JP4653611B2 - Polyolefin-based laminated film and adhesive film - Google Patents

Description

  The present invention is suitable for decorative adhesive films (tapes) such as industrial adhesive films (tapes), signboards, automobiles, etc., stickers, labels and marking films, decorative sheets, etc. The present invention relates to a laminated film used for and an adhesive film made of the film.

Conventionally, decorative adhesive films (tapes), such as industrial adhesive films (tapes), signboards, automobiles, etc., and stickers, labels and marking films, etc., and decorative sheets are colored. Films made of polyvinyl chloride resin having excellent properties, workability, scratch resistance, weather resistance, and the like have been frequently used. However, in recent years, there has been a demand for an alternative to a material with a small environmental load, such as a reduction in processing costs related to waste treatment, and the use of polyolefin-based resins has been studied.
Adhesive films such as marking films using polyolefin resin as a base material are known, and an elastomer component is blended with the base material in response to the demand for a film with moderate flexibility. A pressure-sensitive adhesive film having improved scratch resistance and durability by laminating is known (Patent Document 1).
However, the pressure-sensitive adhesive film is not sufficiently scratch-resistant on the surface, and when the pressure-sensitive adhesive film is attached to the three-dimensional curved surface and the film surface is rubbed with a squeegee or the like, it is easily damaged, and the scratch-resistant property on the three-dimensional curved surface is poor. In particular, it was not satisfactory as a high gloss film.
A pressure-sensitive adhesive sheet provided with a protective layer made of an electron beam curable resin on the surface of a polyolefin-based substrate has also been proposed (Patent Document 2), but the pressure-sensitive adhesive sheet slightly stretches the tape when the pressure-sensitive adhesive tape is applied. There was a problem that the coating layer was cracked, peeled off and glossy.

JP 2004-2825 A JP-A-8-302294

  An object of the present invention is to provide a laminated film free from the above-mentioned problems, and specifically includes a marking film excellent in scratch resistance, flexibility, curved surface followability, pasting workability and the like. It aims at providing the laminated | multilayer film suitable for uses, such as decorative films, such as a decorative adhesive film, an industrial adhesive film, and a decorative sheet.

That is, the gist of the present invention is that
(1) A polyolefin laminated film in which the following layers (a) and (b) are formed in this order on one side of a polyolefin resin film having a tensile modulus of 100 to 1200 MPa,
Layer (a) Layer comprising a cured product of a composition containing at least one of a polycarbonate polyurethane resin and an acrylic-modified polycarbonate polyurethane resin in an amount of 30 to 100% by weight Layer (b) Acrylic copolymer, polycaprolactone polyol and isocyanate crosslinking The polyolefin-based laminated film according to the above (1), wherein the layer (2) comprising the cured product of the composition containing the agent (2) has a tensile elastic modulus of 5 to 500 MPa.
(3) The polyolefin-based laminated film according to any one of the above (1) or (2), wherein the polyolefin-based resin film contains a polypropylene-based thermoplastic elastomer produced by a multistage polymerization method,
(4) It exists in the adhesive film by which an adhesive layer is formed in the polyolefin resin film side of the polyolefin laminated film in any one of said (1)-(3).

  The polyolefin-based laminated film of the present invention can be processed and handled in the same manner as a polyvinyl chloride-based resin film, has excellent flexibility, excellent performance such as curved surface followability and scratch resistance, and decorations such as marking films. It is suitably used for applications such as decorative films such as pressure-sensitive adhesive films, industrial pressure-sensitive adhesive films, and decorative sheets.

Details of the present invention will be described below.
The polyolefin laminated film of the present invention is a polyolefin laminated film in which the following layers (a) and (b) are formed in this order on one side of a polyolefin resin film having a tensile modulus of 100 to 1200 MPa.
Layer (a) Layer comprising a cured product of a composition comprising at least one of a polycarbonate polyurethane resin and an acrylic-modified polycarbonate polyurethane resin Layer (b) A composition comprising an acrylic copolymer, a polycaprolactone polyol and an isocyanate crosslinking agent When the tensile modulus of the base film is too small, the polyolefin laminate film (hereinafter referred to as “laminated film”) can be applied to the adherend, or when the laminate film is peeled off from the adherend. The film may stretch and become difficult to peel off, which may result in poor handling, and the film may become sticky and easily blocked. Moreover, when too large, there exists a possibility that it may be inferior to a softness | flexibility and it may be inferior to the construction property with respect to a curved surface or bending. The tensile elastic modulus of the base film is preferably 150 to 900 MPa, more preferably 150 to 700 Mpa, and particularly preferably 150 to 400 Mpa.

The base film is mainly composed of a polyolefin resin. The content of the polyolefin-based resin in the base film is preferably 50 to 100% by weight because various properties such as followability to a curved surface are improved.
Examples of the polyolefin resin include a polyethylene resin, a polypropylene resin, and a mixture thereof.

  Polyethylene resins include ethylene homopolymers, copolymers of ethylene as the main component with other monomers copolymerizable with ethylene (low density polyethylene (LDPE), high pressure low density polyethylene, linear Low density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene-α-olefin copolymer (metallocene polyethylene) obtained by polymerization using a metallocene catalyst, a mixture of two or more of these, etc. Can be illustrated.

Examples of the polypropylene resin include a propylene homopolymer (homopolypropylene), a propylene copolymer, a reactor-type polypropylene thermoplastic elastomer, and a mixture of two or more thereof. The polypropylene resin used in the present invention preferably has a flexural modulus of 50 to 900 MPa, particularly 100 to 700 MPa.
The propylene copolymer may be a random copolymer (random polypropylene) or block copolymer (block polypropylene) of propylene and ethylene or another α-olefin, a block copolymer or a graft copolymer containing a rubber component. Etc. Other α-olefins copolymerizable with propylene preferably have 4 to 12 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4 -Methyl-1-pentene, 1-decene, etc. are mentioned, The 1 type (s) or 2 or more types of mixture is used. Usually, the mixing ratio of the α-olefin is about 1 to 10% by weight with respect to propylene.

