JP2006021531A - 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 as 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 base material layer A, a printing layer B containing a polyester polyurethane 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 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 films have been widely used, but polyvinyl chloride films cannot be processed with simple incineration equipment because of the danger of generating hydrogen chloride gas during incineration and disposal. In recent years, replacement with other materials such as polyolefin resin has been progressing.

As lamination processing of a polyolefin film, dry lamination processing 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 lamination, and the heat laminating process generally used for laminating vinyl chloride films is sufficient for adhesion. There was a problem that sex could not be obtained.
Various studies have been made to solve this problem. For example, in order to improve adhesiveness in thermal lamination, ethylene ionomer resin or ethylene as a laminate film and a general formula CH ₂ = C (R ₁ ) -COOR _{2 are used.} (Wherein R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms) and a resin such as a copolymer with a monomer represented by A polyolefin laminate obtained by thermally laminating a layer having thermocompression bonding and a base film having a printed layer has been proposed (Patent Document 1).
However, even in the laminate, the adhesive force between the layer having the thermocompression bonding property and the printed layer is not sufficient, and sufficient adhesive strength and productivity at the thermal laminate interface are not compatible. There has been a demand for improvement, particularly in adhesive strength in heat laminating at low temperatures.

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 (1) a laminate having at least a polyolefin resin substrate layer A, a printing layer B containing a polyester polyurethane resin, and a polyurethane resin layer C mainly composed of a polycarbonate polyurethane resin in this order, (2) polyester The laminate according to (1), in which the polyurethane resin is mainly composed of a reaction product obtained by reacting isophorone diisocyanate and polycaprolactone polyol, (3) the polyurethane resin layer C is a polycarbonate polyurethane resin, and (X) fat A reaction product obtained by reacting at least one selected from the group consisting of an adduct of an aromatic diisocyanate, an adduct of an alicyclic diisocyanate and an adduct of an aromatic diisocyanate, and (Y) an isocyanurate polymer (1 ) Or (2) Layer body, (4) 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 having a hydroxyl group at the molecular end The laminate according to any one of (1) to (3), which is mainly composed of a polycarbonate polyurethane resin having an average molecular weight of 15,000 to 150,000, and any one of (5) (1) to (4) The laminate is a laminate in which at least one polyolefin resin layer is provided on the polyurethane resin layer C side of the laminate.

  The laminate of the present invention is excellent in adhesiveness of each layer, and it is not necessary to use the dry laminating method conventionally used for bonding a polyolefin resin film to a non-polyolefin resin adherend. It can be laminated on a kimono. 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 polyolefin resin substrate layer A (hereinafter referred to as “substrate layer A”), a printing layer B containing a polyester polyurethane resin (hereinafter referred to as “printing layer B”), and a polycarbonate polyurethane resin as main components. It is a laminate having a polyurethane resin layer C (hereinafter referred to as “polyurethane resin layer C”), and the laminate and the polyolefin resin layer are laminated, and particularly by being thermally bonded, a decorative sheet, a decorative sheet, and the like can be easily obtained. Can be manufactured.

Examples of the polyolefin resin used for the base material 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 propylene homopolymer (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 dynamic crosslinking the mixture of propylene 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 synthetic 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.

  The content of the polyolefin resin in the base material layer A is preferably 50 to 100% by weight, and more preferably 60 to 100% by weight.

The base material layer A of the present invention preferably contains 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-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 material layer A after a lapse of time.
The compounding 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 the base material layer A. 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 L) 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-piperidyl) 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 base material layer A after time and the long-term weather resistance is good. In particular, a compound having a hindered amine skeleton is copolymerized with polyolefin. Things are preferred because they are difficult to blow out.
The 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 the base material layer A. 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 base material layer A of the present invention may be added with resins other than those listed above and additives such as antioxidants, slip agents, colorants, fillers, nucleating agents, and the like, if necessary. You may mix | blend within the range which is not. Moreover, about these additives, it is common to use what was previously mix | blended with resin at high concentration (masterbatch).
The method for producing the base material layer A is not particularly limited as long as a general polyolefin resin film molding method such as a T-die extrusion molding method, an inflation molding method, and a calendar molding method may be used. Further, in order to improve the adhesion with the printing layer B, the surface is subjected to a pretreatment such as a corona discharge treatment, or other layers such as a primer layer made of an acrylic resin, a urethane resin, an acrylic urethane resin, etc. It may be provided between the printing layers B.

  The thickness of the base material layer A 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, particularly 0.05 to 5 in terms of post-processing or ease of handling. 0.50 mm is preferable.

The printing layer B of the present invention contains a polyester polyurethane resin from the viewpoint of compatibility with the polyurethane resin layer C used in the present invention in order to improve thermal adhesiveness. The content of the polyester polyurethane resin is preferably 10 to 95% by weight, and 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 B is made of other resin such as an acrylic copolymer mainly composed of an acrylic ester, a methacrylic ester or a mixture thereof, and the adhesion to the base layer A, etc. Can be appropriately blended.
Furthermore, in addition to the colorant (pigment, dye), the printing layer B can be blended with auxiliary agents such as a solvent, a dispersing agent and an antifoaming agent. That's fine.

