Self-healing resin composition and self-healing membrane structure

Abstract

To provide a self-healing resin composition and a self-healing membrane structure.SOLUTION: The self-healing resin composition includes 20 pts.wt. to 50 pts.wt. of a self-healing resin, 1 pt.wt. to 10 pts.wt. of a curing agent, 0.1 pt.wt. to 3 pts.wt. of a matting agent, and 40 pts.wt. to 80 pts.wt. of a solvent. The self-healing resin is synthesized from a polyester polyol, a diisocyanate monomer, and a bisphenol monomer. A molar ratio of a hydroxyl group to a cyanate group in the monomer mixture to synthesize the self-healing resin ranges from 1.33 to 2.0. A number average molecular weight of the self-healing resin ranges from 30000 g / mol to 200000 g / mol.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a self-repairing resin composition and a self-repairing film structure, and in particular to a self-repairing resin composition and a self-repairing film structure that have high transparency and can adjust the haze value. [Background technology]

[0002] Current commercially available substrates have insufficient scratch resistance on the surface, such as car cases, mobile phone cases, laptop cases, etc. They are prone to permanent scratches during use, which affects the appearance. In order to extend the life of the substrate, a protective layer is generally attached to the surface of the substrate to maintain its beauty.

[0003] With the development of technology and the discovery of self-healing materials, the industry has begun to apply self-healing materials to substrates. A protective layer can be formed on the surface of the substrate, and when the substrate is scratched by external force, the surface of the substrate can be heated to restore the original appearance. However, existing self-healing materials cannot combine high transparency with matte or glossy gloss properties.

[0004] For example, in order to adjust the matte properties of the protective layer, the prior art provides a technical means of performing a matte treatment on the self-repairing material and adding scattering particles to the self-repairing material. However, the matte treatment destroys the properties of the self-repairing material itself, and the scattering particles are likely to fall off after being added, so the preparation of a self-repairing resin composition by designing and improving the components is an important problem that this project aims to solve. Summary of the Invention [Problem to be solved by the invention]

[0005] The technical problem that the present invention seeks to solve is to provide a self-repairing resin composition and a self-repairing film structure in response to the deficiencies of the prior art. [Means for solving the problem]

[0006] In order to solve the above technical problems, one technical means adopted by the present invention provides a self-repairing resin composition. The self-repairing resin composition includes 20 to 50 parts by weight of a self-repairing resin, 1 to 10 parts by weight of a curing agent, 0.1 to 3 parts by weight of a matting agent, and 40 to 80 parts by weight of a solvent. The self-repairing resin is synthesized from a polyester polyol, a diisocyanate monomer, and a bisphenol monomer, and in the monomer mixture for synthesizing the self-repairing resin, the molar ratio of the hydroxyl group to the cyanate group is 1.33 to 2.0, and the number average molecular weight of the self-repairing resin is 30,000 g / mol to 200,000 g / mol.

[0007] In one embodiment, the total weight of the monomer mixture for synthesizing the self-repairing resin is 100% by weight, the content of the polyester polyol is 75% by weight to 90% by weight, the content of the diisocyanate monomer is 3% by weight to 10% by weight, and the content of the bisphenol monomer is 5% by weight to 15% by weight.

[0008] In one embodiment, the number average molecular weight of the polyester polyol is from 3000 g / mol to 5000 g / mol.

[0009] In one embodiment, the polyester polyol is synthesized with adipic acid, 1,4-butanediol, 1,6-hexanediol, and 2-methyl-1,3-propanediol.

[0010] In one embodiment, the molar ratio of 1,4-butanediol:1,6-hexanediol is 1:0.5 to 1:2, and the molar ratio of 1,4-butanediol:2-methyl-1,3-propanediol is 1:0.33 to 1:3.

[0011] In one embodiment, the diisocyanate monomer is selected from the group consisting of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate trimer (HDI-trimer).

[0012] In one embodiment, the bisphenol monomer is selected from the group consisting of bisphenol A, bis(4-hydroxyphenyl)cyclohexane, 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis((4-hydroxyethoxy)phenyl)fluorene, and dimethylbisphenol A.