As the reactor type polypropylene-based thermoplastic elastomer, a low crystalline propylene homopolymer having a heat of crystal fusion (ΔH) of 100 g / J or less (Idemitsu Petrochemical Co., Ltd. Idemitsu TPO, Ube Industries Ltd. CAP, UT2115 manufactured by Ube Lexen Co., Ltd.) and polypropylene-based thermoplastic elastomers manufactured by a multistage polymerization method ((Cataloy manufactured by Sun Allomer Co., Ltd., Zelas manufactured by Mitsubishi Chemical Corporation, Tokuyama P.E.R., etc.)). Is mentioned.
The heat of crystal fusion (ΔH) is the crystal on the DSC chart when the resin is melted once above the melting point using a differential scanning calorimeter (DSC) and then cooled at a rate of 10 ° C./min. It is a value calculated from the peak area.
In the present invention, the multi-stage polymerization method is a polymerization method in which a plurality of types of polymers can be continuously produced by performing multi-stage polymerization of two or more stages, rather than completing the polymerization once. This is a method completely different from the so-called normal polymer blend method in which a mixed resin composed of different kinds of polymers is obtained using a mechanical method. By this method, it is possible to produce a blend type copolymer resin at a molecular level. If such a polymerization method is adopted, for example, it is possible to contain up to about 80 to 95% by weight of the second component with respect to polypropylene, and for the first time to have the same physical properties as plasticized polyvinyl chloride resin. It becomes possible. In a blend method using an ordinary extruder or the like, if a rubber component having a high molecular weight is used, a resin having a fine dispersion morphology such as the polypropylene resin used in the present invention cannot be produced because the melt viscosity is high. is there.

  The polypropylene-based thermoplastic elastomer obtained by the multistage polymerization method is a copolymer obtained by multistage polymerization of (i) a hard segment and (ii) a soft segment in two or more stages in a reactor. (I) As the hard segment, a propylene homopolymer block or a copolymer block of propylene and an α-olefin, for example, 2 such as propylene / ethylene, propylene / 1-butene, propylene / ethylene / 1-butene, etc. Examples include original or ternary copolymer blocks. (Ii) As the soft segment, an ethylene homopolymer block or a copolymer block of ethylene and α-olefin, such as ethylene / propylene, ethylene / 1-butene, ethylene / propylene / 1-butene, etc. Binary or ternary copolymer block of Polyolefin thermoplastic elastomers including polypropylene thermoplastic elastomers copolymerized by such a specific polymerization method are disclosed in, for example, JP-A-4-224809, but as an actual commercial product, Tokuyama (Product name = PER), manufactured by Sun Allomer (product name = Cataloy), manufactured by Mitsubishi Chemical Corporation (product name = Zeras), and the like.

  In the present invention, among polypropylene-based thermoplastic elastomers produced by a multistage polymerization method, in particular, the melt flow rate (MFR) is 0.1 to 30, and the proportion of xylene solubles at 23 ° C. is 30 to 30. 75% by weight, preferably 40-60% by weight is preferred. Here, MFR is a value measured according to JIS K 7210. The proportion of xylene solubles is determined as follows. 1 g of sample is placed in 300 ml of xylene in an oil bath and dissolved at 140 ° C. with stirring. From 1 hour after the addition of the sample, the mixture of the sample and xylene is cooled to 100 ° C. within 1 hour while continuing to stir. Thereafter, the mixture of the sample and xylene is transferred to a quenching oil bath, rapidly cooled to 23 ° C. ± 2 ° C. while continuing stirring, and kept at that temperature for 20 minutes or more. The resulting precipitate is removed by natural drying with filter paper. The filtrate is evaporated to dryness using an evaporator, and the resulting solid is dried under reduced pressure at 120 ° C. for 2 hours and then allowed to cool to room temperature. The solid content is measured to calculate the room temperature xylene solubles.

Also, other synthetic resins can be mixed with the polyethylene resin and / or the polypropylene resin. Examples of other resins to be mixed include diene rubbers (elastomers) such as isoprene rubber, butadiene rubber, butyl rubber, ethylene-butadiene rubber, propylene-butadiene rubber, acrylonitrile-butadiene rubber and acrylonitrile-isoprene rubber, ethylene-propylene rubber, ethylene -Polyolefin thermoplastic elastomers other than the above reactor type polypropylene thermoplastic elastomers such as propylene non-conjugated diene rubber, styrene-butadiene thermoplastic elastomers such as styrene-butadiene rubber (SBR) and styrene-butadiene block copolymers, and styrene -Styrenic thermoplastic elastomers (including these hydrogenated products) such as isoprene rubber.
These elastomer components can be blended in an amount of 0 to 60 parts by weight with respect to 100 to 40 parts by weight of a polyethylene resin and / or a polypropylene resin.

As described above, the base film preferably contains 50 to 100% by weight of a polyolefin resin, more preferably has a polypropylene resin as a main component, and other than the polypropylene resin with respect to 50 to 100 parts by weight of the polypropylene resin. What contains 50-0 weight part of resin is preferable. In particular, it is preferable to contain a polypropylene-based thermoplastic elastomer produced by a multistage polymerization method, since the adhesion to the layer (a) is good and the followability of the layer (a) to the base film is improved. Examples of resins other than polypropylene resins include the above-described polyethylene resins and elastomers. Among them, low density metallocene polyethylene having a density of 0.900 g / cm ³ or less, polyolefin thermoplastic elastomer, and hydrogenated styrene-butadiene rubber. At least one selected from is preferred.

The base film may be a single layer, but is preferably a multilayer having two or more layers, and is preferably a multilayer having at least an inner layer, an intermediate layer and an outer layer. When the base film is a multilayer, a layer in which the tensile elastic modulus (E1) of the inner layer and the tensile elastic modulus (E2) of the layer excluding the inner layer have a relationship of E1 ≧ E2 (this is a layer of three or more layers) Assuming that only the inner layer is taken out from the base film made of the film, the tensile elastic modulus (E1) of the film 1 composed only of the inner layer and the tensile elastic modulus (E2) of the film 2 composed of the layers excluding the inner layer ) Is preferably in a relationship of E1 ≧ E2. In addition, an inner layer means the layer by which the adhesive layer is laminated | stacked when a base film is post-processed for adhesive films, and the layer on the opposite side is called an outer layer.
Moreover, when the base film is a multilayer having at least an inner layer, an intermediate layer, and an outer layer, it is preferable that the thickness of the intermediate layer is 50% or more of the total thickness of the base film.
The base film may have at least one other layer between the inner layer and the intermediate layer and between the outer layer and the intermediate layer. In this case, the other layer may contain a polyolefin-based resin, but contains other resin, for example, a resin that enhances the adhesion between the inner layer (and / or outer layer) and the intermediate layer. You may do it.

