JP5366526B2 - Acrylic resin-based laminate film, laminate and method for producing laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic resin-based laminate film having excellently heat resistant and weather durable adhesion to a base material such as a polypropylene resin and the like, and to provide a laminate made by piling up the acrylic resin-based laminate film on a surface of the base material and a method of manufacturing the laminate. <P>SOLUTION: The acrylic resin-based laminate film is made by piling up a layer of a chlorinated polypropylene resin modified with maleic anhydride and having a chlorine content of 20 to 30 mass% on at least one surface of the acrylic resin film. The laminate is made by piling up the acrylic resin-based laminate film on the surface of the base material via the chlorinated polypropylene resin layer constructing the acrylic resin-based laminate film. The method of manufacturing the laminate includes vacuum-forming or pressure-forming the laminate and the acrylic resin-based laminate film piled up on the surface of the base material in an injection-molding mold, and then injection-molding a resin of the base material in the injection-molding mold for lamination and integration. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an acrylic resin-based laminated film, a laminate obtained from the acrylic resin-based laminated film, and a method for producing the laminate.

  As a method for imparting design properties to a molded product at a low cost, there are an insert molding method and an in-mold molding method. In the insert molding method, a decorative film or sheet of polyester resin, polycarbonate resin, acrylic resin or the like that has been decorated by printing or the like is previously molded into a three-dimensional shape by vacuum molding or the like, unnecessary portions are removed, and injection is performed. This is a method of obtaining a molded product in which a decorative film or sheet and a base material are integrated by injection molding a resin which becomes a base material after being inserted into a molding die. On the other hand, the in-mold molding method is to place a decorative film or sheet in an injection mold, perform vacuum molding in the mold, and then injection mold a resin as a base material in the same mold. Is a method for obtaining a molded product in which a decorative film or sheet and a substrate are integrated.

  Acrylic resin film excellent in various performances such as surface hardness, molding processability, heat resistance, and plasticizer whitening resistance, which can be used for insert molding or in-mold molding, contains a rubber-containing polymer and a thermoplastic polymer. Various acrylic resin films have been proposed (for example, Patent Documents 1 to 4). These acrylic resin films not only provide decorative properties to the molded product, but can also be used as an alternative material for clear coating.

  In a method for obtaining a molded product in which a decorative film or sheet and a base material are integrated by an insert molding method or an in-mold molding method, acrylic resin, ABS resin are generally used for constituting the base material. , Polycarbonate resin or a mixture thereof.

  On the other hand, when decorating the surface of an injection-molded product made of an inexpensive polyolefin-based resin, a molded product without decoration such as printing is created in advance, and primer treatment or the like is applied to the decorated part of the molded product. In most cases, a desired molded product is obtained by decorating by a hydraulic transfer method or the like. However, compared with the insert molding method or the in-mold molding method, the hydraulic transfer method has a remarkably large number of steps, and even if the material cost is reduced, the manufacturing cost is high, resulting in an increase in cost.

Adhesion with excellent heat resistance, surface gloss, scratch resistance, transparency, weather resistance, warping resistance, using insert molding method or in-mold molding method, based on inexpensive polyolefin resin Acrylic resin-based decorative molded products having excellent peeling resistance and the like have been proposed (for example, Patent Documents 5 to 7). However, these acrylic resin-based decorative molded products are exposed to heat when vacuum-decorating the decorative film, heat during injection molding of the base resin, and exposure to sunlight, etc. to the acrylic resin-based decorative molded products. Due to the influence of environmental factors such as heat, ultraviolet irradiation, and rain, the durability of the adhesion between the substrate and the decorative film is not sufficient.
JP-A-8-323934 Japanese Patent Laid-Open No. 11-147237 JP 2002-80678 A JP 2002-80679 A JP 2000-33665 A JP 2000-33677 A JP-A-11-245261

  The object of the present invention is to provide an acrylic resin-based laminated film having adhesiveness excellent in heat resistance and weather resistance durability to a substrate such as polypropylene resin, and acrylic resin-based on the surface of the substrate It is providing the laminated body on which the laminated film was laminated | stacked, and the manufacturing method of the laminated body.

  The gist of the present invention is that the acrylic resin film is laminated with a layer of chlorinated polypropylene resin modified with maleic anhydride and having a chlorine content of 20 to 30% by mass on at least one surface of the acrylic resin film. A resin-based laminated film (hereinafter referred to as “the present laminated film”) is the first invention.

  Further, the gist of the present invention is that the present laminate film is laminated on the surface of the substrate through the surface of the chlorinated polypropylene resin layer constituting the present laminate film (hereinafter referred to as “this laminate”). Is referred to as a second invention.

  Further, the gist of the present invention is that the laminated film is formed by vacuum forming or pressure forming the laminated film in an injection mold and then injecting and molding a resin as a base material in the injection mold. A method for manufacturing a body is a third invention.

