JP2006021530A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate suitably used in a medical or industrial pressure-sensitive adhesive film, a decorative film such as a sticker, a marking film or the like stuck on a signboard or various parts, an interior or exterior finish material of a building such as a dwelling or the like or a decorative sheet used in a surface decorative material of articles of furniture or household electric products and capable of being easily and strongly bonded to an adherend by thermal bonding. <P>SOLUTION: The laminate has at least a polyolefin resin layer A, a resin layer B containing an adhesive polyolefin resin and a polyurethane resin layer C based on a polycarbonate polyurethane resin in this order. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to adhesive films (tapes) for medical and industrial use, decorative adhesive films (tapes) such as stickers and marking films for the purpose of sticking to signboards and various parts, and buildings such as houses. The present invention relates to a polyolefin resin laminate used for a decorative sheet used as a decorative material for exterior materials, furniture fixtures, home appliances, and the like.

  Conventionally, adhesive films (tapes) for medical and industrial use, stickers and marking films for decorative purposes such as stickers and marking films, and interiors and exteriors of buildings such as houses As a film for laminating used in decorative sheets used for surface decorative materials such as wood, furniture, furniture, and home appliances, it is excellent in coloring, heat laminating, embossing, printing suitability, etc. Polyvinyl chloride resin films have been widely used, but polyvinyl chloride resin films cannot be treated with simple incineration equipment because of the danger of hydrogen chloride gas, etc. generated during incineration and disposal. Due to the problem of reducing the durability of incineration facilities, replacement with other materials such as polyolefin resin has been progressing in recent years.

  As a lamination process of the polyolefin resin film, a dry lamination process using an adhesive is performed. However, this method has a problem that the productivity is poor, for example, it takes a long time to cure the adhesive for dry laminating, and the thermal laminating process generally used for laminating polyvinyl chloride resin films is sufficient. There was a problem that a good adhesion could not be obtained.

Various studies have been made to solve this problem. For example, in order to improve adhesiveness in heat laminating, ethylene ionomer resin or ethylene and CH ₂ = C (R ₁ ) -COOR ₂ ( In the formula, R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms) and a layer containing a resin such as a copolymer with a monomer represented by A laminate with a polyolefin resin layer has been proposed (Patent Document 1).
However, even if such a polyolefin resin laminate is used, sufficient adhesive strength and productivity are not achieved at the same time, and further improvement, in particular, improvement in adhesive strength in thermal lamination at low temperatures has been desired. .

Japanese Patent Laid-Open No. 2003-340991

  The present invention has been made to solve the problems in the prior art, and an object of the present invention is to provide a polyolefin resin laminate particularly suitable for heat laminating.

The gist of the present invention is as follows.
<1> a laminate having at least a polyolefin resin layer A, a resin layer B containing an adhesive polyolefin resin, and a polyurethane resin layer C mainly composed of a polycarbonate polyurethane resin in this order;
<2> Adhesive polyolefin resin
(1) ethylene ionomer resin,
(2) ethylene and the general formula _{CH 2 = C (R 1)} -COOR 2 ( wherein, _{R 1} represents a hydrogen or a methyl group, _{R 2} represents hydrogen or a C 1 -C 10 alkyl group) A copolymer of monomers represented by
(3) The laminate according to <1>, comprising as a main component at least one selected from the group consisting of a copolymer of ethylene and maleic anhydride and (4) a maleic anhydride-modified polyolefin resin,

<3> adhesive polyolefin resin, the ethylene and the general formula _{CH 2 = C (R 1)} -COOR 2 ( wherein, _{R 1} represents a hydrogen or a methyl group, _{R 2} represents hydrogen or from 1 to 10 carbon atoms The laminate according to <1>, comprising as a main component at least one selected from the group consisting of a copolymer of a monomer represented by a maleic anhydride and a maleic anhydride-modified polyethylene resin,
<4> Polyurethane resin layer C is polycarbonate polyurethane resin;
(X) an adduct of an aliphatic diisocyanate, an adduct of an alicyclic diisocyanate and an adduct of an aromatic diisocyanate, and (y) a reaction product obtained by reacting with at least one selected from the group consisting of isocyanurate polymers <1> to <3> comprising the laminate according to any one of
<5> Polycarbonate polyurethane resin is a reaction product obtained by reacting at least one selected from the group consisting of polycarbonate diol, aliphatic diisocyanate and alicyclic diisocyanate, and the weight average molecular weight having a hydroxyl group at the molecular end is 15 <1>-<4> the laminate according to any one of <1> to <4>, comprising, as a main component, a polycarbonate polyurethane resin having a viscosity of 15,000 to 150,000,
<6> A laminate in which a printed layer D and a base material layer E are provided in this order on the polyurethane resin layer C side of the laminate according to any one of <1> to <5>,
<7> The printing layer D includes a polyester polyurethane resin, and the <8> laminate and <8> the polyester polyurethane resin are mainly composed of a reaction product obtained by reacting isophorone diisocyanate and polycaprolactone polyol. 7>.