[0013] In order to solve the above technical problems, another technical means adopted by the present invention provides a self-repairing film structure. The self-repairing film structure includes a substrate layer having a first surface and a second surface, a self-repairing film layer formed on the first surface, an adhesive layer disposed on the second surface, and a release layer disposed on the adhesive layer. The self-repairing film layer is formed from the self-repairing resin composition. The adhesive layer is disposed between the substrate layer and the release layer.

[0014] In one embodiment, the material of the substrate layer is polyurethane or polyvinyl chloride.

[0015] In one embodiment, the thickness of the self-repairing film structure is between 5 μm and 50 μm. Effect of the Invention

[0016] As an advantageous effect of the present invention, the self-repairing resin composition and self-repairing film structure according to the present invention have technical features such as "the self-repairing resin is synthesized from a polyester polyol, a diisocyanate monomer, and a bisphenol monomer," "in the monomer mixture for synthesizing the self-repairing resin, the molar ratio of hydroxyl groups to cyanate groups is 1.33 to 2.0," and "the number average molecular weight of the self-repairing resin is 30,000 g / mol to 200,000 g / mol," which provide the self-repairing film layer formed from the self-repairing resin composition with the ability to self-repair when heated for a short period of time or in a room temperature environment. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic side view of a self-repairing film structure according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] In order to better understand the features and technical contents of the present invention, please refer to the following detailed description of the present invention and the accompanying drawings, which are provided for reference and explanation only and are not intended to limit the scope of the present invention.

[0019] Hereinafter, the "self-repairing resin composition and self-repairing film structure" according to the embodiment of the present invention will be described by certain specific embodiments, and those skilled in the art can understand the advantages and effects of the present invention based on the contents disclosed in this specification. The present invention can be implemented or applied by other different specific embodiments, and various modifications and changes can be made to each detail in this specification based on different perspectives and applications without departing from the concept of the present invention. In addition, as described in advance, the accompanying drawings of the present invention are simple schematic illustrations and are not drawn based on actual size. The technical contents according to the present invention will be described in more detail based on the following embodiments, but the scope of protection of the present invention is not limited by the disclosed contents. In addition, the term "or" used in this specification may include any one or more combinations of the items listed in relation to each other according to the actual situation.

[0020] The self-repairing resin composition according to the present invention has a relatively low chemical bond energy, and therefore can self-repair at a relatively low temperature. The self-repairing resin composition according to the present invention has high transparency and can maintain a self-repairing function even when matte particles are added. The self-repairing resin composition is applied to a substrate, cured, and then a self-repairing material is formed, thereby fulfilling a protective function.

[0021] For ease of application, the present invention provides a self-repairing film structure formed of a self-repairing resin composition. The self-repairing film structure can be laminated to the surface to be protected. The self-repairing film structure itself has a self-repairing function and can restore the material to its original state. After the self-repairing film structure is cracked or deformed by an external force, it can be returned to its original state by thermal expansion by appropriate heating (physical repair), or the bonds broken by thermal expansion can come into contact and bond again (chemical repair).

[0022] In the present invention, when heated at a temperature of 80°C to 130°C for a short time or placed in a room temperature environment (eg, 50°C), the self-repairing material can repair cracks by intermolecular forces.

[0023] It is particularly noteworthy that the self-repairing resin composition according to the present invention is particularly suitable for application to a substrate made of polyurethane material or polyvinyl chloride material, thereby forming a self-repairing film layer (self-repairing material) on the surface layer of the substrate, thereby achieving the effect of protecting the substrate.

[0024] In the present invention, the self-repairing material can be given a self-repairing function by selecting a monomer, designing the monomer structure, and controlling the content of the monomer. In addition, the self-repairing resin composition according to the present invention can form a self-repairing film layer with high transparency, and can adjust the surface to be a matte surface or a glossy surface.

[0025] Assuming the total weight of the self-repairing resin composition is 100 parts by weight, the self-repairing resin composition of the present invention contains 20 to 50 parts by weight of a self-repairing resin, 1 to 10 parts by weight of a curing agent, 0.1 to 3 parts by weight of a matting agent, and 40 to 80 parts by weight of a solvent.

