JP2019130802A - Decorative material - Google Patents

Abstract

To provide a decorative material having excellent water resistance and weather resistance.SOLUTION: A decorative material has a base material, an adhesive layer, and a top film stacked in this order, the base material composed of an acrylonitrile-butadiene-styrene copolymer resin, the adhesive layer being a cured product of an adhesive composition containing an acrylic adhesive and an epoxy curing agent, the top film containing polyvinyl chloride and an ultraviolet absorber, the content of the ultraviolet absorber being 0.1-5 pts.wt. relative to 100 pts.wt. of the polyvinyl chloride.SELECTED DRAWING: None

Description

The present invention relates to a decorative material.

2. Description of the Related Art Conventionally, a decorative material to which a design has been imparted is produced by attaching a decorative film to a substrate (adhered body). As literature which disclosed the prior art related to a cosmetic material or a cosmetic film, patent documents 1-4 are mentioned, for example.

Patent Document 1 discloses a cosmetic material comprising at least a pattern layer and a fluororesin surface layer on a base material.

In Patent Document 2, a polyvinyl chloride film layer, an adhesive layer, and a separator are laminated in this order, and the adhesive layer is a copolymer of methyl acrylate and an alkyl acrylate ester containing an alkoxy group having 4 carbon atoms. And (meth) acrylic acid alkyl ester having a glass transition temperature of 115 ° C. or less and a weight average molecular weight of 5,000 to 100,000, and the content of the (meth) acrylic acid alkyl ester is A decorative molding film is disclosed which is 1 to 40 parts by weight with respect to 100 parts by weight of the copolymer.

Patent Document 3 discloses a decorative sheet having at least a decorative layer, a primer layer, and a surface protective layer in this order on a substrate, the surface protective layer comprising (A) an ionizing radiation curable resin and (B) a reaction. It is a layer formed by crosslinking and curing an ionizing radiation curable resin composition containing an ultraviolet absorber having a functional functional group A, and the (A) ionizing radiation curable resin has an alkyl group having 13 to 25 carbon atoms and ionizing radiation. A decorative sheet having a curable functional group and modified with polycaprolactone is disclosed.

Patent Document 4 discloses a decorative sheet having a base material, an adhesive layer, a colored layer, and a transparent resin layer. The colored layer contains a high-brilliance pigment, and vinyl chloride and acetic acid are used as a binder resin. A decorative sheet is disclosed in which a vinyl copolymer and an acrylic resin are used, and the transparent resin layer has an ultraviolet transmittance of 8% or less (380 nm).

Japanese Patent Laid-Open No. 10-44329 JP 2017-132205 A JP 2012-206376 A JP 2007-261143 A

By the way, for cosmetic materials used for wall coverings in bathrooms, toilets, etc., not only weather resistance that can prevent discoloration of the decorative film due to long-term use, but also peeling (floating) of the decorative film against water immersion such as warm water. ), Water resistance capable of preventing discoloration and lowering of adhesive strength has been demanded. However, the adhesive strength of the decorative film varies depending not only on the composition of the pressure-sensitive adhesive layer but also on the relationship between the material of the base material and the material of the resin film. It was difficult to obtain a cosmetic material that improved both.

This invention is made | formed in view of the said present condition, and aims at providing the cosmetics excellent in water resistance and a weather resistance.

This inventor pays attention to the cosmetics which stuck the top film containing a polyvinyl chloride to the base material comprised with an acrylonitrile butadiene styrene copolymer resin, and various about the method of improving water resistance and a weather resistance. investigated. As a result, it was found that the use of a pressure-sensitive adhesive layer containing an acrylic pressure-sensitive adhesive and an epoxy curing agent optimizes the relationship between the base material and the top film material and provides good water resistance. . Furthermore, the present inventor has found that good weather resistance can be obtained without impairing water resistance by blending a specific amount of an ultraviolet absorber with the top film, and has completed the present invention.

The decorative material of the present invention is a decorative material in which a base material, a pressure-sensitive adhesive layer, and a top film are sequentially laminated. The base material is composed of an acrylonitrile-butadiene-styrene copolymer resin, and the pressure-sensitive adhesive. The layer is a cured product of an adhesive composition containing an acrylic adhesive and an epoxy curing agent, the top film contains polyvinyl chloride and an ultraviolet absorber, and the content of the ultraviolet absorber is It is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyvinyl chloride.

The thickness of the pressure-sensitive adhesive layer is preferably 20 to 80 μm. The content of the epoxy curing agent is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the acrylic pressure-sensitive adhesive. The decorative material of the present invention may include a base film containing polyvinyl chloride between the pressure-sensitive adhesive layer and the top film, and a printing layer between the base film and the top film. May be provided. The top film preferably contains an antibacterial agent, antifungal agent or antibacterial antifungal agent.

