JP2012233089A - Fluorine matte film, fluorine matte laminated film, fluorine matte decoration-laminated film, laminated sheet and laminated formed product obtained by laminating them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fluorine matte film having a good outer appearance, and excellent in fine matte properties and solvent resistance even under a highly productive condition.SOLUTION: There are provided the fluorine matte film (F1) including (A) a fluorine resin and (B) a non-crosslinked acrylic resin, wherein the solubility parameter (SPF) of (A) the fluorine resin and the solubility parameter (SPA) of the acrylic resin (B) satisfy formula (1) and the shearing viscosity (SVA) of the acrylic resin (B) and the sharing viscosity (SVF) of (A) the fluorine resin at 220°C at 60 secshearing speed satisfy formula (2); laminated film (F2) obtained by laminating the fluorine matte resin layer (I) having the same composition as above with an acrylic resin layer (II); film (F3) having a designed layer (III) on the film (F2); laminated sheet (F4) obtained by laminating any of the films (F1) to (F3) with a thermoplastic resin layer (IV); and a laminated product obtained by laminating any of the films (F1) to (F3) and sheet (F4) with a substrate material (V). (1) SPA-SPF≥4.0Jcm. (2) SVA/SVF≤2.0.

Description

  The present invention is a fluorine-matte film, fluorine-matte laminated film, fluorine-matte-decorated laminated film, laminated film that has a good appearance even under high production conditions and has excellent fine-matte and solvent resistance. The present invention relates to a sheet and a laminated molded product in which these are laminated.

  Fluorine films such as vinylidene fluoride resins have excellent weather resistance, solvent resistance, and contamination resistance, so they can be laminated on the surface of various substrates such as plastic, glass, slate, rubber, metal plate, and wood board. Widely used as a film. 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 recent years, particularly for base materials such as wallpaper and leather furniture used indoors, there has been a demand for higher-quality images, and the use of laminated matte films has increased.

  The matte film is produced mainly by (1) a method in which fine irregularities are imparted to the film surface by a metal or rubber mat roll having a rough surface, and (2) fine particles such as sand or metal. Spraying the surface of the film to be treated to give fine irregularities (sand blasting method), (3) coating the film to be treated with a matting agent, and (4) fine organic or inorganic filler (matting) A method is known in which an agent is added to a resin for film construction.

  However, the matte film mat mating method (1) has a problem that the mat roll is easily clogged by an additive such as an ultraviolet absorber added to the fluororesin, and a thin film becomes a glossy spot as it is. There is a problem that it is difficult to obtain a uniform matte film.

  In addition, the sand blasting method (2) has a problem that a film to be processed is stretched or broken during sand blasting in a thin and soft film.

  Further, in the method (3) of coating the matting agent, the matting agent cannot be easily coated on the surface of the fluororesin because the matting agent is non-adhesive (non-adhesive) to the fluororesin.

  In addition, in the method (4) of adding a matting agent to the resin constituting the film, when an inorganic matting agent is used, voids are easily generated in the obtained film, and the mechanical strength is low. There may be a problem that the fluororesin is colored due to a problem of lowering, a problem of lowering the transparency of the film, and high-temperature heating in the process of melt extrusion film formation.

  For example, Patent Document 1 proposes a vinylidene fluoride resin film having a surface layer containing a crosslinked acrylic resin and a vinylidene fluoride resin and having excellent appearance, surface gloss, tensile elongation, and thermal processability. Yes. Patent Document 2 describes the appearance, surface glossiness, thermal workability and weather resistance using a resin composition containing a vinylidene fluoride resin, a methacrylic ester resin and a cross-linked acrylic resin having a specific particle size. An excellent surface protective film for interior and exterior building materials has been proposed.

  However, none of the films obtained in Patent Document 1 and Patent Document 2 have sufficient solvent resistance.

  Further, Patent Document 3 discloses an acrylic resin film having surface hardness, heat resistance, transparency and matteness that can be used for vehicle applications without whitening of a molded product when insert molding or in-mold molding is performed. Forms have been proposed. In Patent Document 3, a method of kneading inorganic fillers or crosslinkable polymer particles, a method of copolymerizing an epoxy group-containing monomer, a method of using a linear polymer having a hydroxyl group, a fluororesin film It is disclosed that the outermost layer is provided.

  However, Patent Document 3 does not disclose any specific measures for achieving good appearance and fine mattness while maintaining solvent resistance.

JP 2001-205755 A JP 2008-7709 A JP 2005-139416 A

  An object of the present invention is to provide a fluorine-matte film, a fluorine-matte laminated film, and a fluorine-matte-decorated laminated film that have a good appearance even under high production conditions and are excellent in fine mattness and solvent resistance. Another object of the present invention is to provide a laminated sheet and a laminated molded product obtained by laminating these.