  Since this laminate has adhesiveness excellent in heat resistance and weather resistance even when using a polyolefin-based resin that is difficult to adhere as a base material, a vehicle member such as an automotive interior member, an automotive exterior member, It can be used for many applications such as building materials such as building interior materials and building exterior materials, various surface decorative materials, and optical members.

  A publicly known acrylic resin film is mentioned as an acrylic resin film used for the present invention. Specific examples of acrylic resin films include insert molded products with excellent surface hardness, inexpensive decoration, molding processability, heat resistance, heat resistance plasticizer whitening, fragrance resistance, hair styling resistance, and heat aging resistance. Or JP-A-8-323934, JP-A-11-147237, JP-A-2002-80678, JP-A-2002-80679, and JP-A-2005-97351 for in-mold molded products. What is described is mentioned. Also, Japanese Patent Application Laid-Open No. 2005-163003 and Japanese Patent Application Laid-Open No. 2005-163003, which can be used for insert molding or in-mold molding, have the purpose of whitening resistance, surface hardness, heat resistance, chemical resistance, transparency, or matte properties. Examples thereof include an acrylic resin film described in JP-A-2005-139416. Furthermore, the acrylic resin film of Unexamined-Japanese-Patent No. 2008-106252 aiming at the trimming workability at the time of shaping | molding etc. is mentioned.

  The thickness of the acrylic resin film is preferably 10 to 500 μm. By setting the thickness of the acrylic resin film to 500 μm or less, rigidity suitable for insert molding and in-mold molding can be obtained, and the film tends to be stably manufactured. Moreover, it exists in the tendency which can fully provide a feeling of depth to this laminated body with the protective property of the base material used by this invention by the thickness of an acrylic resin film being 10 micrometers or more. The thickness of the acrylic resin film is more preferably 30 μm or more, and particularly preferably 50 μm or more. The thickness of the acrylic resin film is more preferably 300 μm or less, and particularly preferably 200 μm or less.

  In the present invention, the pencil hardness of the acrylic resin film is preferably 2B or more, more preferably HB or more, and particularly preferably F or more in terms of the surface hardness of the laminated film.

  In the present invention, an acrylic resin film that does not shrink as much as possible during heating is preferable.

  As the shrinkage rate of the acrylic resin film, for example, the point of suppressing the appearance defect of the molded product due to wrinkling of the laminated film when insert molding or in-mold molding is performed, or when the laminated body is manufactured or to the laminated body Heating in the MD direction (flow direction during film formation) by heat treatment for 60 minutes in an atmosphere at 130 ° C., in order to suppress poor adhesion due to delamination between the acrylic resin film and chlorinated polypropylene resin due to exposure to sunlight, etc. The shrinkage rate is preferably 50% or less, and the heat shrinkage rate in the TD direction (direction perpendicular to the MD direction) is preferably −10 to 10%. The heat shrinkage rate in the MD direction of the acrylic resin film is more preferably 30% or less, and particularly preferably 15% or less. Further, the heat shrinkage rate in the MD direction of the acrylic resin film is preferably 0% or more. The heat shrinkage rate in the TD direction of the acrylic resin film is more preferably 0 to 5%.

  In the present invention, the acrylic resin film may be a stabilizer, a lubricant, a processing aid, a plasticizer, a foaming agent, a filler, an antibacterial agent, an antifungal agent, a mold release agent, an antistatic agent, or a colorant, if necessary. , UV absorbers, light stabilizers and the like can be included.

  In the said compounding agent, in order to provide a weather resistance to an acrylic resin film, it is preferable to mix | blend a ultraviolet absorber in an acrylic resin film.

  A well-known thing can be used as a ultraviolet absorber, You may use a copolymerization type thing.

  The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. When the molecular weight of the ultraviolet absorber is 300 or more, there is a tendency to prevent mold contamination due to volatilization of the ultraviolet absorber when performing vacuum molding or pressure molding in an injection mold. In addition, the higher the molecular weight of the ultraviolet absorber, the longer the bleed out after processing into a film will occur in the long term, and the UV absorption performance tends to be sustained for a longer period than the one having a low molecular weight. Further, the molecular weight of the ultraviolet absorber is 300 or more, and the amount of the ultraviolet absorber that volatilizes tends to be small before the acrylic resin film is extruded from the T-die and cooled by the cooling roll. In addition, the film is produced after the UV absorber has a molecular weight of 300 or more and the evaporated UV absorber is recrystallized on the chain or exhaust hood on the top of the T die and grown over time. There is also a tendency for the problem of falling to a defect of the film appearance to be reduced.

  As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber having a molecular weight of 400 or more or a triazine-based ultraviolet absorber having a molecular weight of 400 or more is particularly preferable.

