JP2013063537A - Vinylidene fluoride resin laminated film, vinylidene fluoride resin decorative laminated film, laminated sheet, laminated body, sheet-like article for decoration material, and molded body for vehicle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinylidene fluoride resin laminated film, a vinylidene fluoride resin decorative laminated film, a laminated sheet, a laminated body, a sheet-like article for decoration material, and a molded body for vehicle having good appearance and good matte property and being excellent in solvent resistance.SOLUTION: A vinylidene fluoride resin laminated film can be obtained by laminating a vinylidene fluoride resin layer (α) which contains 100 mass% of vinylidene fluoride resin (A) and 1 to 30 mass% of organic matting agent (B) and in which the refractive index Nof the vinylidene fluoride resin (A) at 23°C and the refractive index Nof the organic matting agent (B) at 23°C satisfy a following formula (X) and an acrylic resin layer (β). |N-N|≤0.15...(X).

Description

  The present invention relates to a vinylidene fluoride resin laminated film, a vinylidene fluoride resin decorated laminated film, a laminated sheet, a laminated body, a laminated sheet material for a decorative material, and a molded article for a vehicle.

  Fluorine films obtained from fluorine-containing resins such as vinylidene fluoride resins have excellent weather resistance, solvent resistance, and contamination resistance, so various substrates such as plastic, glass, slate, rubber, metal plate, wood board, etc. Widely used as a protective film laminated on the surface.

  In addition, substrates whose surfaces are protected with a fluorine film are used in many applications such as interior materials, exterior materials, and furniture for buildings.

  In such a situation, in recent years, particularly in applications such as wallpaper and leather furniture used indoors, there has been an increasing demand for image enhancement, and the use of materials laminated with a matte film has increased.

  As a method for producing this matte film, for example, (1) a method of imparting fine irregularities to the film surface with a metal or rubber mat roll whose surface has been roughened during thermoforming, (2) sand or A method of applying fine irregularities by spraying fine particles such as metal on the film surface (sand blasting method), (3) a method of coating a matting coating on the surface of the film, and (4) a matting agent dispersed in the film The method of making it known is known.

  However, in the mat matting method (1) using the mat roll, there is a problem that the mat roll is easily clogged by an additive such as an ultraviolet absorber added to the fluororesin. There is a problem that it is difficult to obtain a matte film.

  In the sandblasting method (2), there is a problem that the film is stretched or broken during sandblasting when applied to a thin and soft film.

  Furthermore, in the method (3) of coating the matting coating, the matting coating is not easy to coat on the surface of the fluororesin because the matting coating is non-adhesive (non-adhesive) to the fluororesin. There is a problem.

  In order to solve these problems, as a method (4) for dispersing a matting agent in a film, for example, Patent Document 1 proposes a matting fluorine film in which an inorganic matting agent is dispersed in a fluorine film. ing.

  However, in the matte fluorine film disclosed in Patent Document 1, decomposition of the resin is accelerated by the presence of an inorganic matting agent during melt extrusion, and foaming and coloring problems of the resulting film may occur.

JP 2002-80674 A

  The present invention provides a vinylidene fluoride-based resin laminated film, a vinylidene fluoride-based resin-decorated laminated film, a laminated sheet, a laminate, and a cosmetic material that have a good appearance and good matting properties and are excellent in solvent resistance. An object of the present invention is to provide a laminated sheet material for a vehicle and a molded article for a vehicle.

The gist of the present invention includes 100 parts by mass of vinylidene fluoride resin (A) and 1 to 30 parts by mass of an organic matting agent (B), and the refractive index of vinylidene fluoride resin (A) at 23 ° C. N _a and organic matting agents in 23 ° C. and a refractive index N _B and the vinylidene fluoride resin layer satisfying the following formula (X) (b) and the acrylic resin layer (B) (ii) are laminated The vinylidene fluoride-based resin laminated film (hereinafter referred to as “laminated film (F1)”) obtained in this way is the first invention.

| N _B −N _A | ≦ 0.15 (X)
Further, the gist of the present invention is to provide a vinylidene fluoride resin-decorated laminated film (hereinafter referred to as “laminated film (F2)”) having a pattern layer (c) on at least one side of the laminated film (F1). It is set as invention of 2.

  Furthermore, the gist of the present invention is that a laminated sheet (hereinafter referred to as “laminated sheet (S1)”) in which a laminated film (F1) is laminated on the surface of the thermoplastic resin layer (d) is referred to as the third invention. To do.

  Further, the gist of the present invention is that a laminated sheet (hereinafter referred to as “laminated sheet (S2)”) in which a pattern layer (c) and then a laminated film (F1) are sequentially laminated on the surface of the thermoplastic resin layer (d). Is referred to as a fourth invention.

  Further, the gist of the present invention is a laminate in which a picture layer (c) and then a laminated film (F1) are laminated on the surface of the substrate (e) (hereinafter referred to as “the present laminate (1)”). Is a fifth invention.

  Further, the gist of the present invention is that a laminate (hereinafter referred to as “book”) in which a thermoplastic resin layer (d), a pattern layer (c) and then a laminated film (F1) are laminated on the surface of the substrate (e). The laminated body (2) ”is a sixth invention.

  Furthermore, the gist of the present invention is that the laminated sheet (F1), the laminated film (F2), the laminated sheet (S1) or the laminated sheet for decorative material using the laminated sheet (S2) is the seventh invention. To do.

  Moreover, the place made into the summary of this invention uses a laminated | multilayer film (F1), a laminated | multilayer film (F2), a laminated sheet (S1), a laminated sheet (S2), this laminated body (1), or this laminated body (2). The molded article for vehicles is the eighth invention.

  According to the present invention, it is possible to obtain a laminated film, a laminated sheet, and a laminated body having a solvent resistance and a good appearance and a matte state, so that it is used for vehicles such as automobiles, interior / exterior uses of buildings, and severe direct sunlight. Suitable for various applications such as exterior applications.

[Vinylidene fluoride resin (A)]
Examples of the vinylidene fluoride resin (A) used in the present invention include a homopolymer of vinylidene fluoride or a mixture thereof, and other vinyl compound monomers copolymerizable with vinylidene fluoride and vinylidene fluoride. Examples thereof include a copolymer or a mixture thereof and a mixture of a homopolymer of vinylidene fluoride, a copolymer of vinylidene fluoride and another vinyl monomer copolymerizable with vinylidene fluoride.

  Examples of other vinyl monomers copolymerizable with vinylidene fluoride include fluorine-containing vinyl monomers such as vinyl fluoride, tetrafluoroethylene, ethylene trifluoride chloride, and hexafluoropropylene, and styrene. , Vinyl monomers not containing fluorine, such as ethylene, butadiene, and propylene. These can be used alone or in combination of two or more.

As the vinylidene fluoride resin (A), the shear viscosity under the conditions of 220 ° C. and a shear rate of 60 sec ⁻¹ is 1, in that the resin temperature when obtaining the laminated film (F1) or the laminated film (F2) can be lowered. What is 500 Pa.s or less is preferable. In addition, the vinylidene fluoride resin (A) has a shear viscosity of 1 at 220 ° C. and a shear rate of 60 sec ⁻¹ in terms of film forming properties when obtaining a laminated film (F1) or a laminated film (F2). , 300 Pa · s or less is more preferable.

  In the present invention, the shear viscosity was measured using a twin capillary rheometer “Rosand RH-7D” manufactured by Malvern. Further, as the shear viscosity, a value obtained by performing Bagley correction after the measurement and correcting the pressure loss in the capillary portion was used.

[Organic matting agent (B)]
In the present invention, the organic matting agent (B) has a refractive index satisfying the formula (X).

  By using the organic matting agent (B) whose refractive index satisfies the formula (X), the 60 ° surface glossiness of the laminated film (F2), the laminated sheet (S1) or the laminated sheet (S2) is 60%. Good matte appearance (good delustering agent dispersibility or excessive haze increase can be prevented, and good decorative layer design without reducing design) Can be obtained.

Examples of the organic matting agent (B), those having a refractive index N _A more refractive index N _B in terms of raw material cost are preferred.

In the present invention the measurement of the refractive index N _B organic matting agent (B) was carried out in the following manner.

  First, an organic matting agent (B) was placed on a slide glass, a refractive index standard solution was dropped on the organic matting agent (B), and a cover glass was covered to prepare a sample.

Next, the sample set at 23 ° C. was observed with a microscope, and the refractive index of the refractive index standard solution in which the contour of the organic matting agent (B) was most difficult to be seen at the interface with the refractive index standard solution was measured with the organic matting agent ( refractive index of B) was _{N B.}

The measurement of the refractive index N _A vinylidene fluoride resin (A) was carried out in the following manner.

  First, the vinylidene fluoride resin (A) was heated and pressed at 200 ° C. and 5 MPa, and then cooled to obtain a test piece having a thickness of 0.5 mm.

Then, the resulting test pieces and 23 ° C., the refractive index was determined in accordance with the test method of JIS K7142, and the refractive index N _A vinylidene fluoride resin (A).

  The organic matting agent (B) used in the present invention uses an organic compound, and may be either a crosslinked matting agent or a non-crosslinked matting agent.

  As the organic matting agent (B), a crosslinked matting agent is preferable from the viewpoint of a good matte appearance of the laminated film (F1).

  Examples of crosslinked matting agents include crosslinked styrene polymers, crosslinked acrylic polymers, crosslinked acrylic-styrene copolymers, benzoguanamine / melamine / formaldehyde condensates, crosslinked polyurethane polymers, silica and acrylic polymers. And a composite of silicone rubber and silicone rubber and silicone resin.

  The mass average particle diameter of the organic matting agent (B) is preferably 0.8 to 20 μm.

  By setting the mass average particle size of the organic matting agent (B) to 0.8 μm or more, the laminated film (F1), the laminated film (F2), and the laminated film can be added with an appropriate amount of the organic matting agent (B). It exists in the tendency which can give favorable matte property to a sheet | seat (S1) and a lamination sheet (S2). Moreover, the impact resistance of a laminated film (F1), a laminated film (F2), a laminated sheet (S1), and a laminated sheet (S2) is made by setting the mass average particle diameter of the organic matting agent (B) to 20 μm or less. It tends to be possible to reduce physical property degradation such as.