  The heat-adhesive laminate of the present invention does not require the use of the dry laminating method conventionally used for adhering polyolefin resin films to non-polyolefin resin adherends, and can be easily and firmly laminated on adherends by thermal bonding. can do. Moreover, since it can be bonded at a lower temperature than conventional thermal bonding, sufficient adhesive strength can be obtained without sacrificing productivity, and it can be applied to medical and industrial adhesive films (tapes), signs, and various parts. Suitable for decorative films (tapes) such as stickers and marking films for attachment, and interior / exterior materials for buildings such as houses, and decorative sheets used for surface decorative materials such as furniture fixtures and home appliances Used.

Hereinafter, the present invention will be described in detail.
The laminate of the present invention comprises a polyurethane resin mainly composed of a polyolefin resin layer A (hereinafter referred to as “layer A”), a resin layer B containing an adhesive polyolefin resin (hereinafter referred to as “layer B”), and a polycarbonate polyurethane resin. It is a laminated body having a layer C (hereinafter referred to as “layer C”) in this order and capable of thermal bonding. Further, a polyolefin resin layer may be further laminated on the outer surface of the layer A of the laminate. The polyolefin resin layer provided outside the layer A may have the same composition as the layer A, but is preferably a polyolefin resin layer having a composition different from that of the layer A.

  Examples of the polyolefin resin used for the layer A in the present invention include a polyethylene resin, a polypropylene resin, a polyolefin-based thermoplastic elastomer, a mixture thereof, and a mixture of these and other resins.

  Polyethylene resins include ethylene homopolymers, copolymers of ethylene with other monomers copolymerizable with ethylene (low density polyethylene (LDPE), high pressure method low density polyethylene, linear low Examples thereof include high density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene-α-olefin copolymer (metallocene polyethylene) obtained by polymerization using a metallocene catalyst, a mixture thereof, and the like.

  Examples of the polypropylene resin include a homopolymer of propylene (homopolypropylene), a copolymer, and a mixture thereof. Examples of the copolymer include a random copolymer of propylene and ethylene or other α-olefin (random polypropylene), a block copolymer (block polypropylene), a block copolymer containing a rubber component, or a graft polymer. Can be mentioned.

  Other α-olefins copolymerizable with propylene are preferably those having 4 to 12 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4- Examples thereof include methyl-1-pentene and 1-decene, and one or a mixture of two or more thereof is used. Usually, the mixing ratio of α-olefin (including ethylene) is 1 to 10% by weight, particularly 2 to 6% by weight, based on propylene.

  Examples of polyolefin-based thermoplastic elastomers 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-propylene non-conjugated diene rubber, low crystalline propylene homopolymer with a crystal melting heat (ΔH) of 100 g / J or less (Idemitsu Petrochemical Co., Ltd., Idemitsu TPO, Ube Industries, Ltd. CAP, Ube Lexen) UT2115, etc.), polyolefin resin obtained by a multistage polymerization method (Cataloy manufactured by Sun Allomer Co., Ltd., Zelas manufactured by Mitsubishi Chemical Co., Ltd., PER manufactured by Tokuyama Co., Ltd.), the rubber (component) and polyethylene resin And / or Polyolefin resin obtained by dynamically crosslinking a mixture of a polypropylene resin (Mitsubishi Chemical Co. THERMORUN, Advanced Elastomer Systems Corp. Santoprene, Mitsui Chemicals Co., Ltd. MILASTOMER), and the like.

  The heat of crystal fusion (ΔH) is the value on the DSC chart when the resin is melted once at the melting point or higher using a differential scanning calorimeter (DSC) and then cooled at a rate of 10 ° C./min. It is a value calculated from the crystal peak area. The polyolefin resin 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 a hard segment, a propylene homopolymer block or a copolymer block of propylene and an α-olefin, for example, binary such as propylene / ethylene, propylene / 1-butene, propylene / ethylene / 1-butene Or a terpolymer block is mentioned. In addition, (ii) as a 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. Examples include binary or ternary copolymer blocks.

