, and physically crosslinks with the polyurethane, is embedded in the polyurethane, forms a pure crosslinking protection system, and simultaneously utilizes the PH response and cavity structure of the crystalline material to introduce toner and fixing agent molecules into the cavity structure, increases the adhesion and adsorption of the toner, prevents pigment migration, and further forms an interactive hydrogen bond network, a dynamic covalent disulfide bond and a reversible hydrogen bond synergistic double hard phase domain crosslinking structure in the waterborne polyurethane, which can endow the waterborne polyurethane with self-repairing capability, relies on the physical crosslinking network of the reversible multiple hydrogen bonds to form microcrystals, thereby maintaining the stability of the polyurethane structure system, increasing the color fastness of the pigment, and the formation of the multiple hydrogen bonds in the system strengthens the interaction between the polyurethane segments, resulting in a more compact and ordered molecular structure. DETAILED DESCRIPTION

[0016] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. In addition, it is particularly stated that the raw materials and equipment of the present application can be obtained from the market, and will not be listed one by one. Among them, the raw materials of the present application can be obtained from the market and are well known to those skilled in the art. Embodiment one

[0017] A color migration resistant polyurethane composite film comprises the following raw materials in parts by weight: 40 parts of crystalline modified polyurethane, 30 parts of waterborne polyurethane, 10 parts of vinyl triethoxysilane, 5 parts of graphene, 5 parts of fixing agent, 6 parts of toner and 1 part of silicon dioxide.

[0018] A preparation method of a color migration resistant polyurethane composite film comprises the following steps: S1: mixing the above-mentioned crystalline modified polyurethane, waterborne polyurethane, vinyl triethoxysilane, graphene, fixing agent, toner and silicon dioxide in parts by weight to obtain a coating liquid; S2: placing the coating liquid in a mold, performing ultraviolet curing treatment after annealing, and obtaining the color migration resistant polyurethane composite film.

[0019] The preparation method of the crystalline modified polyurethane is as follows: S11: preparing a crystalline material: mixing zirconium oxychloride octahydrate, 1,4-terephthalic acid, N,N-dimethylformamide and glacial acetic acid according to a weight ratio of 1:1:1:2, reacting at 80℃ for 10h, centrifuging, drying, and obtaining the crystalline material; S12: polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid and dibutyl tin dilaurate were mixed, reacted at 80℃ for 2h, then 1,4-butanediol and crystalline material were added, the weight ratio of polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid, dibutyl tin dilaurate, 1,4-butanediol and crystalline material was 2:1:1:2:3:3, and the reaction was continued for 1h, deionized water was added, emulsification treatment was carried out at a temperature of 35℃ and a speed of 1200r / s, and the crystalline modified polyurethane was obtained after cooling to room temperature.

[0020] The preparation method of the water-based polyurethane is as follows: polytetramethylene ether glycol, isophorone diisocyanate, dibutyl tin dilaurate and dimethylol butyric acid are mixed, reacted at 80℃ for 2h, then triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide are added, the weight ratio of polytetramethylene ether glycol, isophorone diisocyanate, dibutyl tin dilaurate, dimethylol butyric acid, triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide is 2:1:1:2:3:1:1:3, and the reaction is continued for 1h, deionized water is added, emulsification treatment is carried out at a temperature of 35℃ and a speed of 1200r / s, and the water-based polyurethane is obtained after cooling to room temperature.

[0021] The preparation method of the fixing agent is as follows: isopropyl alcohol, isomeric tridecanol polyoxyethylene ether, methacrylic acid and ammonium persulfate are mixed in a weight ratio of 3:2:3:1, reacted at 100℃ for 12h in a nitrogen environment, filtered and dried to obtain the fixing agent.

[0022] An application of a color migration resistant polyurethane composite film in shoe materials. Example two

[0023] A color migration resistant polyurethane composite film, comprising the following raw materials in parts by weight: 45 parts of crystalline modified polyurethane, 35 parts of water-based polyurethane, 12 parts of vinyl triethoxysilane, 6 parts of graphene, 6 parts of fixing agent, 7 parts of toner and 2 parts of silicon dioxide.

[0024] A preparation method of a color migration resistant polyurethane composite film, comprising the following steps: S1: mixing the above-mentioned crystalline modified polyurethane, water-based polyurethane, vinyl triethoxysilane, graphene, fixing agent, toner and silicon dioxide in parts by weight to obtain a coating liquid; S2: placing the coating liquid in a mold, carrying out ultraviolet curing treatment after annealing to obtain the color migration resistant polyurethane composite film.