  Specific examples of the benzotriazole ultraviolet absorber include Tinuvin 234 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd. and Adeka Stub LA-31 (trade name) manufactured by ADEKA Corporation. Moreover, as a specific example of a triazine type ultraviolet absorber, Ciba Specialty Chemicals Co., Ltd. Tinuvin 1577 (brand name) is mentioned.

  As a compounding quantity of a ultraviolet absorber, 0.1 mass part or more is preferable with respect to 100 mass parts of raw material resin of an acrylic resin film at a weather resistance point, 0.5 mass part or more is more preferable, 1 mass part or more Is particularly preferred. In addition, the blending amount of the ultraviolet absorber is preferably 10 parts by mass or less with respect to 100 parts by mass of the raw resin of the acrylic resin film in terms of roll dirt during film formation, chemical resistance and transparency of the acrylic resin film. 5 mass parts or less are more preferable, and 3 mass parts or less are especially preferable.

  In the present invention, known light stabilizers can be used, and hindered amine light stabilizers are preferred from the viewpoint of durability.

  The blending amount of the hindered amine light stabilizer is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the raw resin of the acrylic resin film, in terms of light resistance. 2 parts by mass or more is particularly preferable. Moreover, as a compounding quantity of a hindered amine type light stabilizer, 5 mass parts or less are preferable with respect to 100 mass parts of raw material resin of an acrylic resin film at the point of the roll dirt at the time of film forming, and 2 mass parts or less are more preferable, 1 part by mass or less is particularly preferable.

  As a method of blending the compounding agent in the acrylic resin film, a method of supplying the raw material resin of the acrylic resin film together with the raw material resin of the acrylic resin film and a method of blending the compounding agent into the raw material resin of the acrylic resin film. Examples of the method include kneading and mixing with various kneaders. Examples of the kneader used in the latter method include a single screw extruder, a twin screw extruder, a Banbury mixer, and a roll kneader.

  Examples of the method for producing the acrylic resin film include known methods such as a melt casting method such as a melt casting method, a T-die method, and an inflation method, and a calendar method. Of these, the T-die method is preferable in terms of economy.

  When producing an acrylic resin film by the T-die method, it is preferable to use a method in which a film is formed by being sandwiched between a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts. By this method, it is possible to improve the surface smoothness of the obtained laminated film, and to suppress defects when laminating the chlorinated polyolefin resin on the acrylic resin film or printing omission when printing on the acrylic resin film. It is in.

  Examples of the metal roll include a metal mirror touch roll, a metal sleeve (metal thin-film pipe) described in Japanese Patent No. 2,808,251 or International Publication No. 97 / 28,950, and a molding roll. Examples thereof include a roll used in a sleeve touch system composed of a roll.

  Examples of the non-metallic roll include a touch roll made of silicon rubber.

  Examples of the metal belt include a metal endless belt.

  These metal rolls, non-metal rolls and metal belts can be used in combination.

  In a method of forming a film by sandwiching a plurality of rolls or belts selected from metal rolls, non-metal rolls and metal belts, the raw material resin of the acrylic resin film after melt extrusion is substantially a bank (resin pool). It is preferable to form a film by holding the film in a non-existent state and performing surface transfer without substantially rolling. When the film is formed without forming a bank, since the raw resin of the acrylic resin film in the cooling process is surface-transferred without being rolled, the resulting acrylic resin film can reduce the heat shrinkage rate. There is a tendency.

  Further, when melt extrusion is performed by the T-die method or the like, it is preferable to extrude while filtering the raw material resin of the acrylic resin film in a molten state with a screen mesh of 200 mesh or more.

  The chlorinated polypropylene resin used in the present invention is modified with maleic anhydride, and the chlorine content in the chlorinated polypropylene resin is 20 to 30% by mass or less.

  By modifying the chlorinated polypropylene resin with maleic anhydride, a result of excellent adhesion durability between the base material and the acrylic resin film is obtained in the weather resistance exposure test of the laminate obtained by insert molding or in-mold molding, preferable.

  The amount of maleic anhydride modified in the chlorinated polypropylene resin is preferably 5% by mass or less, and more preferably 3% by mass or less. By setting the modified amount of maleic anhydride to 5% by mass or less, when a layer of chlorinated polypropylene resin is laminated on the acrylic resin film, the storage stability of the solvent solution of chlorinated polypropylene resin, which will be described later, is improved, and chlorine It is preferable because it is excellent in the coating workability of the solvent solution of the fluorinated polypropylene resin.

  Adhesion is good when the chlorine content of the chlorinated polypropylene resin is 20% by mass or more. Further, the chlorine content of the chlorinated polypropylene resin is 30% by mass or less, preferably 25% by mass or less, such as heat at the time of molding to obtain the laminate, heat due to exposure to sunlight, ultraviolet irradiation, rain, etc. A laminate having a good appearance with excellent smoothness can be obtained even under the influence of environmental factors.