  In the present invention, the mass average particle diameter of the organic matting agent (B) was measured using a laser diffraction / scattering particle size distribution measuring device (trade name: LA-910, manufactured by Horiba, Ltd.). .

[Vinylidene fluoride resin layer (I)]
The vinylidene fluoride resin layer (A) used in the present invention is one of the components of the laminated film (F1) described later.

  The vinylidene fluoride resin layer (I) contains 100 parts by mass of the vinylidene fluoride resin (A) and 1 to 30 parts by mass of the organic matting agent (B).

  By setting the content of the organic matting agent (B) to 1 part by mass or more, the matte properties of the laminated film (F1), the laminated film (F2), the laminated sheet (S1) and the laminated sheet (S2) are good. can do.

  Further, the content of the organic matting agent (B) is preferably 3 parts by mass or more. By setting the content of the organic matting agent (B) to 3 parts by mass or more, the 60 ° surface glossiness of the laminated film (F1), the laminated film (F2), the laminated sheet (S1) and the laminated sheet (S2) can be increased. It can be made low and it exists in the tendency which can give the high-class feeling of a laminated film (F1), a laminated film (F2), a laminated sheet (S1), and a laminated sheet (S2). In general, the 60 ° surface glossiness that expresses a high-class feeling is 60% or less.

  The 60 ° surface glossiness of the laminated film (F1), the laminated film (F2), the laminated sheet (S1), and the laminated sheet (S2) is dispersed in the vinylidene fluoride resin layer (a). It can also be appropriately controlled by controlling the particle size of the eraser (B) and the thickness of the vinylidene fluoride resin layer (a).

  Moreover, the solvent resistance of the laminated film (F1), the laminated film (F2), the laminated sheet (S1) and the laminated sheet (S2) is reduced by setting the content of the organic matting agent (B) to 30 parts by mass or less. Can be good. Furthermore, the content of the organic matting agent (B) is preferably 15 parts by mass or less from the viewpoint of cost effectiveness.

  In the present invention, an inorganic matting agent other than the organic matting agent (B) such as an inorganic matting agent may be blended in the vinylidene fluoride resin layer (a) as necessary. it can.

  Examples of the inorganic matting agent include alumina, sodium oxide, calcium carbonate, magnesium oxide, zinc oxide, cobalt oxide, asbestos, positively charged inorganic filler, titanium oxide, silica, aluminosilicate, and crystalline quartz.

  Further, in the present invention, an antioxidant, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, a filler, a processing aid, an anti-resistant agent in the vinylidene fluoride resin layer (a) as necessary. Various additives such as an impact aid, an antibacterial agent, an antifungal agent, a foaming agent, a release agent, a colorant, an ultraviolet absorber, and a thermoplastic polymer can be blended.

  Examples of the antioxidant include phenolic antioxidants, sulfur antioxidants, and phosphorus antioxidants.

  Examples of the heat stabilizer include a hindered phenol heat stabilizer, a sulfur heat stabilizer, and a hydrazine heat stabilizer.

  Examples of the plasticizer include phthalic acid esters, phosphoric acid esters, fatty acid esters, aliphatic dibasic acid esters, oxybenzoic acid esters, epoxy compounds, and polyesters.

  Examples of the lubricant include fatty acid esters, fatty acids, metal soaps, fatty acid amides, higher alcohols and paraffins.

  Examples of the antistatic agent include a cationic antistatic agent, an anionic antistatic agent, a nonionic antistatic agent, and a zwitterionic antistatic agent.

  Examples of flame retardants include brominated flame retardants, phosphorus flame retardants, chlorine flame retardants, nitrogen flame retardants, aluminum flame retardants, antimony flame retardants, magnesium flame retardants, boron flame retardants and zirconium flame retardants. Examples include flame retardants.

  Examples of the filler include calcium carbonate, barium sulfate, talc, wax, and kaolin.

  These additives can be used alone or in combination of two or more. Moreover, as a compounding quantity of these additives in vinylidene fluoride resin layer (I), 10 mass% or less is preferable.

  As a method of blending vinylidene fluoride resin (A), organic matting agent (B) and various additives as required, for example, a vinylidene fluoride resin (A) in a molding machine for obtaining a molded product, A method of supplying an organic matting agent (B) and various additives as required, and a raw material mixture containing a vinylidene fluoride resin (A), an organic matting agent (B), and various additives as required. The method of kneading | mixing with various kneaders is mentioned.

  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. In addition, in the case of melt extrusion, cores that cause printing failure or poor appearance when printing on the surface of the laminated film (F1), laminated film (F2), laminated sheet (S1), and laminated sheet (S2). In order to remove foreign substances and foreign matters, for example, it is preferable to extrude while filtering a material for forming a molten vinylidene fluoride resin layer (a) with a screen mesh of 200 mesh or more.

[Acrylic resin layer (b)]
The acrylic resin layer (b) used in the present invention is one of the components of the laminated film (F1) described later.

  Examples of the raw material for forming the acrylic resin layer (b) include an acrylic resin composition.

  Examples of the acrylic resin composition include an acrylic resin composition containing a rubber-containing polymer.

  When the laminated film (F1) needs flexibility for building materials, etc., examples of the acrylic resin composition include resins described in JP-B-62-19,309 and JP-B-63-8,983. A composition.

  In addition, when the laminated film (F1) needs to have scratch resistance, pencil hardness, heat resistance and chemical resistance for use in vehicles or the like, as an acrylic resin composition, for example, JP-A-8-323,934, Examples thereof include resin compositions described in JP-A Nos. 11-147,237, 2002-80,678, 2002-80,679, and 2005-97,351.

  Furthermore, when molding whitening resistance is required in insert molding or in-mold molding, examples of the acrylic resin composition include JP-A-2004-137,298 and JP-A-2005-163,003. Examples thereof include the resin compositions described in Kaikai 2005-139,416 and JP-A-2008-106,252.

  Examples of the acrylic resin composition suitably used for the acrylic resin layer (b) include rubber-containing multistage polymer particles containing at least a (meth) acrylic acid alkyl ester unit and a graft crossing agent unit.

  In the present invention, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”.

  Specific examples of the rubber-containing multistage polymer particles include units of an alkyl acrylate ester (S1) (hereinafter referred to as “monomer (S1)”) having an alkyl group having 1 to 8 carbon atoms and 1 to 4 carbon atoms. At least one monomer unit selected from alkyl methacrylate-containing alkyl ester (S2) (hereinafter referred to as “monomer (S2)”) units, graft crossing agent (S5) (hereinafter referred to as “monomer”) Unit (referred to as “S5)”) and other monomer (S3) (hereinafter referred to as “monomer (S3)”) having a double bond capable of copolymerization and a crosslinkable monomer S4) containing an elastic polymer (S) containing at least one selected from units (hereinafter referred to as “monomer (S4)”) and a methacrylic acid alkyl ester unit having an alkyl group having 1 to 4 carbon atoms. Hard polymer (H) Rubber-containing multistage polymer particles obtained by forming sequentially the like.

  The monomer (S1), which is a raw material for constituting the elastic polymer (S), may be either linear or branched.

  Specific examples of the monomer (S1) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and n-octyl acrylate. These can be used alone or in combination of two or more.

  As the monomer (S1), one having a low glass transition temperature (Tg) is preferable, and butyl acrylate is preferable.

  The monomer (S2), which is a raw material for constituting the elastic polymer (S), may be either linear or branched.

  Specific examples of the monomer (S2) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. These can be used alone or in combination of two or more.

  As a total amount of the monomer (S1) and the monomer (S2) in the monomer raw material for constituting the elastic polymer (S), the total amount of the monomers (S1) to (S4) is 100. 60-100 mass parts is preferable with respect to mass parts.

  In addition, (meth) acrylic acid alkyl ester of the same kind as the (meth) acrylic acid alkyl ester used in the elastic polymer (S) is used as one component of the monomer raw material for constituting the hard polymer. preferable.

  Specific examples of the monomer (S3) include acrylic acid alkyl esters having an alkyl group having 9 or more carbon atoms, acrylic acid alkoxy esters having an alkoxy group having 4 or less carbon atoms, acrylic acid esters such as cyanoethyl acrylate, and acrylamide. Acrylic acid, methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile and methacrylonitrile.

  As content of the monomer (S3) in the monomer raw material for comprising an elastic polymer (S), it is 0 with respect to 100 mass parts of total amounts of monomer (S1)-(S4). 40 parts by mass is preferred.

  Specific examples of the monomer (S4) include diethylene methacrylate alkylene glycol such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate. And polyvinylbenzene such as divinylbenzene and trivinylbenzene.

  Even when the elastic polymer (S) does not contain a monomer (S4) unit, it is possible to provide a rubber-containing multistage polymer particle that is considerably stable as long as the monomer (S5) unit is present.

  As content of the monomer (S4) in the monomer raw material for constituting the elastic polymer (S), for example, when heat resistance is strictly required, the monomers (S1) to (S4) ) To 0 to 10 parts by mass with respect to 100 parts by mass in total.

  Specific examples of the monomer (S5) include copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid allyl, methallyl or crotyl ester, triallyl cyanurate and triallyl isocyanurate.

  Of these, allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid are preferred, and allyl methacrylate is more preferred.

  In the monomer (S5), the conjugated unsaturated bond of the ester mainly reacts much faster than the allyl group, methallyl group or crotyl group, and chemically bonds.

  As content of the monomer (S5) in the monomer raw material for comprising an elastic polymer (S), it is 0. 0 with respect to 100 mass parts of total amounts of monomers (S1)-(S4). 1-5 mass parts is preferable and 0.5-2 mass parts is more preferable.

  By setting the content of the monomer (S5) to 0.1 parts by mass or more, molding whitening resistance is improved, and molding can be performed without deteriorating optical properties. Moreover, the elastic fall of an elastic polymer (S) can be suppressed by making content of a monomer (S5) into 5 mass parts or less.

  As the content of the elastic polymer (S) in the rubber-containing multistage polymer particles, the molding whitening resistance is good, and the film forming property and the toughness capable of insert molding and in-mold molding can be compatible with each other. -70 mass% is preferable, and 5-50 mass% is more preferable.