[0026] In the present invention, the self-repairing resin is synthesized from polyester polyol, diisocyanate monomer and bisphenol monomer. By using different monomers, designing monomer structure and controlling monomer content, the cured self-repairing resin composition (self-repairing material) has more hydrogen bonds. When deformation occurs due to external force, the self-repairing material can return to its original shape at an appropriate temperature.

[0027] In one exemplary embodiment, the total weight of the monomer mixture for synthesizing the self-repairing resin is 100% by weight, the content of the polyester polyol is 75% by weight to 90% by weight, the content of the diisocyanate monomer is 3% by weight to 10% by weight, and the content of the bisphenol monomer is 5% by weight to 15% by weight.

[0028] Preferably, the content of the polyester polyol is 85% by weight to 90% by weight, the content of the diisocyanate monomer is 3% by weight to 5% by weight, and the content of the bisphenol monomer is 5% by weight to 10% by weight.

[0029] In the present invention, the number average molecular weight of the self-repairing resin is 30000g / mol to 200000g / mol. If the number average molecular weight of the self-repairing resin exceeds the above range, the effect of repair cannot be achieved. For example, the number average molecular weight of the self-repairing resin may be 40000g / mol, 50000g / mol, 60000g / mol, 70000g / mol, 80000g / mol, 90000g / mol, 100000g / mol, 110000g / mol, 120000g / mol, 130000g / mol, 140000g / mol, 150000g / mol, 160000g / mol, 170000g / mol, 180000g / mol or 190000g / mol.

[0030] In all monomers used to synthesize self-repairing resins, the functional group ratio between hydroxyl and cyanate groups is also an important index. In the present invention, the functional group ratio between hydroxyl and cyanate groups in the monomer mixture used to synthesize self-repairing resins is 1.33 to 2.0. For example, the functional group ratio between hydroxyl and cyanate groups in the monomer used to synthesize self-repairing resins may be 1.35, 1.40, 1.45, 1.50, 1.55, 1.6, 1.65, 1.70, 1.75, 1.80, 1.85, 1.90 or 1.95.

[0031] That is, the content of hydroxyl group in the monomer mixture for synthesizing the self-repairing resin is greater than the content of cyanate group. After carrying out the polymerization reaction of polyester polyol, diisocyanate monomer and bisphenol monomer, the self-repairing resin still has a suitable content of hydroxyl group to form hydrogen bond, so that it can perform the function of self-repairing.

[0032] The polyester polyol is synthesized from a diol monomer and a dibasic acid monomer. The diol monomer includes 1,4-butanediol, 1,6-hexanediol, and 2-methyl-1,3-propanediol. The dibasic acid monomer includes hexanedicarboxylic acid. When 1,4-butanediol, 1,6-hexanediol, and 2-methyl-1,3-propanediol are combined with hexanedicarboxylic acid, the polyester polyol according to the present invention can have an optimal intermolecular distance and sufficient hydroxyl groups, and can balance the optimal repair properties, compared with using other monomers.

[0033] In one exemplary embodiment, the total weight of the monomer mixture for the polyester polyol is 100% by weight, the content of 1,4-butanediol is 30% to 40% by weight, the content of 1,6-hexanediol is 20% to 30% by weight, the content of 2-methyl-1,3-propanediol is 15% to 20% by weight, and the content of adipic acid is 20% to 40% by weight.

[0034] Specifically, in the diol monomer mixture for synthesizing the polyester polyol, the molar ratio of 1,4-butanediol:1,6-hexanediol is 1:0.5 to 1:2, and the molar ratio of 1,4-butanediol:2-methyl-1,3-propanediol is 1:0.33 to 1:3, thereby providing the polyester polyol with ideal properties.

[0035] It should be noted that in the present invention, the polyester polyol is first polymerized with diol monomer and dibasic acid monomer, and then the polyester polyol, diisocyanate monomer, and bisphenol monomer are polymerized. The monomers (diol monomer and dibasic acid monomer) for synthesizing the polyester polyol, diisocyanate monomer, and bisphenol monomer are not all mixed together to perform the polymerization reaction. In this way, the properties of the polyester polyol can be precisely controlled so that the finally obtained self-repairing resin can achieve the ideal self-repairing effect.