ADVANTAGE OF THE INVENTION According to this invention, the cosmetics excellent in water resistance and a weather resistance are realizable.

It is sectional drawing which showed an example of the decorative material of this invention typically. It is sectional drawing which showed typically another example of the decorative material of this invention. It is sectional drawing which showed typically another example of the decorative material of this invention.

The decorative material of the present invention is a decorative material in which a base material, a pressure-sensitive adhesive layer, and a top film are sequentially laminated. The base material is composed of an acrylonitrile-butadiene-styrene copolymer resin, and the pressure-sensitive adhesive. The layer is a cured product of an adhesive composition containing an acrylic adhesive and an epoxy curing agent, the top film contains polyvinyl chloride and an ultraviolet absorber, and the content of the ultraviolet absorber is It is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyvinyl chloride. In this specification, “film” is synonymous with “sheet”, and the two are not distinguished by thickness.

FIG. 1 is a cross-sectional view schematically showing an example of the decorative material of the present invention. The decorative material shown in FIG. 1 has a structure in which a base material 11, an adhesive layer 12, and a top film 13 are sequentially laminated. By attaching the top film 13 to the outer surface side of the base material 11 via the pressure-sensitive adhesive layer 12, it is a highly design member having an appearance different from the appearance of the base material 11 itself. That is, the top film 13 constitutes the outer surface of the decorative material.

[Base material]
The substrate 11 is made of acrylonitrile-butadiene-styrene copolymer resin (ABS resin). ABS resin is excellent in rigidity, impact resistance, heat resistance, cold resistance, workability, and the like, and is easy to surface-treat.

The ABS resin may be a foamed ABS resin. By setting it as a foam, it can reduce in weight and can improve workability, heat insulation, a flame retardance, etc. As a foaming method, a conventionally known method can be used. For example, azodicarboxylic acid amide or the like may be used as a foaming agent, and zinc acetate, metal soap, talc or the like may be used as a foaming aid.

Although the shape of the base material 11 is not specifically limited, For example, flat form is mentioned.

[Adhesive layer]
The pressure-sensitive adhesive layer 12 is a cured product of a pressure-sensitive adhesive composition containing an acrylic pressure-sensitive adhesive and an epoxy-based curing agent. The pressure-sensitive adhesive composition is cured when the epoxy-based curing agent chemically reacts or interacts with the functional group in the acrylic pressure-sensitive adhesive and the acrylic pressure-sensitive adhesive is crosslinked.

The acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive containing an acrylic polymer. The acrylic pressure-sensitive adhesive is excellent in adhesiveness, workability, heat aging resistance, moisture aging resistance, and weather resistance, and is relatively inexpensive.

Examples of the acrylic polymer include a homopolymer of (meth) acrylic acid alkyl ester or a copolymer thereof.

Examples of the (meth) acrylic acid alkyl ester include esters obtained from a primary to tertiary alcohol having 2 to 18 carbon atoms, preferably 4 to 12 carbon atoms, and acrylic acid or methacrylic acid. Is mentioned. Specific examples include methyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.

The copolymerizable monomer used for the synthesis of the copolymer has at least one unsaturated double bond involved in the copolymerization reaction in the molecule, and a carboxyl group [for example, (meth) acrylic acid, Itaconic acid, maleic acid, maleic anhydride, etc.], hydroxyl group (eg, (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester, etc.), sulfoxyl group (eg, styrene sulfonic acid, allyl sulfonic acid, (Meth) acrylic acid sulfopropyl ester, (meth) acryloyloxynaphthalene sulfonic acid, acrylamidomethylpropane sulfonic acid, etc.], amino group [for example, (meth) acrylic acid aminoethyl ester, (meth) acrylic acid dimethylaminoethyl ester, (Meth) acrylic acid tert-butyl Ruaminoethyl ester, etc.], amide groups [e.g. (meth) acrylamide, dimethyl (meth) acrylamide, N-butylacrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide etc.), alkoxyl groups [ For example, (meth) acrylic acid methoxyethyl ester, (meth) acrylic acid ethoxyethyl ester, (meth) acrylic acid methoxyethylene glycol ester, (meth) acrylic acid methoxydiethylene glycol ester, (meth) acrylic acid methoxypolyethylene glycol ester, ( And (meth) acrylic acid methoxypolyethylene glycol ester, (meth) acrylic acid tetrahydrofurfuryl ester and the like] and the like. These may be used alone or in combination of two or more.