Other resins to be mixed include styrene-butadiene-based thermoplastic elastomers such as styrene-butadiene rubber (SBR) and styrene-butadiene block copolymers, and styrene-based thermoplastic elastomers such as styrene-isoprene rubber (these hydrogenated products). Are included).
These other resins can be blended in an amount of 0 to 60 parts by weight with respect to 100 to 40 parts by weight of the polyolefin resin. As the polyolefin resin, those mainly comprising a polypropylene resin are preferred, and those containing 50 to 0 parts by weight of a resin other than the polypropylene resin with respect to 50 to 100 parts by weight of the polypropylene resin are preferred.

  Layer A contains the above-mentioned polyolefin resin, preferably 50 to 100% by weight, more preferably 60 to 100% by weight.

As the adhesive polyolefin resin used for the layer B,
(1) ethylene ionomer resin,
(2) ethylene and the general formula _{CH 2 = C (R 1)} -COOR 2 ( wherein, _{R 1} represents a hydrogen or a methyl group, _{R 2} represents hydrogen or a C 1 -C 10 alkyl group) A copolymer of monomers represented by
The main component is preferably at least one selected from the group consisting of (3) a copolymer of ethylene and maleic anhydride and (4) a maleic anhydride-modified polyolefin resin, particularly those containing 50 to 100% by weight. preferable.

As the ethylene ionomer resin, an ethylene / α, β-unsaturated carboxylic acid copolymer partially neutralized with a metal ion, ethylene / α, β-unsaturated carboxylic acid / α, Those in which some of the carboxyl groups of the β-unsaturated carboxylic acid ester copolymer are neutralized with metal ions are preferred. The proportion of the ethylene units in the copolymer before neutralization (referring to units derived from ethylene in the copolymer, that is, “—CH ₂ —CH ₂ —”; the same shall apply hereinafter) is preferably 75 to 99. 0.5 mol%, more preferably 88 to 98 mol%, and the proportion of α, β-unsaturated carboxylic acid units is preferably 0.5 to 15 mol%, more preferably 1 to 6 mol%. The proportion of the α, β-unsaturated carboxylic acid ester unit is preferably 0 to 10 mol%, more preferably 0 to 6 mol%. If the proportion of the α, β-unsaturated carboxylic acid unit in the copolymer is less than 0.5 mol%, the adhesiveness of the resulting ethylene ionomer resin may be impaired. There is a risk that the heat resistance of the obtained ethylene ionomer resin will be lowered. The presence of the α, β-unsaturated carboxylic acid ester unit is preferable because flexibility can be imparted to the obtained ethylene ionomer resin, but when it exceeds 10 mol%, the heat resistance of the obtained ethylene ionomer resin May decrease.

  The α, β-unsaturated carboxylic acid constituting the copolymer is preferably one having 3 to 8 carbon atoms, more preferably acrylic acid, methacrylic acid or phthalic acid. The α, β-unsaturated carboxylic acid ester is preferably one having 4 to 8 carbon atoms, more preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, methacrylic acid. Butyl, dimethyl phthalate, etc. are used.

Of the carboxyl groups in the copolymer, the proportion of carboxyl groups neutralized by metal ions is preferably 5 to 80%, more preferably 10 to 75% in all the carboxyl groups in the copolymer. . Examples of the metal ion include metal ions having 1 to 3 valences, particularly metal ions having 1 to 3 valences of groups 1, 2, 3, 4 or 7 in the periodic table. For example, Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ , Cu ⁺ , Be ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Sr ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , Cd ⁺⁺ , Hg ⁺⁺ , Sn ⁺⁺ , Pb ⁺⁺ , Fe ⁺⁺ , Co ⁺⁺ , Ni ⁺⁺ , Zn ⁺⁺ , Al ⁺⁺⁺ , Sc ⁺⁺⁺ , Fe ⁺⁺⁺ , Yt ⁺⁺⁺ etc. are raised. These metal ions may be a mixture of two or more kinds, or may be used by mixing with ammonium ions. Of these, Zn ⁺⁺ and Na ⁺ are particularly preferable.

The copolymer of ethylene and a monomer represented by the general formula CH ₂ ═C (R ₁ ) —COOR ₂ is a _binary of the monomer represented by ethylene and CH ₂ ═C (R ₁ ) —COOR _2. Examples thereof include a copolymer and a multi-component copolymer of ethylene and a monomer represented by CH ₂ ═C (R ₁ ) —COOR ₂ and another monomer. In addition, the multicomponent copolymer said in this invention means the copolymer obtained by copolymerizing 3 or more types of monomers.