As a preferred embodiment of the base film, specifically, for example, (1) 95-50% by weight of a polypropylene resin composed of 0-100% by weight of homopolypropylene and 100-0% by weight of random polypropylene and a hydrogenated styrene-butadiene copolymer are used. A layer containing 5 to 50% by weight of polymer rubber, (2) 90 to 20% by weight of a polypropylene resin consisting of 0 to 100% by weight of homopolypropylene and 100 to 0% by weight of random polypropylene, and a polyolefin-based thermoplastic elastomer and / or A layer containing 10 to 80% by weight of a low density metallocene polyethylene having a density of 0.900 g / cm ³ or less, (3) 50 to at least one of homopolypropylene, random polypropylene and reactor type polypropylene thermoplastic elastomer Contains 100% by weight Layer (4) a layer having a layer containing 45 to 100% by weight of a polypropylene-based thermoplastic elastomer produced by a multistage polymerization method, (5) having at least an inner layer, an intermediate layer and an outer layer, and the intermediate layer being formed by a multistage polymerization method It is a layer containing 50 to 100% by weight of a copolymerized polyolefin resin, and the inner layer and / or the outer layer contains a polyolefin resin other than the polyolefin resin copolymerized by a multistage polymerization method, that is, the inner layer and // Layer containing other polyolefin resin instead of polyolefin resin copolymerized by multistage polymerization method or other polyolefin resin in addition to polyolefin resin copolymerized by multistage polymerization method And the like.

It is preferable that a base film contains at least one of light stabilizers, such as a ultraviolet absorber and a hindered amine light stabilizer (HALS), from a viewpoint of a weather resistance.
Examples of the ultraviolet absorber include salicylic acid ester-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, and triazine-based ultraviolet absorbers. Of these, triazine ultraviolet absorbers and benzotriazole ultraviolet absorbers having a molecular weight of 400 or more are particularly preferable.
Specifically, salicylic acid ester ultraviolet absorbers include phenyl salicylate, 4-t-butyl-phenyl-salicylate, and the like.
Examples of benzophenone ultraviolet absorbers include 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the like. 2,2′-dihydroxybenzophenone ultraviolet absorbers, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2- 2-hydroxybenzophenone ultraviolet absorbers such as hydroxy-4-benzoyloxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxy-5-sulfonbenzophenone, 2,4-dihydroxybenzophenone, bis- (2-methoxy-4- Hydroxy-5-benzoylphenyl) methane and the like.

As a benzotriazole ultraviolet absorber, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole (molecular weight 388) 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (molecular weight 448), 2,2-methylenebis [4- (1,1,3,3- And tetramethylbutyl-6- (2H-benzotriazol-2-yl) phenol) (molecular weight 659).
Examples of cyanoacrylate ultraviolet absorbers include 2-ethyl-hexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl. An acrylate etc. are mentioned.
Examples of triazine ultraviolet absorbers include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) 1,3,5-triazine, 2- (4, 6-Diphenyl-1,3,5-triazin-2-yl) -5-((hexyl) oxy) -phenol, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazin-2-yl) -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (octyloxy) phenol, 2- (4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5- (hexyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-((methyl) oxy Phenol, and the like.

  Among them, a benzotriazole-based or triazine-based ultraviolet absorber having a molecular weight of 300 or more is preferable in that it hardly blows out to the surface of the base film after a lapse of time. The blending amount of the ultraviolet absorber is not particularly limited as long as it is in a range not to blow out from the base film, and is usually about 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component in the base film. The amount is preferably 0.05 to 5 parts by weight.

  Examples of hindered amine light stabilizers include 2,2,6,6-tetramethylpiperidinyl-4-benzoate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and tris (2,2 , 6,6-tetramethyl-4-piperidinyl) phosphite (“Chimasoap 944” manufactured by Ciba-Geigy Co., Ltd.), 1,3,8-triaza-7,7,9,9-tetramethyl-3-n -Octylpyro [4,5] decane-2,4-dione ("Tinuvin 144" manufactured by Ciba-Geigy Co., Ltd.), 1,2,3,4-tetra (4-carbonyloxy-2,2,6,6) -Tetramethylpiperidinyl) -butane, 1,3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxo-spiro [4,5] decane, tri (4-acetoxy-2 , 2,6,6-tetrame Lupiperidinyl) amine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenylcarbamoyloxy-2,2,6 6 tetramethylpiperidine, 4-p-toluenesulfonyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidinyl) terephthalate, and the like.

Among them, it is preferable to use a polymer having a molecular weight of 1000 or more because it is difficult to blow out to the surface of the substrate film after a long period of time and long-term weather resistance is good, and particularly, a polyolefin having a hindered amine skeleton copolymerized. Is preferable because it is difficult to blow out. Examples of the hindered amine light stabilizer having a molecular weight of 1000 or more include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl-1 , 6-Hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidinyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino -1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidinyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, N, N ′, N ″ N ″ ′-tetramekis- (4 6-bis- ( Til- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, or polyethylene resin There are those obtained by copolymerizing hindered amine light stabilizers, and these may be used alone or in admixture of two or more.
The blending amount is not particularly limited as long as it is in a range not to blow out from the base film, and is about 0.01 to 10 parts by weight, preferably about 0.1 parts by weight with respect to 100 parts by weight of the resin component in the base film. 05 to 5 parts by weight.

Furthermore, the base film preferably contains an antioxidant.
Examples of the antioxidant include phenol-based, sulfide-based, phosphorus-based, and isocyanurate-based antioxidants. Among these, a phenolic antioxidant is preferable because it has an excellent antioxidant effect, and a combination of phenolic and phosphorus antioxidants is particularly preferable because thermal stability is improved.

  Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,6-di-isopropyl-4-ethylphenol, 2,6-di-t-amyl-4- Methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol, 2 -Cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, dl-α-tocopherol, t-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4, 4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol) 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 2,2'-thiodiethylenebis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octyl) Thio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonic acid ethyl) nickel Bis [3,3-bis (3-t-butyl-4-hydroxyphenyl) butyric acid] glycol ester, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionyl] hydrazine, 2,2′-oxamide bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis (3- (3,5-di) -T-butyl-4-hydroxyphenyl) propionate), bis [2-t-butyl-4-methyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) fur Nyl] terephthalate, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10 Tetraoxaspiro [5,5] undecane, 2,2-bis [4- [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)] ethoxyphenyl] propane and stearyl-β And β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester such as-(4-hydroxy-3,5-di-t-butylphenol) propionate.

Examples of the sulfide-based antioxidants include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, and 3,3′-thiobispropionic acid diocdecyl ester.
Phosphorus antioxidants include bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di -Phosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol-di-phosphite, methylenebis (2,4-di-t-butylphenyl) octyl phosphite, tris (nonylphenyl) phos Phyto, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphonite, tetrakis (2,4-di -T-butyl-5-methylphenyl) -4,4'-biphenylene-diphosphonite, 2-[[2,4,8,10-tetrakis 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxafesfepin6-yl] oxy] -N, N-bis [2-[[2,4,810-tetrakis ( 1,1 dimethylethyl) dibenzo [d, f] [1,3,2] dioxafesfepin-6-yl] oxy] -ethyl] ethanamine and the like.
Examples of the isocyanurate antioxidant include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate.
The addition amount of the antioxidant is usually 0.01 to 5 parts by weight per 100 parts by weight of the resin component in the base film.