Other copolymerizable monomers include, for example, (meth) acrylonitrile, vinyl acetate, vinyl propionate, N-vinyl-2-pyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine , Vinyl pyrrole, vinyl imidazole, vinyl caprolactam, vinyl oxazole, vinyl morpholine and the like. These may be used alone or in combination of two or more.

The acrylic pressure-sensitive adhesive is preferably a polymer obtained by polymerizing (meth) acrylic acid alkyl ester in a proportion of 40% by weight or more. In particular, a copolymer obtained by copolymerizing 50 to 98% by weight of one or more alkyl esters of (meth) acrylic acid and 2 to 50% by weight of one or more copolymerizable monomers. Coalescence is preferred.

The acrylic adhesive preferably has a weight average molecular weight of 600,000 to 1,000,000. When the weight average molecular weight is in the range of 600,000 to 1,000,000, it is advantageous in that sufficient adhesive force can be expressed. On the other hand, if the weight average molecular weight is less than 600,000, adhesive residue may be generated. On the other hand, if the weight average molecular weight exceeds 1,000,000, a desired adhesive force is exhibited due to a decrease in wettability. May be difficult. The weight average molecular weight of the acrylic pressure-sensitive adhesive is more preferably 700,000 to 900,000.

The weight average molecular weight (Mw) of the acrylic pressure-sensitive adhesive is a measured value in terms of polystyrene by GPC (gel permeation chromatography) measurement. Measurement conditions are as follows.
Device name: HLC-8120 (manufactured by Tosoh Corporation)
Column: G7000HXL 7.8mmID × 30cm 1 GMHXL 7.8mmID × 30cm 2 G2500HXL 7.8mmID × 30cm 1 (Tosoh Corporation)
Sample concentration: diluted with tetrahydrofuran to 1.5 mg / ml Mobile phase solvent: tetrahydrofuran Flow rate: 1.0 ml / min
Column temperature: 40 ° C

The epoxy curing agent is a compound having an epoxy group, and specific examples thereof include, for example, bisphenol A epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether. 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis ( N, N′-diamine glycidylaminomethyl) cyclohexane and other compounds having two or more epoxy groups in the molecule.

It is preferable that content of the said epoxy-type hardening | curing agent is 0.05-5 weight part with respect to 100 weight part (solid content) of an acrylic adhesive. If the content is less than 0.05 parts by weight, the crosslink density is low, so that the cohesive force of the pressure-sensitive adhesive layer 12 becomes insufficient and adhesive residue is generated. If the content exceeds 5 parts by weight, the adhesive strength may be reduced. As for content of an epoxy-type hardener, it is more preferable that it is 0.1-4.0 weight part with respect to 100 weight part (solid content) of an acrylic adhesive.

The pressure-sensitive adhesive composition may further contain a catalyst. Examples of the catalyst include a catalyst used for the reaction of an epoxy curing agent, for example, an organic tin compound such as di-n-butyltin dilaurate, dimethyltin dilaurate, dibutyltin oxide, and octane tin; an organic titanium compound; Examples include organic zirconium compounds; carboxylic acid tin salts; carboxylic acid bismuth salts; and amine-based catalysts such as triethylenediamine.

The pressure-sensitive adhesive composition may further contain a solvent such as a hydrophobic organic solvent. Examples of the hydrophobic organic solvent include ethyl acetate, toluene, hexane, mineral oil, petroleum ether and the like.

In addition, the pressure-sensitive adhesive composition includes a stabilizer, a plasticizer, a softener, a filler, a tackifier, a dye, and a pigment as necessary, as long as the properties required for the cosmetic material of the present invention are not impaired. Various additives such as these may be added.

The coating amount of the pressure-sensitive adhesive composition is preferably 10 to 90 g / m ² (in terms of weight when dried). In other words, it is preferable that the coating amount of the pressure-sensitive adhesive layer 12 obtained by drying the pressure-sensitive adhesive composition is 10 to 90 g / m ² . By adjusting the coating amount in the range of 10 to 90 g / m ² , the adhesive strength of the pressure-sensitive adhesive layer 12 can be ensured. When the coating amount is less than 10 g / m ² , the adhesive strength may be insufficient. When the coating amount exceeds 90 g / m ² , the pressure-sensitive adhesive layer 12 tends to remain as an adhesive. A more preferable lower limit of the coating amount is 30 g / m ² . When the coating amount is 30 g / m ² or more, sufficient followability to the irregularities on the surface of the substrate 11 is obtained. A more preferable upper limit of the coating amount is 70 g / m ² .

