JP2009202367A - Ornamental adhesive sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ornamental adhesive sheet having a satisfactory metallic luster and excellent in followability to a curved surface, weatherability and chemical resistance. <P>SOLUTION: In the ornamental adhesive sheet A, one surface of a substrate sheet 1 is integrally laminated with a metal thin film layer 3 through a urethane adhesive agent layer 2, an ink receiving sheet 4 and a coating layer 5 are integrally laminated on the metal thin film layer 3, the coating layer 5 contains an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, and the other surface of the substrate sheet 1 is integrally laminated with an adhesive agent layer 6. The adhesive sheet, characterized by the above, has excellent metallic luster and excels in followability to a curved surface, weatherability and chemical resistance. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a decorative pressure-sensitive adhesive sheet that is used by being attached to the outer surface of an automobile, a motorcycle, a home appliance, or the like.

  As a decorative pressure-sensitive adhesive sheet, a sheet in which a pressure-sensitive adhesive layer is formed on one surface of a resin film made of vinyl chloride resin, acrylic resin, fluorine-based resin, or the like is known. The above-mentioned decorative adhesive sheet is a material in which the pressure-sensitive adhesive layer is adhered to a material to be decorated and exhibits a decorative effect by the color and pattern of the resin film. In recent years, instead of painting, automobiles, motorcycles, home appliances are used. It is used in decoration fields such as products, display fields such as advertisements, signs, labels and stickers, and fleet marking fields such as wrapping buses.

  As such a decorative adhesive sheet, there has been proposed a marking film laminated sheet in which a protective film layer is laminated on a marking film layer via an adhesive layer (1). And in this marking film lamination sheet, the said protective film layer consists of polyolefin resin films, and the said adhesive layer (1) is ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. It is disclosed that it is preferable to consist of at least one resin selected from polymers.

  However, since the marking film laminated sheet is difficult to stick in a state where it follows a surface with a large curvature without changing the appearance, it has a curved surface with a large curvature such as an automobile or a motorcycle body. It was not suitable for sticking to the body.

  In addition, as a decorative pressure-sensitive adhesive sheet with excellent followability to curved surfaces, in Patent Document 2, a urethane resin film layer has a two-layer structure, and a metal vapor-deposited film is formed on the surface of the film layer made of a cross-linked urethane resin. A metal-deposited urethane film, characterized in that the cross-linked film layer has a 100% modulus of 5 to 30 MPa.

  However, since the metal-deposited urethane film is easily scratched on the surface, there is a problem that the decorativeness is impaired and the dirt is difficult to remove. The metal-deposited urethane film is unsuitable for decorative adhesive sheets for automobiles and motorcycles because it is discolored / denatured and delamination occurs when exposed to gasoline vapor for a long period of time.

  As a decorative pressure-sensitive adhesive sheet that can be used in the presence of gasoline vapor and has excellent followability to a curved surface, Patent Document 3 discloses a light-transmitting coating film containing a vinyl chloride resin, a saturated polyester. Or a light-transmitting tie layer comprising a layer comprising an aminoethylated resin and a layer comprising a polyester having a siloxane bond in the molecule or a polyurethane resin comprising a polyester unit having a siloxane bond in the molecule; A decorative sheet in which metal layers are laminated and integrated in this order has been proposed.

  However, the decorative sheet cannot obtain a sufficient metallic luster and is inferior in decorative properties.

Japanese Patent Application Laid-Open No. 8-118531 JP 2004-299190 A JP-A-11-207863

  The present invention provides a decorative pressure-sensitive adhesive sheet that has a sufficient metallic luster and is excellent in followability to curved surfaces, weather resistance, and chemical resistance.

  In the decorative pressure-sensitive adhesive sheet of the present invention, a metal thin film layer is laminated and integrated on one surface of a substrate sheet via a urethane adhesive layer, and an ink receiving sheet and a coating layer are laminated on the metal thin film layer. The coating layer is integrated and contains an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, and an adhesive layer is laminated and integrated on the other surface of the base sheet.

  The decorative adhesive sheet is characterized in that, in the decorative adhesive sheet, the coating layer has a thickness of 0.5 to 10 μm.

  The decorative pressure-sensitive adhesive sheet is characterized in that in the above-mentioned decorative pressure-sensitive adhesive sheet, the ink receiving sheet contains at least one resin of an acrylic resin, an acrylic urethane resin or a urethane resin.

  The decorative adhesive sheet is characterized in that, in the decorative adhesive sheet, the base sheet contains a vinyl chloride resin.

  The decorative pressure-sensitive adhesive sheet is characterized in that, in the decorative pressure-sensitive adhesive sheet, the base sheet and the metal thin film layer are integrated via a urethane adhesive layer by a dry laminating method.