  The elastic polymer (S) in the rubber-containing multistage polymer particles may be a multistage polymer obtained by polymerization in two or more stages. When the polymerization is carried out in two or more stages, the ratio of monomer components constituting each stage may be changed.

  The hard polymer (H) constituting the rubber-containing multistage polymer particles is a component involved in properties such as moldability and mechanical properties of the rubber-containing multistage polymer particles.

  Specific examples of the hard polymer (H) include a methacrylic acid alkyl ester (H2) (hereinafter referred to as “monomer (H2)”) unit having an alkyl group having 1 to 4 carbon atoms, and a copolymer as necessary. Examples thereof include a polymer containing a unit of another monomer (H3) having a possible double bond (hereinafter referred to as “monomer (H3)”).

  Specific examples of the monomer (H2) include the same monomers as the monomer (S2). These can be used alone or in combination of two or more.

  Specific examples of the monomer (H3) include the same monomers as the monomer (S3).

As the content of the monomer (H2) in the monomer raw material for constituting the hard polymer (H),
51-100 mass parts is preferable with respect to a total of 100 mass parts of a monomer (H2) and a monomer (H3) at the surface hardness and heat resistant point of a laminated film (F1) or a laminated film (F2).

  As Tg of a hard polymer (H), 60 degreeC or more is preferable and 80 degreeC or more is more preferable at the point of the surface hardness and heat resistance of laminated film (F1) or laminated film (F2).

  The content of the hard polymer (H) in the rubber-containing multistage polymer particles is preferably 30 to 95% by mass in terms of surface hardness and heat resistance of the laminated film (F1) or laminated film (F2), and 40 to 40%. 70 mass% is more preferable.

  The rubber-containing multistage polymer particles have an elastic polymer (S) and a hard polymer (H) as basic structural units. If necessary, after the elastic polymer (S) is polymerized, the hard polymer (H) One or more intermediate polymers (M) can be formed before polymerizing.

  Specific examples of the intermediate polymer (M) include an alkyl acrylate ester (M1) (hereinafter referred to as “monomer (M1)”) unit having an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. Methacrylic acid alkyl ester (M2) (hereinafter referred to as “monomer (M2)”) unit having an alkyl group, other monomer (M3) having a copolymerizable double bond as required (hereinafter referred to as “monomer (M2)”) “Monomer (M3)” unit, optionally a crosslinkable monomer (M4) (hereinafter referred to as “monomer (M4)”) unit, and optionally a graft crossing agent (M5) ( Hereinafter, the monomer (M5) unit content is included, and the monomer (M1) unit amount has a content that monotonously decreases from the elastic polymer (S) toward the hard polymer (H). A polymer is mentioned.

  Here, the amount of the monomer (M1) unit decreases monotonously. The content of the monomer (M1) unit of the intermediate polymer (M) is the content of the monomer (S1) unit of the elastic polymer (S). The monomer and the content of the monomer (H1) unit of the hard polymer (H), and the monomer from the elastic polymer (S) toward the hard polymer (H). (M1) This means that the unit content decreases continuously or stepwise.

  In the present invention, as the rubber-containing multistage polymer particles, those having the intermediate polymer (M) are preferable from the viewpoint of the transparency of the laminated film (F1).

  Specific examples of the monomer (M1) that is a raw material for constituting the intermediate polymer (M) include the same monomers as the monomer (S1).

  Specific examples of the monomer (M2) that is a raw material for constituting the intermediate polymer (M) include the same monomers as the monomer (S2).

  Specific examples of the monomer (M3) that is a raw material for constituting the intermediate polymer (M) include the same monomers as the monomer (S3).

  Specific examples of the monomer (M4) that is a raw material for constituting the intermediate polymer (M) include the same monomers as the monomer (S4).

  Specific examples of the monomer (M5) that is a raw material for constituting the intermediate polymer (M) include the same monomers as the monomer (S5).

  In the present invention, as the intermediate polymer (M), each polymer in the rubber-containing multistage polymer particles is closely bonded, and the whitening resistance and surface hardness of the laminated film (F1) or laminated film (F2) are determined. In addition, it is preferable to contain a monomer (M5) unit in terms of achieving both good heat resistance and film-forming properties, and toughness capable of insert molding and in-mold molding.

As the content of the monomer (M1) in the monomer raw material for constituting the intermediate polymer (M),
10-90 mass% in the monomer raw material for comprising an intermediate | middle polymer (M) at the point of coexistence of the shaping | molding whitening resistance of a laminated film (F1) or a laminated film (F2), surface hardness, and heat resistance. preferable.

As the content of the monomer (M2) in the monomer raw material for constituting the intermediate polymer (M),
10-90 mass% is preferable in the monomer raw material for comprising an intermediate polymer (M) at the point of coexistence of shaping | molding whitening resistance, surface hardness, and heat resistance.

As the content of the monomer (M3) in the monomer raw material for constituting the intermediate polymer (M),
0-20 mass% is preferable in the monomer raw material for comprising an intermediate polymer (M).

As the content of the monomer (M4) in the monomer raw material for constituting the intermediate polymer (M),
In the monomer raw material for constituting the intermediate polymer (M), 0 to 10% by mass is preferable.

As the content of the monomer (M5) in the monomer raw material for constituting the intermediate polymer (M),
0.1 in the monomer raw material for constituting the intermediate polymer (M) in that the laminated film (F1) or the laminated film (F2) can be formed without deteriorating good molding whitening resistance and optical properties. -5 mass% is preferable.

  The content of the intermediate polymer (M) in the rubber-containing multistage polymer particles is preferably 0 to 35% by mass.

  The mass average particle diameter of the rubber-containing multistage polymer particles is preferably 0.08 to 0.3 μm from the viewpoint of mechanical properties and transparency of the laminated film (F1).

  Among the rubber-containing multi-stage polymer particles, the following rubber-containing multi-stage polymer particles are preferable as a polymer in view of compatibility between molding whitening resistance of the laminated film (F1) or laminated film (F2), surface hardness and heat resistance. (R).

  The rubber-containing multistage polymer particles (R) include a first elastic polymer (RA) monomer (S1) unit (hereinafter referred to as monomer (S1-1)) unit and a first elastic polymer (RA). At least one selected from monomer (S2) (hereinafter referred to as monomer (S2-1)) units and monomer (S5) for first elastic polymer (RA) (hereinafter referred to as monomer (S5) -1)) units containing at least a first elastic polymer (RA), a second elastic polymer (RB) monomer (S1) (hereinafter referred to as monomer (S1-2)) unit and Second elastic polymer (RB) containing at least monomer (S5) (hereinafter referred to as monomer (S5-2)) unit for bielastic polymer (RB), monomer (M1) unit and unit Intermediate polymer (RD) containing at least one selected from monomer (M2) units and at least monomer (M5) units , As well as rubber-containing multistage polymer particles obtained by forming a hard polymer containing at least monomer (H2) units (RC) in this order.

  The first elastic polymer (RA) which is a constituent component of the rubber-containing multistage polymer particles (R) is, for example, at least one selected from a monomer (S1-1) unit and a monomer (S2-1) unit. Species, monomer (S5-1) unit, first elastic polymer (RA) monomer (S3) unit (hereinafter referred to as monomer (S3-1)) unit, if necessary A polymer containing a monomer (S5-1) unit, which is obtained by first polymerizing the rubber-containing multistage polymer particles (R).

  Specific examples of the monomer that is a raw material of each monomer unit constituting the first elastic polymer (RA) include a single monomer that is a raw material for each monomer unit constituting the elastic polymer (S). It is the same as a mer.

The content of the first elastic polymer (RA) in the rubber-containing multistage polymer particles (R) is:
5 to 35% by mass is preferable because the whitening resistance of the laminated film (F1) or the laminated film (F2) is improved and the film forming property and the toughness capable of insert molding and in-mold molding are compatible. -15 mass% is more preferable. Further, it is preferably less than the content of the second elastic polymer (RB).

  The second elastic polymer (RB), which is a constituent component of the rubber-containing multistage polymer particles (R), is a main component that imparts rubber elasticity to the rubber-containing multistage polymer particles (R). What has the monomer unit similar to the monomer unit of an elastic polymer (S) is mentioned.

  The crystallization temperature (Tg) of the second elastic polymer (RB) is preferably 0 ° C. or lower, and more preferably −30 ° C. or lower. When the Tg of the second elastic polymer (RB) is 0 ° C. or less, the elasticity of the rubber-containing multistage polymer particles (R) tends to be good.

  The content of the second elastic polymer (RB) in the rubber-containing multistage polymer particles (R) is good for the molding whitening resistance of the laminated film (F1) or the laminated film (F2), 10-45 mass% is preferable at the point which can make the toughness which can perform insert molding and in-mold molding. Further, the content of the second elastic polymer (RB) in the rubber-containing multistage polymer particles (R) is preferably larger than the content of the first elastic polymer (RA).

  The hard polymer (RC), which is a constituent component of the rubber-containing multistage polymer particles (R), is a component involved in properties such as moldability and mechanical properties of the rubber-containing multistage polymer particles (R). A polymer containing a monomer (H2) unit and, if necessary, a monomer (H3) unit, which is obtained by finally polymerizing the rubber-containing multistage polymer particles (R). .

  As a specific example of the monomer that is a raw material of each monomer unit constituting the hard polymer (RC), a monomer that is a raw material of each monomer unit constituting the hard polymer (H) It is the same.

  The content of the monomer (H2) as a raw material of the monomer (H2) unit constituting the hard polymer (RC) is the surface hardness and heat resistance of the laminated film (F1) or laminated film (F2). The point is preferably 51 to 100 parts by mass.

  Moreover, as content of the monomer (H3) used as the raw material of the monomer (H3) unit which comprises a hard polymer (RC), surface hardness and heat resistance of a laminated film (F1) or a laminated film (F2) From the viewpoint of properties, 0 to 49 parts by mass are preferable.

  In addition, content of said monomer (H2) and monomer (H3) is the quantity with respect to 100 mass parts of total amounts of a monomer (H2) and a monomer (H3).

  For example, a chain transfer agent (H6) for adjusting the molecular weight can be added to the monomer raw material used to obtain the hard polymer (RC).