Examples of the copolymer of ethylene and maleic anhydride include a binary copolymer of ethylene and maleic anhydride, and a copolymer of ethylene, maleic anhydride and a monomer represented by CH ₂ ═C (R ₁ ) —COOR _2. Examples thereof include multi-component copolymers of ethylene, maleic anhydride and other monomers such as polymers.

The weight ratio of each structural unit constituting the copolymer of ethylene and a monomer represented by the general formula CH ₂ ═C (R ₁ ) —COOR ₂ is ethylene and the general formula CH ₂ ═C (R ₁ ) —. In terms of the weight of COOR ₂ , ethylene: CH ₂ ═C (R ₁ ) —COOR ₂ = 20 to 95:80 to 5, more preferably 50 to 95:50 to 5. More preferably, it is 60-90: 40-10.

Further, ethylene and maleic anhydride and _CH 2 ₌ C (R 1) in the case of a copolymer of a monomer represented by -COOR _2, said ethylene and _CH 2 = C (R ₁₎ weight -COOR ₂ In addition to the ratio conditions, the content of maleic anhydride units in terms of maleic anhydride may be 0.1 to 10% by weight in terms of moldability and thermal adhesiveness, and more preferably 0. 0.5 to 5% by weight.

  Examples of the maleic anhydride-modified polyolefin resin include those modified by adding maleic anhydride to a polyolefin resin, and examples of the polyolefin resin include a polyethylene resin, a polypropylene resin, and an ethylene-vinyl acetate copolymer. In addition, what was quoted in description of the layer A can be used as a polyethylene resin and a polypropylene resin. As the maleic anhydride-modified polyolefin resin, maleic anhydride-modified polyethylene resin and maleic anhydride-modified polypropylene resin are particularly preferable.

Among the adhesive polyolefin resins, among others, from the group consisting of a copolymer of ethylene and a monomer represented by the general formula CH ₂ = C (R ₁ ) -COOR ₂ and maleic anhydride and a maleic anhydride-modified polyethylene resin Those containing at least one selected as a main component, particularly those containing 50 to 100% by weight, are preferable because they can be bonded at a thermal bonding temperature lower than the conventional thermal bonding temperature and are excellent in adhesiveness. A terpolymer of maleic anhydride and a monomer represented by CH ₂ ═C (R ₁ ) —COOR ₂ is more preferable.

As the content of the adhesive polyolefin resin in the layer B, the general formula CH ₂ = C (R ₁ ) -COOR ₂ unit, α, β-unsaturated carboxylic acid unit, ethylene / α, β-unsaturated carboxylic acid Unit in which part of carboxyl group of polymer is neutralized by metal ion, part of carboxyl group of ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer is metal The amount in the layer B of a unit that imparts adhesiveness to a polyolefin resin such as a unit neutralized by ions or a maleic anhydride unit (hereinafter referred to as “adhesive component”) is converted to the weight of the monomer. Thus, the amount of the adhesive polyolefin resin may be adjusted and blended in the layer B so that the total amount is preferably 0.5 to 50% by weight, more preferably 2 to 25% by weight. If the content of the adhesive component is small, sufficient adhesive strength cannot be obtained, and if the content of the adhesive component is large, the laminate is made into a product such as a film, and the blocking phenomenon tends to occur after the product is wound and stored. This is not preferable.

  Furthermore, the polyolefin resin mentioned in the description of the layer A can be blended with the layer B.

  It is preferable that the layer A and the layer B of the present invention contain an ultraviolet absorber and / or a hindered amine light stabilizer.

  Examples of the ultraviolet absorber include salicylic acid ester-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, and triazine-based ultraviolet absorbers.

  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-Met Shi-4-hydroxy-5-benzoylphenyl) methane, and the like.

  As the 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- (1,1,1, 3,3-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 layer after time.

  The blending amount of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, per 100 parts by weight of the resin component in each layer. If the blending amount is less than 0.01 part by weight, the effect of preventing browning and deterioration tends to be insufficient, and even if it exceeds 10 parts by weight, the effect commensurate with the blending amount cannot be obtained, and bleeding may occur. There is.