  In the decorative pressure-sensitive adhesive sheet of the present invention, a metal thin film layer is laminated and integrated on one surface of a substrate sheet via a urethane adhesive layer, and an ink receiving sheet and a coating layer are laminated on the metal thin film layer. Since the integrated coating layer contains an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, an adhesive layer is laminated and integrated on the other surface of the base sheet. It has excellent metallic luster and has excellent followability to curved surfaces, weather resistance and chemical resistance.

  An example of the decorative adhesive sheet of the present invention will be described with reference to the drawings. The decorative pressure-sensitive adhesive sheet A has a metal thin film layer 3 laminated and integrated on one surface of a base material sheet 1 via a urethane adhesive layer 2, and an ink receiving sheet 4 and a coating on the metal thin film layer 3. The layer 5 is laminated and integrated, the coating layer 5 contains an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, and the pressure-sensitive adhesive layer 6 is laminated and integrated on the other surface of the base sheet.

  The decorative pressure-sensitive adhesive sheet A of the present invention has a base sheet 1 for the purpose of ensuring the mechanical strength of the decorative pressure-sensitive adhesive sheet and improving the workability when it is attached to an adherend. The base sheet 1 is not particularly limited, and examples thereof include synthetic resin sheets such as a vinyl chloride resin sheet, an acrylic resin sheet, and a propylene resin sheet, and a curved surface having a large curvature such as a car body of an automobile or a motorcycle. A vinyl chloride resin sheet is preferred because of good adherence to the adherend having.

  The vinyl chloride resin constituting the vinyl chloride resin sheet is not particularly limited. For example, a homopolymer of a vinyl chloride monomer, a copolymer of a vinyl chloride monomer and another monomer copolymerizable therewith. Examples include coalescence.

  In addition, it does not specifically limit as another monomer copolymerizable with the said vinyl chloride monomer, For example, a vinyl acetate monomer, a urethane monomer, an ethylene monomer etc. are mentioned.

  The vinyl chloride resin sheet preferably contains an adipic acid polyester plasticizer for the purpose of improving its flexibility.

  The adipate polyester plasticizer contained in the vinyl chloride resin sheet is not particularly limited, and an adipate polyester resin obtained by homopolymerizing or copolymerizing an adipate ester monomer, an adipate ester monomer, and this And a copolymer with another monomer copolymerizable with.

  The adipic acid ester monomer is obtained by esterifying adipic acid with an alcohol. Examples of the alcohol used for the esterification include propylene glycol and 1,3-butylene glycol.

  And as a commercial item of the said adipic acid polyester plasticizer, the brand name "Adekasizer PN-250", "Adekasizer PN-260", "Adekasizer PN-280" marketed, for example, by Asahi Denka Co., Ltd. "Adekasizer PN-310", "Adekasizer PN-350", "Adekasizer PN-400", "Adekasizer PN-446", "Adekasizer PN-606", "Adekasizer PN-650", “Adekasizer PN-1030”, “Adekasizer PN-1430”, “Adekasizer PN-3030”, “Adekasizer PN-3130” and the like can be mentioned. These adipic acid polyester plasticizers may be used alone or in combination of two or more.

  As the plasticizer, in addition to the above adipic acid polyester plasticizer, a plasticizer formed by polymerizing a dibasic acid ester monomer obtained by esterifying a dibasic acid such as azelaic acid, sebacic acid or phthalic acid, A plasticizer formed by polymerizing a monobasic acid ester monomer obtained by esterifying a basic acid is also commercially available, but among these plasticizers, among these plasticizers, the transition to the adhesive layer described later is carried out. It is preferable to use an adipic acid polyester plasticizer that is less likely to generate odor.

  That is, the above-mentioned adipic acid polyester plasticizer is difficult to migrate from the vinyl chloride resin sheet to the adhesive layer 6 and (1) the flexibility of the vinyl chloride resin sheet is lost, so that the decorative adhesive sheet is curved. Followability decreases, (2) The pressure-sensitive adhesive layer is softened, so that an appropriate pressure-sensitive adhesive force to the adherend of the decorative pressure-sensitive adhesive sheet is impaired. (3) The pressure-sensitive adhesive layer is softened and the cohesive force is reduced. However, when the decorative adhesive sheet is peeled off from the adherend, it is difficult to cause problems such as adhesive residue on the surface of the adherend, so an adipic acid polyester plasticizer is contained in the vinyl chloride resin sheet. The decorative pressure-sensitive adhesive sheet thus formed has an appropriate adhesive force to the adherend, hardly causes adhesive residue on the surface of the adherend when peeled off from the adherend, and is capable of following a curved surface. It will be excellent.