The thickness of the pressure-sensitive adhesive layer 12 is preferably 20 to 80 μm. When the thickness is less than 20 μm, sufficient tackiness may not be obtained. When the thickness exceeds 80 μm, the tackiness is not improved so much. Moreover, when a solvent is contained in the pressure-sensitive adhesive composition, if the thickness exceeds 80 μm, bubbles may remain in the pressure-sensitive adhesive layer when the solvent is volatilized in a drying furnace, and the design may be damaged. . Furthermore, the time for volatilizing the solvent in the pressure-sensitive adhesive composition becomes longer, and the productivity may be significantly reduced. A more preferable thickness of the pressure-sensitive adhesive layer 12 is 20 to 60 μm.

[Top film]
The top film 13 contains polyvinyl chloride (PVC). If polyvinyl chloride is used, it is easy to stretch and hardly break when molding the top film 13 on the base material 11, so that excellent followability (formability) to the surface shape of the base material 11 can be obtained.

Examples of the polyvinyl chloride include a homopolymer of vinyl chloride and a copolymer of vinyl chloride and other monomers.

Examples of the other monomer include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate. Maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinylidene chloride and vinyl bromide; Examples thereof include vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. These may be used alone or in combination of two or more.

The content of the other monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. If it exceeds 50% by weight, the bending resistance of the top film 13 may be lowered. Among the polyvinyl chlorides, a homopolymer of vinyl chloride is preferable from the viewpoint of obtaining dimensional stability.

The average degree of polymerization of the polyvinyl chloride is not particularly limited, and is adjusted according to the required film hardness and the amount of plasticizer used for adjusting the hardness, for example, 800 to 1300. . A preferable upper limit of the average degree of polymerization is 1050. When the average polymerization degree is in the range of 800 to 1300, the moldability at a relatively low temperature is particularly good. On the other hand, if the average degree of polymerization is less than 800, it may be difficult to maintain the embossed shape during molding. On the other hand, if the average degree of polymerization exceeds 1300, the followability to the surface shape of the substrate may be insufficient.

The top film 13 contains an ultraviolet absorber. Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers and benzotriazole ultraviolet absorbers. If a benzophenone ultraviolet absorber or a benzotriazole ultraviolet absorber is used, the compatibility with polyvinyl chloride is sufficiently ensured, so that the top film 13 with good weather resistance can be obtained.

Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxy). Benzophenone) and the like. These benzophenone ultraviolet absorbers may be used alone or in combination of two or more.

Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, and 2- (2-hydroxy- 3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy- 3,5-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) ) Polyethylene glycol ester of benzotriazole, 2- [2-hydroxy 3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2- Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chloro Benzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole , 2- [2-hydroxy-3-tert Amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [ 2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy- 4- (3-methacryloyloxypropyl) phenyl] benzotriazole and the like. These benzotriazole-based UV absorbers may be used alone or in combination of two or more.

Content of the said ultraviolet absorber is 0.1-5 weight part with respect to 100 weight part of polyvinyl chloride. When the content is less than 0.1 part by weight, the weather resistance is not sufficiently improved by the ultraviolet absorber. When the said content exceeds 5 weight part, there exists a possibility that a ultraviolet absorber may transfer to the surface of the top film 13, and may bleed. It is preferable that content of a ultraviolet absorber is 0.2-2.0 weight part with respect to 100 weight part of polyvinyl chloride.

The top film 13 may contain a plasticizer. The plasticizer is not particularly limited, and those conventionally used in polyvinyl chloride can be used. For example, diisononyl phthalate (DINP), octyl phthalate (di-2-ethylhexyl phthalate (DOP)) Phthalic acid diesters such as dibutyl phthalate and dinonyl phthalate; dibasic acid diesters such as dioctyl adipate; dioctyl sebacate; phosphate triesters such as tricresyl phosphate and trioctyl phosphate; Mention may be made of epoxy plasticizers such as soybean oil and epoxy resins; polymer polyester plasticizers and the like.

Examples of the polymer polyester plasticizer include polyalkylene glycol diesters such as polyethylene glycol diester, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester of phthalic acid; polyethylene glycol diesters of aliphatic dibasic acids such as adipic acid and sebacic acid. And polyalkylene glycol diesters such as polypropylene glycol diester and polyethylene glycol polypropylene glycol diester. These may be used alone or in combination of two or more.

The number average molecular weight of the plasticizer is preferably 350 to 3000. If the number average molecular weight is less than 350, the plasticizer may bleed on the film surface. On the other hand, when the number average molecular weight exceeds 3000, the effect of softening the film by adding a plasticizer cannot be obtained sufficiently, and the top film 13 becomes too hard, so that workability may be deteriorated.