If necessary, a colorant, a filler, a slip agent (lubricant), an antiblocking agent and the like can be added to the base film as long as the purpose and performance are not impaired.
Examples of the colorant include general organic and inorganic pigments, and any colorant can be appropriately selected according to the purpose as long as it has heat resistance at a temperature around 300 ° C. which is a normal molding temperature of polyolefin resin. For example, various organic pigments such as (poly) azo, phthalocyanine, selenium, dye lake, quinacridone and dioxazine, oxides such as titanium oxide, chromic molybdate, sulfide and selenide And various inorganic pigments such as ferrocyanide, calcium carbonate, and carbon black. A compounding quantity is about 1-30 weight part normally with respect to 100 weight part of resin components in a base film.
Further, when the base film has a multilayer structure having at least an inner layer, an intermediate layer, and an outer layer, it is difficult for the colorant to plate out during the molding process of the film (base film) by blending the colorant into the intermediate layer. It is preferable because the appearance of the film is not impaired and the hue of the film is stabilized.
As the filler, inorganic fillers such as talc, calcium carbonate, titanium oxide, clay, mica, barium sulfate, whiskers, and magnesium hydroxide are generally used. Among these, talc is preferably used. The average particle size of the inorganic filler is not particularly limited, but is preferably 0.1 to 10 μm. When the base film has a multilayer structure having at least an inner layer, an intermediate layer, and an outer layer, the inorganic filler may be contained only in the intermediate layer.

The content of the inorganic filler is usually 1 to 100 parts by weight per 100 parts by weight of the resin component in the base film.
Examples of the lubricant include saturated fatty acid amides such as lauric acid amide and stearic acid amide, and unsaturated fatty acid amides such as erucic acid amide and oleic acid amide. Of these, erucic acid amide is preferred.
The addition amount of the lubricant is usually 0.01 to 10 parts by weight per 100 parts by weight of the resin component in the base film.
Antiblocking agents include organic powders such as urethane resin beads, polyacrylic resin beads, and polycarbonate resin beads, pigments such as carbon black, calcium carbonate, barium sulfate, silica, silica alumina, clay, talc, and titanium oxide. An inorganic type powder is mentioned.
The amount of the antiblocking agent added is usually 0.01 to 10 parts by weight per 100 parts by weight of the resin component in the base film.

Examples of the method for forming the base film include generally known film forming methods such as an extrusion forming method such as a T-die forming method, an inflation forming method, and a calendar forming method.
When the base film is a multilayer film such as having an inner layer, an intermediate layer and an outer layer, as a method of laminating each layer, a method of laminating individual formed films (layers) with a laminator or a method of pressure laminating simultaneously with film forming However, a method of forming a laminated film simultaneously with molding by the multilayer T-die extrusion method is preferable because the number of steps can be reduced.
Although the thickness of a base film is suitably selected in consideration of a resin composition, concealability, and followability of a curved surface, it is usually 30 to 500 μm, preferably 50 to 300 μm.
The base film of the present invention is preferably subjected to an easy-adhesion treatment on the surface of the film in order to enhance adhesion with a coating layer such as layer (a), an adhesive layer, a primer layer, and the like.
Examples of the easy adhesion treatment include known methods such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, etc. The treatment conditions are the composition of the base film (A) and the decay rate of the Nule index (JIS K 6768). In view of the above, it is necessary to make an appropriate selection, and it may be adjusted so that the wet index of the easy-adhesion treated surface of the base film during primer treatment is at least 37 mN / m.

The laminated film of the present invention comprises a layer (a) a layer made of a cured product of a composition containing at least one of a polycarbonate polyurethane resin and an acrylic-modified polycarbonate polyurethane resin, and a layer (b) acrylic on one side of the base film. The layer which consists of a hardened | cured material of the composition containing a system copolymer, a polycaprolactone polyol, and an isocyanate type crosslinking agent is formed in this order.
Examples of the polycarbonate polyurethane resin of the layer (a) include a reaction product of a polycarbonate diol and a diisocyanate compound, and the reaction product preferably has a weight average molecular weight of 15,000 to 150,000. If the weight average molecular weight is less than 15,000, an excessive amount of a crosslinking agent is required to improve the drying property. As a result, the degree of crosslinking becomes too high and it becomes difficult to obtain a flexible layer (a). The blocking property of the layer (a) in the state tends to be inferior. On the other hand, when the weight average molecular weight exceeds 150,000, the solution viscosity at the time of forming the layer (a) is increased, workability and drying properties are deteriorated, excessive solvent remaining, and the occurrence frequency of bubbles is increased. This is not preferable because it causes a decrease in the adhesion to b) and the substrate film.
The polycarbonate diol is represented by the following general formula (p).

HO — [— R—O—COO—] n—R—OH (p)
(R is an aliphatic or alicyclic substituent; n is an integer)
The polycarbonate diol is, for example, one or more compounds selected from the group consisting of alkylene carbonate, diaryl carbonate, dialkyl carbonate and one or more compounds selected from the group consisting of diols and polyether polyols. Obtained by reaction.

Examples of the alkylene carbonate include ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate and the like.
Examples of diaryl carbonates include diphenyl carbonate, phenyl-naphthyl carbonate, dinaphthyl carbonate, 4-methyl diphenyl carbonate, 4-ethyl diphenyl carbonate, 4-propyl diphenyl carbonate, 4,4'-dimethyl-diphenyl carbonate, 4,4 Examples include '-diethyl-diphenyl carbonate and 4,4'-dipropyl-diphenyl carbonate.
Examples of dialkyl carbonates include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n-amyl carbonate, diisoamyl carbonate. Etc.

As a co-reactant for these carbonates, as examples of diols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2- Methyl-1,3-propanediol, neopentyl glycol, 2-methyl-pentanediol, 3-methyl-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,3,5-trimethylpentane Diol etc. are mentioned.
Examples of polyether polyols include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran and alkylene oxide adducts of diols. Examples of diols used herein include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomer pentanediols, and isomer hexane. Diols or octanediols such as 2-ethyl-1,3-hexanediol, 1,2-bis (hydroxymethyl) -cyclohexanone, 1,3-bis (hydroxymethyl) -cyclohexanone, 1,4-bis (hydroxymethyl) ) -Cyclohexanone, trimethylolpropane, glycerin and the like. Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, and tetrahydrofuran. , Styrene oxide, epichlorohydrin and the like, which are also possible to use a mixture of two or more.
The weight average molecular weight of the polycarbonate diol is 500 to 4000, preferably 1000 to 3000.