[0036] The diisocyanate monomer may be selected from the group consisting of hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (4,4'-diisocyanato dicyclohexylmethane (H12MDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), and hexamethylene diisocyanate trimer (HDI-trimer).

[0037] The bisphenol monomer may be selected from the group consisting of bisphenol A (BPA), bis(4-hydroxyphenyl)cyclohexane (BPZ), 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BP-TMC), 9,9-bis((4-hydroxyethoxy)phenyl)fluorene (BP-EF), and dimethyl-bisphenol A (DMBPA).

[0038] Based on the above, the self-healing resin may be represented by formula (I): [ka]

[0039] In formula (I), "X" represents a structure formed after polymerization of polyester polyol, "Y" represents a structure formed after polymerization of diisocyanate monomer, and "Z" represents a structure formed after polymerization of bisphenol monomer. The number average molecular weight of polyester polyol may be 3000 g / mol to 5000 g / mol, but the present invention is not limited thereto.

[0040] In one exemplary embodiment, the diisocyanate monomer may be hexamethylene diisocyanate, and the bisphenol monomer may be bisphenol A. The self-repairing resin synthesized with polyester polyol, hexamethylene diisocyanate, and bisphenol A may be represented by formula (II): [ka]

[0041] In formula (II), "X" represents the structure formed after the polyester polyol is polymerized. The number average molecular weight of the self-repairing resin may be 30000 g / mol to 200000 g / mol, but the present invention is not limited thereto.

[0042] In the self-repairing resin composition, the curing agent may be selected from the group consisting of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate.

[0043] In the self-repairing resin composition, the matting agent may be selected from the group consisting of polymethacrylic acid particles, polystyrene particles, and silicon dioxide particles. The particle size (D 50 ) is 0.5μm~10μm.

[0044] In the present invention, since the self-repairing resin is synthesized from a specific monomer mixture, the self-repairing effect of the self-repairing resin will not be adversely affected even if a matting agent is added in the future.

[0045] In the self-repairing resin composition, the solvent may be selected from the group consisting of ethyl acetate, acetone, propylene glycol methyl ether acetate, dimethylacetamide, butanone, isopropyl alcohol, and ethanol. Preferably, the solvent may be dimethylacetamide. In consideration of processability, the solid content of the self-repairing resin composition may be 35% to 45%.

[0046] In addition to the above components, the self-repairing resin composition may further include an ultraviolet absorber, a leveling agent, an antifoaming agent, a catalyst, or a combination thereof.

[0047] For example, the catalyst may be stannous octanoate, dibutyltin dilaurate, dimethyl methylphosphonate, or diethyl ethylphosphonate, but the present invention is not limited thereto. In addition, the addition of the catalyst is useful for the synthesis of the self-repairing film layer and the repair of the self-repairing film layer. The amount of the catalyst added may be 1 part by weight to 5 parts by weight, with the total weight of the self-repairing resin composition being 100 parts by weight.

[0048] As shown in FIG. 1, the self-repairing film structure according to the present invention includes a base layer 1, a self-repairing film layer 2, an adhesive layer 3, and a release layer 4.

[0049] The substrate layer 1 has a first surface 11 and a second surface 12 .

[0050] After the self-repairing resin composition is applied to the first surface 11 of the base layer 1, a drying and aging process is performed, and the self-repairing film layer 2 can be formed on the first surface 11. That is, the self-repairing film layer 2 is formed after the self-repairing resin composition is cured.

[0051] An adhesive layer 3 is applied to the second surface 12 of the substrate layer 1 .

[0052] The release layer 4 is placed on the adhesive layer 3 so that the adhesive layer 3 is placed between the base layer 1 and the release layer 4. In addition, since the peel strength between the release layer 4 and the adhesive layer 3 is relatively low, the release layer 4 is first separated before use, and the base layer 1 and the self-repairing film layer 2 are placed on the surface to be protected via the adhesive layer 3.

[0053] Since the self-repairing film structure of the present invention is flexible, it can be attached to any surface via the adhesive layer 3 after the release layer 4 is separated, so as to provide a surface protection effect.