  As a usage-amount of a chain transfer agent (H6), 0.15-2 mass parts is preferable with respect to 100 mass parts of total amounts of a monomer (H2) and a monomer (H3).

  The mass average molecular weight of the hard polymer (RC) is preferably 80,000 or less, more preferably 70,000 or less, as measured by gel permeation chromatography.

  As Tg of a hard polymer (RC), 60 degreeC or more is preferable and 80 degreeC or more is more preferable at the point of the surface hardness and heat resistance of a laminated film (F1) or a laminated film (F2).

  The content of the hard polymer (RC) in the rubber-containing multistage polymer particles (R) is preferably 10 to 80% by mass and more preferably 40 to 60% by mass in terms of surface hardness and heat resistance.

  Specific examples of the intermediate polymer (RD) constituting the rubber-containing multistage polymer particles (R) include those similar to the intermediate polymer (M).

  The content of the intermediate polymer (RD) in the rubber-containing multistage polymer particles (R) is preferably 5 to 35% by mass. When the content of the intermediate polymer (RD) is 5% by mass or more, the whitening resistance of the laminated film (F1) or laminated film (F2) as the intermediate polymer tends to be compatible with the surface hardness and the heat resistance. If it is 35% by mass or less, the film-forming property of the laminated film (F1) or the laminated film (F2) and the toughness capable of insert molding and in-mold molding tend to be good.

  The mass average particle diameter of the rubber-containing multistage polymer particles (R) is preferably 0.08 to 0.2 μm from the viewpoint of mechanical properties and transparency of the laminated film (F1).

  In the present invention, examples of the method for producing rubber-containing multistage polymer particles include an emulsion polymerization method.

  As a method of obtaining rubber-containing multistage polymer particles (R) by emulsion polymerization, for example, from monomer (S1-1) and monomer (S2-1) for obtaining a first elastic polymer (RA) An emulsion prepared by mixing a monomer mixture containing at least one selected monomer and at least a monomer (S5-1) with water and a surfactant is supplied to the reactor and then polymerized, and then the second elasticity Examples include a method in which a monomer or a monomer mixture for obtaining a polymer (RB), an intermediate polymer (RD), and a hard polymer (RC) is sequentially supplied to a reactor and polymerized.

  Examples of the surfactant used when preparing the above emulsion include anionic, cationic and nonionic surfactants. Of these, anionic surfactants are preferred.

  A well-known thing can be used as a polymerization initiator used for superposition | polymerization.

  Examples of the method of adding the polymerization initiator include a method of adding either the aqueous phase or the monomer phase or both the aqueous phase and the monomer phase.

  Specific examples of the polymerization initiator include peroxides, azo initiators, and redox initiators that are a combination of an initiator and an oxidizing agent / reducing agent. Among these, a redox initiator is preferable, and a sulfoxylate initiator combined with ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroxy peroxide is more preferable.

  The polymerization temperature varies depending on the type and amount of the polymerization initiator used, but is preferably 40 to 120 ° C, more preferably 60 to 95 ° C.

  The latex of the rubber-containing multistage polymer particles (R) obtained by emulsion polymerization can be treated using a filtration device provided with a filter medium, if necessary.

  Examples of the method of recovering the rubber-containing multistage polymer particles (R) in powder form include, for example, a method of recovering the latex of the rubber-containing multistage polymer particles (R) by drying after salting out or acidifying and coagulating, and spraying The method of collect | recovering by drying or freeze-drying is mentioned.

  In the present invention, in the acrylic resin layer (b), for example, a stabilizer, a lubricant, a processing aid, a plasticizer, an impact aid, a foaming agent, a filler, a colorant, and an ultraviolet absorber as necessary. Etc. can be included.

  In particular, it is preferable to add an ultraviolet absorber in the acrylic resin layer (b) in order to provide weather resistance in terms of protecting the base material described later.

  Specific examples of the ultraviolet absorber include a benzotriazole ultraviolet absorber having a molecular weight of 400 or more and a triazine ultraviolet absorber having a molecular weight of 400 or more.

  Examples of commercially available benzotriazole ultraviolet absorbers having a molecular weight of 400 or more include Tinuvin 234 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd. and Adeka Stub LA-31 (trade name) manufactured by ADEKA Corporation. .

  Examples of commercially available triazine ultraviolet absorbers having a molecular weight of 400 or more include Tinuvin 1577 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd. and Adeka Stub LA-46 (trade name) manufactured by ADEKA Corporation.

  As the addition amount of the ultraviolet absorber, the acrylic resin layer (b) is used in terms of the weather resistance of the product using the laminated film (F1), laminated film (F2), laminated sheet (S1) or laminated sheet (S2). Is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the resin constituting the resin.

  Moreover, as addition amount of a ultraviolet absorber, the process stain | pollution | contamination at the time of film forming of a laminated film (F1), and the solvent resistance of laminated film (F1), laminated film (F2), laminated sheet (S1), or laminated sheet (S2) 10 parts by mass or less is preferable, and 5 parts by mass or less is more preferable, and 3 parts by mass or less is still more preferable in terms of property and transparency.

  In the present invention, it is light stable in the acrylic resin layer (b) in terms of the weather resistance of the product using the laminated film (F1), laminated film (F2), laminated sheet (S1) or laminated sheet (S2). It is preferable that an agent is added.

  Specific examples of the light stabilizer include radical scavengers such as hindered amine light stabilizers.

  Examples of commercially available hindered amine light stabilizers include ADK STAB LA-57, ADK STAB LA-67, and SANOL LS-770 (trade name) manufactured by ADEKA Corporation.

  The amount of the hindered amine light stabilizer added is the acrylic resin layer (b) in terms of the weather resistance of the product using the laminated film (F1), laminated film (F2), laminated sheet (S1) or laminated sheet (S2). Is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more with respect to 100 parts by mass of the resin.

  In addition, the amount of the hindered amine light stabilizer added is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and more preferably 1 part by mass or less from the viewpoint of preventing process contamination during film formation of the laminated film (F1). Is more preferable.

  As a method of adding these compounding agents, for example, a method of supplying them together with a material for forming an acrylic resin layer (B) to an extruder and a material for forming an acrylic resin layer (B) in advance. A method in which the added mixture is mixed and mixed in various kneaders.

  Examples of the kneader used in the latter method include a normal single screw extruder, a twin screw extruder, a Banbury mixer, and a roll kneader.

  In addition, in the case of melt extrusion, a core that causes printing failure or poor appearance when printing on the surface of the laminated film (F1), laminated film (F2), laminated sheet (S1) or laminated sheet (S2). In order to remove foreign matter and foreign matter, for example, it is preferable to extrude while filtering a material for forming a molten acrylic resin layer (b) with a screen mesh of 200 mesh or more.

[Laminated film (F1)]
The laminated film (F1) is obtained by laminating a vinylidene fluoride resin layer (I) and an acrylic resin layer (B).

  The thickness of the laminated film (F1) is preferably 300 μm or less from the viewpoint that rigidity suitable for insert molding and in-mold molding can be obtained and the film can be manufactured more stably.

  Moreover, as thickness of a laminated film (F1) in the case of being used for this laminated body, 50-300 micrometers is preferable. When the thickness of the laminated film (F1) is 50 μm or more, an appearance having a sufficient depth in the laminated body tends to be obtained. In addition, the thickness of the laminated film (F1) is 50 μm or more, and there is a tendency that a sufficient thickness can be obtained even if the laminated film is obtained by forming it into a complicated shape and obtaining this laminate. On the other hand, since the laminated film (F1) has a thickness of 300 μm or less and the laminated film (F1) tends to have appropriate rigidity, workability such as laminating property and secondary workability tends to be improved. Moreover, when the thickness of the laminated film (F1) is 300 μm or less, it is economically advantageous in terms of mass per unit area. Furthermore, when the thickness of the laminated film (F1) is 300 μm or less, the film forming property tends to be stable and the production of the laminated film (F1) tends to be easy.

  In the present invention, the ratio of the layer thickness of the vinylidene fluoride resin layer (a) and the acrylic resin layer (b) (hereinafter referred to as “(a) / (b)”) is not particularly limited.

  However, in terms of the surface hardness, cost, and matte appearance of the laminated film (F1), (i) / (b) = 1/99 to 20/80 is preferable, and (b) / (b) = 2/98 to 10/90 is more preferable.

  In the present invention, the thickness of each of the vinylidene fluoride resin layer (A) and the acrylic resin layer (B) passes through five samples obtained by cutting the laminated film (F1) to a thickness of 70 nm in the cross-sectional direction. It observed by the type | mold electron microscope, measured each thickness, and computed by averaging them. Examples of commercially available transmission electron microscopes include J100S (trade name) manufactured by JEOL Ltd.

  As the surface hardness of the laminated film (F1), the pencil hardness (JIS K5400) is preferably higher than B, more preferably HB or higher, and even more preferably F or higher. By using the laminated film (F1) having a pencil hardness higher than B, scratches are hardly formed in molding such as insert molding or in-mold molding described later, and the resulting molded article tends to have good scratch resistance. .

  When the product in which the laminated film (F1) is used is used for a vehicle, the pencil hardness of the laminated film (F1) is preferably HB or higher. When the pencil hardness of the laminated film (F1) is HB or higher, the product in which the laminated film (F1) is used is suitable for various vehicle members such as door waist garnish, front control panel, power window switch panel, and airbag cover. It is.

  In addition, when the pencil hardness of the laminated film (F1) is higher than F, the scratches are hardly noticeable even when the surface of the laminated film (F1) is scratched with a cloth having a rough surface such as gauze. Becomes higher.

  The surface hardness of the laminated film (F1) can be adjusted by selecting a material for forming (b) / (b) or the acrylic resin layer (b).

  In the present invention, by reducing the 60 ° surface glossiness of the surface of the laminated film (F1) on the vinylidene fluoride resin layer (a) side, there is a tendency that a high-class feeling can be imparted to the laminated film (F1). In general, the 60 ° surface glossiness that expresses a high-class feeling is 60% or less.

  In the present invention, the surface glossiness of the laminated film (F1), laminated film (F2), laminated sheet (S1) and laminated sheet (S2) is a value measured according to JIS Z8741.

