阅读说明：本技术 耐候性粘合剂组合物 (Weather resistant adhesive composition ) 是由 冈岛裕树 示野胜也 于 2019-03-25 设计创作，主要内容包括：本申请提供一种通过低温且短时间老化而发挥实用水平的粘合性、耐湿热性及耐候性的聚酯多元醇及耐候性粘合剂。一种聚酯多元醇(A),以多元羧酸成分和多元醇成分为共聚成分,并且作为多元醇成分含有羟基特戊酸新戊二醇成分,以全部多元羧酸成分为100摩尔％时,对苯二甲酸成分为10摩尔％以下,聚酯多元醇(A)的酸值为20～150当量/10<Sup>6</Sup>g。(The present application provides a polyester polyol which exhibits practical levels of adhesion, moist heat resistance and weather resistance by aging at low temperature for a short time, and a polyester polyol having such propertiesA weatherable adhesive. A polyester polyol (A) comprising a polycarboxylic acid component and a polyol component as copolymerized components, and a hydroxypivalyl hydroxypivalate component as a polyol component, wherein the terephthalic acid component is 10 mol% or less based on 100 mol% of the total polycarboxylic acid component, and the acid value of the polyester polyol (A) is 20 to 150 equivalents/10 6 g。)

1. A polyester polyol A which comprises a polycarboxylic acid component and a polyol component as copolymerized components, a hydroxypivalyl hydroxypivalate component as a polyol component, a terephthalic acid component in an amount of 10 mol% or less based on 100 mol% of the total polycarboxylic acid component, and an acid value of 20 to 150 equivalents/10⁶g。

2. The polyester-polyol A according to claim 1, which contains a hydroxypivalyl hydroxypivalate component in an amount of 10 mol% or more based on 100 mol% of the total polyol component.

3. The polyester polyol A according to claim 1 or 2, which further contains a 3-methyl-1, 5-pentanediol component.

4. The polyester polyol A according to any one of claims 1 to 3, having a glass transition temperature of-20 to 20 ℃ and a number average molecular weight of 4000 to 50000.

5. A weather-resistant adhesive composition comprising the polyester polyol A according to any one of claims 1 to 4 and a polyisocyanate compound B containing an aliphatic polyisocyanate compound and/or an alicyclic polyisocyanate compound.

6. The weather-resistant adhesive composition according to claim 5, wherein the polyisocyanate compound B is 1 or 2 or more selected from the group consisting of an adduct of hexamethylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, a biuret of hexamethylene diisocyanate, an adduct of isophorone diisocyanate, an isocyanurate of isophorone diisocyanate, and a biuret of isophorone diisocyanate.

7. The weather-resistant adhesive composition according to claim 5 or 6, wherein the mixing ratio of the polyester polyol A and the polyisocyanate compound B is 1 to 20 parts by mass relative to 100 parts by mass of the polyester polyol A.

8. A laminate comprising a substrate and an adhesive layer comprising the weather-resistant adhesive composition according to any one of claims 5 to 7 laminated thereon.

9. The laminate according to claim 8, wherein the substrate is one or more than 2 films selected from the group consisting of a polyester film, a fluorine-based polymer film, a polyethylene film and a vinyl acetate copolymer film.

Technical Field

The present invention relates to a polyester polyol and a weather-resistant adhesive composition suitable for outdoor industrial use and the like.

Background

As an adhesive composition having weather resistance for outdoor industrial use, for example, in building materials, solar cell panels, and the like, a polyurethane adhesive containing a polyester polyol is known.

Patent document 1 discloses a specific polyurethane-based adhesive, which is considered to be excellent in long-term moist heat resistance. Patent document 2 discloses a laminate in which at least 2 or more layers of substrates are bonded together with a polyurethane adhesive, and this is considered to have excellent weather resistance.