  In the present invention, the melting point of the chlorinated polypropylene resin is preferably 80 ° C. or higher. By setting the melting point of the chlorinated polypropylene resin to 80 ° C. or higher, blocking failure between the films when the laminated film is wound up and stored in a roll shape tends to be suppressed.

  In the present invention, the mass average molecular weight (hereinafter referred to as “Mw”) of the chlorinated polypropylene resin is preferably 50,000 or less. By setting the Mw of the chlorinated polypropylene resin to 50,000 or less, the viscosity of the solvent solution of the chlorinated polypropylene resin can be designed to be low when laminating the chlorinated polypropylene resin layer on the acrylic resin film. Thus, the coating workability tends to be excellent.

  Examples of the chlorinated polypropylene resins modified with maleic anhydride include, for example, hardene CY-9122P, hardlen CY-9124P, hardlen HM-21P, hardlen M-28P, hardlen F-2P and hardlen F-6P (all Toyo Kasei Kogyo Co., Ltd., trade name).

  Examples of the method for laminating the chlorinated polypropylene resin layer on the acrylic resin film include a printing method and a coating method. When laminating a layer of chlorinated polypropylene resin by these methods, it can be produced by the following method as a specific example.

  First, a paint is prepared by dissolving or dispersing a chlorinated polypropylene resin in a solvent. Next, the obtained coating film is applied on at least one surface of the acrylic resin film, and further dried by heating to remove the solvent, thereby obtaining the present laminated film.

  The above method is preferable for improving the initial adhesion between the chlorinated polypropylene resin and the acrylic resin film.

  Examples of the printing method include a gravure printing method, a screen printing method, and an offset printing method.

  Examples of the coating method include a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a gravure reverse coating method, a kiss reverse coating method, a micro gravure coating method, a roll coating method, a blade coating method, Examples thereof include a rod coating method, a roll doctor coating method, an air knife coating method, a comma roll coating method, a reverse roll coating method, a transfer roll coating method, a kiss roll coating method, a curtain coating method, and a dipping coating method.

  Although the thickness of the layer of the chlorinated polypropylene resin in this laminated film can be appropriately selected according to the purpose, it is usually about 1 to 100 μm.

  Examples of the solvent used above include alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, and ethylene glycol; aromatic solvents such as xylene, toluene, and benzene; aliphatic hydrocarbon solvents such as hexane and pentane; Halogenated hydrocarbon solvents such as chloroform and carbon tetrachloride; phenol solvents such as phenol and cresol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone; diethyl ether, methoxytoluene and 1,2-dimethoxyethane Ether solvents such as 1,2-dibutoxyethane, 1,1-dimethoxymethane, 1,1-dimethoxyethane, 1,4-dioxane and tetrahydrofuran (THF); fatty acid solvents such as formic acid, acetic acid and propionic acid An acid such as acetic anhydride Water-based solvents; ester solvents such as ethyl acetate, n-propyl acetate, butyl acetate, and butyl formate; nitrogen-containing solvents such as ethylamine, toluidine, dimethylformamide, and dimethylacetamide; sulfur-containing solvents such as thiophene and dimethyl sulfoxide; Diacetone alcohol, 2-methoxyethanol (methyl cellosolve), 2-ethoxyethanol (ethyl cellosolve), 2-butoxyethanol (butyl cellosolve), diethylene glycol, 2-aminoethanol, acetocyanohydrin, diethanolamine, morpholine, 1-acetoxy-2- Examples thereof include a solvent having two or more functional groups such as ethoxyethane and 2-acetoxy-1-methoxypropane, and water. These can be used alone or in combination of two or more.

  In the present invention, the chlorinated polypropylene resin has a solution such as an anti-skinning agent, a thickening agent, an anti-settling agent, an anti-sagging agent, an antifoaming agent, and a leveling agent depending on the printability or coatability as a paint. Known additives for improving properties and known additives for improving coating film performance such as extender pigments, light stabilizers, ultraviolet absorbers, antioxidants, antibacterial agents, fungicides, flame retardants, etc. Can be added.

  A pattern layer can be formed on the laminate film in order to impart design properties to the laminate.

  When a pattern layer is formed on the laminated film, the pattern is protected on the surface of the chlorinated polypropylene resin of the laminated film in terms of protecting the pattern layer, imparting a high-class feeling to the laminate, and adhesion to the substrate. It is preferable to form a layer.

  Examples of the method for forming the picture layer include a printing method, a vapor deposition method, and a method in which the printing method and the vapor deposition method are combined.

  Examples of the pattern by the printing method include wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, and a solid solid pattern.

  Examples of the paint for forming a picture include ink containing a binder, a pigment or a dye, and a solvent.

  Examples of the binder include polyvinyl resins such as vinyl chloride-vinyl acetate copolymer, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, and cellulose. Examples include ester resins, alkyd resins, and chlorinated polyolefin resins.