  As a production method of the laminated film (F1), for example, a vinylidene fluoride resin layer (A) and an acrylic resin layer (B) are laminated by a coextrusion molding method through a die such as a feed block die or a multi-manifold die. And two types of films obtained by forming a vinylidene fluoride resin layer (A) and an acrylic resin layer (B) into a film by a melt extrusion method using a T die, etc. There is a method of laminating.

  The laminated film (F1) may be produced by an extrusion lamination method in which an acrylic resin layer (B) is laminated on the vinylidene fluoride resin layer (A) formed into a film by a melt extrusion method. In this case, the vinylidene fluoride resin layer (A) and the acrylic resin layer (B) may be exchanged for production.

  Among the production methods of the above laminated film (F1), in terms of economy and process simplification, a vinylidene fluoride resin layer (b) is formed by a coextrusion molding method through a die such as a feed block die or a multi-manifold die. ) And an acrylic resin layer (b) is preferable.

  Further, for example, as described in JP-A-2002-361,712, a vinylidene fluoride resin layer (A) and an acrylic resin by a coextrusion molding method through a feed block die or a multi-manifold die It is preferable to manufacture by laminating between a mirror roll and a rubber roll when forming a laminated structure of layers (b). When the acrylic resin layer (b) side constituting the laminated film (F1) is in contact with the mirror roll, the mirror smoothness of the laminated film (F1) on which the acrylic resin layer (b) is laminated is excellent. As a result, excellent printability tends to be imparted. The vinylidene fluoride resin layer (A) side is preferably in contact with the rubber roll. In this case, the surface smoothness of the acrylic resin layer (b) can be improved while maintaining a good matte level without increasing the surface gloss of the vinylidene fluoride resin layer (a), and the industrial utility value Is expensive.

  The rubber roll to be used is not particularly limited, but the rubber roll is preferably a silicone rubber roll in terms of heat resistance.

  In the present invention, a surface-finished silicone rubber roll can be used.

  As the surface-finished silicone rubber roll, a room temperature curing type silicone rubber is used in view of the consistency between the surface appearance of the laminated film (F1) and the surface appearance of the laminate finally obtained by insert molding or in-mold molding. A rubber roll whose outermost surface is coated is preferable.

  The vinylidene fluoride resin layer (A) and the acrylic resin layer (B) constituting the laminated film (F1) can each be composed of a plurality of layers.

  Further, when the vinylidene fluoride resin layer (A) and the acrylic resin layer (B) are formed by a melt extrusion method, in order to remove nuclei and foreign substances that cause printing omission on the surface of the laminated film (F1), It is preferable to extrude while filtering the material for forming each layer in a molten state with a screen mesh of 200 mesh or more.

[Picture layer (c)]
The pattern layer (c) used in the present invention is one of the components of the laminated film (F2), the laminated sheet (S2), the laminate (1), and the laminate (2).

  As a method for forming the pattern layer (c), for example, a method in which a printing layer formed by a printing method is used as a pattern layer (c), a method in which a deposition layer formed by a vapor deposition method is used as a pattern layer (c), and printing There is a method in which both the printed layer formed by the method and the vapor-deposited layer formed by the vapor deposition method are used to form the pattern layer (c).

  The pattern layer (c) obtained in the printed layer can form a pattern on the surface of the laminate described later.

  Examples of the pattern include wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, full face solid, and metallic.

  As a formation method of the printing layer as a pattern layer (c), the method of printing using the coloring ink containing a binder and the pigment or dye of a suitable color, for example and forming a printing layer is mentioned.

  Examples of the binder include polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, and cellulose esters. Resin such as olefin resin, alkyd resin, and chlorinated polyolefin resin.

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

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

  Specific examples of the red pigment include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals.

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

  Specific examples of black pigments include organic pigments such as aniline black.

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

  Examples of the dye include various known dyes.

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

  The thickness of the printing layer is usually about 0.5 to 30 μm. The printed layer may be appropriately selected according to the degree of expansion at the time of molding when a product using the laminated film (F2) or the laminated sheet (S2) is obtained so that a desired surface appearance can be obtained in the laminate. .

  Examples of the material used for forming the vapor deposition layer as the pattern layer (c) include aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead and zinc. Examples thereof include at least one metal selected from the group or an alloy or metal compound thereof.

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

  The thickness of the vapor deposition layer may be appropriately selected according to the degree of expansion at the time of forming the product using the laminated film (F2) or the laminated sheet (S2) so that a desired surface appearance can be obtained in the laminate. .

[Laminated film (F2)]
The laminated film (F2) has a pattern layer (C) on at least one side of the laminated film (F1).

  As the laminated film (F2), a film having a pattern layer (c) on the acrylic resin layer (b) side is preferable from the viewpoint of printability of the pattern layer (c).

  In the present invention, by reducing the 60 ° surface glossiness of the surface of the laminated film (F2) on the vinylidene fluoride resin layer (A) side, there is a tendency that a high-grade feeling can be imparted to the laminated film (F2). In general, the 60 ° surface glossiness that expresses a high-class feeling is 60% or less.

[Thermoplastic resin layer (d)]
The thermoplastic resin layer (d) used in the present invention is one of the components of the laminated sheet (S1) and the laminated sheet (S2).

  In the present invention, the pattern layer (c) can be formed on the surface of the thermoplastic resin layer (d).

  As the thermoplastic resin used for forming the thermoplastic resin layer (d), a resin having compatibility with the substrate (e) in that the adhesion to the substrate (e) described later is good. The same resin as that used in the substrate (e) is more preferable.

  Specific examples of the thermoplastic resin used to form the thermoplastic resin layer (d) include acrylic resin; ABS resin; AS resin; chlorine-based resin such as polyvinyl chloride and polyvinylidene chloride; polyethylene, polypropylene, polybutene Polyolefin resins such as polymethylpentene; ethylene-vinyl acetate copolymers or saponified products thereof; polyolefin copolymers such as ethylene- (meth) acrylate copolymers; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate Polyester resins such as phthalate, polyarylate, polycarbonate, copolyester; polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon; polystyrene resins; cellulose acetate, nitrocellulose A fluorocarbon resin such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer; and two or more kinds of copolymers, mixtures, composites selected from these resins A laminated body is mentioned.

  Among these, acrylic resin, ABS resin, vinyl chloride resin, polyolefin and polycarbonate are preferable in terms of the formability of the pattern layer (c) and the secondary formability of the laminated sheet (S1) or laminated sheet (S2).

  In the thermoplastic resin layer (d), for example, a stabilizer, an antioxidant, a lubricant, a processing aid, a plasticizer, an impact-resistant agent, a foaming agent, a filler, an antibacterial agent, and an antifungal agent are used as necessary. 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.

  The thickness of the thermoplastic resin layer (d) is usually about 20 to 500 μm.

  The thermoplastic resin layer (d) absorbs the surface thickness of the laminated film (F1) in the laminated sheet (S1) or laminated sheet (S2) and the surface defect of the substrate (e) in the laminated body. It is preferable to have such a thickness that the pattern layer does not disappear during molding such as injection molding or the like for obtaining the present laminate.

[Laminated sheet (S1)]
The laminated sheet (S1) is a laminated sheet in which the laminated film (F1) is laminated on the surface of the thermoplastic resin layer (d).

  In the present invention, the laminate film (F1) is laminated so that the surface on the side of the acrylic resin layer (b) where the smoothness of the laminate film (F1) is excellent is in contact with the thermoplastic resin layer (d) in that good lamination suitability is obtained. It is preferable to do.

  In the present invention, by reducing the 60 ° surface glossiness of the surface of the laminated sheet (S1) on the vinylidene fluoride resin layer (A) side, there is a tendency that a high-class feeling can be imparted to the laminated sheet (S1).

  Examples of the method of laminating the thermoplastic resin layer (d) and the laminated film (F1) for obtaining the laminated sheet (S1) include a thermal lamination method, a dry lamination method, a wet lamination method, and a hot melt lamination method. It is done.

  In addition to the above method, the laminated film (F1) and the thermoplastic resin layer (d) can be laminated by extrusion lamination.

  In the present invention, when the thermoplastic resin layer (d) and the laminated film (F1) are laminated, it is necessary between the thermoplastic resin layer (d) and the laminated film (F1) in order to increase the interlayer strength. Accordingly, a heat seal layer can be provided.

  Examples of the heat sealant used for the heat seal layer include acrylic-polyester-vinyl chloride resin.

[Laminated sheet (S2)]
The laminated sheet (S2) is a laminated sheet in which the pattern layer (c) and then the laminated film (F1) are laminated in order on the surface of the thermoplastic resin layer (d).

  In the present invention, there is a tendency that a high-class feeling can be imparted to the laminated sheet (S2) by reducing the 60 ° surface glossiness of the surface of the laminated sheet (S2) on the vinylidene fluoride resin layer (A) side.

  In the present invention, when the thermoplastic resin layer (d) and the laminated film (F1) or the laminated film (F2) are laminated, the thermoplastic resin layer (d) and the laminated film (F1) are used to increase the interlayer strength. Or a heat seal layer can be provided between the laminated film (F2) as required.

  Examples of the heat sealant used for the heat seal layer include acrylic-polyester-vinyl chloride resin.

  As a method for producing the laminated sheet (S2), for example, a method of laminating the thermoplastic resin layer (d) on the patterned layer (c) side of the laminated film (F2) and a patterned layer on the surface of the thermoplastic resin layer (d) The method of laminating | stacking a laminated | multilayer film (F1) on the surface of a pattern layer (c) after forming (c) is mentioned.

[Base material (e)]
The base material (e) used in the present invention is one of the constituent components of the laminate (1) and the laminate (2).

  Examples of the base material (e) include resin materials; wood products such as wood veneer, wood plywood, particle board, medium density fiber board (MDF); water quality boards such as wood fiber board; and metals such as iron and aluminum The material made is mentioned.