  The weight average molecular weight of the adipic acid polyester plasticizer is preferably 1700 to 2500, and more preferably 1800 to 2400. This is because when the weight average molecular weight of the adipic acid polyester plasticizer is small, the adipic acid polyester plasticizer moves to the adhesive layer, and (1) the flexibility of the vinyl chloride resin sheet is lost, and the decorative adhesive The followability to the curved surface of the sheet is reduced. (2) The pressure-sensitive adhesive layer is softened, whereby an appropriate adhesive force to the adherend of the decorative pressure-sensitive adhesive sheet is impaired. (3) The pressure-sensitive adhesive layer is softened. This is because the cohesive force is lowered, and when the decorative pressure-sensitive adhesive sheet is peeled off from the adherend, problems such as the occurrence of adhesive residue on the surface of the adherend may occur. On the other hand, if the weight average molecular weight of the adipic acid polyester plasticizer is large, the viscosity of the adipic acid polyester plasticizer increases, and the resin composition constituting the vinyl chloride resin sheet during film formation of the vinyl chloride resin sheet This is because it becomes difficult to uniformly knead and film formation of the vinyl chloride resin sheet may be difficult.

  Here, the weight average molecular weight of the adipic acid polyester plasticizer refers to a value measured by a light scattering method. The light scattering method is a weight-average molecular weight analysis method that utilizes the fact that the intensity of light scattering generated when light collides with a molecule in a solution is proportional to the mass of the molecule. For the measurement of the weight average molecular weight by the light scattering method, a light scattering photometer or the like is used.

  The content of the adipic acid polyester plasticizer in the vinyl chloride resin sheet is preferably 5 to 100 parts by weight, more preferably 10 to 90 parts by weight, with respect to 100 parts by weight of the vinyl chloride resin. -70 parts by weight are particularly preferred. This is because when the content of the adipic acid polyester plasticizer in the vinyl chloride resin sheet is small, the flexibility of the vinyl chloride resin sheet is lowered. This is because shrinkage occurs and the decorativeness is lowered, or the followability of the decorative adhesive sheet to the curved surface is lowered and the workability when the decorative adhesive sheet is attached to the adherend may be lowered. is there. On the other hand, if the content of the adipic acid polyester plasticizer is large, the vinyl chloride resin sheet becomes too soft, and the decorative pressure-sensitive adhesive sheet is elongated particularly under high temperature conditions such as summertime, or the decorativeness is lowered, or This is because positioning with respect to the adherend becomes difficult, and workability when adhering the decorative adhesive sheet to the adherend may be lowered.

  Further, the vinyl chloride resin sheet preferably contains an alkyl tin mercapto compound represented by the following formula (1) for the purpose of preventing discoloration during film formation.

(R ¹ ) _n —Sn— (SCH ₂ CH ₂ COOR ² ) _4-n (1)
(Wherein n is 1 or 2, R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms or a derivative of an alkyl group having 1 to 8 carbon atoms)

In the above formula (1), R ¹ is an alkyl group having 1 to 8 carbon atoms. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, normal octyl group, 2- An ethylhexyl group, an isooctyl group, etc. are mentioned. In the above formula (1), when the value of n is 2, two R ¹ may not be the same.

In the above formula (1), R ² is an alkyl group having 1 to 8 carbon atoms or a derivative of an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include those similar to the above R ^1, and examples of the derivatives thereof include a hydroxyalkyl group and a hydroxyalkyloxy group. In the above formula (1), a plurality of R ² may not be the same.

  Further, the vinyl chloride resin sheet preferably contains an organic phosphite for the purpose of preventing discoloration during film formation.

  The film forming method of the vinyl chloride resin sheet is not particularly limited, and examples thereof include a solution casting method and a calendar molding method, and the solution casting method is preferable.

  When the thickness of the base sheet 1 is thin, the mechanical strength of the decorative adhesive sheet is lowered and the weather resistance may be lowered. On the other hand, when the thickness is thick, the flexibility of the decorative adhesive sheet is lowered. Then, the followability to the curved surface of the decorative pressure-sensitive adhesive sheet may be reduced, or cracks may occur in the metal thin film layer, so 20 to 110 μm is preferable, and 30 to 70 μm is more preferable.

  Furthermore, a metal thin film layer 3 is laminated and integrated on one surface of the base sheet 1 via a urethane adhesive layer 2 for the purpose of imparting a metallic luster to the decorative pressure-sensitive adhesive sheet A and enhancing its decorativeness. ing. Here, the urethane adhesive is used for laminating and integrating the metal thin film layer 3 on one surface of the base sheet 1, when the adhesive other than the urethane adhesive is used, the chemical resistance is insufficient. This is because it is deteriorated by chemicals such as gasoline vapor, and delamination is likely to occur between the base sheet 1 and the metal thin film layer 3.

  The urethane adhesive is not particularly limited. For example, by mixing a main agent made of a urethane prepolymer and a curing agent made of a polyisocyanate, the hydroxyl group in the urethane prepolymer and the isocyanate group in the polyisocyanate are urethane. Examples thereof include a two-component urethane adhesive that forms a bond and cures.