[0025] The preparation method of the crystalline modified polyurethane is as follows: S11: Preparation of a crystalline material: Zirconium oxide hydroxide, 1,4-terephthalic acid, N,N-dimethylformamide and glacial acetic acid are mixed in a weight ratio of 1:1:1:2, reacted at 85℃ for 11h, centrifuged, dried, and the crystalline material is obtained; S12: Polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid and dibutyltin dilaurate are mixed, reacted at 85℃ for 3h, then 1,4-butanediol and the crystalline material are added, the weight ratio of polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid, dibutyltin dilaurate, 1,4-butanediol and the crystalline material is 2:1:1:2:3:3, and the reaction is continued for 1.5h, deionized water is added, emulsification treatment is carried out at a temperature of 35℃ and a speed of 1200r / s, and the crystalline modified polyurethane is obtained after cooling to room temperature.

[0026] The preparation method of the water-based polyurethane is as follows: polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate and dimethylol butyric acid are mixed, reacted at 85℃ for 3h, then triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide are added, the weight ratio of polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate, dimethylol butyric acid, triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide is 2:1:1:2:3:1:1:3, and the reaction is continued for 1.5h, deionized water is added, emulsification treatment is carried out at a temperature of 35℃ and a speed of 1200r / s, and the water-based polyurethane is obtained after cooling to room temperature.

[0027] The preparation method of the water-based polyurethane is as follows: polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate and dimethylol butyric acid are mixed, reacted at 85℃ for 3h, then triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide are added, the weight ratio of polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate, dimethylol butyric acid, triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide is 2:1:1:2:3:1:1:3, and the reaction is continued for 1.5h, deionized water is added, emulsification treatment is carried out at a temperature of 35℃ and a speed of 1200r / s, and the water-based polyurethane is obtained after cooling to room temperature.

[0028] An application of a color migration resistant polyurethane composite film in shoe materials. Example Three

[0029] A color migration resistant polyurethane composite film, comprising the following raw materials in weight parts: 50 parts of a crystalline modified polyurethane, 40 parts of a water-based polyurethane, 15 parts of vinyl triethoxysilane, 8 parts of graphene, 8 parts of a color fixing agent, 8 parts of color powder and 3 parts of silicon dioxide.

[0030] A preparation method of a color migration resistant polyurethane composite film, comprising the following steps: S1: The crystalline modified polyurethane, the water-based polyurethane, the vinyl triethoxysilane, the graphene, the color fixing agent, the color powder and the silicon dioxide are mixed to obtain a coating liquid. S2: The coating liquid is placed in a mold, and after annealing, ultraviolet curing treatment is performed to obtain a color migration resistant polyurethane composite film.

[0031] The preparation method of the crystalline modified polyurethane is as follows: S11: Preparation of crystalline material: zirconium oxychloride octahydrate, 1,4-terephthalic acid, N,N-dimethylformamide and glacial acetic acid are mixed in a weight ratio of 1:1:1:2, reacted at 90℃ for 12h, centrifuged, dried to obtain crystalline material; S12: Polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid and dibutyltin dilaurate are mixed, reacted at 90℃ for 4h, then 1,4-butanediol and crystalline material are added, and the weight ratio of polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid, dibutyltin dilaurate, 1,4-butanediol and crystalline material is 2:1:1:2:3:3, and the reaction is continued for 2h, deionized water is added, and emulsification treatment is carried out at a temperature of 35℃ and a speed of 1200r / s, and then cooled to room temperature to obtain a crystalline modified polyurethane.

[0032] The preparation method of the water-based polyurethane is as follows: polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate and dimethylol butyric acid are mixed, reacted at 90℃ for 4h, then triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide are added, and the weight ratio of polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate, dimethylol butyric acid, triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide is 2:1:1:2:3:1:1:3, and the reaction is continued for 2h, deionized water is added, and emulsification treatment is carried out at a temperature of 35℃ and a speed of 1200r / s, and then cooled to room temperature to obtain a water-based polyurethane.

[0033] The preparation method of the color fixing agent is as follows: isopropyl alcohol, isomeric tridecanol polyoxyethylene ether, methacrylic acid and ammonium persulfate are mixed in a weight ratio of 3:2:3:1, reacted at 120℃ for 18h under nitrogen environment, filtered and dried to obtain a color fixing agent.