  Examples of the pigment include a yellow pigment, a red pigment, a blue pigment, a black pigment, and a white pigment.

  Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as yellow lead.

  Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals.

  Examples of the blue pigment include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue.

  Examples of the black pigment include organic pigments such as aniline black.

  Examples of the white pigment include inorganic pigments such as titanium dioxide.

  Moreover, a well-known dye can be used as said dye.

  As a solvent, the thing similar to the solvent used when laminating | stacking the layer of chlorinated polypropylene resin on an acrylic resin film is mentioned.

  Examples of the method for printing a pattern include an offset printing method, a gravure rotary printing method, a screen printing method, a roll coating method, a spray coating method, and a flexographic printing method.

  The thickness of the pattern layer by the printing method may be appropriately determined as necessary, and is usually about 0.5 to 30 μm.

The number of missing prints in the pattern layer by the printing method is preferably 10 pieces / m ² or less, more preferably 5 pieces / m ² or less, and particularly preferably 1 piece / m ² or less in terms of design and decoration. preferable. By setting the number of printing omissions to 10 / m ² or less, the appearance of the laminate tends to be better.

  The pattern layer by vapor deposition is formed of at least one metal such as aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, or an alloy thereof or a metal compound thereof. The

  The thickness of the pattern layer by the vapor deposition method can be appropriately determined as necessary.

  Examples of the method for forming the picture layer by the vapor deposition method include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method.

  In this invention, it can be set as the laminated body mentioned later by laminating | stacking a base material on this laminated film.

  Examples of the base material include acrylic resin; ABS resin (acrylonitrile-butadiene-styrene copolymer); AS resin (acrylonitrile-styrene copolymer); vinyl chloride resin; polyolefin such as polyethylene, polypropylene, polybutene, and polymethylpentene. -Based resin; ethylene-vinyl acetate copolymer or saponified product thereof; polyolefin-based copolymer such as ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Polyester resins such as polyarylate and polycarbonate; Polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon and 12-nylon; Polystyrene resins; Cellulose acetate; Fibrin derivatives such as cellulose; fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer; and two or more kinds of copolymers selected from these, mixtures, A composite or a laminated body is mentioned.

  Among these, as the base material, a polypropylene resin is preferable from the viewpoints of low cost, versatility, versatility of application, and application effect of the present laminated film.

  Specific examples of the polypropylene resin include Novatec OX-1042, Novatec NX-1045, and Novatec NX-1060 (all manufactured by Nippon Polypro Co., Ltd., trade names).

  In the present invention, in the base material, if necessary, for example, a stabilizer, an antioxidant, a lubricant, a processing aid, a plasticizer, an impact agent, a foaming agent, a filler, an antibacterial agent, and an antifungal agent. Compounding agents such as a release agent, an antistatic agent, a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a flame retardant can be blended.

  Further, in the present invention, the shrinkage rate of the base material after the injection molding can be reduced by eliminating the problems such as warpage of the laminate obtained by in-mold molding, insert molding, etc. or peeling of the film or sheet. It is preferable to approximate the shrinkage rate.

  Examples of the method for adjusting the shrinkage rate of the substrate include a method of blending a filler and an elastomer component in the substrate.

  Examples of the filler include talc, calcium carbonate, silica, mica, glass fiber, and carbon fiber.

  This laminated body is obtained by laminating the laminated film on the surface of the base material through the surface of the layer of chlorinated polypropylene resin constituting the laminated film.

  Applications of this laminate include, for example, automotive interior parts such as instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards, weather strips, bumpers, bumper guards, Automotive exterior components such as side mudguards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows, headlamp covers, tail lamp covers, windshield parts Various front panels for AV equipment, etc .; surface decorative materials such as buttons and emblems; various parts such as mobile phone housings, display windows and buttons; furniture exterior materials; Architectural interior materials such as surfaces, ceilings, floors; exterior walls such as siding, fences, roofs, gates, windbreak boards, etc .; surface decorative materials for furniture such as window frames, doors, handrails, sills, and duck Optical members such as various displays, lenses, mirrors, goggles, and window glass; members for interior and exterior of various vehicles other than automobiles such as trains, airplanes, and ships; and various packaging containers such as bottles, cosmetic containers, accessory cases, and packaging materials It can be suitably used for various other uses such as miscellaneous goods such as prizes and accessories.

  As a manufacturing method of this laminated body, the thermal lamination method is mentioned in the case of the laminated body of a two-dimensional shape, for example.

  Moreover, in the case of a three-dimensional laminated body, for example, an insert molding method and an in-mold molding method can be mentioned. Among these, the in-mold molding method is preferable from the viewpoint of workability and economy because the film molding and injection molding can be performed in one step.

  The heating temperature at the time of in-mold molding may be set as appropriate depending on the thermal properties of the film or the shape of the laminate, but is preferably at or above the temperature at which the laminate film softens. Specifically, the heating temperature during in-mold molding is usually 70 ° C. or higher.