Disclosure of Invention

Problems to be solved by the invention

In the curing reaction of polyurethane, for example, in the case of coating on metal plates or adhesion between metal plates, a high temperature of approximately 200 ℃ may be applied, and the curing time may be shortened. However, depending on the type and form of the substrate to be bonded, high temperature cannot be applied in many cases. As a typical example of such a case, the production of a laminate including resin films as described in patent document 1 and patent document 2 is carried out by aging at 60 ℃ for 7 days in the example of patent document 1, and aging at 50 ℃ for 5 days in the example of patent document 2. Thus, in the prior art, the aging treatment is generally performed at a relatively low temperature of about 50 to 60 ℃ for a long time of about 5 to 7 days. If the aging temperature is set to be as low as or lower than the current temperature and the aging time can be shortened, it is preferable from the viewpoint of energy saving, workability, productivity and cost reduction.

Accordingly, an object of the present invention is to provide a weather-resistant adhesive which exhibits practical levels of adhesion, moist heat resistance and weather resistance by aging at low temperatures for a short period of time.

Means for solving the problems

The present inventors have intensively studied to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by providing an adhesive composition containing hydroxypivalyl hydroxypivalate, a polyester polyol having an acid value within a specific range, and a polyisocyanate compound, which exhibits excellent adhesion, moist heat resistance, and weather resistance by aging for a short time of about 1 day at a relatively low temperature of about 40 to 60 ℃. That is, the present invention includes the following configurations.

A polyester polyol (A) which comprises a polycarboxylic acid component and a polyol component as copolymerized components, and a hydroxypivalic acid neopentyl glycol component as a polyol component, wherein 100 mol% of the total polycarboxylic acid component has a terephthalic acid component of 10 mol% or less, and has an acid value of 20 to 150 equivalents/10⁶g。

It is preferable that the polyester polyol (A) contains not less than 10 mol% of hydroxypivalyl hydroxypivalate component, and preferably further contains 3-methyl-1, 5-pentanediol component, based on 100 mol% of the total polyol component. The polyester polyol (A) preferably has a glass transition temperature of-20 to 20 ℃ and a number average molecular weight of 4,000 to 50,000.

A weather-resistant adhesive composition comprising the polyester polyol (A) and a polyisocyanate compound (B) containing an aliphatic polyisocyanate compound and/or an alicyclic polyisocyanate compound.

The polyisocyanate compound (B) is 1 or 2 or more selected from the group consisting of an adduct of hexamethylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, a biuret of hexamethylene diisocyanate, an adduct of isophorone diisocyanate, an isocyanurate of isophorone diisocyanate, and a biuret of isophorone diisocyanate.

The mixing ratio of the polyester polyol (A) and the polyisocyanate compound (B) is preferably: 1 to 20 parts by mass of a polyisocyanate compound (B) per 100 parts by mass of the polyester polyol (A).

A laminate comprising a base material and an adhesive layer comprising any one of the weather-resistant adhesive compositions described above laminated thereon. The substrate is preferably one or more than 2 films selected from the group consisting of polyester films, fluorine-based polymer films, polyethylene films and vinyl acetate copolymer films.

Effects of the invention

The adhesive composition using the polyester polyol of the present invention exhibits excellent adhesion, moist heat resistance and weather resistance by aging for a short time of about 1 day at a relatively low temperature of about 40 to 60 ℃. Therefore, energy saving, improvement in workability and productivity, and reduction in cost can be achieved.

Detailed Description

A polyester polyol (A) which comprises a polycarboxylic acid component and a polyol component as copolymerized components, and a hydroxypivalic acid neopentyl glycol component as a polyol component, wherein 100 mol% of the total polycarboxylic acid component has a terephthalic acid component of 10 mol% or less, and the acid value of the polyester polyol (A) is 20 to 150 equivalents/10⁶g. A weather-resistant adhesive composition comprising the polyester polyol (A) and a polyisocyanate compound (B) containing an aliphatic polyisocyanate compound and/or an alicyclic polyisocyanate compound.