  In addition, as a commercial item of the said 2 liquid type urethane type adhesive agent, the brand names "Takelac A-626", "Takelac A-543" etc. which are marketed from Mitsui Chemicals Polyurethanes company are mentioned.

  And it does not specifically limit as a metal which comprises the metal thin film layer 3, For example, aluminum, silver, chromium, gold | metal | money etc. are mentioned, Since aluminum is cheap, aluminum is preferable.

  On the other hand, if the thickness of the metal thin film layer 3 is thin, the metallic gloss of the decorative pressure-sensitive adhesive sheet may be insufficient and the decorative property may be deteriorated. On the other hand, if it is thick, the metal thin film layer may be cracked. 200 to 1000 Å is preferable, and 400 to 800 Å is more preferable.

  An ink receiving sheet 4 is laminated and integrated on the metal thin film layer 3. Desired characters and designs can be printed on the ink receiving sheet 4. The ink receiving sheet 4 has such light transmittance as to allow the metal thin film layer 3 to be seen through the ink receiving sheet 4, and is preferably transparent and colorless and transparent. More preferred. In the present invention, “transparent” means that the total light transmittance measured in accordance with JIS K7105 is 30% or more.

  The synthetic resin constituting the ink receiving sheet 4 is not particularly limited as long as the surface can be printed using a general-purpose ink, but has flexibility and transparency, and the metal thin film layer is formed by metal vapor deposition. Acrylic resin, acrylic urethane resin, and urethane resin are preferable.

  If the thickness of the ink receiving sheet 4 is thin, cracks may occur when the decorative adhesive sheet is bonded to the curved surface, and if it is thick, the decorative adhesive sheet may be insufficiently glossy. .6 to 20 μm is preferable, and 1 to 10 μm is more preferable.

  The acrylic resin constituting the ink receiving sheet 4 is not particularly limited, and examples thereof include (meth) acrylic acid alkyl ester resins obtained by homopolymerization or copolymerization of (meth) acrylic acid alkyl ester monomers, and (meth). Examples thereof include a copolymer of an acrylic acid alkyl ester monomer and another vinyl monomer copolymerizable therewith, and a (meth) acrylic acid alkyl ester resin is preferred. In the present invention, “(meth) acrylic acid” means “methacrylic acid or acrylic acid”.

  The (meth) acrylic acid alkyl ester monomer is not particularly limited, and can be obtained by an esterification reaction between a primary or secondary alkyl alcohol having 1 to 12 carbon atoms in the alkyl group and (meth) acrylic acid. Specific examples include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and the like. Octyl (meth) acrylate Is more preferable. In addition, the said (meth) acrylic-acid alkylester monomer may be used independently, or 2 or more types may be used together.

  When an acrylic resin sheet is used as the ink receiving sheet 4, the decorative pressure-sensitive adhesive sheet A has an excellent metallic luster that allows the metal thin film layer 3 to be sufficiently visible through the acrylic resin sheet 4. At the same time, it is excellent in followability to a curved surface and excellent in weather resistance.

  The acrylic urethane resin constituting the ink receiving sheet 4 is not particularly limited, and examples thereof include those obtained by reacting an acrylic polyol with a polyisocyanate crosslinking agent. 100 parts by weight of an acrylic polyol and a polyisocyanate crosslinking agent 30 are included. What reacted -100 weight part is preferable. As the acrylic polyol, it is preferable that the weight average molecular weight is 1000 to 200000 and the glass transition temperature is 0 to 100 ° C. because the resulting acrylic urethane resin is excellent in heat resistance.

  Further, as the polyisocyanate crosslinking agent, a trimethylolpropane adduct of hexamethylene diisocyanate, a biuret, an isocyanurate, a mixture or a condensate thereof is preferable because the resulting acrylic urethane resin is excellent in heat resistance. As a polyisocyanate crosslinking agent, the distance between crosslinking points (weight average molecular weight of polyisocyanate / number of NCO groups of polyisocyanate) is preferably 200 to 400.

  The urethane resin constituting the ink receiving sheet 4 is not particularly limited, and examples thereof include a thermoplastic polyurethane elastomer, and a linear structure type polyurethane resin obtained by a reaction between polyisocyanate and polyol.

  The acrylic resin preferably contains a curing agent such as a photocuring agent or a thermosetting agent for the purpose of improving the heat resistance of the decorative pressure-sensitive adhesive sheet A by crosslinking the acrylic resin.

  The photocuring agent is not particularly limited, and examples thereof include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 1- (4-isopropylphenyl) -2. -Hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, a mixture of 2,4-diethylthioxanthone and ethyl p-dimethylaminobenzoate, a mixture of isopropylthioxanthone and ethyl p-dimethylaminobenzoate, and the like. It is done. In addition, a photocuring agent may be used independently or 2 or more types may be used together.