  Moreover, the heating temperature at the time of in-mold molding is usually 170 ° C. or less in terms of surface appearance and releasability.

  Furthermore, the preheating temperature at the time of vacuum forming is preferably 135 ° C. or less from the viewpoint of energy efficiency. Moreover, when this laminated film can be shape | molded even if preheating temperature is low, instead of making preheating temperature low, preheating time can also be shortened. In this case, high-cycle vacuum forming is possible, and industrial utility value is high.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” in the examples represent “part by mass” and “% by mass”, respectively. However, “%” regarding the heat shrinkage rate, the injection speed, and the injection pressure is not limited to this. Abbreviations in the examples are as shown in Table 1.

In the following, the glass transition temperature (hereinafter referred to as “Tg”) and the mass average particle diameter of the obtained rubber-containing polymer, the reduced viscosity of the thermoplastic polymer used, the heat shrinkage rate and the pencil hardness of the acrylic resin film are obtained. The thickness of the chlorinated polypropylene resin layer in the acrylic resin-based laminated film, the initial adhesion of the resulting laminate, and the adhesion after the weathering exposure test were evaluated by the following methods.
(1) Tg of rubber-containing polymer
The Tg of the rubber-containing polymer was calculated from the FOX equation using the values described in Polymer Handbook [Polymer Handbook Third Edition (J. Brandrup, Wiley-Interscience, 1989)].
(2) Mass average particle diameter of rubber-containing polymer Rubber-containing polymer latex is used by a dynamic light scattering method using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd. The mass average particle size of the coalesced was measured.
(3) Reduced viscosity of thermoplastic polymer 0.1 g of the thermoplastic polymer was dissolved in 100 mL of chloroform, and the reduced viscosity was measured at 25 ° C.
(4) Heat shrinkage rate of acrylic resin film On the surface of the test piece of acrylic resin film cut out to A4 size, three parallel straight lines are drawn at intervals of 5 cm in the MD direction and TD direction, and the interval is calipered. Accurately measured. The measurement of the distance between the parallel straight lines was performed at two locations, and the measured locations were marked. Next, the test piece was left in an atmosphere of 130 ° C. for 60 minutes and then cooled to room temperature. The interval of the same part as the previously measured part of this test piece was measured once more. Using the average value of the distance between two parallel straight lines, the heat shrinkage rate was calculated by the following equation.

Heat shrinkage rate (%) = ((interval before heating−interval after heating) / interval before heating) × 100
In addition, in the acrylic resin film in which MD direction and TD direction are unknown, in order to specify MD direction and TD direction, it carries out as follows, for example.

Draw a circle with a specific radius on the film, heat-treat under the above conditions, determine the direction in which the shrinkage rate is maximized from the shape of the circle (or ellipse if there is anisotropy) on the obtained film, The direction is the MD direction, and the direction perpendicular to the direction is the TD direction.
(5) Pencil hardness of acrylic resin film The pencil hardness of the acrylic resin film was measured according to JIS K5600.
(6) Thickness of layer of chlorinated polypropylene resin in acrylic resin-based laminated film A sample obtained by cutting the acrylic resin-based laminated film to a thickness of 70 nm in the cross-sectional direction was used as a transmission electron microscope (J100S, manufactured by JEOL Ltd.). Product name)), the thickness of the layer of the chlorinated polypropylene resin was measured at five locations, and the average value thereof was taken as the thickness of the layer of the chlorinated polypropylene resin.
(7) Initial adhesion of laminated body According to JIS K5600, the surface of the laminated body is cut until the depth reaches the substrate, the adhesion is measured, and the peeled state of the crosscut portion is observed, and the following is observed. Evaluated by criteria.
○: No peeling (remaining number of crosscut portions; 25/25)
Δ: Partially peeled (remaining number of crosscut portions; 1 to 24/25)
X: All peeled (remaining number of crosscut portions; 0/25)
(8) Adhesion after weathering exposure test of laminate Super accelerated exposure test (Isuper UV tester, manufactured by Iwasaki Electric Co., Ltd., trade name “eye super UV tester SUV-F1”, illuminance: 100 mw / □, exposure temperature: 63 ° C, exposure time: 200 hours) After using the laminate, in accordance with JIS K5600, cut the surface of the laminate until the depth reaches the base material, measure the adhesion, and peel off the crosscut part. The state was observed and evaluated according to the following criteria.
○: No peeling (remaining number of crosscut portions; 25/25)
Δ: Partially peeled (remaining number of crosscut portions; 1 to 24/25)
X: All peeled (remaining number of crosscut portions; 0/25)
[Example 1]
(Production of rubber-containing polymer)
After charging 10.8 parts deionized water into a vessel equipped with a stirrer, 0.3 parts MMA, 4.5 parts n-BA, 0.2 parts 1,3-BD, 0.05 parts AMA and 0.025 parts CHP are mixed. The monomer mixture (1) was added and stirred and mixed at room temperature. Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Industry Co., Ltd., trade name “Phosphanol RS610NA”) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  In a polymerization vessel equipped with a condenser, 139.2 parts of deionized water was added and the temperature was raised to 75 ° C. Thereafter, a mixture prepared by adding 0.20 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate and 0.0003 part of EDTA to 5 parts of deionized water was charged into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the monomer mixture (1). A polymer latex was obtained. The Tg of the first stage polymer was -48 ° C.