Next, examples of the diisocyanate compound include aliphatic and alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, and xylene diisocyanate.
The reaction product of the polycarbonate diol and the diisocyanate compound is produced by a known method by reacting the polycarbonate diol with the diisocyanate compound in a molar ratio of polycarbonate diol: diisocyanate compound = 1: 0.7 to 1: 5. Can do. As such a method, a method of producing a high molecular weight polyurethane by prepolymerization and then using a crosslinking agent or a chain extender, or a method of producing a high molecular weight polyurethane by reacting all components in one step, etc. The method is mentioned.

As the acrylic-modified polycarbonate polyurethane resin, the above-mentioned polycarbonate polyurethane resin, an acrylic component comprising at least one of a radical polymerizable unsaturated monomer containing an acrylic radical polymerizable unsaturated monomer and a polymer thereof, and An acrylic-modified polycarbonate polyurethane resin obtained by copolymerization of
Examples of the acrylic radical polymerizable unsaturated monomer constituting the acrylic component include acrylic acid, methacrylic acid (hereinafter referred to as “(meth) acrylic acid”), derivatives of (meth) acrylic acid, and these Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (meth) acrylic. (Meth) acrylic monomers such as lauryl acid, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like Two or more types of mixtures can be mentioned.
Production of the acrylic-modified polycarbonate polyurethane resin of the present invention is, for example, a radical polymerizable double bond as exemplified in JP-A-4-159318, JP-B-5-43756, JP-B-7-78105, JP-A-9-268215, and the like. A method of graft-copolymerizing a radically polymerizable unsaturated monomer to a urethane resin having a hydrogen atom, and addition polymerization of an acrylic macromer having active hydrogen to a urethane resin as exemplified in JP-A-5-262646 and JP-A-5-262847 And a method of polymerizing a radical polymerizable unsaturated monomer in the presence of a urethane resin having at least one diazo bond in the molecule as exemplified in JP-A-2-229873.
The total amount of the polycarbonate polyurethane resin and the acrylic-modified polycarbonate polyurethane resin in the composition is preferably 30 to 100% by weight (if only one of them is contained), 30% by weight If it is less than the range, the adhesiveness of the layer (b) tends to decrease, which is not preferable.

  Furthermore, it is preferable to mix an isocyanate-based crosslinking agent into the composition. The scratch resistance of the layer (a) can be further improved by crosslinking with an isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate (IPDI), 4,4′-methylenebis ( Cyclohexyl isocyanate) (H12MDI), alicyclic diisocyanates such as ω, ω'-diisocyanate dimethylcyclohexane, xylylene diisocyanate, tetramethylxylylene diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate (TDI), 4,4'-diphenylmethane Aromatic diisos such as diisocyanate (MDI), naphthalene-1,5-diisocyanate, tolidine diisocyanate Obtained by addition polymerization of any one or more of cyanate and the like, the aliphatic, alicyclic or aromatic diisocyanate and one or more of ethylene glycol, propylene glycol, hexanetriol, trimethylolpropane, Examples thereof include adducts such as aliphatic, alicyclic or aromatic diisocyanates, and isocyanurates obtained by polymerizing aliphatic, alicyclic or aromatic diisocyanates. These isocyanate crosslinking agents may be used as a mixture of two or more.

  The amount of the isocyanate-based crosslinking agent varies depending on the hydroxyl value of the polycarbonate polyurethane resin and / or the acrylic-modified polycarbonate polyurethane resin (when only one of them is contained, the hydroxyl value of one of them). The molar ratio of the OH groups (NCO / OH) in the NCO group and the polycarbonate polyurethane resin and / or the acrylic-modified polycarbonate polyurethane resin is preferably 1.01 to 10, more preferably 1.5 to 5.

The layer (a) is formed on the base film by dissolving each of the above components in a known organic solvent, and adjusting the concentration to an appropriate level using a diluent as necessary. Bar coating, knife coating, roll coating The coating can be carried out by coating by a known method such as die coating or gravure roll coating, followed by drying and curing by heating at 50 to 200 ° C. for several seconds to several minutes using a hot air dryer or the like. When the curing rate is slow, it is preferable to promote the curing reaction for several days at room temperature of 40 to 50 ° C. after coating and drying.
The thickness of the layer (a) thus formed is preferably 0.2 to 10 μm.
If the thickness is too thin, sufficient adhesion cannot be obtained. On the other hand, if the thickness is too large, curling of the laminated film and occurrence of cracks in the coating film layer are not preferable.

Next, as the acrylic copolymer of the layer (b), the (co) polymer of the acrylic radical polymerizable unsaturated monomer described above, the acrylic radical polymerizable unsaturated monomer and itaconic acid are used. , Maleic anhydride, (meth) acrylic acid amide, (meth) acrylic acid N-hydroxymethylamide, alkylaminoalkyl (meth) acrylate (eg, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, etc.), vinyl acetate , A copolymer with at least one selected from the group consisting of styrene, acrylonitrile, methacrylic acid-modified polydimethylsiloxane, and the like.
As the polycaprolactone polyol, bifunctional polycaprolactone diols represented by the following general formula (1), trifunctional polycaprolactone triols represented by the following general formula (2), and other tetrafunctional polycaprolactone polyols should be used. Can do.

アクリル系共重合体とポリカプロラクトンポリオールに更にイソシアネート系架橋剤を加えて反応させることにより、層（ｂ）の耐傷付き性等を更に向上することができる。イソシアネート系架橋剤としては、上述したものが挙げられる。
組成物中のアクリル系共重合体の量は３０〜９０重量％であるのが好ましい。またアクリル系共重合体とポリカプロラクトンポリオールの重量比は、９０／１０〜３０／７０であるのが好ましい。ポリカプロラクトンポリオールの量が少ないと、層（ｂ）の耐傷付き性が低下し、またポリカプロラクトンポリオールの量が多いと耐汚染性が低下する傾向となり、実用上好ましくない。
イソシアネート系架橋剤の量はアクリル系共重合体及びポリカプロラクトンポリオールの水酸基価により異なるが、通常ＯＨ基とイソシアネート系架橋剤中のＮＣＯ基の比（ＮＣＯ／ＯＨ）がモル比で１．０１〜１０、更に１．５〜５であるのが好ましい。

By adding an isocyanate crosslinking agent to the acrylic copolymer and polycaprolactone polyol and reacting them, the scratch resistance of the layer (b) can be further improved. Examples of the isocyanate-based crosslinking agent include those described above.
The amount of the acrylic copolymer in the composition is preferably 30 to 90% by weight. The weight ratio of the acrylic copolymer to the polycaprolactone polyol is preferably 90/10 to 30/70. When the amount of the polycaprolactone polyol is small, the scratch resistance of the layer (b) is lowered, and when the amount of the polycaprolactone polyol is large, the stain resistance tends to be lowered, which is not practically preferable.
The amount of the isocyanate-based crosslinking agent varies depending on the hydroxyl value of the acrylic copolymer and the polycaprolactone polyol, but the ratio of the OH group to the NCO group in the isocyanate-based crosslinking agent (NCO / OH) is generally 1.01 to 1.01. 10 and more preferably 1.5 to 5.