The plasticizer content in the top film 13 is preferably 10 to 35 parts by weight with respect to 100 parts by weight of polyvinyl chloride. When the content is within the above range, the moldability at a relatively low temperature is particularly good. If the said content is less than 10 weight part, there exists a possibility that workability may fall because the top film 13 becomes hard too much. On the other hand, when the content exceeds 35 parts by weight, the plasticizer may bleed on the film surface. The content of the plasticizer is more preferably 15 to 28 parts by weight with respect to 100 parts by weight of polyvinyl chloride.

The top film 13 preferably contains an antibacterial agent, an antifungal agent or an antibacterial antifungal agent. Even if antibacterial agent, antifungal agent or antibacterial antifungal agent is added, the cosmetic material of the present invention can be used as a cosmetic material for wall coverings in bathrooms, kitchens, toilets, toilets, etc. And mold prevention performance. As the antibacterial agent, for example, an inorganic metal ion compound is used. As the fungicide, for example, an organic fungicide is used. As the antibacterial and antifungal agent, for example, organic nitrogen sulfur compounds and organic heterocyclic compounds are used.

The organic nitrogen-sulfur compound is not limited as long as it is an organic compound containing a nitrogen atom and a sulfur atom in the molecule, and examples thereof include a thiazole compound, an isothiazolone compound, and a thiocarbamate compound. A compound is preferably used. Specific examples of thiazole compounds include 2- (1,3-thiazol-4-yl) -1H-benzimidazole. In addition, only 1 type may be used for an organic nitrogen sulfur type compound, and 2 or more types may be used for it.

The content of the organic nitrogen sulfur compound is preferably 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the polyvinyl chloride. If the said content is less than 0.5 weight part, there exists a possibility that the effect which mix | blended the organic nitrogen sulfur type compound may not fully be acquired. On the other hand, if the content exceeds 5.0 parts by weight, the weather resistance may decrease.

The organic heterocyclic compound is not limited as long as it is an organic compound containing a heterocyclic ring in the molecule, and examples thereof include pyridine compounds, quinoline compounds, triazine compounds, triazole compounds, and imidazole compounds. A pyridine compound is preferably used. In addition, only 1 type may be used for an organic heterocyclic compound, and 2 or more types may be used for it.

The organic heterocyclic compound is preferably blended in an amount of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the polyvinyl chloride. If the said content is less than 0.1 weight part, there exists a possibility that the effect which mix | blended the organic heterocyclic compound may not fully be acquired. On the other hand, if the content exceeds 5.0 parts by weight, the weather resistance may decrease.

The top film 13 may contain other additives such as a stabilizer, a colorant, a foaming agent, a lubricant, a modifier, a filler, and a diluent as necessary. As these additives, those generally blended with polyvinyl chloride can be used.

Although the thickness of the top film 13 is not specifically limited, It is preferable that it is 50-450 micrometers. When the thickness is less than 50 μm, the strength of the film itself is insufficient, and the durability and weather resistance may be lowered. On the other hand, when the thickness exceeds 450 μm, the stiffness of the film is too strong and it may be difficult to apply the film to the base material 11. Further, if the content of the ultraviolet absorber is not increased in accordance with the above thickness, the effect of improving the weather resistance may not be obtained sufficiently, but the ultraviolet absorber is increased by increasing the content of the ultraviolet absorber. May move to the surface of the top film 13 and bleed.

The top film 13 may be provided with a design. The kind of design is not specifically limited, Arbitrary colors and patterns (patterns) can be imparted. The design may be applied to the entire surface of the top film 13 or may be applied partially. The method for applying the design is not particularly limited, and examples thereof include embossing. The design of the top film 13 can be changed according to the specifications of the emboss.

In the embossing, a mold is pressed against the surface of the top film 13 to give an emboss shape (uneven shape). Since the top film 13 uses polyvinyl chloride as a resin component, it has good moldability at a relatively low temperature (about 130 ° C.) and is suitable for embossing.

The decorative material of the present invention may include other layers such as a base film, a printing layer, and a primer layer in addition to the base material 11, the pressure-sensitive adhesive layer 12, and the top film 13.

FIG. 2 is a cross-sectional view schematically showing another example of the decorative material of the present invention. The decorative material shown in FIG. 2 has a structure in which a base material 11, an adhesive layer 12, a base film 14, and a top film 13 are laminated in order. By providing the base film 14, the color of the decorative material can be adjusted and the design can be enhanced.