< polyester polyol (A) >

The polyester polyol (a) of the present invention is preferably a polyester polyol having a chemical structure obtained by polycondensation of a polycarboxylic acid and a polyhydric alcohol. As the polycarboxylic acid, one or more of aliphatic dibasic acids (aliphatic dicarboxylic acids) such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, dimer acid and hydride thereof, and aromatic dibasic acids (aromatic dicarboxylic acids) such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and the like can be used.

From the viewpoint of improving weather resistance, it is effective to suppress the copolymerization ratio of the terephthalic acid component to a low level, and the terephthalic acid component must be 10 mol% or less when the total polycarboxylic acid component is 100 mol%. Preferably, the amount is less than 10 mol%, more preferably 5 mol% or less, still more preferably 1 mol% or less, and may be 0 mol%.

By being within the above range, good weather resistance can be exhibited.

From the viewpoint of improving the moist heat resistance, the aromatic dicarboxylic acid component is preferably an isophthalic acid component, a phthalic acid component, or a 2, 6-naphthalenedicarboxylic acid component, and more preferably an isophthalic acid component or a phthalic acid component. The total amount of the isophthalic acid component and the phthalic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% or more, based on 100 mol% of the total polybasic acid component. Further, it is preferably 99 mol% or less, and more preferably 98 mol% or less. By setting within the above range, good adhesion can be exhibited.

The aromatic dicarboxylic acid component is preferably a mixture of an isophthalic acid component and a phthalic acid component, and the mixing ratio (molar ratio) of the isophthalic acid component to the phthalic acid component is preferably 90 to 50/10 to 50, more preferably 80 to 60/20 to 40, and still more preferably 75 to 65/25 to 35. By setting within the above range, excellent adhesion, moist heat resistance and weather resistance can be exhibited.

The polyol component must contain a hydroxypivalic acid neopentyl glycol component. By containing the hydroxypivalyl hydroxypivalate component, excellent adhesion can be exhibited. The hydroxypivalyl hydroxypivalate component is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and particularly preferably 20 mol% or more, based on 100 mol% of the total polyol component. Further, it is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 45 mol% or less. By setting within the above range, good adhesion to the substrate can be exhibited.

As the polyol component other than hydroxypivalic acid neopentyl glycol, one or more of aliphatic diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, 1, 12-dodecanediol, 2-methyl-1, 3-propanediol, and 2-butyl-2-ethyl-1, 3-propanediol, alicyclic diols such as cyclohexanediol and hydrogenated benzenedimethanol, and diols containing aromatic rings such as benzenedimethanol can be used.

The aliphatic diol component containing a long-chain aliphatic structure is preferable, and from the viewpoint of moisture and heat resistance, the aliphatic diol component having 5 or more carbon atoms is preferably used, and the aliphatic diol component having 6 or more carbon atoms and 12 or less carbon atoms is more preferably used. Among them, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, 1, 12-dodecanediol, or 3-methyl-1, 5-pentanediol are more preferable, and 3-methyl-1, 5-pentanediol is particularly preferable. The aliphatic diol component containing a long-chain aliphatic structure is preferably contained in an amount of 50 mol% or more, more preferably 60 mol% or more, based on 100 mol% of the total polyol component. Further, it is preferably 99 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less, and particularly preferably 80 mol% or less. When the lower limit is not less than the above-mentioned lower limit, good moist heat resistance can be exhibited, and when the upper limit is not more than the above-mentioned upper limit, good adhesiveness can be exhibited.

The total content of the hydroxypivalyl hydroxypivalate component and the 3-methyl-1, 5-pentanediol component is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol% or more, based on 100 mol% of the total polyol component. By being within the above range, excellent adhesion, moist heat resistance and weather resistance can be exhibited. The total amount of the hydroxypivalyl hydroxypivalate component, the 3-methyl-1, 5-pentanediol component, and the other aliphatic diol component having a long-chain aliphatic structure is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and may be 100 mol%.