  Subsequently, a monomer mixture (2) obtained by mixing 9.6 parts of MMA, 14.4 parts of n-BA, 1.0 part of 1,3-BD, 0.25 part of AMA and 0.016 part of CHP was added to the first stage over 90 minutes. After dropping into the polymerization vessel containing the polymer latex, the reaction is continued for 60 minutes to complete the polymerization of the monomer mixture (2) to obtain the first-stage polymer and the second-stage polymer latex. It was. The Tg of the polymer obtained by the polymerization of the monomer mixture (2) was −10 ° C.

  A monomer mixture (3) of 6 parts of MMA, 4 parts of MA, 0.075 part of AMA and 0.0125 part of CHP was dropped into the polymerization vessel containing the latex of the first stage polymer and the second stage polymer over 45 minutes. Thereafter, the reaction was continued for 60 minutes to complete the polymerization, and latexes of the first-stage polymer to the third-stage polymer were obtained. The Tg of the polymer obtained by the polymerization of the monomer mixture (3) was 60 ° C.

  Subsequently, the monomer mixture (4) of 57 parts of MMA, 3 parts of MA, 0.264 part of n-OM and 0.075 part of t-BH was charged with latex of the first stage polymer to the third stage polymer over 140 minutes. After dripping in the polymerization vessel, the reaction was continued for 60 minutes to complete the polymerization of the monomer mixture (4) to obtain a rubber-containing polymer latex. The polymer obtained by the polymerization of the monomer mixture (4) had a Tg of 99 ° C. The mass average particle size of the rubber-containing polymer was 0.11 μm.

  The latex of the rubber-containing polymer obtained was filtered using a vibration type filtration device equipped with a SUS mesh (average opening 62 μm) as a filter medium, and then salted out in an aqueous solution containing 3.5 parts of calcium acetate. The polymer was washed with water, collected, and dried to obtain a powdery rubber-containing polymer.

Further, 214.3 g of the obtained powdery rubber-containing polymer was put into 1,500 mL of acetone filtered through a nylon mesh having an opening of 25 μm, and stirred for 3 hours to obtain an acetone dispersion of the rubber-containing polymer. Prepared. Subsequently, this dispersion was filtered through a nylon mesh having a mesh size of 32 μm, and then the nylon mesh was ultrasonically washed in chloroform for 15 minutes to wash the captured matter on the mesh with chloroform. After that, the captured substance after ultrasonic cleaning is put together with the nylon mesh into a container containing 150 mL of acetone filtered through a nylon mesh having a mesh size of 25 μm, and the contents of the container are subjected to ultrasonic treatment for 15 minutes, and then nylon. The mesh was removed, and 150 mL of an acetone dispersion of the trapped material on the mesh was prepared. Next, with respect to 70 mL of this dispersion, the number of particles having a diameter of 55 μm or more was determined at 25 ° C. with an automatic liquid particle counter (model: KL-01) manufactured by Rion Co., Ltd. It was.
(Manufacture of acrylic resin film)
To 75 parts of the rubber-containing polymer obtained above, MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g) as a thermoplastic polymer 25 Parts and compounding agents: Ciba Specialty Chemicals Co., Ltd., Tinuvin 234 (trade name) 1.4 parts, ADEKA Co., Ltd. Adeka Stub AO-50 (trade name) 0.1 part, and ADEKA Co., Ltd. Adeka Stub LA-67 (Product name) After adding 0.3 part, it mixed using the Henschel mixer. The obtained mixture was supplied to a degassing extruder (Ikegai Iron Works Co., Ltd., PCM-30 (trade name)) heated to 230 ° C., kneaded, and extruded while removing foreign matter with a 300 mesh screen mesh. A pellet was obtained.

  The obtained pellets were dried at 80 ° C. all day and night, and the pellets were cylinder temperature of 180 to 240 ° C. using a 40 mm diameter non-vent screw extruder (L / D = 26) equipped with a 300 mm wide T-die. The sample was extruded while removing foreign matter with a 500 mesh screen mesh under the conditions of a T die temperature of 240 ° C. and a slit width of the T die of 0.3 mm. The obtained acrylic resin film in a molten state is passed between two metal cooling rolls, the resin is sandwiched without a bank (resin pool), and after surface transfer without rolling, this is taken up by a winder An acrylic resin film having a thickness of 125 μm was obtained by winding it in a paper roll.