The base film 14 preferably contains polyvinyl chloride. The polyvinyl chloride in the base film 14 may be the same as or different from the vinyl chloride resin in the top film 13 in terms of composition, average molecular weight, and the like.

The base film 14 may contain a plasticizer. The plasticizer in the base film 14 may be the same as or different from the plasticizer in the top film 13 in terms of composition, content, number average molecular weight, and the like. In addition, since the top film 13 and the base film 14 are laminated | stacked, it is preferable that it is fundamentally the same hardness. Therefore, if the top film 13 and the base film 14 have the same thickness, the plasticizer content is preferably the same.

The base film 14 may contain additives such as a stabilizer, a colorant, a foaming agent, a lubricant, a modifier, a filler, and a diluent as necessary. As these additives, those generally blended with polyvinyl chloride can be used, and they may be the same as or different from the additives in the top film 13. Note that, unlike the top film 13, the base film 14 does not have to include an ultraviolet absorber.

Although the thickness of the base film 14 is not specifically limited, It is preferable that it is 50-200 micrometers.

FIG. 3 is a cross-sectional view schematically showing still another example of the decorative material of the present invention. The decorative material shown in FIG. 3 has a structure in which a base material 11, an adhesive layer 12, a base film 14, a printing layer (ink layer) 15, and a top film 13 are laminated in order. By providing the printing layer 15, the designability can be improved.

The printing layer 15 may cover the entire surface of the base film 14 or may partially cover it. For example, when the printing layer 15 has a planar shape corresponding to an arbitrary design or information, the printing layer 15 partially covers the surface of the base film 14.

It does not specifically limit as a printing method for forming the printing layer 15, For example, inkjet printing, gravure printing, etc. are mentioned. As a specific example of inkjet printing, a method of discharging vinyl chloride-vinyl acetate copolymer / acrylic ink onto the base film 14 by an inkjet printer can be mentioned. As a specific example of gravure printing, a method using a one-component curable ink or a two-component curable ink can be mentioned. Further, the surface of the base film 14 may be subjected to a surface treatment in order to improve printing fixability.

Although it does not specifically limit as a use of the decorative material of this invention, For example, interior materials, such as a decorative board (wall covering material) attached to a wall surface, an indoor door, a closet or a kitchen door, furniture, and a flooring, are mentioned. Moreover, it is used suitably for the wall covering around water, such as a bathroom, a kitchen, a washroom, and a toilet. According to the decorative material of the present invention, a design property equivalent to that of a coated product can be obtained by a simpler and safer method than painting.

The decorative material of the present invention can be manufactured using a conventionally known manufacturing method. As the base material 11, an ABS resin is molded into a shape according to the use of the cosmetic material of the present invention by a molding method such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding, calender molding, and hot melt lamination. Can be used.

The method for forming the pressure-sensitive adhesive layer 12 is not particularly limited. For example, by using a bar coater or the like on the separator to form a coating film by coating the pressure-sensitive adhesive composition, the coating film is dried by heating. A conventionally known method such as a curing method can be used. In this case, a decorative film can be manufactured by bonding the pressure-sensitive adhesive layer 12 formed on the separator to the top film 13 or the base film 14. The decorative film is further subjected to processing such as cutting and winding into a roll as necessary. What is necessary is just to peel a separator just before sticking to the base material 11. FIG. By providing the separator, it is possible to prevent the adhesive layer 12 from being exposed during the production, transportation and storage of the decorative film, thereby preventing the adhesive layer 12 from being deteriorated and improving the handleability of the decorative film.

Although it does not specifically limit as said separator, The thing which can peel easily without damaging the adhesive layer 12 is suitable, for example, by apply | coating a silicone resin, a fluororesin, etc. to the surface which contacts the adhesive layer 12 Resin film (release film) such as polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polypropylene that has been subjected to easy release treatment; paper such as high-quality paper and glassine paper (release paper); paper and coating layer A laminated film etc. are mentioned.

The top film 13 and the base film 14 can be produced by a conventionally known molding method such as calendar molding, extrusion molding, or injection molding. Examples of the calendar format used for the calendar molding include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.

As described above, the printing layer 15 can be formed by a printing method such as inkjet printing or gravure printing.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.