  Examples of hindered amine light stabilizers include 2,2,6,6-tetramethylpiperidyl-4-benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) 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-tetra Methylpiperidyl) -butane, 1,3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxo-spiro [4,5] decane, tri (4-acetoxy-2,2,6 , 6-Tetramethylpiperidi ) Amine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenylcarbamoyloxy-2,2,6,6 Examples include tetramethylpiperidine, 4-p-toluenesulfonyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, and the like. Among them, it is preferable to use a material having a molecular weight of 1000 or more because it is difficult to blow out to the surface of the base material layer after a lapse of time and good long-term weather resistance, and in particular, a polyolefin resin is copolymerized with a compound having a hindered amine skeleton. Things are preferred because they are difficult to blow out.

  The blending amount of the hindered amine light stabilizer is preferably 0.01 to 10 parts by weight per 100 parts by weight of the resin component in each layer. If the blending amount is less than 0.01 parts by weight, the stabilizing effect may be insufficient, and even if it is used in excess of 10 parts by weight, an effect commensurate with the blending amount may not be obtained, and bloom may occur. There is.

  Furthermore, the layers A and B of the laminate of the present invention do not impair the purpose of the present invention with other resins and additives such as antioxidants, slip agents, colorants, fillers, and nucleating agents as necessary. You may mix | blend within the range. Moreover, about these additives, it is common to use what was previously mix | blended with resin at high concentration (masterbatch).

  As a manufacturing method of the layer A and the layer B, a general polyolefin resin film molding method such as a T-die extrusion molding method, an inflation molding method and a calender molding method may be used, and it is not particularly limited. You may manufacture the laminated body which the polyolefin resin layer A and the layer B laminated | stacked. The surface of the layer B may be subjected to a pretreatment such as a corona discharge treatment in order to improve the adhesion with the layer C or the like.

  The thickness of the laminate composed of the layer A and the layer B varies depending on the application to be used, but when used for a decorative film or the like, it is 0.05 to 1 mm from the viewpoint of post-processing or ease of handling, 0.05 to 0.50 mm is particularly preferable.

  The ratio of the thickness of the layer A and the layer B is preferably 99/1 to 10/90, and preferably 90/10 to 50/50. If the layer B is too thin, sufficient adhesion cannot be obtained, and if it is too thick, film (layer) molding becomes difficult.

  In the laminate of the present invention, a polyurethane resin layer C (“layer C”) mainly composed of a polycarbonate polyurethane resin is provided on the surface of the layer B opposite to the surface in contact with the layer A. The content of the polycarbonate polyurethane resin in the layer C is preferably 50 to 100% by weight. Further, the layer C may be blended with a polyurethane resin other than the polycarbonate polyurethane resin and other resins within a range not impairing the object of the present invention.

  Examples of the polycarbonate polyurethane resin include a reaction product obtained by reacting 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 so high that it becomes difficult to obtain the flexible layer C, and the thermal adhesiveness is reduced. Since it falls, it is not preferable.

  On the other hand, when the weight average molecular weight exceeds 150,000, the solution viscosity at the time of forming the layer C is increased, workability and drying properties are deteriorated, excess solvent remains, and the frequency of generation of bubbles is increased. This is not preferable because it causes a decrease in adhesion to the resin layer and the like.

  The polycarbonate diol is represented by the following general formula (p).

HO — [— R—O—COO—] n—R—OH (p)
(R is an aliphatic substituent or alicyclic substituent)
The polycarbonate diol is obtained, for example, by reacting at least one compound selected from the group consisting of alkylene carbonate, diaryl carbonate, and dialkyl carbonate with diols and / or polyether polyols.

  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.

  Examples of diols that can be reacted with these carbonates include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 2-methyl. -1,3-propanediol, neopentyl glycol, 2-methyl-pentanediol, 3-methyl-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,3,5-trimethylpentanediol And mixtures thereof.

  Examples of polyether polyols include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, alkylene oxide adducts of diols, and mixtures thereof. Examples of diols used here 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 (hydroxy Methyl) -cyclohexanone, trimethylolpropane, glycerin and the like. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, Sti Emissions oxide, epichlorohydrin and the like, which are also possible to use a mixture of two or more.

  The above diols and polyether polyols may be used alone or in combination of two or more. Any of these can be reacted with at least one compound selected from the group consisting of the aforementioned alkylene carbonate, diaryl carbonate and dialkyl carbonate by a known method to form a polycarbonate diol.

  The weight average molecular weight of the polycarbonate diol is preferably 500 to 4000, more preferably 1000 to 3000. If it is less than 500, the adhesive strength after heat lamination is lowered, and if it exceeds 4000, the appearance of the coating film is distorted. Phenomenon such as undulation is caused, which is not preferable.