It is a preferred embodiment that a small amount of a trifunctional or higher polycarboxylic acid component such as trimellitic anhydride or pyromellitic anhydride or a trifunctional or higher polyol component such as trimethylolpropane is copolymerized to introduce a branch, and the reactivity with the polyisocyanate compound (B) is improved in some cases. When the total polyacid amount is 100 mol%, the trifunctional or higher polycarboxylic acid component is preferably 5 mol% or less, more preferably 3 mol% or less, and still more preferably 1 mol% or less. The trifunctional or higher polyol component is preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 1 mol% or less, based on 100 mol% of the total polyol component. If the amount is too large, the number of branches may become too large, and the polyester polyol (A) may become gel-like.

In the production of the polyol (A) of the present invention, a conventionally known polymerization catalyst can be used. For example, titanium compounds such as tetra-n-butyl titanate, tetra-isopropyl titanate, titanium acetylacetonate, antimony compounds such as tributoxyantimony and antimony trioxide, germanium compounds such as germanium tetra-n-butoxide and germanium oxide, and the like can be used. These catalysts may be used in combination of 1 or 2 or more. From the viewpoint of reactivity of polymerization, a titanium compound is preferable.

The polyol (A) used in the present invention has an acid value of 20 to 150 equivalents/10⁶g, preferably 50 to 120 equivalents/10⁶g, more preferably 70 to 100 equivalents/10⁶g. When the acid value is not less than the lower limit, the effect of shortening the aging time can be exhibited, and when the acid value is not more than the upper limit, the excellent moist heat resistance of the adhesive layer obtained from the weather-resistant adhesive composition can be exhibited.

The method for adjusting the acid value of the polyol (A) is not particularly limited, and the acid value can be adjusted by a method of intentionally polymerizing a large amount of carboxyl terminals or by introducing carboxyl groups into a polyester polyol. The method for introducing the carboxyl group into the polyester polyol is as follows: a method of imparting an acid value by post-addition of an acid anhydride under normal pressure and a nitrogen atmosphere after polymerization of a polyester polyol; and a method in which the acid anhydride is added to a polyester in an oligomer state before the polyester is polymerized to a high molecular weight, and then the polyester is polymerized to a high molecular weight by polycondensation under reduced pressure. The target acid value is particularly easily obtained by the former method and when trimellitic anhydride is used. As the acid anhydride which can be used in these reactions, in addition to the above-mentioned trimellitic anhydride, aromatic carboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1, 8-naphthalenedicarboxylic anhydride, 1, 2-cyclohexanedicarboxylic anhydride, cyclohexane-1, 2,3, 4-tetracarboxylic acid-3, 4-anhydride, ethylene glycol bistrimellitic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, naphthalene-1, 4,5, 8-tetracarboxylic dianhydride and alicyclic carboxylic acid anhydrides are preferable, and 1 or 2 or more of them can be selected and used.

When an acid anhydride or the like is post-added (post-addition) after the polymerization of the polyester in order to impart an acid value, the total amount of the polycarboxylic acid component may exceed 100 mol%. In this case, the total amount of the polycarboxylic acid component excluding the component to which the (post-addition) acid anhydride or the like is added later is calculated as 100 mol%.

The glass transition temperature range of the polyester polyol (A) is preferably-20 to 20 ℃, and more preferably 0 to 10 ℃. In order to obtain such a polyester polyol, a dibasic acid or a diol having a long aliphatic chain may be introduced into the copolymerization component. In addition, in order to achieve wet heat resistance, it is preferable to copolymerize an aliphatic diol having 5 or more carbon atoms, and from the viewpoint of adhesion, it is particularly preferable to use 3-methyl-1, 5-pentanediol together with hydroxypivalic acid neopentyl glycol. When the glass transition temperature is not more than the upper limit, good adhesive strength to a substrate can be exhibited, and when the glass transition temperature is not less than the lower limit, an adhesive layer made of the weather-resistant adhesive composition can be made not too soft, and excellent adhesive strength and moist heat resistance can be exhibited.