  The printing layer B is formed by using gravure printing or offset printing on the base layer A or a primer layer provided on the base layer A using an ink containing a binder resin such as polyester polyurethane resin, a colorant and a solvent. The printing may be performed by a known printing method such as 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 B may be composed of a pattern layer having a pattern and a solid surface layer.

  In the laminate of the present invention, a polyurethane resin layer C (“polyurethane resin layer C”) mainly composed of a polycarbonate polyurethane resin is provided on the surface of the printed layer B opposite to the surface in contact with the base material layer A. . The content of the polycarbonate polyurethane resin in the polyurethane resin layer C is preferably 50 to 100% by weight. More preferably, it is 60 to 100% by weight. The polyurethane resin 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 too high and it becomes difficult to obtain a flexible polyurethane resin layer C. This is not preferable because the properties are lowered. On the other hand, when the weight average molecular weight exceeds 150,000, the solution viscosity at the time of forming the polyurethane resin layer C is increased, workability and drying properties are deteriorated, excess solvent remains, and the occurrence frequency of bubbles is increased. This is not preferable because it causes a decrease in adhesion to B and the polyolefin resin layer.
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 to be reacted with these carbonates include 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 Examples thereof include diols 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 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 (hydroxy Methyl) -cyclohexanone, trimethylolpropane, glycerin and the like. Examples of alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, The Alkylene 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 polyurethane resin layer C having rubber elasticity has a structure mainly composed of a linear structure. Is preferred.

  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 polyurethane resin layer C of the present invention can be formed using a one-component coating agent containing a polycarbonate polyurethane resin without adding a crosslinking agent. It can also be formed by mixing a small amount of a crosslinking agent (curing agent) with the component as the main component and reacting the polycarbonate polyurethane resin and the crosslinking 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. The polyurethane resin layer C is formed by applying and drying on the printed layer side using any coating method. The dry film thickness of the obtained polyurethane resin 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 polyurethane resin 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 compounding amount of the organic powder and / or the inorganic powder is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the resin component in the polyurethane resin layer C. Desired thermal adhesiveness, surface gloss, non-blocking property Appropriate amount may be used considering the above.

In addition, if necessary, the polyurethane resin layer C may be blended with 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 base material layer A 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 polyurethane resin 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 polyurethane resin 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, other layers such as a primer layer can be provided between the printing layer B and the polyurethane resin layer C within a range that does not impair the object of the present invention.

The laminate of the present invention is provided with a polyolefin resin layer on the polyurethane resin layer C side of the laminate so that it can be attached to medical or industrial adhesive films (tapes), signs, various parts, etc. Appropriately used for decorative sheets used for decorative film (tape) for decoration such as stickers and marking films, and interior / exterior materials for buildings such as houses, and surface cosmetics such as furniture fixtures and home appliances Can do. The thickness of the polyolefin resin layer is preferably 0.05 to 1 mm, particularly preferably 0.05 to 0.50 mm.
The polyolefin resin layer preferably contains 50 to 100% by weight of polyolefin resin, more preferably 60 to 100% by weight.
Examples of the polyolefin resin include the polyolefin resins mentioned in the description of the base layer A, a) ionomer resins such as ethylene ionomer resins, and b) ethylene and the general formula CH ₂ ═C (R ₁ ) -COOR _2. (Wherein R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms), c) ethylene and maleic anhydride And an adhesive polyolefin resin mainly comprising at least one selected from the group consisting of d) maleic anhydride-modified polyolefin resins. These polyolefin resins may be used singly or as a mixture of two or more types, and as the polyolefin resin, those containing an adhesive polyolefin resin are particularly preferable.

As the ethylene ionomer resin, ethylene / α, β-unsaturated carboxylic acid copolymer partially neutralized with metal ions, ethylene / α, β-unsaturated carboxylic acid / Those in which some of the carboxyl groups of the α, 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.

Examples of the copolymer of ethylene and a monomer represented by the general formula CH ₂ ═C (R ₁ ) —COOR ₂ include ethylene and a monomer represented by CH ₂ ═C (R ₁ ) —COOR ₂ . Examples thereof include a binary 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, a monomer represented by ethylene, maleic anhydride, and CH ₂ ═C (R ₁ ) —COOR _2. And multi-component copolymers of ethylene, maleic anhydride, and other monomers.
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 , it is preferably 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 base material 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.