  Next, examples of the diisocyanate compound include aliphatic diisocyanates and alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, and xylene diisocyanate, and mixtures thereof.

  A reaction product obtained by reacting a polycarbonate diol and a diisocyanate compound is known by reacting the diisocyanate compound with the polycarbonate diol in a molar ratio of about polycarbonate diol: diisocyanate compound = 1: 0.7-1: 5. It can be manufactured by the method. 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. Whichever method is used, the reaction product obtained by reacting the polycarbonate diol and the diisocyanate compound for the purpose of forming the rubber-elastic layer C preferably has a structure mainly composed of a linear structure. .

  The polycarbonate polyurethane resin is a reaction product obtained by reacting polycarbonate diol with at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and has a weight average molecular weight of 15, What has 000-150,000 polycarbonate polyurethane resin as a main component is preferable. The polycarbonate polyurethane resin is preferably 50 to 100% by weight, particularly preferably 70 to 100% by weight in the polycarbonate polyurethane resin.

The layer C of the present invention can be formed by using a one-pack type coating agent containing a polycarbonate polyurethane resin without adding a crosslinking agent. Further, a small amount of a cross-linking agent (curing agent) can be mixed and reacted with the polycarbonate polyurethane resin and the cross-linking agent.
Examples of the crosslinking agent to be mixed include (x) at least one diisocyanate compound selected from the group consisting of aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, ethylene glycol, propylene glycol, hexanetriol, trimethylolpropane trimethacrylate, and the like. An adduct of an aliphatic diisocyanate, an adduct of an alicyclic diisocyanate, an adduct of an aromatic diisocyanate, or a mixture thereof obtained by addition polymerization with at least one compound selected from the group consisting of: (y) Examples include isocyanurate polymers obtained by polymerizing aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and the like, and mixtures thereof. It is possible to have.
The mixing ratio of the main agent / crosslinking agent varies depending on the hydroxyl value of the main agent and the isocyanate content of the cross-linking agent, but usually 5 to 40 parts by weight, preferably 10 to 30 parts by weight of the cross-linking agent with respect to 100 parts by weight of the polycarbonate polyurethane resin as the main agent. Part mix.
Usually, these main agents or main agents and cross-linking agents are used by dissolving them in a solvent, and further prepared as a coating agent by using a diluting solvent or the like to prepare a coating agent, such as a reverse roll coating method or a gravure roll coating method. A layer C is formed by applying and drying on the outer surface of the layer B in the layered body of the layer A and the layer B using a different coating method. The dry thickness of the obtained layer C is usually about 0.3 to 3 μm.

Furthermore, in the laminate of the present invention, an organic powder or an inorganic powder may be blended with the layer C for the purpose of preventing blocking in the roll state and the heat laminating step.
Examples of organic powders include polyurethane resin beads, polyacrylic resin beads, and polycarbonate resin beads. Examples of inorganic powders include calcium carbonate, barium sulfate, silica, silica alumina, clay, talc, titanium oxide, and carbon black. These pigments are mentioned.
Among these, it is particularly preferable to use silica powder having an average particle size of 0.1 to 5 μm.
The blending amount of the organic powder and / or inorganic powder is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the resin component in the layer C, considering the desired thermal adhesiveness, surface gloss, and non-blocking properties. Then, the proper amount can be used.

In addition, if necessary, the layer C may contain a known powdery and / or liquid ultraviolet absorber and a light stabilizer such as a hindered amine light stabilizer and an antistatic agent.
As the ultraviolet absorber and the light stabilizer, those mentioned in the description of the layer A and the layer B can be used. The blending ratio of the ultraviolet absorber and the light stabilizer is about 1/3 to 3/1 (weight ratio), and 1 to 70 parts by weight can be blended with respect to 100 parts by weight of the resin component in the layer C.

  As the antistatic agent, 0.5 to 5.0 parts by weight of an antistatic agent having a quaternary ammonium base or the like can be blended with respect to 100 parts by weight of the resin component in the layer C. If the blending amount is less than 0.5 parts by weight, the antistatic effect is low. On the other hand, if the blending amount exceeds 5.0 parts by weight, the thermal adhesiveness is impaired, which is not preferable. Examples of the antistatic agent having a quaternary ammonium base include C1-C20 dimethyl sulfate or diethyl sulfate such as alkyldimethylamine and alkyldiethylamine, and in particular, a hydroxyl group is substituted for hydrogen in the alkyl group. What has is preferable.