[0034] An application of a color migration resistant polyurethane composite film in shoe materials. Comparative Example 1

[0035] The preparation methods of Comparative Example 1 and Example 1 are basically the same, except that the crystalline modified polyurethane and the water-based polyurethane are not used.

[0036] A color migration resistant polyurethane composite film, comprising the following raw materials by weight: polyurethane 70 parts, vinyl triethoxysilane 10 parts, graphene 5 parts, color fixing agent 5 parts, toner 6 parts, and silicon dioxide 1 part.

[0037] A preparation method of a color migration resistant polyurethane composite film, comprising the following steps: S1: mixing the above-mentioned polyurethane, vinyl triethoxysilane, graphene, color fixing agent, toner, and silicon dioxide by weight to obtain a coating liquid; S2: placing the coating liquid in a mold, and performing ultraviolet curing treatment after annealing to obtain the color migration resistant polyurethane composite film.

[0038] The preparation method of the color fixing agent is as follows: mixing isopropyl alcohol, isomeric tridecanol polyoxyethylene ether, methacrylic acid, and ammonium persulfate in a weight ratio of 3:2:3:1, reacting at 100 DEG C for 12 hours in a nitrogen environment, filtering and drying to obtain the color fixing agent.

[0039] An application of a color migration resistant polyurethane composite film in shoe materials. Comparative Example 2

[0040] The preparation methods of Comparative Example 2 and Example 1 are basically the same, except that the color fixing agent is not used.

[0041] A color migration resistant polyurethane composite film, comprising the following raw materials by weight: crystalline modified polyurethane 40 parts, water-based polyurethane 30 parts, vinyl triethoxysilane 10 parts, graphene 5 parts, toner 6 parts, and silicon dioxide 1 part.

[0042] A preparation method of a color migration resistant polyurethane composite film, comprising the following steps: S1: mixing the above-mentioned crystalline modified polyurethane, water-based polyurethane, vinyl triethoxysilane, graphene, toner, and silicon dioxide by weight to obtain a coating liquid; S2: placing the coating liquid in a mold, and performing ultraviolet curing treatment after annealing to obtain the color migration resistant polyurethane composite film.

[0043] The preparation method of the crystalline modified polyurethane is as follows: S11: preparing a crystalline material: mixing zirconium oxychloride octahydrate, 1,4-terephthalic acid, N,N-dimethylformamide, and glacial acetic acid in a weight ratio of 1:1:1:2, reacting at 80 DEG C for 10 hours, centrifuging, and drying to obtain the crystalline material; S12: mixing polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid and dibutyl tin dilaurate, reacting at 80℃ for 2h, then adding 1,4-butanediol and crystalline material, the weight ratio of polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid, dibutyl tin dilaurate, 1,4-butanediol and crystalline material is 2:1:1:2:3:3, continuing to react for 1h, adding deionized water, emulsifying at a temperature of 35℃ and a speed of 1200r / s, cooling to room temperature to obtain the crystalline modified polyurethane.

[0044] The preparation method of the water-based polyurethane is as follows: mixing polytetramethylene ether glycol, isophorone diisocyanate, dibutyl tin dilaurate and dimethylol butyric acid, reacting at 80℃ for 2h, then adding triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide, the weight ratio of polytetramethylene ether glycol, isophorone diisocyanate, dibutyl tin dilaurate, dimethylol butyric acid, triethylamine, 2,2'-diamino diphenyl disulfide, 2,6-dihydroxybenzoic acid methyl ester and N,N-dimethylformamide is 2:1:1:2:3:1:1:3, continuing to react for 1h, adding deionized water, emulsifying at a temperature of 35℃ and a speed of 1200r / s, cooling to room temperature to obtain the water-based polyurethane.

[0045] Application of a color migration resistant polyurethane composite film in shoe materials.

[0046] The films obtained in Examples 1-3, commercially available polyurethane film of Shanghai Xindan Technology Co., Ltd. and Comparative Examples 1-2 were respectively tested for performance. Mechanical properties: the elongation at break and tensile strength of the polyurethane film were tested according to the standard GB / T 1040.1 2018.

[0047] Dye uptake and dry and wet rubbing fastness: the prepared polyurethane film was cut into small squares of 10x10mm size, and tested according to HG T 5070-2016.

[0048] The test results are shown in Table 1.