  Further, the thermosetting agent is not particularly limited, but a thermosetting agent containing an amine and / or a thiol group is preferable. Examples of the thermosetting agent containing an amine and / or thiol group include organic acid dihydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin] and adipic acid dihydrazide; dicyandiamide and guanidine derivatives. , 1-cyanoethyl-2-phenylimidazole, N- [2- (2-methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl -S-triazine, N, N'-bis (2-methyl-1-imidazolylethyl) urea, N, N '-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 2-imidazoline-2-thiol, 2-2'-thiodiethanethiol, etc. Imidazole compounds; and the addition product of an acid anhydride with various amines and epoxy resins. In addition, a thermosetting agent may be used independently or 2 or more types may be used together.

  And if there is little content of the hardening | curing agent in the said acrylic resin, the hardness of an ink receiving sheet will become inadequate and the heat resistance of a decorative adhesive sheet may fall, On the other hand, if it is large, ink Since the receiving sheet becomes too hard and the followability to the curved surface of the decorative pressure-sensitive adhesive sheet may be lowered, 0.1 to 3 parts by weight is preferable with respect to 100 parts by weight of the acrylic resin, and 0.5 to 2 parts by weight is more preferred.

  In addition, a photocuring agent and a thermosetting agent may be used in combination as the curing agent. The content of the curing agent in the acrylic resin sheet when the photocuring agent and the thermosetting agent are used in combination is the total amount of the photocuring agent and the thermosetting agent.

  The film forming method of the ink receiving sheet 4 is not particularly limited. For example, after applying a solution containing a synthetic resin constituting the ink receiving sheet to the release treatment surface of the release film, preferably heating is performed. There is a method of forming a film by evaporating and removing the solvent without evaporation, forming an ink receiving sheet on the release treatment surface of the release film, and then peeling and removing the release film.

  Further, a coating layer 5 is laminated and integrated on the ink receiving sheet 4. The coating layer 5 contains an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, and preferably contains 50 to 100% by weight of an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton.

  Since the coating layer 5 contains the acrylic resin described above, the coating layer 5 is excellent in transparency and curved surface followability, and can be firmly integrated with the ink receiving sheet 4. And delamination between the ink receiving sheet 4 and the ink receiving sheet 4 can be reliably prevented.

  The acrylic resin constituting the coating layer 5 has a hindered amine skeleton, and this hindered amine skeleton captures radical species that can be generated when exposed to ultraviolet rays. Do not alter.

  Furthermore, the acrylic resin constituting the coating layer 5 also has a benzotriazole skeleton. This benzotriazole skeleton absorbs ultraviolet rays and converts light energy into heat energy to generate radical species and low molecular components. And the coating layer 5 is prevented from being altered such as discoloration.

  Thus, the coating layer 5 contains an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, and the coating layer 5 is compared with a case where an ultraviolet stabilizer or an ultraviolet absorber is separately added to the coating layer. The hindered amine skeleton and the benzotriazole skeleton can be uniformly dispersed therein.

  Therefore, the coating layer 5 has excellent transparency, and the decorative pressure-sensitive adhesive sheet has an excellent appearance due to this excellent transparency, and the coating layer 5 has a uniformly dispersed hindered amine skeleton and It also has excellent weather resistance due to the benzotriazole skeleton.

  As the acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, a copolymer of a monomer having a hindered amine skeleton, a monomer having a benzotriazole skeleton, and a (meth) acrylic monomer is preferable. For the polymerization of the monomer, a conventionally known polymerization method may be used. Examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and dispersion polymerization, and solution polymerization is preferable.

  The monomer having a hindered amine skeleton is preferably a monomer having a hindered amine skeleton and a radical polymerizable double bond. Examples of such monomers include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4 -(Meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- ( (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetra Methylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like, Even if it is used independently, 2 or more types may be used together.

  As the monomer having a benzotriazole skeleton, a monomer having a benzotriazole skeleton and a radical polymerizable double bond is preferable. Examples of such a monomer include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl. ] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyhexyl) phenyl]- 2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5′-t-butyl -3 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2 [2'-Hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-methoxy-2H -Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-t-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, 2- [2'-hydroxy-5' -(Β-Methacryloyloxyethoxy) -3'-t-butylphenyl] -4-t-butyl-2 H-benzotriazole is mentioned, and it may be used alone or in combination of two or more.

  Examples of (meth) acrylic monomers include (meth) acrylic acid and (meth) acrylic acid alkyl ester monomers, (meth) acrylic acid alkyl ester monomers are preferred, and the alkyl group has 1 to 12 carbon atoms ( More preferred are (meth) acrylic acid alkyl ester monomers. Specific examples include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate, and octyl (meth) acrylate is more preferable. In addition, the said (meth) acrylic-acid alkylester monomer may be used independently, or 2 or more types may be used together.