  Furthermore, polysiloxane can also be mixed in the layer (b) for the purpose of imparting performance such as contamination resistance. Polysiloxanes include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltoxiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxy. Silane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, Silamines having hydrolyzable silyl groups such as γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, etc. At least one selected from a partially hydrolyzed compound, an organosilica sol in which silicic acid fine particles are stably dispersed in an organic solvent, and an organosilica sol to which the silane compound having radical polymerizability is added. Can be used.

The tensile elastic modulus of the layer (b) is preferably 5 to 500 MPa, and more preferably 10 to 300 MPa. If the tensile modulus of elasticity of the layer (b) is too small, stickiness increases, blocking occurs, and scratch resistance and contamination resistance deteriorate, which is not preferable. If it is too large, it tends to be inferior in shape followability and adhesion, which is not preferable.
In order to form the layer (b) on the layer (a), the composition is dissolved in a known organic solvent in the same manner as the layer (a) is formed on the base film, and further diluted as necessary. It is prepared to an appropriate concentration using an agent, etc., coated by a known method such as bar coating, knife coating, roll coating, die coating or gravure roll coating, and then usually 50 to 200 ° C. using a hot air dryer or the like. For several seconds to several minutes by drying and curing. When the curing speed is slow, a layer (b) is formed on a film imparted with releasability, for example, a polyester film subjected to silicon treatment, and the layer (a) surface of the base film in which the layer (a) is formed in advance By laminating, the layer (b) can be formed on the layer (a). After coating and drying, it is preferable to further promote the curing reaction for several days at a room temperature of 40 to 50 ° C., for example.
The thickness of the layer (b) thus formed is preferably 0.2 to 50 μm.

Further, in the present invention, an antistatic agent is added to at least one of (layer a) and layer (b) in consideration of secondary workability and the like within a range not impairing the performance, or a base material An antistatic layer may be provided between the film and the layer (a) or between the layer (a) and the layer (b).
As an antistatic agent, nonionic antistatic agents such as polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, glycerin fatty acid ester, sorbitan fatty acid ester; alkyl sulfonate, Anionic antistatic agents such as alkylbenzene sulfonate, alkyl sulfate, alkyl phosphate; cationic antistatic agents such as quaternary ammonium chloride, quaternary ammonium sulfate, quaternary ammonium nitrate; alkylbetaine type, alkylimidazoline type, Amphoteric antistatic agents such as alkylalanine type and conductive resins such as polyvinylbenzyl type cation and polyacrylic acid type cation are used. Examples of the antistatic layer include those obtained by dispersing a conductive filler such as tin oxide, indium oxide, and zinc oxide in a binder made of an organic compound, and a layer made of a charge transfer boron polymer resin. It is done.

Further, at least one of the layer (a) and the layer (b) is blended with an ultraviolet absorber and / or a hindered amine light stabilizer for the purpose of imparting weather resistance under long-term and severe conditions outdoors. Is preferred. As the ultraviolet absorber and the light stabilizer, the following can be used in addition to those mentioned in the description of the base film.
Examples of ultraviolet absorbers include 2- (2′-hydroxy-3′lauryl-5′-methylphenyl) benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl). -4-hydroxyphenyl] propionate-polyethylene glycol condensate, hydroxyphenylbenzotriazole derivatives, etc., and hindered amine light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl), 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, dimethyl succinate -1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and the like. .
The blending amount of the ultraviolet absorber or the hindered amine light stabilizer can be added in an amount of 1 to 70 parts by weight with respect to 100 parts by weight of the resin component in the layer, even when each is used alone or in combination. Is preferred. When the ultraviolet absorber and the light stabilizer are used in combination, the addition ratio is not particularly limited, but is usually about ultraviolet absorber / hindered amine light stabilizer = 1/3 to 3/1 (weight ratio).
When there are few compounding quantities of a ultraviolet absorber and / or a hindered amine light stabilizer, there exists a possibility that a weather resistance may be inferior. On the other hand, if the blending amount is too large, the solvent resistance and scratch resistance performance deteriorate, which is not preferable.

Further, a curing catalyst may be added to at least one of the layer (a) and the layer (b) for the purpose of promoting the crosslinking reaction. Examples of the curing catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, and monobutyl. Mention may be made of organometallic compounds such as tin trioctate, lead 2-ethylhexanoate, zinc octylate and mixtures thereof. The amount of the curing catalyst used is not particularly limited, but it is usually suitable that it is 0.005 to 5% by weight, particularly 0.01 to 3% by weight, based on the solid content in the layer.
In addition, at least one of an antioxidant, an organic powder, and an inorganic powder may be added to at least one of the layers (a) and (b) as long as the performance is not impaired.

The laminated film of the present invention can be made into various pressure-sensitive adhesive films by forming a pressure-sensitive adhesive layer on the surface of the base film where the layers (a) and (b) are not formed.
The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer may be either an acrylic or rubber-based pressure-sensitive adhesive, but an acrylic pressure-sensitive adhesive having high weather resistance is preferred when used outdoors. Examples of the monomer constituting the acrylic pressure-sensitive adhesive include a (meth) acrylic acid ester monomer, and the (meth) acrylic acid ester monomer includes (meth) acrylic acid as an alcohol having an alkyl group having 2 to 12 carbon atoms. An ester, preferably a (meth) acrylic acid ester having an alkyl group having 4 to 12 carbon atoms is used. Specifically, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Isooctyl acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, and the like. These can be used alone or in combination. In view of the balance between adhesiveness and cohesiveness, etc., the homopolymer glass transition temperature (Tg) is usually -50 ° C. or less and the main component is (meth) acrylic acid ester, and lower alcohols such as ethyl (meth) acrylate ( It is preferable to use a (meth) acrylic acid ester in combination.