  In addition, between the layer A and the layer B, and between the layer B and the layer C, you may provide a layer further as needed.

  The laminate of the present invention is a medical or industrial adhesive film (tape), signboard, various parts, etc. by laminating the printed layer D and the base material layer E in this order on the outer surface of the layer C of the laminate. Cosmetics used as decorative films (tapes) for decoration such as stickers and marking films, and interior / exterior materials for buildings such as houses, and cosmetics used for surface cosmetics such as furniture fixtures and home appliances It can be suitably used for a sheet.

  The printed layer D preferably contains a polyester polyurethane resin from the viewpoint of productivity and adhesive strength, and the content thereof is preferably 10 to 95% by weight, more preferably 15 to 90% by weight. Among the polyester polyurethane resins, from the viewpoint of adhesive strength, a reaction product obtained by reacting isophorone diisocyanate and polycaprolactone polyol, that is, a reaction product obtained by reacting at least isophorone diisocyanate and polycaprolactone polyol (for example, isophorone diisocyanate / polyisocyanate). It is preferable that the main component is a caprolactone polyol reaction product, another monomer, isophorone diisocyanate, polycaprolactone polyol reaction product), and the content of the reaction product in the polyester polyurethane resin is particularly 50 to 100% by weight. preferable. In addition to the polyester polyurethane resin, the printed layer D may include other resins such as an acrylic copolymer mainly composed of an acrylic ester, a methacrylic ester, or a mixture thereof. Can be appropriately blended.

  Furthermore, in addition to the colorant (pigment, dye), the printing layer D can contain auxiliary agents such as a solvent, a dispersing agent and an antifoaming agent, and these are appropriately selected and used in consideration of the application. That's fine.

  The base material layer E preferably contains 50 to 100% by weight of a polyolefin resin, and more preferably contains 60 to 100% by weight. As the polyolefin resin, those mentioned in the description of the layer A can be used. As a manufacturing method of the base material layer E, a general polyolefin resin film molding method such as a T-die extrusion molding method, an inflation molding method, or a calendar molding method may be used. Although the thickness of the base material layer E varies depending on its usage and the like, it is 0.05 to 1 mm, particularly 0.05 to 0 in terms of post-processing or ease of handling when used for a decorative film or the like. .50 mm is preferred.

  The printing layer D is formed using a binder resin such as a polyester polyurethane resin, an ink containing a colorant and a solvent, and gravure printing or offset on the base layer E or a primer layer provided on the base layer E. What is necessary is just to perform by well-known printing methods, such as printing, silk screen printing, or transfer printing from a transfer sheet. There is no restriction | limiting in particular as a pattern pattern, What is necessary is just to set it as the pattern according to a use. Specifically, for example, a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, or a solid solid surface can be used. The printing layer D may be composed of a pattern layer having a pattern pattern and a whole surface solid layer.

  In order to thermally laminate the laminate of the present invention on an adherend such as a printing film composed of the printing layer D and the base material layer E, the laminate and the adherend are respectively 120 to 220 ° C. with a heating drum or an electric heater. And then laminating by pressing between a metal roll and a rubber roll, or laminating by pressing between a metal roll and a metal roll, or heating the metal roll to a temperature of 120 to 220 ° C. A method such as laminating at the same time may be used.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited by the following examples, unless the summary is exceeded.

1) Creation of laminated base materials (Layer A / Layer B) Six types (a to f) of laminated base materials were prepared using a two-type two-layer coextrusion molding machine so as to have the configuration shown in Table 1. did. The layer thickness ratio was layer A: layer B = 4: 1.

2) Creation of Laminate Coating Films 1 and 2 were prepared as follows, and a coating film after any of the coating liquids was dried by the gravure roll coating method on layer B of the laminated base material obtained in 1) The coating was applied to a thickness of 1 μm, and the layer C was formed by drying for 10 seconds with a hot air dryer at 80 ° C. to prepare a laminate.

<Preparation of coating solution>
(Coating liquid 1): Polyhexamethylene polycarbonate diol and isophorone diisocyanate were mixed at a molar ratio of 1: 1, and a polycarbonate polyurethane resin having a weight average molecular weight of 50,000 obtained by reaction was used. Prepared.

(Compounding) Compounding amount (parts by weight)
Polycarbonate polyurethane solution (* 1) 100
Crosslinker solution (* 2) 5
Diluting solvent (methyl ethyl ketone) 70

(* 1) Solid content concentration 20% by weight, solvent: methyl ethyl ketone / isopropyl alcohol = 85/15 (weight ratio)
(* 2) Hexamethylene diisocyanate trimer solution, solid concentration 75% by weight, solvent: ethyl acetate

(Coating liquid 2): AR-4 (coating liquid containing acrylic-modified polyurethane) manufactured by The Inktec Co., Ltd. was used.