The number average molecular weight of the polyester polyol (A) of the present invention is not particularly limited, but is preferably 4,000 to 50,000, more preferably 8,000 to 20,000. When the number average molecular weight of the polyester polyol (a) is not less than the lower limit, the crosslinked ring molecular weight does not become excessively low, and the adhesive layer composed of the weather-resistant adhesive composition has appropriate hardness and can exhibit good adhesive strength. When the number average molecular weight of the polyester polyol (a) is not more than the above upper limit, the polyester polyol (a) can sufficiently react with the polyisocyanate (B) to exhibit good moist heat resistance.

< polyisocyanate Compound (B) >

The polyisocyanate compound (B) used in the present invention preferably contains an aliphatic polyisocyanate compound and/or an alicyclic polyisocyanate compound. The aliphatic polyisocyanate compound is preferably an aliphatic diisocyanate compound, and specifically, hexamethylene diisocyanate is a preferred example. The alicyclic polyisocyanate compound is preferably an alicyclic diisocyanate compound, and specifically isophorone diisocyanate is a preferred example. Hexamethylene diisocyanate or isophorone diisocyanate is preferable in terms of improving weather resistance.

The polyisocyanate compound (B) may be an isocyanurate compound, a biuret compound or an adduct compound, and an isocyanurate compound is particularly preferable. Specifically, an adduct of hexamethylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, a biuret of hexamethylene diisocyanate, an adduct of isophorone diisocyanate, an isocyanurate of isophorone diisocyanate, and a biuret of isophorone diisocyanate can be mentioned. These may be used in combination of 1 or 2 or more.

The content of the polyisocyanate compound (B) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more, based on 100 parts by mass of the polyester polyol (a). Further, it is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and further preferably 15 parts by mass or less. By setting within the above range, good adhesion can be exhibited.

< weather resistant adhesive composition >

The weather-resistant adhesive composition of the present invention is preferably a composition containing the polyester polyol (a) and the polyisocyanate compound (B). In the weather-resistant adhesive composition of the present invention, a blocking agent such as a carbodiimide compound, an oxazoline compound, or an epoxy compound may be mixed in an arbitrary ratio in order to block a carboxyl group generated when the polyester polyol (a) is hydrolyzed. The amount of the end-capping agent to be mixed is preferably 1 part by mass or more, more preferably 2 parts by mass or more, relative to 100 parts by mass of the polyester polyol (a). The end-capping effect of the carboxyl group can be obtained by setting the amount to the above-mentioned range. Further, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. By setting the mixing amount as described above, good adhesiveness can be exhibited.

Examples of the carbodiimide compound include N, N '-di-o-toluylcarbodiimide, N' -diphenylcarbodiimide, N '-di-2, 6-dimethylphenylcarbodiimide, N' -bis (2, 6-diisopropylphenyl) carbodiimide, N '-dioctyldecylcarbodiimide, N-tolyl-N' -cyclohexylcarbodiimide, N '-di-2, 2-di-t-butylphenyl carbodiimide, N-tolyl-N' -phenylcarbodiimide, N '-di-p-nitrophenylcarbodiimide, N' -di-p-aminophenylcarbodiimide, N '-di-p-hydroxyphenylcarbodiimide, N' -diphenylcarbodiimide, N '-di-octylcarbodiimide, N' -di-, N, N '-di-cyclohexylcarbodiimide, N' -di-p-toluylcarbodiimide, and the like.

Examples of the oxazoline compound include monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2, 5-dimethyl-2-oxazoline, and 2, 4-diphenyl-2-oxazoline, and bisoxazoline compounds such as 2,2 '- (1, 3-phenylene) -bis (2-oxazoline), 2, 2' - (1, 2-ethylene) -bis (2-oxazoline), 2,2 '- (1, 4-butylene) -bis (2-oxazoline), and 2, 2' - (1, 4-phenylene) -bis (2-oxazoline).