  Further, in addition to the above-mentioned monomers, for example, styrene, butadiene, isoprene, α-methylstyrene, (meth) acrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like are copolymerized within a range not impairing the gist of the present invention. May be. These monomers may be used alone or in combination of two or more.

  An acrylic resin having a hindered amine skeleton and a benzotriazole skeleton is commercially available from Nippon Shokubai Co., Ltd. under the trade name “Hals Hybrid UV-G”.

  The acrylic resin having a hindered amine skeleton and a benzotriazole skeleton may be cross-linked. Examples of the crosslinking agent for crosslinking the acrylic resin include polyfunctional vinyl compounds such as ethylene glycol di (meth) acrylate, p-divinylbenzene, m-divinylbenzene, trimethylolpropane tri (meth) acrylate, and isocyanate compounds ( A block isocyanate), an epoxy compound, an aziridine compound, an oxazoline compound, a polyfunctional acid anhydride, or the like may be used, and these may be used alone or in combination of two or more.

  When the thickness of the coating layer 5 is thin, the weather resistance of the decorative pressure-sensitive adhesive sheet may be lowered. When the thickness is thick, the curved surface followability of the decorative pressure-sensitive adhesive sheet is lowered, and the coating layer is bent when the decorative pressure-sensitive adhesive sheet is bent. Since cracking may occur, the thickness is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.

  The method for forming the coating layer 5 is not particularly limited. For example, after a solution containing a synthetic resin constituting the coating layer is applied to the release treatment surface of the release film, it is preferably dried without heating. And a method of forming a film by peeling and removing the release film after forming the coating layer on the release treatment surface of the release film.

  On the other surface of the substrate sheet 1, a pressure-sensitive adhesive layer 6 for adhering the decorative pressure-sensitive adhesive sheet A to an adherend is laminated and integrated. The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 6 is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives, which are stable to light and oxygen. An acrylic adhesive is preferred.

  When the thickness of the pressure-sensitive adhesive layer 6 is small, the adhesive strength of the decorative adhesive sheet to the adherend may be insufficient, and when the thickness is large, when the decorative adhesive sheet is peeled from the adherend. The pressure-sensitive adhesive layer may cause cohesive failure and adhesive residue may be generated on the surface of the adherend, so 10 to 50 μm is preferable.

  Next, an example of the decorative adhesive sheet manufacturing method of the present invention will be described. First, an ink receiving sheet is formed as described above, and a metal thin film layer 3 is formed by vapor-depositing metal on the other surface of the ink receiving sheet.

  Subsequently, after applying a urethane adhesive to the other surface of the metal thin film layer, the urethane adhesive layer 2 is formed on the other surface of the metal thin film layer by drying.

Here, if the amount of the urethane-based adhesive applied to the back surface of the metal thin film layer is small, the metal thin film layer and the base sheet may be delaminated, and if large, the metal thin film layer is cracked. Since it may generate | occur | produce, 0.5-5.0 g / m < ² > is preferable at the weight of the urethane type adhesive after drying.

  Then, a polymerization sheet in which an ink receiving sheet, a metal thin film layer, and a urethane adhesive layer are laminated and integrated in this order, and a base material sheet that has been formed into a film in advance, the urethane adhesive layer of the polymerization sheet The ink receiving sheet, the metal thin film layer, the urethane adhesive layer, and the base material are so-called dry laminating, which is superposed so as to face the base material sheet, supplied between a pair of rollers, and pressed in the thickness direction. A first laminated sheet is produced in which the sheets are laminated and integrated in this order.

  Then, an adhesive is applied to the other surface of the base sheet of the first laminated sheet by a general-purpose method such as reverse coater method or hot melt coating method, and dried to form an adhesive layer 6 to produce a second laminated sheet. To do.

  Thereafter, a coating layer is formed by applying an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton to one side of the ink receiving sheet of the second laminated sheet and drying it by a general procedure such as reverse coater method or microgravure printing. Thus, the decorative pressure-sensitive adhesive sheet of the present invention can be produced.