The heat shrinkage rate of the obtained acrylic resin film was 7% in the MD direction and 2% in the TD direction. The pencil hardness of the acrylic resin film was H.
(Manufacture of acrylic resin-based laminated film (I))
Chlorinated polypropylene resin having a chlorine content of 21%, a melting point of 87 ° C., Mw of 45,000, and a maleic anhydride modification amount of 1.6% (trade name “Hardren HM-21P” manufactured by Toyo Kasei Kogyo Co., Ltd.) 20% And a paint with a viscosity of 20 cps containing 80% toluene.

  Subsequently, after apply | coating said coating material on the single side | surface of the acrylic resin film obtained above, the solvent was removed in 85 degreeC atmosphere, and the acrylic resin-type laminated | multilayer film (I) was obtained. The thickness of the chlorinated polypropylene resin layer was 5 μm.

When the acrylic resin-based laminated film (I) was wound and stored in a paper tube in a roll shape, no blocking phenomenon was observed between the films.
(Manufacture of laminate (A))
It has a vacuuming function and is a box shape with a shape of 150 mm in length × 120 mm in width × 10 mm in depth and 2 mm in resin injection thickness, with one gate position at the center of the mold and one position at 40 mm above and below the center gate. Using a die that is a pinpoint gate with a gate shape of 1 mm in diameter, using a J85ELII type injection molding machine (trade name) manufactured by Nippon Steel Works and a hot pack system manufactured by Nissha Printing Co., Ltd. The in-mold molding shown below was performed with an in-mold molding apparatus combining (trade name).

  The vacuum forming of the acrylic resin-based laminated film is performed under the conditions of a heater set temperature of about 330 ° C., a heating time of 12 seconds and a heater-film distance of 15 mm, and the acrylic resin-based laminated film is in contact with the mold. Placed and vacuum formed.

Further, the injection molding carried out in the same mold is performed under the conditions of a cylinder temperature of 220 ° C., an injection speed of 27%, an injection pressure of 17% and a mold temperature of 70 ° C. A polypropylene resin (manufactured by Nippon Polypro Co., Ltd., trade name “Novatech NX-1045”) was injected to obtain a laminate (A). Table 2 shows the evaluation results of the initial adhesion and the adhesion after the weathering exposure test of the obtained laminate (A).
[Example 2]
Chlorinated polypropylene resin having a chlorine content of 20%, a melting point of 72 ° C., Mw of 75,000 and a modified amount of maleic anhydride (1.6% by mass) (trade name “Hardren F-2P” manufactured by Toyo Kasei Kogyo Co., Ltd.) ) Was used to prepare a paint having a viscosity of 60 cps. Other than that was carried out similarly to Example 1, and obtained the acrylic resin-type laminated | multilayer film (b) and the laminated body (B). Table 2 shows the evaluation results of the initial adhesion and adhesion after the weather resistance exposure test of the obtained laminate (B).

In addition, when the acrylic resin-based laminated film (b) was wound and stored in a paper tube in a roll shape, a slight blocking phenomenon was confirmed between the films.
[Comparative Example 1]
A laminate in which the same substrate as in Example 1 is directly laminated on the same acrylic resin film as in Example 1 under the same in-mold molding conditions as in Example 1 without using the acrylic resin-based laminated film (I) (C ′) was obtained. Table 2 shows the evaluation results of the initial adhesion and the adhesion after the weathering exposure test of the obtained laminate.
[Comparative Example 2]
Using chlorine content 27%, melting point 80 ° C., Mw 42,000 and chlorinated polypropylene resin not modified with maleic anhydride (manufactured by Toyo Kasei Kogyo Co., Ltd., trade name “Hardlen 14-WL-P”) A paint having a viscosity of 20 cps was prepared. Other than that was carried out similarly to Example 1, and obtained the acrylic resin-type laminated | multilayer film (c) and the laminated body (D '). Table 2 shows the evaluation results of the initial adhesion and the adhesion after the weathering exposure test of the obtained laminate.

Claims (4)

At least on one of the surfaces, an acrylic resin-based laminate layer of chlorinated polypropylene resin modified with maleic anhydride is a laminated film of an acrylic resin film.   The laminated body by which the acrylic resin-type laminated film of Claim 1 was laminated | stacked on the surface of the base material through the surface of the layer of the chlorinated polypropylene resin which comprises an acrylic resin-type laminated film.   The laminate according to claim 2, wherein the resin used as the substrate is a polyolefin resin. The acrylic resin-based laminated film according to claim 1 is placed in an injection mold, and a resin serving as a base material is injection-molded into the surface of the chlorinated polypropylene resin layer and laminated and integrated. The manufacturing method of the laminated body of Claim 2 or 3.