  Examples of the resin used as the resin material include polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, and olefin thermoplastic elastomer; polystyrene General-purpose thermoplastic or thermosetting resin such as resin, ABS resin, AS resin, acrylic resin, urethane resin, unsaturated polyester resin, epoxy resin; polyphenylene oxide / polystyrene resin, polycarbonate resin, polyacetal, polycarbonate modified polyphenylene ether General-purpose engineering resins such as polyethylene terephthalate; polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherimide, polyimide, liquid crystal polyester Super engineering resins such as polyallyl heat-resistant resin; and glass fibers, inorganic fillers (talc, calcium carbonate, silica, mica, etc.) reinforcing materials such as, include composite resin with the addition of modifiers such as rubber component.

  Among these, in terms of melt adhesion, ABS resin, AS resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, polyester resin, and resins containing these as main components are preferable, ABS resin, AS resin, A polycarbonate resin, a vinyl chloride resin, and a resin having these as a main component are more preferable, and an ABS resin, a polycarbonate resin, and a resin having these as a main component are still more preferable.

  In the present invention, an adhesive layer can be provided when using a resin that is not excellent in heat fusibility, such as polyolefin resin.

[This laminate (1)]
The laminate (1) is a laminate sheet in which a pattern layer (C) and then a laminate film (F1) are laminated on the surface of a substrate (e).

  In the present invention, the laminate film (F1) is laminated so that the surface on the side of the acrylic resin layer (b) where the smoothness of the laminated film (F1) is excellent is in contact with the pattern layer (c) in that good laminating suitability is obtained. Is preferred.

  In the present invention, the laminate sheet (S2) tends to have a high-class feeling by reducing the 60 ° surface glossiness of the surface of the laminate (1) on the vinylidene fluoride resin layer (A) side. .

  In the present invention, a heat seal layer can be provided between the base material (e) and the pattern layer (c) as necessary in order to increase the interlayer strength.

  Examples of the heat sealant used for the heat seal layer include acrylic-polyester-vinyl chloride resin.

  The following method is mentioned as a specific example of the manufacturing method of this laminated body (1).

  In the case where the substrate (e) has a two-dimensional shape and has heat-fusibility, a specific example of a method for producing the laminate (1) is a thermal lamination method.

  The base material (e) does not thermally bond wood products such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality board such as wood fiber board, metal such as iron and aluminum, etc. In some cases, there may be mentioned a method in which the substrate (e) and the laminated film (F1) are bonded together via an adhesive layer.

  When the substrate (e) has a three-dimensional shape, for example, a method of manufacturing the laminate (1) by an insert molding method, a method of manufacturing the laminate (1) by an in-mold molding method, and a three-dimensional overlay The method of manufacturing this laminated body (1) by the lamination molding method is mentioned.

  The insert molding method means that a film or sheet that has been decorated such as printing is formed in advance into a three-dimensional shape by a method such as vacuum forming, and unnecessary film or sheet portions are removed by trimming, followed by injection molding. This is a method of obtaining a molded product (laminated body) by transferring into a mold and integrating the resin as a base material by injection molding.

  Also, the in-mold molding method is to place a film or sheet that has been decorated, such as printing, in an injection mold, perform vacuum molding, and then injection mold the resin that is the base material in the same mold It is the method of integrating and obtaining a molded article (laminated body).

  The three-dimensional overlay laminate molding method refers to the following method.

  First, two sealed spaces partitioned by a sheet are formed, a molded body is disposed on one side of the space, and only the space where both the spaces or the molded body are disposed is decompressed.

  Next, the sheet is softened by heating, and in a state where the molded body is pressed against the sheet surface from one space side to the other space side, only the other space where the molded body is not disposed is returned to normal pressure, The sheet is attached to the molded body using pressure.

  In the three-dimensional overlay laminate molding method, the heated sheet is uniformly applied with pressure to the surface of the molded body, so that even if the surface of the molded body is curved, the sheet is satisfactorily adhered to the molded body. Can be attached.

  As an apparatus for performing the three-dimensional overlay laminate molding, for example, “TOM (trade name)” manufactured by Fuse Vacuum Co., Ltd. may be mentioned.

  When an injection molded product is used as the base material (e) used in the laminate (1), the shrinkage rate after injection molding is the shrinkage rate of the laminated film (F1) as the resin material used in the base material (e). A resin material close to is preferable. If the shrinkage ratios of the two are close to each other, there is a tendency that problems such as warpage of a laminate obtained by in-mold molding or insert molding, or peeling of a film or a sheet hardly occur.

  As a formation method of the pattern layer at the time of manufacturing this laminated body (1), for example, a method of forming a pattern layer by laminating a base material (e) on the pattern layer (c) side of the laminated film (F2) and A method of forming a picture layer by laminating a laminated film (F1) on the surface of the picture layer (c) after the picture layer (c) is formed on the surface of the substrate (e).

[This laminate (2)]
This laminate (2) is a laminate sheet in which a thermoplastic resin layer (d), a pattern layer (c) and then a laminate film (F1) are laminated on the surface of a substrate (e).

  In the present invention, by reducing the 60 ° surface glossiness of the surface of the laminate (2) on the vinylidene fluoride resin layer (a) side, it tends to be able to impart a high-class feeling to the laminate (2). is there.

  In the present invention, a heat seal layer can be provided between the thermoplastic resin layer (d) and the pattern layer (c) as necessary to increase the interlayer strength.

  Examples of the heat sealant used for the heat seal layer include acrylic-polyester-vinyl chloride resin.

  As a manufacturing method of this laminated body (2), the method similar to this laminated body (1) is mentioned.

  As a formation method of the pattern layer at the time of manufacturing this laminated body (2), for example, a method of forming a pattern layer by laminating a base material (e) on the pattern layer (c) side of the laminated sheet (S2) and There is a method of forming a picture layer by forming a picture layer (c) on the surface of the substrate (e) and then laminating a laminated sheet (S1) on the surface of the picture layer (c).

Hereinafter, the present invention will be described with reference to examples and comparative examples. In the following description, “part” represents “part by mass”. Various evaluations were performed by the following methods. In addition, the symbol in the following description is as follows.
“MMA”: methyl methacrylate “MA”: methyl acrylate “n-BA”: n-butyl acrylate “1,3-BD”: 1,3-butylene glycol dimethacrylate “AMA”: allyl methacrylate “CHP” ”: Cumene hydroperoxide“ t-BH ”: t-butyl hydroperoxide“ EDTA ”: disodium ethylenediaminetetraacetate“ MEK ”: methyl ethyl ketone (1) Reduced viscosity of thermoplastic polymer 0.1 g of thermoplastic polymer It melt | dissolved in chloroform 100mL and measured at 25 degreeC.
(2) Mass average particle diameter of acrylic resin composition Mass average particle of acrylic resin composition by dynamic light scattering method using a light scattering photometer (manufactured by Otsuka Electronics Co., Ltd., DLS-700 (trade name)). The diameter was measured.
(3) Gel content of acrylic resin composition A predetermined amount (mass before extraction) of the acrylic resin composition powder is extracted under reflux of the acetone solvent, and the resulting treatment liquid is separated by centrifugation, After drying, the mass of acetone-insoluble matter (mass after extraction) was measured. The gel content was calculated by the following formula.

Gel content (%) = (mass after extraction (g) / mass before extraction (g)) × 100
(4) Appearance The number of fish eyes due to poor dispersion of the organic matting agent (B) on the surface of the A4 size vinylidene fluoride resin laminate film or laminate on the vinylidene fluoride resin layer (A) side of the laminate is visually observed. The appearance of the vinylidene fluoride resin laminated film or laminate was evaluated according to the following criteria.
○: 0 to 3 fish eyes due to poor dispersion of organic matting agent (B) Δ: 4 to 10 fish eyes due to poor dispersion of organic matting agent (B) ×: Organic matting agent ( B) 11 or more fish eyes due to poor dispersion (5) 60 degree surface glossiness In accordance with JIS Z8741, using a portable gloss meter (trade name: GM-268, manufactured by Konica Minolta Sensing Co., Ltd.), vinylidene fluoride The 60 degree surface glossiness on the vinylidene fluoride resin layer (I) side of the resin-based resin laminated film or laminate was measured.
(6) Solvent resistance 1
A drop of acetone or MEK as a solvent was dropped on the surface of the vinylidene fluoride resin laminated film or the vinylidene fluoride resin layer (i) of the laminate, and left to dry at room temperature. The sample surface after drying was visually observed, and the solvent resistance 1 was evaluated according to the following criteria.
○: No change on the sample surface.
(Triangle | delta): The trace of a solvent remains on the sample surface.
X: The trace of the solvent remains clearly on the sample surface, or the surface of the sample surface in contact with the solvent is cloudy.
(7) Solvent resistance 2
A gauze is placed on the surface of the vinylidene fluoride resin laminated film or the vinylidene fluoride resin layer (a) of the laminate, and a drop of suntan lotion (manufactured by Merck Ltd., trade name: Coppertone Waterbabies 30SPF) is dropped on the surface. A load of 500 g including an aluminum plate was applied thereon and left at 74 ° C. for 1 hour. The sample surface after the test was visually observed, and the solvent resistance 2 was evaluated according to the following criteria.
○: No change on the sample surface.
(Triangle | delta): The trace of a solvent remains on the sample surface.
X: A trace of solvent or gauze remains clearly on the sample surface, or the surface of the sample surface in contact with the solvent is cloudy.
(8) Solvent resistance 3
One drop of a 10% aqueous lactic acid solution was dropped on the surface of the vinylidene fluoride resin laminated film or the vinylidene fluoride resin layer (a) of the laminate, and left at 80 ° C. for 24 hours. The sample surface after the test was visually observed, and the solvent resistance 3 was evaluated according to the following criteria.
○: No change on the sample surface.
(Triangle | delta): The trace of a solvent remains on the sample surface.
X: The trace of the solvent remains clearly on the sample surface, the film surface is swollen, or the surface in contact with the solvent is cloudy.
(9) Solvent resistance 4
A polyethylene cylinder with an inner diameter of 38 mm and a height of 15 mm is placed on the surface of the vinylidene fluoride resin laminated film or the vinylidene fluoride resin layer (a) of the laminate, and is firmly attached with a crimping machine, and the automobile is installed in the opening of the cylinder. 5 ml of air freshener (Dia Chemical Co., Ltd., Grace Mate Poppy Citrus) was injected. After the opening was covered with a glass plate, it was placed in a thermostatic bath maintained at 55 ° C. and left for 4 hours. After the test, the crimper was removed, the test piece was washed with water and air-dried, the whitening state of the surface of the test part was observed, and the solvent resistance 4 was evaluated according to the following criteria.
○: No change on the sample surface.
(Triangle | delta): The trace of a solvent remains on the sample surface.
X: The trace of the solvent remains clearly on the sample surface, or the surface in contact with the solvent is cloudy.
(10) Solvent resistance 5
A polyethylene cylinder with an inner diameter of 38 mm and a height of 15 mm is placed on the surface of the vinylidene fluoride resin laminated film or the vinylidene fluoride resin layer (a) of the laminate, and is made to adhere strongly with a crimping machine, and plastic is opened in the opening of the cylinder. As a plasticizer, 5 ml of dioctyl phthalate was injected. After the opening was covered with a glass plate, it was placed in a thermostat kept at 80 ° C. and left for 72 hours. After the test, the crimping device was removed, the test piece was washed with water and then air-dried, the whitening state of the surface of the test part was observed, and the solvent resistance 5 was evaluated according to the following criteria.
○: No change on the sample surface.
(Triangle | delta): The trace of a solvent remains on the sample surface.
X: The trace of the solvent remains clearly on the sample surface, or the surface in contact with the solvent is cloudy.
(11) Solvent resistance 6
One drop of N, N-diethyl-m-toluamide was dropped on the surface of the vinylidene fluoride-based resin laminated film or the vinylidene fluoride-based resin layer (I) of the laminate, and left at 80 ° C. for 24 hours. The sample surface after the test was visually observed, and the solvent resistance 6 was evaluated according to the following criteria.
○: No change on the sample surface.
(Triangle | delta): The trace of a solvent remains on the sample surface.
X: The trace of the solvent remains clearly on the sample surface, the film surface is swollen, or the surface in contact with the solvent is cloudy.
(12) Thicknesses of vinylidene fluoride resin layer (a) and acrylic resin layer (b) A sample obtained by cutting a vinylidene fluoride resin laminated film to a thickness of 70 nm in the cross-sectional direction was used as a transmission electron microscope (JEOL Ltd. ), Manufactured under the trade name: J100S), the thickness was measured at five locations, and averaged to determine the thicknesses of the vinylidene fluoride resin layer (I) and the acrylic resin layer (B). .
(13) Printability of vinylidene fluoride-based resin laminated film A silver metallic pattern was provided by gravure printing as a pattern layer (c) on the acrylic resin layer (b) side. The number of missing prints was counted and printability was evaluated according to the following criteria.
○: The number of missing prints is less than 1 / m ² .
△: number of missing printing is 1 to 10 / m ^2.
X: The number of missing prints exceeds 10 / m ² .
(14) Surface hardness of laminate The surface hardness of the laminate was measured according to JIS K5400 using the surface of the vinylidene fluoride resin layer (a) of the laminate.
Preparation Example 1 Production of Acrylic Resin Composition (A) After charging 8.5 parts of deionized water into a container equipped with a stirrer, the monomer mixture (a-A-1) shown below was added to CHP0. The solution was added together with 025 parts and stirred and mixed at room temperature.

Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Co., Ltd., trade name: Phosphanol RS610NA) was charged into the vessel while stirring, and stirring was continued for 20 minutes to prepare an emulsion.
<Monomer mixture (a-A-1)>
MMA: 0.3 part n-BA: 4.5 part 1,3-BD: 0.2 part AMA: 0.05 part Next, 186.5 parts of deionized water was put into a polymerization vessel equipped with a condenser. The temperature was raised to 70 ° C.

  Further, 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 ion-exchanged water was put into the polymerization vessel at once.

  Next, the above emulsion was dropped into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to complete the first stage polymerization of the monomer mixture (a-A). .

Subsequently, the monomer mixture (a-A-2) shown below was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP, and then the reaction was continued for 60 minutes to obtain the monomer mixture (a-A). The second stage polymerization was completed.
<Monomer mixture (a-A-2)>
MMA: 1.5 parts n-BA: 22.5 parts 1,3-BD: 1.0 part AMA: 0.25 part FOX with respect to the monomer mixture (a-A-1) used for the first stage polymerization Tg calculated | required from the type | formula of -48 degreeC, and Tg calculated | required from the FOX type | formula regarding the monomer mixture (aA-2) used for the 2nd step | paragraph polymerization was -48 degreeC.

Subsequently, the monomer mixture (a-B) shown below was added dropwise to the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes. Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (a-B) was 20 degreeC.
<Monomer mixture (a-B)>
MMA: 6 parts n-BA: 4 parts AMA: 0.075 parts Subsequently, the monomer mixture (a-C) shown below is added together with 0.19 parts of n-OM and 0.08 parts of t-BH. After dropping into the polymerization vessel over 140 minutes, the reaction was continued for 60 minutes to obtain a latex of the rubber-containing polymer (a).
<Monomer mixture (a-C)>
MMA: 55.2 parts MA: 4.8 parts The Tg determined from the FOX equation for the monomer mixture (a-C) was 84 ° C. The mass average particle diameter of the rubber-containing polymer (a) measured after polymerization was 0.12 μm.

  The latex of the resulting rubber-containing polymer (a) is filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then an aqueous solution containing 3.5 parts of calcium acetate. The mixture was salted out, washed with water, collected, and dried to obtain a powdery rubber-containing polymer (a). The gel content of the rubber-containing polymer (a) was 60% by mass.

  100 parts of a powdered rubber-containing polymer (a) and 1.4 parts of an ultraviolet absorber (Ciba Specialty Chemicals, trade name: Tinuvin 234) as a compounding agent, an antioxidant (Asahi Denka Kogyo ( Co., Ltd., trade name: ADK STAB AO-50) 0.1 part and light stabilizer (trade name: LA-67, manufactured by ADEKA) 0.3 part were mixed using a Henschel mixer.

The obtained mixture was supplied to a degassing extruder heated to 230 ° C. (product name: PCM-30, manufactured by Ikekai Tekko Co., Ltd.), extruded while removing foreign matter with a 300 mesh screen mesh, pelletized, and acrylic. A system resin composition (A) was obtained.
Preparation Example 2 Production of Acrylic Resin Composition (I) After charging 10.8 parts of deionized water in a container equipped with a stirrer, the monomer mixture (b-A-1) shown below was added to CHP0. The solution was added together with 025 parts and stirred and mixed at room temperature.

Next, 1.3 parts of an emulsifier (manufactured by Toho Chemical Co., Ltd., trade name: Phosphanol RS610NA) was charged into the vessel while stirring, and stirring was continued for 20 minutes to prepare an emulsion.
<Monomer mixture (b-A-1)>
MMA: 0.3 part n-BA: 4.5 part 1,3-BD: 0.2 part AMA: 0.05 part Next, 139.2 parts of deionized water was put into a polymerization vessel equipped with a condenser. The temperature was raised to 75 ° C.

  Further, 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 ion-exchanged water was put into the polymerization vessel at once.

  Next, the above emulsion was dropped into the polymerization vessel over 8 minutes while stirring under nitrogen, and then the reaction was continued for 15 minutes to complete the first stage polymerization of the monomer mixture (b-A). .

Subsequently, the monomer mixture (b-A-2) shown below was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP, and then the reaction was continued for 60 minutes to obtain the monomer mixture (a-A). The second stage polymerization was completed.
<Monomer mixture (b-A-2)>
MMA: 9.6 parts n-BA: 14.4 parts 1,3-BD: 1.0 part AMA: 0.25 part FOX with respect to the monomer mixture (b-A-1) used in the first stage polymerization Tg calculated | required from the type | formula of -48 degreeC, and Tg calculated | required from the formula of FOX regarding the monomer mixture (b-A-2) used for the 2nd step | paragraph superposition | polymerization was -10 degreeC.

Subsequently, the monomer mixture (b-B) shown below was dropped into the polymerization vessel over 45 minutes together with 0.0125 part of CHP, and then the reaction was continued for 60 minutes. Tg calculated | required from the formula of FOX of the polymer obtained from a monomer mixture (b-B) was 60 degreeC.
<Monomer mixture (b-B)>
MMA: 6 parts MA: 4 parts AMA: 0.075 parts Subsequently, the monomer mixture (b-C) shown below is mixed with 0.264 parts of n-OM and 0.08 parts of t-BH for 140 minutes. Then, the reaction was continued for 60 minutes to obtain a latex of a rubber-containing polymer (b).
<Monomer mixture (b-C)>
MMA: 57 parts MA: 3 parts The Tg determined from the FOX equation for the monomer mixture (b-C) was 99 ° C. The mass average particle diameter of the rubber-containing polymer (b) measured after polymerization was 0.11 μm.

  The latex of the obtained rubber-containing polymer (b) was filtered, collected and dried in the same manner as in Preparation Example 1 to obtain a powdery rubber-containing polymer (b). The gel content of the rubber-containing polymer (b) was 70% by mass.

  45 parts of powdery rubber-containing polymer (b), 55 parts of MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced viscosity: 0.06 L / g) as a thermoplastic polymer, and As a compounding agent, ultraviolet absorber (Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 234) 1.4 parts, antioxidant (Asahi Denka Kogyo Co., Ltd., trade name: ADK STAB AO-50) 1 part and 0.3 part of a light stabilizer (manufactured by ADEKA, trade name: LA-67) were mixed using a Henschel mixer.

This mixture was supplied to a degassing extruder (trade name: PCM-30, manufactured by Ikekai Tekko Co., Ltd.) heated to 230 ° C., extruded while removing foreign matter with a 300 mesh screen mesh, pelletized, and acrylic resin A composition (I) was obtained.
[Example 1]
KYNAR720 as polyvinylidene fluoride (A) (Arkema Co., Ltd., refractive index at 23 ℃ _N A: 1.42,220 ℃ and shear viscosity at the conditions of a shear rate of 60sec ^-1: 700.8Pa · s, product Name) 100 parts and a cross-linked acrylic polymer (manufactured by Nippon Shokubai Co., Ltd., trade name: Eposta MA1004, refractive index N _{B at} 23 ° C .: 1.49, mass average particle size: organic matting agent (B) 4 μm) 5 parts was mixed, mixed for 30 seconds using a Henschel mixer, cylinder temperature 180-200 ° C. and die head temperature 220 ° C. using a twin screw extruder (trade name: TEM35, manufactured by Toshiba Machine Co., Ltd.). Extrude while removing foreign matter with a 300 mesh screen mesh under the conditions of the above, cut and pelletized, vinylidene fluoride resin layer (I ) To obtain pellets of a vinylidene fluoride resin composition.