Example 1
20 parts by weight of diisononyl phthalate (DINP) as a plasticizer and epoxidized soybean oil (“W-100-EL” manufactured by DIC) 3 per 100 parts by weight of polyvinyl chloride (PVC) having an average polymerization degree of 1000 Parts by weight, 1.5 parts by weight of a thiazole-based compound (manufactured by Sumika Environmental Science Co., Ltd., “Neocintol AF-80”) as an organic nitrogen sulfur-based compound, and a pyridine-based compound (Daiwa Chemical Industry Co., Ltd.) as an organic heterocyclic compound 0.5 parts by weight of “Bioden SK-40H” manufactured by the company and 1 part by weight of a benzotriazole ultraviolet absorber (“LA-29” manufactured by ADEKA) were added to obtain a PVC compound. The obtained PVC compound was melt-kneaded with a Banbury mixer and then molded into a sheet having a thickness of 80 μm with an inverted L-shaped calendar to produce a PVC film. The obtained PVC film was used as a top film.

For 100 parts by weight of polyvinyl chloride (PVC) having an average polymerization degree of 1000, 20 parts by weight of diisononyl phthalate (DINP) as a plasticizer and 3 parts by weight of epoxidized soybean oil (manufactured by DIC, “W-100-EL”) Part was added to obtain a PVC compound. The obtained PVC compound was melt-kneaded with a Banbury mixer and then molded into a sheet having a thickness of 80 μm with an inverted L-shaped calendar to produce a PVC film. The obtained PVC film was used as a base film.

Next, a printing layer was formed on one surface of the base film using a vinyl chloride-vinyl acetate copolymer / acrylic ink by an inkjet printer. Subsequently, the top film was bonded to the surface of the base film on which the printed layer was formed by thermal lamination to produce a laminated film.

In addition, an acrylic pressure-sensitive adhesive solution was applied to one surface of a separator (biaxially stretched polyester (PET) film) having a thickness of 100 μm with a comma bar coater so that the dry thickness was 40 μm. Formed. In the acrylic adhesive solution, 1.2 parts by weight of an epoxy curing agent (“E-AXM” manufactured by Soken Chemical Co., Ltd.) is blended with 100 parts by weight of the acrylic adhesive (“SK2094” manufactured by Soken Chemical Co., Ltd.). It was a thing. The above-mentioned coating film was heated and dried at 80 ° C. for 1 minute in a drying furnace to remove the solvent in the coating film and produce an adhesive layer.

Next, a separator and a laminated film were bonded together through the adhesive layer, and the decorative film was produced. Then, the adhesive layer which peeled and exposed the separator of the decorative film and the flat base material made from ABS resin were bonded together, and the decorative material of Example 1 was obtained.

(Examples 2 to 4 and Comparative Examples 1 to 5)
As shown in Tables 1 and 2 below, a decorative film and a decorative material were produced in the same manner as in Example 1 except that the top film, the pressure-sensitive adhesive layer, and the base material were changed.

(Example 5)
20 parts by weight of diisononyl phthalate (DINP) as a plasticizer and epoxidized soybean oil (“W-100-EL” manufactured by DIC) 3 per 100 parts by weight of polyvinyl chloride (PVC) having an average polymerization degree of 1000 Parts by weight, 0.56 parts by weight of an inorganic metal ion compound as an antibacterial agent (manufactured by Fuji Chemical Co., Ltd., “Bactekiller BM-102MT”), and an organic antifungal agent (manufactured by MIC Co., Ltd.) 0.75 parts by weight of PBM-OJ ") and 1 part by weight of a benzotriazole ultraviolet absorber (ADEKA," LA-29 ") were added to obtain a PVC compound. The obtained PVC compound was melt-kneaded with a Banbury mixer, and then molded into a sheet having a thickness of 70 μm with an inverted L-shaped calendar to produce a PVC film (top film). Thereafter, as shown in Table 1 below, a decorative film and a decorative material were produced in the same manner as in Example 1 except that the pressure-sensitive adhesive layer was changed.

(Examples 6 to 9)
As shown in Tables 1 and 2 below, a decorative film and a decorative material were produced in the same manner as in Example 5 except that the top film and the pressure-sensitive adhesive layer were changed.

(Evaluation test)
The decorative materials or decorative films produced in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 1 below.

(1) The weather resistant decorative film was put into an accelerated weather resistance tester (Sunshine weather meter) for 500 hours. It was confirmed whether discoloration had occurred on the surface of the decorative film taken out after the test on the PVC film side.
(Criteria)
○: No significant discoloration occurred ×: Significant discoloration occurred

(2) The water-resistant cosmetic material was immersed in warm water at 60 ° C. for 1 day, taken out from the warm water, wiped off the moisture and air-dried for 2 hours, and then visually checked for appearance.
(Criteria)
◯: No surface float or significant discoloration ×: Surface float or significant discoloration occurred

(3-1) Adhesive strength decorative film after aging was cut into a length of 150 mm and a width of 25 mm, and the separator was peeled off to obtain a test piece. The adhesive layer of each test piece was affixed to a flat substrate made of ABS resin and then aged at 40 ° C. for 3 days. Thereafter, a 180 ° peel test was performed by a method based on JIS Z 0237, and the adhesive strength (unit: N / 25 mm) of the decorative material was measured.