In addition to these vinyl monomers, monomers copolymerizable with these may be copolymerized. Examples of such copolymerizable monomers include carboxyl group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid or anhydrides thereof, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl acrylate. And hydroxyl group-containing monomers such as polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and caprolactone-modified (meth) acrylate.
The pressure-sensitive adhesive may be a solvent-type acrylic pressure-sensitive adhesive polymerized in a solvent, an emulsion-type pressure-sensitive adhesive polymerized in water, or a block polymerization pressure-sensitive adhesive that is irradiated with ultraviolet rays on a monomer mixture. Good.
The thickness of the pressure-sensitive adhesive layer varies depending on the composition of the pressure-sensitive adhesive and is not particularly limited, but is usually 20 to 50 μm.
The pressure-sensitive adhesive layer is formed on the laminated film of the present invention by dissolving the above-mentioned pressure-sensitive adhesive or the like in a known organic solvent, and adjusting the concentration to an appropriate level using a diluent or the like as necessary. Coated with a known method such as bar coating, knife coating, roll coating, die coating or gravure roll coating, and then dried using a hot air dryer or the like, and then laminated film It can carry out by laminating | stacking an adhesive layer on the base film side of this.
In addition, the laminated film and the adhesive film of the present invention include at least one selected from the group consisting of an acrylic resin, a urethane resin, and an acrylic modified urethane resin in order to improve adhesion between the base film and the adhesive layer. You may provide the primer layer to contain.

Embodiments of the present invention will be described in detail below using examples, but the present invention is not limited to the following examples unless it exceeds the gist.

<Evaluation>
(1) Evaluation of Adhesive Tape A) Steel Wound Scratch Test The coating layer side surface of the adhesive tape was subjected to 50 reciprocating polishing with a steel wool # 0000 with a load of 100 g, and the surface damage state was visually evaluated.
◎: No scratches are observed. ○: Very small scratches are observed. △: Scratches are observed. ×: Significant scratches are observed.

B) Car wash brush scratch test After peeling the adhesive tape separator and pasting it on the three-dimensional curved surface of the light car body, washing the car with a general gas station car wash machine, the surface of the adhesive tape coating layer The scratched state was visually evaluated.
◎: No scratches are observed. ○: Very small scratches are observed. △: Scratches are observed. ×: Significant scratches are observed.

C) Followability of coating film layer to substrate film Peel off the adhesive tape separator and apply it to the surface of the metal three-dimensional curved surface shown in FIG. The state of the coating layer was visually observed.
◎: No change is observed in the coating layer △: Microcracks are generated in the coating layer or the gloss is slightly reduced ×: The coating layer is completely cracked and the gloss is remarkably reduced

D) Adhesiveness between coating film layer and substrate film After carrying out the peeling operation described in c) above, the coating film layer side surface of the adhesive tape and the adhesive surface of a commercially available adhesive tape are adhered using a roller. The peeled state of the coating layer when peeled 180 ° was visually evaluated. The peeling was performed manually and at an instantaneous high speed.
◎: No peeling at all ○: Peeling of the coating layer is slightly observed △: Peeling of the coating layer is partially observed ×: The coating layer is completely transferred to the commercially available adhesive tape side

<Examples 1-4, Comparative Examples 1 and 2>
(1) Production of base film (A) 100 parts by weight of random polypropylene (Grand Polymer Co., Ltd., Grand Polypro F327) and 0.1 part by weight of a hindered amine light stabilizer (Ciba Specialty Chemicals Co., Ltd.) A polyolefin resin film having a thickness of 0.1 mm was prepared using an extrusion molding machine manufactured by Mitsubishi Heavy Industries, Ltd. The resulting film had a tensile modulus of 600 MPa. Next, the both sides of the film were subjected to corona treatment so that the Nule index was 45 mN / m to obtain a base film.

  (B) Using a composition comprising 100 parts by weight of homopolypropylene (manufactured by Nippon Polypro Co., Ltd., Novatec PP-FY6HA) and 0.1 part by weight of a hindered amine light stabilizer (manufactured by Ciba Specialty Chemicals) Then, a polyolefin resin film having a thickness of 0.1 mm was prepared by an extrusion molding machine manufactured by Mitsubishi Heavy Industries, Ltd. The resulting film had a tensile modulus of 1000 MPa. Next, the both sides of the film were subjected to corona treatment so that the Nule index was 45 mN / m to obtain a base film.

(C) 50 parts by weight of random polypropylene (Grand Polypro F327, manufactured by Grand Polymer Co., Ltd.), 50 parts by weight of a polypropylene-based thermoplastic elastomer manufactured by a multistage polymerization method (Cataloy C200F manufactured by Sun Allomer Co., Ltd.) and hindered amine light A polyolefin resin film having a thickness of 0.1 mm by an extrusion molding machine manufactured by Mitsubishi Heavy Industries, Ltd., using a composition comprising 0.1 part by weight of a stabilizer (Ciba Specialty Chemicals Co., Ltd., Kimasorb 944). It was created. The film obtained had a tensile modulus of 350 MPa. Next, the both sides of the film were subjected to corona treatment so that the Nule index was 45 mN / m to obtain a base film.

(2) Formation of layer (a) (2) -1 Production of polycarbonate polyurethane resin coating solution (X) Isophorone diisocyanate 31 in a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer .4 parts by weight of polycarbonate glycol heated to 90 ° C. and melted with stirring (Placcel CD220, hydroxyl value 56.1 KOH mg / g, weight average molecular weight 2000, manufactured by Daicel Chemical Industries, Ltd.) 128.4 parts by weight 2.2 parts by weight of glycerin monomethacrylate (Blenmer GLM, manufactured by Nippon Oil & Fats Co., Ltd.) and 0.02 parts by weight of methylhydroquinone were added dropwise over about 1 hour. After keeping the internal temperature at 90 ° C. and reacting for 4 hours, 208.9 parts by weight of methyl ethyl ketone was added, and the mixture was diluted by stirring at 60 ° C. for 1 hour. Next, a solution of 8.7 parts by weight of isophorone diamine and 52.2 parts by weight of isopropanol was added dropwise over 1 hour with stirring, and 3.3 parts by weight of di-n-butylamine was further added to block the end, and a polycarbonate polyurethane system A resin solution was obtained. 100 parts by weight of the obtained polycarbonate polyurethane resin solution, 7 parts by weight of hexamethylene diisocyanate trimer solution (solid content concentration: 75% by weight, solvent: ethyl acetate), 200 parts by weight of methyl ethyl ketone, and 45 parts by weight of ethyl acetate are mixed. The mixture was stirred to produce a polycarbonate polyurethane resin coating liquid (X) having a solid content concentration of 10% by weight.