3) Creation of adherend
After a corona treatment is applied to a 80 μm thick propylene random copolymer film (base material layer E), a polyester polyurethane resin (reactant obtained by reacting isophorone diisocyanate and polycaprolactone diol) on one side of the film binder A wood grain pattern is formed by a gravure printing method (printing layer D) using a printing ink having a composition of 30% by weight, 5% by weight of a color pigment, 50% by weight of methyl ethyl ketone, and 15% by weight of methyl isobutyl ketone. did.

4) Evaluation of laminate The layer C and the printed layer D adhere the laminate obtained in 2) and the adherend obtained in 3) using a heat sealer (TP-701 manufactured by Tester Sangyo Co., Ltd.). After heat-bonding (heat-sealing) as described above, the laminate was fixed after being cooled to room temperature, peeled off by a method of pulling the adherend, and the adhesive strength was evaluated qualitatively. The results are shown in Table-2. The thermal bonding conditions and evaluation criteria are as follows.

<Thermal bonding conditions>
(I) Temperature: 130 ° C., pressure: 0.1 MPa, time: 2 seconds (ii) Temperature: 150 ° C., pressure: 0.1 MPa, time: 2 seconds (iii) Temperature: 180 ° C., pressure: 0.1 MPa, Time: 2 seconds

<Evaluation criteria>
A: Adhered to the extent that the laminate is cut at the time of peeling. O: The laminate is not cut, but is firmly adhered (partial cohesive failure).
Δ: Adhered but peeled relatively easily (peeled at the interface between layer C and print layer D)
X: Easily peeled off at the interface between the layer C and the printing layer D

Side sectional view which shows embodiment of the laminated body of this invention Side sectional view which shows embodiment of the laminated body of this invention Side sectional view which shows embodiment of the laminated body of this invention Side sectional view which shows embodiment of the laminated body of this invention

Explanation of symbols

1: Layer C
2: Layer B
3: Layer A
4: Polyolefin resin layer 5: Print layer D
6: Base material layer E
7: Primer layer

Claims (8)

A laminate having at least a polyolefin resin layer A, a resin layer B containing an adhesive polyolefin resin, and a polyurethane resin layer C mainly composed of a polycarbonate polyurethane resin in this order. Adhesive polyolefin resin
(1) ethylene ionomer resin,
(2) ethylene and the general formula _{CH 2 = C (R 1)} -COOR 2 ( wherein, _{R 1} represents a hydrogen or a methyl group, _{R 2} represents hydrogen or a C 1 -C 10 alkyl group) A copolymer of monomers represented by
The laminate according to claim 1, comprising at least one selected from the group consisting of (3) a copolymer of ethylene and maleic anhydride and (4) a maleic anhydride-modified polyolefin resin. Adhesive polyolefin resin, ethylene with the general formula _{CH 2 = C (R 1)} -COOR 2 ( wherein, _{R 1} represents a hydrogen or a methyl group, _{R 2} is hydrogen or C 1 -C 10 alkyl group 2. The laminate according to claim 1, comprising at least one selected from the group consisting of a copolymer of a monomer represented by: maleic anhydride and a maleic anhydride-modified polyethylene resin as a main component. Polyurethane resin layer C is polycarbonate polyurethane resin,
(X) an adduct of an aliphatic diisocyanate, an adduct of an alicyclic diisocyanate and an adduct of an aromatic diisocyanate, and (y) a reaction product obtained by reacting at least one selected from the group consisting of isocyanurate polymers The laminate according to any one of claims 1 to 3. The polycarbonate polyurethane resin is a reaction product obtained by reacting polycarbonate diol with at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates, and has a weight average molecular weight of 15,000 having a hydroxyl group at the molecular end. The laminate according to any one of claims 1 to 4, comprising a polycarbonate polyurethane resin of -150,000 as a main component. The laminated body which provides the printing layer D and the base material layer E in this order on the polyurethane resin layer C side of the laminated body of any one of Claims 1-5. The laminate according to claim 6, wherein the printing layer D contains a polyester polyurethane resin. The laminate according to claim 7, wherein the polyester polyurethane resin is mainly composed of a reaction product obtained by reacting isophorone diisocyanate and polycaprolactone polyol.