  Subsequently, the pellet of the vinylidene fluoride resin composition and the pellet of the acrylic resin composition (ii) for forming the acrylic resin layer (b) obtained in Preparation Example 2 were dried at 80 ° C. overnight.

  The dried acrylic resin composition (ii) pellets were put into a non-vented screw type 65 mmφ extruder provided with a 500 mesh screen mesh set at a cylinder temperature of 240 ° C. for plasticization. Further, the dried vinylidene fluoride resin composition pellets were put into a 25 mmφ extruder provided with a 500 mesh screen mesh set at a cylinder temperature of 180 to 220 ° C. for plasticization.

  Next, using a two-kind two-layer multi-manifold die set at 240 ° C., the above two kinds of plasticized products are 125 μm thick so that the acrylic resin composition (ii) side is in contact with the mirror surface cooling roll. The vinylidene fluoride resin laminated film was prepared. Various evaluations of the obtained laminate were performed. The results are shown in Table 1.

  In addition, when the cross section of the vinylidene fluoride resin laminated film was observed, the thickness of the vinylidene fluoride resin layer (A) was 5 μm, and the thickness of the acrylic resin layer (B) was 120 μm.

  The acrylic resin was dissolved in MEK and toluene (= 1/1 vol / vol) at a solid content of 25% as a pattern layer (c) on the acrylic resin layer (b) side of the obtained vinylidene fluoride resin laminated film. With respect to 10 parts of gravure ink, a silver metallic pattern (thickness of about 5 μm) was provided by gravure printing using an ink containing 2 parts of scaly aluminum pigment to obtain a vinylidene fluoride resin-decorated laminated film. The printability evaluation at this time was “◯”.

A 0.35 mm thick ABS sheet (Technopolymer Co., Ltd.) having an adhesive layer as a thermoplastic resin layer (d) on the vinylidene fluoride resin-decorated laminated film having the pattern layer (c) obtained above. (Product name: Valuetech) was laminated by thermal lamination so that the adhesive layer and the pattern layer (c) were in contact with each other to obtain a laminated sheet.

  This laminated sheet was placed in a mold having a vacuum drawing function so that the vinylidene fluoride resin laminated film side became the cavity side, heated with a heater until the laminated sheet reached 190 ° C., and then vacuum-formed. .

  Unnecessary portions of the vacuum-formed laminated sheet (portions that do not adhere to the substrate (e) in the resulting laminate) were trimmed from the vinylidene fluoride-based resin laminated film side using a Thomson die.

The laminated sheet with trimmed unnecessary parts is placed on the bottom of the mold with a recess of 1 cm ² and 1 mm deep at a position 3 cm in the lateral direction from the central gate of the mold on the cavity side. It arrange | positioned so that the system resin laminated | multilayer film side might become a cavity side.

  Next, an ABS resin (UMG ABS Co., Ltd., trade name: Diapet ABS Bulk Sum TM25) serving as a base material (e) is injection-molded on the surface of the thermoplastic resin layer (d) of the laminated sheet by insert molding and laminated. A body (laminated molded product) was obtained.

  The shape of the laminate is a box shape having a length of 150 mm, a width of 120 mm, a thickness of 2 mm, and a depth of 10 mm.

  In addition, the gate position of the mold is one in the center of the laminated body, and three places in total, one place each at a position 40 mm above and below the central gate (vertical direction of the laminated body). .

  Furthermore, the corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. Corner R was measured with a radius gauge (trade name) manufactured by Fuji Tool Co., Ltd.

  The injection molding machine was J85EL II type injection molding machine (trade name) manufactured by Nippon Steel, Ltd., and was injected under the conditions of cylinder temperature 250 ° C, injection speed 30%, injection pressure 43%, and mold temperature 60 ° C. Molded. Various evaluations of the obtained laminate were performed. The evaluation results are shown in Table 2.

[Example 2]
Crosslinked acrylic-styrene copolymer (manufactured by Sekisui Plastics Co., Ltd., trade name: Techpolymer SMX-5, refractive index N _{B at} 23 ° C .: 1.56, mass average particle as organic matting agent (B) Diameter: 5 μm) A vinylidene fluoride resin laminated film and a laminate were produced in the same manner as in Example 1 except that 5 parts were blended. Various evaluations of the obtained vinylidene fluoride-based resin laminate film and laminate were performed. The results are shown in Tables 1 and 2.
[Examples 3 and 4]
A vinylidene fluoride resin laminated film and a laminate were produced in the same manner as in Example 1 except that the blending amounts of the vinylidene fluoride resin (A) and the organic matting agent (B) were changed to the amounts shown in Table 1. Various evaluations of the obtained vinylidene fluoride-based resin laminate film and laminate were performed. The results are shown in Tables 1 and 2.
[Example 5]
The pellet made of Example 3 was used as the pellet of the vinylidene fluoride resin composition for forming the vinylidene fluoride resin layer (a), and 80 pellets for forming the acrylic resin layer (b) were used. The acrylic resin composition (A) obtained in Preparation Example 2, which was dried overnight at 0 ° C., was used. Other than that was carried out similarly to Example 1, and produced the vinylidene fluoride type resin laminated film. Table 1 shows the results of various evaluations of the obtained vinylidene fluoride-based resin laminated film.

  When the cross section of the vinylidene fluoride resin laminated film was observed, the thickness of the vinylidene fluoride resin layer (A) was 5 μm, and the thickness of the acrylic resin layer (B) was 45 μm.

  Next, a 90 μm-thick film (Riken Technos Co., Ltd.) containing a hindered phenolic antioxidant, a UV absorber, a hindered amine light stabilizer and iron oxide (pigment) in a randomly polymerized polypropylene resin as a thermoplastic resin layer (d) ), Trade name: rivest TPO), and the surface of the thermoplastic resin layer (d) is a binder resin containing isopropylene, vinyl chloride / vinyl acetate resin and isoindoline, diketopyrrolopyrrole, carbon black and phthalocyanine. A pattern was printed by gravure printing using an ink having at least one pigment selected from blue to form a pattern layer (c).

  After the vinylidene fluoride resin laminated film obtained above is laminated on the surface of the pattern layer (c) of the thermoplastic resin layer (d) obtained above so as to be in contact with the acrylic resin layer (b), fluorination is performed. A laminated sheet was obtained by heat laminating under the condition of a vinylidene-based resin laminated film surface temperature of 130 ° C. Various evaluations of the obtained laminated sheet were performed. The evaluation results are shown in Table 1.

  As is apparent from Examples 1 to 5, the vinylidene fluoride resin-decorated laminated film and laminated sheet of the present invention are excellent in solvent resistance and matte appearance, and are suitable for cosmetic materials and vehicle applications. It is.

  Further, as is clear from Examples 1 to 4, the laminate of the present invention is suitable for vehicle use because it has excellent solvent resistance and a matte appearance.

  The vinylidene fluoride resin laminated film, vinylidene fluoride resin decorated laminated film, laminated sheet and laminate of the present invention are an instrument panel, console box, meter cover, door lock pzel, steering wheel, power window switch base, center cluster, Automotive interior applications such as dashboards; weather strips, bumpers, bumper guards, side mud guards, body panels, spoilers, front grills, strut mounts, wheel caps, center pillars, door mirrors, center ornaments, side moldings, door moldings, wind moldings, windows , Head lamp covers, tail lamp covers, windshield parts, etc. for automotive exteriors; front panels, buttons, emblems, surfaceization of AV equipment and furniture products Use of materials, etc .; Use of housings such as mobile phones, display windows, buttons, etc .; Use of furniture exterior materials; Use of interior materials for buildings such as walls, ceilings, floors, etc .; Architectural exterior materials such as boards; surface decorative materials for furniture such as window frames, doors, handrails, sills, and duck; optical materials such as various displays, lenses, mirrors, goggles, and window glass; trains, aircraft, Suitable for interior / exterior use of various vehicles other than automobiles such as ships; various packaging containers such as bottles, cosmetic containers and accessory cases; and miscellaneous goods such as materials, prizes and accessories.

Claims (8)

100 parts by weight of vinylidene fluoride resin (A) and an organic matting agent (B) containing 1 to 30 parts by weight, organic luster in the refractive index _{N A} and 23 ° C. of vinylidene fluoride resin (A) at 23 ° C. mending agent (B) a vinylidene fluoride resin layer having a refractive index and N _B satisfy the following formula (X) in (b) and the acrylic resin layer (b) and stacked to vinylidene fluoride resin laminate obtained by the film.
| N _B −N _A | ≦ 0.15 (X)   A vinylidene fluoride resin-decorated laminated film having a pattern layer (c) on at least one surface of the vinylidene fluoride resin laminated film according to claim 1.   A laminated sheet in which the vinylidene fluoride resin laminated film according to claim 1 is laminated on the surface of the thermoplastic resin layer (d).   A laminated sheet in which the pattern layer (c) and then the vinylidene fluoride resin laminated film according to claim 1 are laminated in order on the surface of the thermoplastic resin layer (d).   The laminated body by which the pattern layer (c) and the vinylidene fluoride resin laminated | multilayer film of Claim 1 are laminated | stacked on the surface of a base material (e) next.   A laminate in which the thermoplastic resin layer (d), the pattern layer (c), and the vinylidene fluoride resin laminated film according to claim 1 are laminated on the surface of the substrate (e).   A laminated sheet-like article for a cosmetic material using the vinylidene fluoride resin laminated film according to claim 1, the vinylidene fluoride resin decorated laminated film according to claim 2, or the laminated sheet according to claim 3 or 4. .   The vinylidene fluoride resin laminated film according to claim 1, the vinylidene fluoride resin decorated laminated film according to claim 2, the laminated sheet according to claim 3 or 4, or the laminate according to claim 5 or 6. A molded body for vehicles using the body.