(2) -2 Production of acrylic-modified polycarbonate polyurethane-based resin coating liquid (Y) 31.4 parts by weight of isophorone diisocyanate was charged into a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer. Polycarbonate glycol (Placcel CD220, hydroxyl value 56.1 KOHmg / g, weight average molecular weight 2000, manufactured by Daicel Chemical Industries, Ltd.) 128.4 parts by weight heated to 90 ° C. and stirred, glycerin monomethacrylate (Blemmer GLM, 2.2 parts by weight of Nippon Oil & Fats Co., Ltd. and 0.02 parts by weight of methylhydroquinone were added dropwise in about 1 hour. After keeping the internal temperature at 90 ° C. and reacting for 4 hours, 208.9 parts by weight of methyl ethyl ketone was added, and the mixture was diluted by stirring at 60 ° C. for 1 hour. Next, a solution of 8.7 parts by weight of isophoronediamine and 52.2 parts by weight of isopropanol was added dropwise over 1 hour with stirring, and 3.3 parts by weight of di-n-butylamine was further added to block the ends. Subsequently, 157.9 parts by weight of methyl methacrylate, 16.1 parts by weight of 2-hydroxyethyl methacrylate, and 385.4 parts by weight of methyl ethyl ketone were charged and heated to 70 ° C. in a nitrogen stream to 5.2 weights of azobisisobutyronitrile. The portion was divided into 3 portions and added at 1 hour intervals, and the reaction was further continued for 10 hours. 100 parts by weight of the resulting acrylic-modified polycarbonate polyurethane resin solution, 7 parts by weight of hexamethylene diisocyanate trimer solution (solid content concentration 35% by weight, solvent: ethyl acetate), 250 parts by weight of methyl ethyl ketone, and 46 parts by weight of ethyl acetate are mixed. The mixture was stirred to produce an acrylic-modified polycarbonate polyurethane-based resin coating solution (Y) having a solid content concentration of 10% by weight.

(2) -3 Production of acrylic resin coating liquid (Z) 140 parts by weight of methyl methacrylate and 38 parts by weight of 2-ethylhexyl acrylate in a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer 20 parts by weight of 2-hydroxyethyl methacrylate, 2 parts by weight of methacrylic acid, and 335 parts by weight of methyl ethyl ketone were added, heated to 70 ° C. under a nitrogen stream, and 2.4 parts by weight of azobisisobutyronitrile was added. Reacted for hours. 100 parts by weight of the resulting acrylic resin solution, 5 parts by weight of hexamethylene diisocyanate trimer solution (solid content concentration 35% by weight, solvent: ethyl acetate), 240 parts by weight of methyl ethyl ketone, and 42 parts by weight of ethyl acetate were mixed and stirred to form a solid. An acrylic resin solution coating solution (Z) having a partial concentration of 10% by weight was produced.

(2) The coating liquid obtained in 1-3 is applied to one side of the substrate film obtained in (1) with a gravure roll coater, and then heated and dried in a hot air dryer at 80 ° C. for 1 minute. (A) was formed. In addition, the thickness of the coating film layer after drying was 0.5 μm.

(3) Formation of layer (b) (3) -1 Production of acrylic copolymer (I) 50 parts by weight of toluene in a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 50 parts by weight of methyl isobutyl ketone was charged and the temperature was raised to 80 ° C. Separately, 30 parts by weight of methyl methacrylate, 26 parts by weight of butyl methacrylate, 23 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid, methacrylic acid-modified polydimethylsiloxane (X-22-174DX, manufactured by Shin-Etsu Chemical Co., Ltd., 20 parts by weight of molecular weight 5000) and 1 part by weight of azobis-2-methylbutyronitrile (manufactured by Nippon Hydrazine Kogyo Co., Ltd., ABN-E) are mixed, and this mixture is mixed with the above mixture of toluene and methyl isobutyl ketone for 3 hours. And then reacted for 6 hours to obtain an acrylic copolymer (I) solution having a solid concentration of 50% by weight.

(3) -2 Production of acrylic copolymer (II) 140 parts by weight of methyl methacrylate and 38 parts by weight of 2-ethylhexyl acrylate in a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer 20 parts by weight of 2-hydroxyethyl methacrylate, 2 parts by weight of methacrylic acid, and 335 parts by weight of methyl ethyl ketone were added, heated to 70 ° C. under a nitrogen stream, and 2.4 parts by weight of azobisisobutyronitrile was added. The mixture was reacted for a time to obtain an acrylic copolymer (II) solution having a solid content of 35% by weight.

(3) Using the acrylic copolymers obtained in (1) and (2), a coating solution having the composition shown in Table-1 was prepared, and the coating solution was subjected to silicon release treatment, and a polyethylene having a thickness of 25 μm. It was coated on a terephthalate film so that the coating thickness after drying by a reverse roll coating method was 15 μm, dried for 5 minutes with a hot air dryer at 80 ° C., and obtained in (2). The above-mentioned coating film is bonded onto the layer (a) of the film (base film / layer (a)), the polyethylene terephthalate film is peeled off, and the layer (b) is formed on the layer (a) to form a laminated film (base Material film / layer (a) / layer (b)) was obtained. Then, in order to accelerate | stimulate a crosslinking reaction, it stored for 5 days in a 40 degreeC heat retention box.

(4) Formation of pressure-sensitive adhesive layer An acrylic pressure-sensitive adhesive (SK Dyne 1502C, manufactured by Soken Chemical Co., Ltd.) was applied onto the separator by a comma coating method so that the thickness of the pressure-sensitive adhesive layer after drying was 25 μm. , Dried for 5 minutes in a hot air dryer at 80 ° C., and then laminated with the base film side surface of the laminated film obtained in (3) to form an adhesive layer, and an adhesive tape (separator / adhesive) Layer / base film / layer (a) / layer (b)) was obtained.
The obtained laminated film and adhesive tape were evaluated, and the results are shown in Table-2.

The perspective view of the metal three-dimensional curved surface used in the evaluation of <followability of the coating layer to the base film> in the examples

Claims (4)

A polyolefin-based laminated film in which the following layers (a) and (b) are formed in this order on one side of a polyolefin-based resin film having a tensile modulus of 100 to 1200 MPa.
Layer (a) Layer comprising a cured product of a composition containing 30 to 100% by weight of at least one of a polycarbonate polyurethane resin and an acrylic modified polycarbonate polyurethane resin Layer (b) Acrylic copolymer, polycaprolactone polyol and isocyanate crosslinking Made of a cured product of a composition containing an agent   The polyolefin-based laminated film according to claim 1, wherein the layer (b) has a tensile modulus of 5 to 500 MPa.   The polyolefin-type laminated film of any one of Claim 1 or 2 in which a polyolefin-type resin film contains the polypropylene-type thermoplastic elastomer manufactured by the multistage polymerization method.   The adhesive film by which an adhesive layer is formed in the polyolefin resin film side of the polyolefin laminated film of any one of Claims 1-3.

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