[0049] Table 1: Test data of polyurethane films of Examples 1-3, commercially available and Comparative Examples 1-2

[0050] As can be seen from the above table, the polyurethane films of Examples 1-3 have better color fastness and excellent mechanical properties than the polyurethane films of Comparative Examples 1-2 and commercially available.

[0051] The foregoing description of the disclosed embodiments enables a person skilled in the art to make or use the application. Modifications of these embodiments will occur to persons of skill in the art, and that the appended claims are intended to cover all such modifications that do not depart from the true spirit and scope of the application. Therefore, the application is not limited to the embodiments shown but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A polyurethane composite film for preventing color migration, characterized in that, The raw materials include the following parts by weight: 40-50 parts of crystalline modified polyurethane, 30-40 parts of waterborne polyurethane, 10-15 parts of vinyltriethoxysilane, 5-8 parts of graphene, 5-8 parts of fixing agent, 6-8 parts of color powder, and 1-3 parts of silica.

2. A method for preparing the anti-color migration polyurethane composite film as described in claim 1, characterized in that, Includes the following steps: S1: Mix crystalline modified polyurethane, waterborne polyurethane, vinyltriethoxysilane, graphene, fixing agent, color powder and silica to obtain a coating liquid; S2: Place the coating liquid in a mold, anneal it, and then perform ultraviolet curing treatment to obtain an anti-color migration polyurethane composite film.

3. The method for preparing the anti-color migration polyurethane composite film as described in claim 2, characterized in that, The preparation method of the crystalline modified polyurethane is as follows: S11: Preparation of crystalline materials; S12: Polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid and dibutyltin dilaurate are mixed and reacted at 80-90℃ for 2-4 hours. Then, 1,4-butanediol and crystalline material are added, and the reaction continues for 1-2 hours. Deionized water is added, and emulsification is carried out at 35℃ and 1200r / s. After cooling to room temperature, the crystalline modified polyurethane is obtained.

4. The method for preparing the anti-color migration polyurethane composite film as described in claim 3, characterized in that, The weight ratio of polypropylene glycol, isophorone diisocyanate, 2,2-bis(hydroxymethyl)propionic acid, dibutyltin dilaurate, 1,4-butanediol and crystalline material is 2:1:1:2:3:

3.

5. The method for preparing the anti-color migration polyurethane composite film as described in claim 4, characterized in that, The specific method for preparing the crystalline material is as follows: Zirconium oxychloride octahydrate, 1,4-terephthalic acid, N,N-dimethylformamide and glacial acetic acid were mixed in a weight ratio of 1:1:1:2, reacted at 80-90℃ for 10-12 h, centrifuged and dried to obtain crystalline material.

6. The method for preparing the anti-color migration polyurethane composite film as described in claim 2, characterized in that, The waterborne polyurethane is prepared by mixing polytetramethylene ether glycol, isophorone diisocyanate, dibutyltin dilaurate and dimethylolbutyric acid, reacting at 80-90℃ for 2-4 hours, adding triethylamine, 2,2'-diaminodiphenyl disulfide, methyl 2,6-dihydroxybenzoate and N,N-dimethylformamide, continuing the reaction for 1-2 hours, adding deionized water, emulsifying at 35℃ and 1200 r / s, and cooling to room temperature to obtain the waterborne polyurethane.

7. The method for preparing the anti-color migration polyurethane composite film as described in claim 2, characterized in that, The weight ratio of polytetramethylene ether diol, isophorone diisocyanate, dibutyltin dilaurate, dimethylolbutyric acid, triethylamine, 2,2'-diaminodiphenyl disulfide, methyl 2,6-dihydroxybenzoate and N,N-dimethylformamide is 2:1:1:2:3:1:1:

3.

8. The method for preparing the anti-color migration polyurethane composite film as described in claim 2, characterized in that, The method for preparing the fixing agent is as follows: isopropanol, isotridecyl alcohol polyoxyethylene ether, methacrylic acid and ammonium persulfate are mixed and reacted at 100-120℃ for 12-18h under nitrogen atmosphere, filtered and dried to obtain the fixing agent.

9. The method for preparing the anti-color migration polyurethane composite film as described in claim 8, characterized in that, The weight ratio of isopropanol, isotridecyl alcohol polyoxyethylene ether, methacrylic acid and ammonium persulfate is 3:2:3:

1.

10. The application of the anti-color migration polyurethane composite film as described in claim 1 in footwear materials.

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