  When the decorative pressure-sensitive adhesive sheet A is stored in a wound state, the coating layer sheet and the pressure-sensitive adhesive layer stick together, and it may be difficult to feed out the decorative pressure-sensitive adhesive sheet A. 5 is preferably subjected to a mold release treatment.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1
100 parts by weight of vinyl chloride resin (trade name “PSH10” manufactured by Kaneka Chemical Co., Ltd.), 30 parts by weight of adipic acid polyester plasticizer (trade name “Adekasizer PN-446” manufactured by Asahi Denka Co., Ltd., weight average molecular weight: 1800), Alkyl tin mercapto compound (trade name “TM-181FSJ” manufactured by Katsuta Chemical Co., Ltd.), monomethyltin tris (normal octyl-3-mercaptopropionate) {(CH ₃ ) —Sn— (SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₃ } And a mixture of dimethyltin bis (normal octyl-3-mercaptopropionate) {(CH ₃ ) ₂ —Sn— (SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ }), 5 parts by weight, organic phosphite ( 2 parts by weight of Katsuta Chemical Co., Ltd.) and 4 parts by weight of a benzophenone ultraviolet absorber (trade name “Mark 1413” manufactured by Asahi Denka Co., Ltd.) The grayed method to obtain a vinyl chloride resin sheet having a thickness of 50 [mu] m. In addition, the release sheet was laminated | stacked on the other surface of the vinyl chloride resin sheet so that peeling was possible.

  Next, a solvent-based urethane resin adhesive main agent (trade name “Takelac A-626” manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) and an aliphatic curing agent (trade name “Takenate A-50” manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) are mixed. Then, a urethane-based adhesive solution was prepared.

  Subsequently, 100 parts by weight of an acrylic resin (trade name “Excelol 910” manufactured by Asia Industries Co., Ltd.) and 1 part by weight of a thermosetting agent (trade name “Excel Hardener D” manufactured by Asia Industries Ltd.) are uniformly kneaded, and the solution casting method is used. Thus, an acrylic resin sheet (total light transmittance: 70%) having a thickness of 5 μm was obtained.

  Aluminum was vapor-deposited on the acrylic resin sheet to produce an aluminum vapor-deposited sheet. The urethane-based resin adhesive solution obtained as described above is applied onto the aluminum thin film layer of the aluminum vapor-deposited sheet and dried to remove the solvent, thereby removing the urethane-based resin on the aluminum thin-film layer of the aluminum vapor-deposited sheet. The adhesive layer was laminated and integrated.

  And the said aluminum vapor deposition sheet is piled up on a vinyl chloride resin sheet in the state in which the urethane type adhesive bond layer faced the one surface of the said vinyl chloride resin sheet, and the aluminum thin film layer of the aluminum vapor deposition sheet was passed through the adhesive bond layer. After being laminated and integrated with the vinyl chloride resin sheet, the release sheet of the vinyl chloride resin sheet is peeled off, so that the aluminum thin film layer and the acrylic resin sheet are placed on one surface of the vinyl chloride resin sheet via the urethane adhesive layer. A first laminated sheet obtained by laminating and integrating in this order was obtained.

  Next, an acrylic resin pressure-sensitive adhesive solution (trade name “NM2” manufactured by Sekisui Chemical Co., Ltd.) 100 parts by weight is dissolved in a solvent to prepare an acrylic resin pressure-sensitive adhesive solution. 2 parts by weight of an agent (trade name “Coronate L-28E” manufactured by Nippon Polyurethane Co., Ltd.) was added and stirred to be uniform.

  Subsequently, a release sheet whose surface was subjected to a release treatment with a silicone resin release agent was prepared, and the acrylic resin pressure-sensitive adhesive solution was applied to the release treatment surface of the release sheet using a comma coater. The adhesive layer having a thickness of 30 μm was formed by applying and drying to remove the solvent.

  Then, the adhesive layer formed on the release treatment surface of the release sheet is overlaid on the other surface of the vinyl chloride resin sheet of the first laminated sheet, whereby an acrylic resin sheet, an aluminum thin film layer, a urethane type A second laminated sheet in which an adhesive layer, a vinyl chloride resin sheet, and an adhesive layer were laminated and integrated in this order was obtained. In addition, the release sheet was laminated | stacked on the adhesive layer so that peeling was possible.

  Next, an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton (trade name “UV-G301” manufactured by Nippon Shokubai Co., Ltd.) is applied onto the acrylic resin sheet by microgravure printing and dried, and then the acrylic resin sheet is applied. The coating layer was laminated and integrated to obtain a decorative adhesive sheet.

(Example 2)
A decorative adhesive sheet was obtained in the same manner as in Example 1 except that the thickness of the acrylic resin sheet was 15 μm instead of 5 μm.

(Example 3)
A decorative pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the thickness of the vinyl chloride resin sheet was changed to 150 μm instead of 50 μm.

Example 4
A decorative adhesive sheet was obtained in the same manner as in Example 1 except that the thickness of the acrylic resin sheet was changed to 0.5 μm instead of 5 μm.

(Comparative Example 1)
A decorative adhesive sheet was obtained in the same manner as in Example 1 except that no coating layer was formed.