[0054] In order to explain the effect of the self-repairing resin composition according to the present invention, a polyester polyol was prepared by the following method, and a self-repairing resin was synthesized from the polyester polyol, an isocyanate monomer, and a bisphenol monomer. However, the following examples are merely for illustrative purposes, and the present invention is not limited thereto. EXAMPLES

[0055] [Synthesis of polyester polyol] 50g of 1,4-butanediol, 60g of 1,6-hexanediol, 60g of 2-methyl-1,3-propanediol, and 190g of adipic acid were mixed and reacted at a temperature of 150°C to 200°C for 1 to 2 hours to obtain a polyester polyol. In this example, the number average molecular weight of the polyester polyol was 4000g / mol.

[0056] [Synthesis of self-repairing resin] Based on Table 1 and the equivalent ratios in Table 1, polyester polyol and hexamethylene diisocyanate (diisocyanate monomer) were mixed and reacted at a temperature of 80°C for 1 to 2 hours, and then bisphenol A (bisphenol monomer) and dibutyltin dilaurate (catalyst) were further added and reacted at a temperature of 100°C for 5 to 6 hours to obtain self-repairing resins according to Examples 1 to 5 and Comparative Examples 1 to 4.

[0057] In order to test the repair effect of the self-repairing film layer, 100 parts by weight of the self-repairing resin, 10 parts by weight of the curing agent, 0.5 parts by weight of the matting agent, and 300 parts by weight of the solvent were mixed to obtain the self-repairing resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 4.

[0058] When the solid content of the self-repairing resin composition is 40%, the viscosity of the self-repairing resin composition is 500 cps to 10,000 cps, and may be, for example, 1,000 cps, 2,000 cps, 3,000 cps, 4,000 cps, 5,000 cps, 6,000 cps, 7,000 cps, 8,000 cps or 9,000 cps, but the present invention is not limited thereto.

[0059] After preparing the self-repairing resin composition, the self-repairing resin composition was applied to a base layer of a polyurethane material or polyvinyl chloride. It was dried at a temperature of 80°C to 120°C for 3 to 5 minutes, then aged at a temperature of 40°C to 70°C, and stored for 24 to 120 hours to form a self-repairing film layer with a thickness of 5 μm to 50 μm on the base layer, and a test sample was obtained.

[0060] In the test on repair time, a copper brush was used to scratch the surface of the test sample, and the scratched test sample was placed in an environment of 100°C, and the time it took for the surface of the test sample to return to its original state was observed. This evaluated the effect of repairing the scratches on the test sample to their original state, and the results are shown in Table 1.

[0061] [Table 1]

[0062] [Table 2]

[0063] According to Tables 1 and 2, the self-repairing resin composition of the present invention can form a self-repairing film layer having a self-repairing function. When heated at a temperature of 80°C to 130°C for a short period of time, the cracks can be repaired by intermolecular forces.

[0064] According to Tables 1 and 2, the functional group ratio of the monomer for the self-repairing resin affects the repair effect of the self-repairing resin. According to the results of Example 1 and Comparative Example 1, a self-repairing film layer in which the functional group ratio value of the hydroxyl group to the cyanate group in the self-repairing resin (OH / NCO functional group ratio value) is less than 1.33 does not have a self-repairing effect. According to the results of Example 2 and Comparative Example 2, a self-repairing film layer in which the functional group ratio value of the hydroxyl group to the cyanate group in the self-repairing resin is 2.5 or more does not have a self-repairing effect. Thus, the functional group ratio value of the hydroxyl group to the cyanate group in the self-repairing resin needs to be 1.33 to 2.0, and is preferably 1.33 to 1.66.

[0065] According to Tables 1 and 2, the molecular weight of the self-repairing resin also affects the repair effect of the self-repairing resin. According to the results of Comparative Example 3, if the molecular weight of the self-repairing resin is less than 30000 g / mol, the self-repairing film layer does not have the self-repairing effect. According to the results of Example 5 and Comparative Example 4, if the molecular weight of the self-repairing resin is more than 200000 g / mol, the self-repairing film layer also does not have the self-repairing effect. Thus, the number average molecular weight of the self-repairing resin needs to be 30000 g / mol to 200000 g / mol, and is preferably 50000 g / mol to 150000 g / mol.