Examples of the epoxy compound include diglycidyl ethers of aliphatic diols such as 1, 6-hexanediol, neopentyl glycol and polyalkylene glycol, polyglycidyl ethers of aliphatic polyols such as sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol and trimethylolpropane, polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol, diglycidyl esters or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid and sebacic acid, diglycidyl ethers or polyglycidyl ethers of polyhydric phenols such as resorcinol, bis- (p-hydroxyphenyl) methane, 2, 2-bis- (p-hydroxyphenyl) propane, tris- (p-hydroxyphenyl) methane and 1,1,2, 2-tetrakis (p-hydroxyphenyl) ethane, n, N-diglycidylaniline, N-diglycidyltoluidine, N-glycidyl derivatives of amines such as N, N' -tetraglycidyl-bis- (p-aminophenyl) methane, triglycidyl derivatives of aminophenol, triglycidyl tris (2-hydroxyethyl) isocyanurate, triglycidyl isocyanurate, o-cresol-type epoxy compounds, phenol novolak-type epoxy compounds, bisphenol-type polyfunctional epoxy compounds.

The weather-resistant adhesive composition of the present invention may contain known additives such as an ultraviolet absorber and an antioxidant, and may further improve weather resistance and moist heat resistance.

The weather-resistant adhesive composition of the present invention is used as an adhesive layer, and a laminate in which the adhesive layer and a substrate are laminated can be obtained. Examples of the substrate include 1 or 2 or more films selected from the group consisting of polyester films, fluorine-based polymer films, polyethylene films, and vinyl acetate copolymer films. The laminate may be not only a 3-layer laminate of film/adhesive layer/film but also a 5-layer laminate of film/adhesive layer/film or a laminate of a larger number of layers. The films constituting the laminate may be made of the same material or different materials.

The laminate may be one obtained by applying a weather-resistant adhesive composition to a substrate and drying the composition, or one obtained by separately preparing an adhesive layer made of a weather-resistant adhesive composition in advance and adhering the adhesive layer to a substrate. The conditions for applying the weather-resistant adhesive composition to the substrate and drying the composition are not particularly limited, and preferably 40 to 250 ℃. Below 40 ℃ it takes time to dry, and this is not reasonable as an industrial production. In addition, there is a possibility that drying of the coating film is incomplete. In addition, if the temperature exceeds 250 ℃, a drying furnace having high capacity is required, which is not preferable. The drying method is not limited, and known methods such as a hot air dryer, induction heating, near infrared heating, far infrared heating, and indirect heating can be applied. The thickness of the dried adhesive layer is generally 5 to 30 μm, preferably 10 to 20 μm.

Examples of the polyester constituting the polyester film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polycyclohexanedimethanol terephthalate (PCT).

The fluoropolymer constituting the fluoropolymer film includes, for example, fluorinated polyolefins and polyolefin-fluorinated polyolefin copolymers, and specific examples thereof include polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), Polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and the like.

Examples of the polymer constituting the polyethylene film include low-density polyethylene, high-density polyethylene, ultrahigh-molecular-weight polyethylene, and polymers obtained by adding various additives to these polymers.

Examples of the polymer constituting the vinyl acetate copolymer film include an ethylene-vinyl acetate copolymer, and a polymer obtained by adding various additives thereto.

The substrate used in the present invention may or may not be surface-treated. For the purpose of improving the adhesion between the coated surface and the adhesive surface, surface treatment such as corona treatment, flame treatment, and plasma treatment is preferably performed.

The application claims priority benefits based on the Japanese patent application No. 2018-076800 filed on 12.4.4.2018. The entire contents of the specification of the above-mentioned japanese patent application No. 2018-076800 are incorporated herein by reference.