The content of the adhesive polyolefin resin in the polyolefin resin layer is as follows: General formula CH ₂ = C (R ₁ ) -COOR ₂ units, α, β-unsaturated carboxylic acid units, ethylene / α, β-unsaturated carboxylic acid A unit in which a part of the carboxyl group of the copolymer is neutralized by a metal ion, a part of the carboxyl group of the ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer is The unit in the polyolefin resin layer of the unit (hereinafter referred to as “adhesive component”) that imparts adhesiveness to the polyolefin resin such as a unit neutralized with metal ions or a maleic anhydride unit is based on the weight of the monomer. The amount of the adhesive polyolefin resin is adjusted so that the total amount is preferably 0.5 to 50% by weight, more preferably 2 to 25% by weight. It is sufficient. 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.

  Further, a plurality of polyolefin resin layers may be provided. In this case, it is preferable to provide a layer containing an adhesive polyolefin resin on the polyurethane resin layer C side. As such, it contains an adhesive polyolefin resin on the polyurethane resin layer C side (preferably the amount of the adhesive component of the adhesive polyolefin resin in the polyolefin resin layer is converted to the weight of the monomer, A layered product in which a layer and a polyolefin resin layer are sequentially provided is preferably 0.5 to 50% by weight, more preferably 2 to 25% by weight. In the above case, the ratio of the thickness of the polyolefin resin layer and the layer containing the adhesive polyolefin resin is preferably 99/1 to 10/90, and preferably 90/10 to 50/50. If the layer containing the adhesive polyolefin resin is too thin, sufficient adhesion cannot be obtained, and if it is too thick, film formation becomes difficult.

  Moreover, it is preferable to mix | blend the ultraviolet absorber and / or hindered amine light stabilizer which were mentioned in description of the above-mentioned base material layer A with a polyolefin resin layer, and it is preferable that the compounding quantity shall also be the range mentioned above.

  In order to thermally laminate the laminate of the present invention and the polyolefin resin layer (film), after heating the laminate and the polyolefin resin layer to a temperature of 120 to 220 ° C. with a heating drum or an electric heater, respectively, a metal roll and a rubber roll Lamination by laminating or laminating by laminating between metal roll and metal roll, or heating the metal roll to a temperature of 120-220 ° C. and 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) Preparation of polyolefin resin base layer A / printing layer B Propylene random copolymer (80 μm thick) by propylene random copolymer (Mitsui Chemicals Co., Ltd., propylene random copolymer F327) by T-die extrusion molding method After creating a coalesced film (polyolefin resin substrate layer A) and subjecting one side to corona treatment, a gravure printing method is used to print a wood grain pattern using a printing ink having the composition described in Table 1. A printing layer B was formed to obtain a laminate.

2) Creation of laminated body The following coating liquids 1 and 2 were prepared, and the coating film after drying any of the coating liquids on the printed layer B of the laminated body obtained in 1) by a gravure roll coating method Coating was performed so that the thickness was 1 μm, and the layer C was formed by drying for 10 seconds with a hot air dryer at 80 ° C., and a laminate P was prepared.

<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 laminated film Laminated films (I) to (V) composed of polyolefin resin layers D and E were produced using a two-type two-layer coextrusion molding machine so as to have the configuration shown in Table-2. The layer thickness ratio was layer D: layer E = 4: 1.

4) Evaluation of laminate After heat-sealing (heat-sealing) using a heat sealer, the laminate P obtained in 2) and the laminate film obtained in 3) were bonded together so that layer C and layer D would be adhered. After cooling to room temperature, the laminated film was fixed, peeled off by a method of pulling the laminated body P, and the adhesive strength was qualitatively evaluated. The results are shown in Table-3. 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 P is cut at the time of peeling. O: The laminate P is not cut, but is firmly adhered (partial cohesive failure).
Δ: Adhering but peeling relatively easily (peeling at the interface between layer C and layer D)
X: Easily peeled off at the interface between layer C and 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

Explanation of symbols

1 Polyolefin resin substrate layer A
2 Printing layer B
3 Polyurethane resin layer C
4 Polyolefin resin layer D
5 Polyolefin resin layer E
6 Primer layer

Claims (5)

A laminate having at least a polyolefin resin base layer A, a printing layer B containing a polyester polyurethane resin, and a polyurethane resin layer C mainly composed of a polycarbonate polyurethane resin in this order. The laminate according to claim 1, wherein the polyester polyurethane resin is mainly composed of a reaction product obtained by reacting isophorone diisocyanate and polycaprolactone polyol. Polyurethane resin layer C is polycarbonate polyurethane resin,
(X) From a reaction product obtained by reacting at least one selected from the group consisting of an adduct of an aliphatic diisocyanate, an adduct of an alicyclic diisocyanate and an adduct of an aromatic diisocyanate, and (Y) an isocyanurate polymer The laminate according to claim 1 or 2. 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 3, comprising a polycarbonate polyurethane resin of -150,000 as a main component. A laminate comprising at least one polyolefin resin layer provided on the polyurethane resin layer C side of the laminate according to any one of claims 1 to 4.