(3-2) Adhesive strength after hot water test The adhesive layer and the base material were bonded together, immersed in warm water at 60 ° C. for 1 day, taken out from the warm water, air-dried for 2 hours and then air-dried. The adhesive strength of the decorative material was measured in the same manner as in 3-1).

(4) Shrinkage resistance (opening test)
After the pressure-sensitive adhesive layer and the substrate were bonded together and left for one day, a cross-shaped cut was made in the decorative film. After leaving at 60 ° C. for 48 hours, the distance between the films at the cut portion was measured.

In Table 1 above, the unit “phr” of the content of the curing agent represents the number of parts by weight with respect to 100 parts by weight of the adhesive. The product numbers of the pressure-sensitive adhesives A to E and the curing agents A to D shown in Table 1 are as follows. Adhesives A to E are all acrylic adhesives. Curing agents A and B are epoxy curing agents, curing agent C is an isocyanate curing agent, and curing agent D is a metal chelate curing agent.

<Adhesive>
A: SK2094 (manufactured by Soken Chemical)
B: EXK-14-136 (manufactured by Toyo Ink)
C: EXK-16-128 (manufactured by Toyo Ink Co.)
D: Vainsol R-8510E (manufactured by Lion Specialty Chemicals)
E: EXK-14-434 (Toyo Ink Co., Ltd.)

<Curing agent>
A: E-AXM (manufactured by Soken Chemical)
B: BXX5983TF (manufactured by Toyo Ink)
C: B-45 (Lion Specialty Chemicals)
D: BXX 4805 (manufactured by Toyo Ink)

The following Table 2 shows the details of the ultraviolet absorber formulations A to D in Table 1 above. The product numbers of the ultraviolet absorbers A and B shown in Table 2 are as follows.

<Ultraviolet absorber>
A: Adeka 1413 (benzophenone UV absorber, manufactured by ADEKA)
B: LA-29 (benzotriazole ultraviolet absorber, manufactured by ADEKA)

As can be seen from Table 1, the decorative materials (decorative films) of Examples 1 to 9 had good results in all of weather resistance, water resistance, adhesive strength and shrinkage resistance. On the other hand, the decorative materials (decorative films) of Comparative Examples 1 and 5 had insufficient weather resistance since no ultraviolet absorber was added. Since the combination of the adhesive and the curing agent contained in the adhesive layer of the decorative material (decorative film) of Comparative Example 2 was different from that of the examples, the water resistance and the adhesive strength after the hot water test were insufficient. It was. In the decorative material (decorative film) of Comparative Example 3, the combination of the pressure-sensitive adhesive and the curing agent contained in the pressure-sensitive adhesive layer was the same as that in Example 1, but the material of the base material was different from Example 1, The adhesive strength after the hot water test was insufficient. The decorative material (decorative film) of Comparative Example 4 had insufficient water resistance because the combination of the pressure-sensitive adhesive and the curing agent contained in the pressure-sensitive adhesive layer was different from that of the example.

11 Base material 12 Adhesive layer 13 Top film 14 Base film 15 Print layer

Claims (6)

A base material, a pressure-sensitive adhesive layer, and a top material laminated in order,
The base material is composed of acrylonitrile-butadiene-styrene copolymer resin,
The pressure-sensitive adhesive layer is a cured product of a pressure-sensitive adhesive composition containing an acrylic pressure-sensitive adhesive and an epoxy-based curing agent,
The top film contains polyvinyl chloride and an ultraviolet absorber,
Content of the said ultraviolet absorber is 0.1-5 weight part with respect to 100 weight part of said polyvinyl chlorides, The cosmetics characterized by the above-mentioned. The cosmetic material according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 20 to 80 μm. The cosmetic material according to claim 1 or 2, wherein the content of the epoxy curing agent is 0.05 to 5 parts by weight with respect to 100 parts by weight of the acrylic pressure-sensitive adhesive. The cosmetic material according to any one of claims 1 to 3, further comprising a base film containing polyvinyl chloride between the pressure-sensitive adhesive layer and the top film. The decorative material according to claim 4, further comprising a printed layer between the base film and the top film. The said top film contains an antibacterial agent, a fungicide, or an antibacterial antifungal agent, The cosmetic material in any one of Claims 1-5 characterized by the above-mentioned.

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