[0066] [Advantageous Effects of the Embodiments] As an advantageous effect of the present invention, the self-repairing resin composition and self-repairing film structure according to the present invention have technical features such as "the self-repairing resin is synthesized from a polyester polyol, a diisocyanate monomer, and a bisphenol monomer," "in the monomer mixture for synthesizing the self-repairing resin, the molar ratio of hydroxyl groups to cyanate groups is 1.33 to 2.0," and "the number average molecular weight of the self-repairing resin is 30,000 g / mol to 200,000 g / mol," which give the self-repairing film layer formed from the self-repairing resin composition the ability to self-repair when heated for a short period of time or in a room temperature environment.

[0067] To be more specific, in order to improve the self-repairing effect of the self-repairing resin composition, the present invention controls the type and content of the monomer of the self-repairing resin, and uses a specific type of polyester polyol, diisocyanate monomer and bisphenol monomer to improve the self-repairing effect of the self-repairing film layer.In addition, the present invention further controls the type and ratio of the monomer of the polyester polyol and the molecular weight of the polyester polyol to control the properties of the polyester polyol.

[0068] The above disclosure is merely a preferred embodiment of the present invention, and the scope of the claims of the present invention is not limited thereto. Therefore, all equivalent technical modifications made by utilizing the specification and drawings of the present invention are included in the scope of the claims of the present invention. [Explanation of symbols]

[0069] 1...Base material layer 11...First surface 12...Second Surface 2. Self-repairing film 3... Adhesive layer 4...Release layer

Claims

1. 20 to 50 parts by weight of a self-repairing resin; 1 part by weight to 10 parts by weight of a curing agent; 0.1 to 3 parts by weight of a matting agent; 40 to 80 parts by weight of a solvent; Including, The self-repairing resin is synthesized from a polyester polyol, a diisocyanate monomer, and a bisphenol monomer; In the monomer mixture for synthesizing the self-repairing resin, the molar ratio of hydroxyl groups to cyanate groups is 1.33 to 2.0; The self-repairing resin composition, characterized in that the number average molecular weight of the self-repairing resin is 30,000 g / mol to 200,000 g / mol.

2. The total weight of the monomer mixture for synthesizing the self-repairing resin is 100% by weight, The content of the polyester polyol is 75% by weight to 90% by weight, The content of the diisocyanate monomer is 3% by weight to 10% by weight, The self-repairing resin composition according to claim 1, wherein the content of the bisphenol monomer is 5% by weight to 15% by weight.

3. The self-repairing resin composition according to claim 1, wherein the number average molecular weight of the polyester polyol is 3000 g / mol to 5000 g / mol.

4. 2. The self-repairing resin composition of claim 1, wherein the polyester polyol is synthesized from adipic acid, 1,4-butanediol, 1,6-hexanediol and 2-methyl-1,3-propanediol.

5. The self-repairing resin composition according to claim 4, wherein the molar ratio of 1,4-butanediol:1,6-hexanediol is 1:0.5 to 1:2, and the molar ratio of 1,4-butanediol:2-methyl-1,3-propanediol is 1:0.33 to 1:

3.

6. 2. The self-repairing resin composition of claim 1, wherein the diisocyanate monomer is selected from the group consisting of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate trimer.

7. The self-repairing resin composition of claim 1, wherein the bisphenol monomer is selected from the group consisting of bisphenol A, bis(4-hydroxyphenyl)cyclohexane, 1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis((4-hydroxyethoxy)phenyl)fluorene, and dimethylbisphenol A.

8. a substrate layer having a first surface and a second surface; A self-repairing film layer disposed on the first surface and formed from the self-repairing resin composition according to any one of claims 1 to 7; an adhesive layer disposed on the second surface; a release layer disposed on the adhesive layer; Equipped with A self-repairing film structure, wherein the adhesive layer is disposed between a base layer and a release layer.

9. 9. The self-repairing film structure of claim 8, wherein the material of the substrate layer is polyurethane or polyvinyl chloride.

10. 9. The self-repairing film structure of claim 8, wherein the thickness of the self-repairing film structure is between 5 μm and 50 μm.

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