(Comparative Example 2)
Instead of an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, 100 parts by weight of an acrylic resin (trade name “Excelol 170” manufactured by Asia Industries), a thermosetting agent (trade name “Excel Hardener D” manufactured by Asia Industries) ) 1 part by weight, 0.5 parts by weight of UV stabilizer (trade name “CHIMASSORB 944” manufactured by Ciba Specialty Chemical) and 0.05 part by weight of UV absorber (trade name “TINUVIN 326” manufactured by Ciba Specialty Chemical) A decorative pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that a coating layer was formed using a resin composition comprising:

(Comparative Example 3)
A coating layer is formed using an acrylic resin having a hindered amine skeleton but no benzotriazole skeleton (trade name “UWS-2816” manufactured by Nippon Shokubai Co., Ltd.) instead of the acrylic resin having a hindered amine skeleton and a benzotriazole skeleton. A decorative adhesive sheet was obtained in the same manner as in Example 1 except that.

  Next, for the decorative adhesive sheets obtained in Examples 1 to 4 and Comparative Examples 1 to 3, initial decorativeness, cracking of the aluminum thin film layer, accelerated weather resistance and gasoline resistance were evaluated in the following manner. The results are shown in Table 1.

(Initial decoration)
The obtained decorative adhesive sheet was irradiated with light, and the clearness and glossiness of the color due to the reflected light of the decorative adhesive sheet were visually observed, and the initial decorativeness of the decorative adhesive sheet was evaluated according to the following criteria.
A: The decorative pressure-sensitive adhesive sheet was very clear in color and had an excellent gloss.
○: The decorative pressure-sensitive adhesive sheet was clear in color and glossy.
X: The decorative pressure-sensitive adhesive sheet was not clear or glossy.

(Crack of aluminum thin film layer)
After releasing the release film from the obtained decorative sheet at a rate of 25 mm / sec, the aluminum thin film layer of the decorative adhesive sheet was visually observed and evaluated according to the following criteria.
A: The aluminum thin film layer was not cracked at all.
A: Some cracks were generated in the aluminum thin film layer, but it was at a level that would not cause any problems in use.
X: The aluminum thin film layer was cracked on the entire surface, and there was a problem in use.

(Accelerated weather resistance)
Using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.), the weather resistance of the decorative pressure-sensitive adhesive sheet was tested according to JIS D0205 (weather resistance test for automobile parts). The appearance of the adhesive sheet for decoration at the time and after 1500 hours was visually observed, and the accelerated weather resistance of the decorative adhesive sheet was evaluated according to the following criteria. The appearance was judged by comprehensive judgment of glossiness and color vividness.
A: No change in the decorative property of the decorative adhesive sheet was observed after 1500 hours.
○: No change was observed in the decorative property of the decorative adhesive sheet after 400 hours, but the decorative property of the decorative adhesive sheet was slightly decreased after 1000 hours.
(Triangle | delta): At the time of 400 hours progress, the decorativeness of the adhesive sheet for decorations fell slightly.
X: The decorative property of the decorative pressure-sensitive adhesive sheet was deteriorated after 400 hours.

(Gasoline resistance)
The obtained decorative adhesive sheet was immersed in a commercially available high-octane gasoline at 20 ° C. for 60 minutes, and the decorative adhesive sheet was taken out from the high-octane gasoline and allowed to stand at a temperature of 23 ° C. for 3 minutes. Next, after wiping off high-octane gasoline adhering to this decorative adhesive sheet with unused gauze, the appearance of the decorative adhesive sheet is visually observed, and the gasoline resistance of the decorative adhesive sheet is evaluated according to the following criteria did.
A: Discoloration and delamination were not observed in the decorative adhesive sheet.
X: Discoloration or delamination was observed in the decorative adhesive sheet.

It is the longitudinal cross-sectional view which showed the adhesive sheet for decoration of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material sheet 2 Urethane-type adhesive layer 3 Metal thin film layer 4 Ink receiving sheet 5 Coating layer 6 Adhesive layer A Adhesive sheet for decoration

Claims (5)

A metal thin film layer is laminated and integrated on one surface of the base sheet via a urethane-based adhesive layer, and an ink receiving sheet and a coating layer are laminated and integrated on the metal thin film layer. A decorative pressure-sensitive adhesive sheet comprising an acrylic resin having a hindered amine skeleton and a benzotriazole skeleton, wherein a pressure-sensitive adhesive layer is laminated and integrated on the other surface of the base sheet. The decorative adhesive sheet according to claim 1, wherein the coating layer has a thickness of 0.5 to 10 µm. The decorative pressure-sensitive adhesive sheet according to claim 1, wherein the ink receiving sheet contains at least one resin selected from an acrylic resin, an acrylic urethane resin, and a urethane resin. The decorative pressure-sensitive adhesive sheet according to claim 1, wherein the base sheet contains a vinyl chloride resin. 2. The decorative pressure-sensitive adhesive sheet according to claim 1, wherein the base sheet and the metal thin film layer are integrated via a urethane-based adhesive layer by a dry laminating method.

Images