The gist of the present invention includes a fluororesin (A) and a non-crosslinked acrylic resin (B), the solubility parameter (SPF) of the fluororesin (A) and the solubility parameter of the noncrosslinked acrylic resin (B). (SPA) satisfies the following formula (1) is, 220 ° C., shear viscosity (SVA) and 220 ° C. uncrosslinked acrylic resin under conditions of shear rate of 60 sec ^-1 (B), the conditions of a shear rate of 60 sec ^-1 The fluorine matte film (F1) in which the shear viscosity (SVF) of the fluororesin (A) below satisfies the following formula (2).

SPA-SPF ≧ 4.0J ^1/2 cm ^-3/2 (1)
SVA / SVF ≦ 2.0 (2)
Further, the gist of the present invention includes the fluororesin (A) and the non-crosslinked acrylic resin (B), and includes the solubility parameter (SPF) of the fluororesin (A) and the noncrosslinked acrylic resin (B). solubility parameter (SPA) satisfies the above formula (1), 220 ℃, shear viscosity (SVA) and 220 ° C. uncrosslinked acrylic resin under conditions of shear rate of 60sec ^-1 (B), a shear rate of 60 sec ^-1 Fluorine-matted laminate formed by laminating a fluorine-matte resin layer (I) in which the shear viscosity (SVF) of the fluororesin (A) satisfies the formula (2) and an acrylic resin layer (II) It is a film (F2).

  The gist of the present invention is a fluorine mat decorative laminated film (F3) further having a picture layer (III) on at least one side of the above fluorine mat laminated film (F2).

  Further, the gist of the present invention is that the fluorine matte film (F1), the fluorine matte laminated film (F2), and the fluorine matte laminated film (F3) are used. This is a laminated sheet (F4) formed by laminating the selected film and the thermoplastic resin layer (IV).

  Further, the gist of the present invention is that the above-mentioned fluorine matte film (F1), the above-mentioned fluorine matte laminated film (F2), the above-mentioned fluorine matte decorative laminated film (F3), and the above laminate It is a laminated molded product obtained by laminating a film or sheet selected from the group consisting of a sheet (F4) on a base material (V).

  According to the present invention, it is possible to obtain a film, a sheet, and a laminated molded product that have solvent resistance, have a good appearance even under high production conditions, and have a fine and fine matte state. These can be suitably used for various applications such as interior and exterior applications of automobiles and buildings, and exterior applications that are severe in direct sunlight.

[Fluororesin (A)]
Examples of the fluororesin (A) used in the present invention include polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, polytetrafluoroethylene, polyvinyl fluoride, tetrafluoroethylene-hexa. Acrylic monomers such as fluoropropylene copolymer, tetrafluoroethylene-perfluoro (propyl vinyl ether) copolymer, tetrafluoroethylene-vinylidene fluoride copolymer, vinylidene fluoride and (meth) acrylic acid alkyl ester And a mixed resin with another resin mainly composed of a vinylidene fluoride polymer. These can be used alone or in combination of two or more. In particular, a vinylidene fluoride polymer is preferable in terms of the light transmittance and fine matte expression of the resulting fluorine matte film and the compatibility between the fluororesin (A) and the non-crosslinked acrylic resin (B). .

  The vinylidene fluoride polymer is not particularly limited as long as it is a vinyl polymer having a vinylidene fluoride monomer unit, and may be a homopolymer of vinylidene fluoride. It may be a copolymer with a monomer. Examples of other vinyl monomers copolymerizable with vinylidene fluoride include fluorinated vinyl monomers such as vinyl fluoride, ethylene tetrafluoride, ethylene trifluoride chloride, propylene hexafluoride, and styrene. , Vinyl monomers such as ethylene, butadiene, and propylene.

Fluorocarbon resin (A), 220 ° C., and the shear viscosity of the non-crosslinked acrylic resin under conditions of shear rate of ^{60sec -1 (B) (SVA)} , 220 ℃, fluorine resin under conditions of shear rate of 60 sec ^-1 ( It is necessary that the shear viscosity (SVF) of A) is a fluororesin that satisfies the following formula (2).

SVA / SVF ≦ 2.0 (2)
By using such a fluororesin (A), the resulting fluorine mat film (F1), fluorine mat laminate film (F2), fluorine mat decorating laminate film (F3) and laminate sheet (F4) Appearance can be improved. In particular, since a good dispersion state can be achieved under high production conditions, the industrial utility value is high.

These shear viscosities (SVA and SVF) are values obtained by measurement with a twin capillary rheometer.
<Twin capillary rheometer measurement conditions>
Equipment used: Malvern Rosand RH-7D
Bagley correction was performed, and a value obtained by correcting the pressure loss at the capillary portion was used.

  In particular, from the viewpoint of film forming properties of the fluorine matte film (F1) and the fluorine matte laminated film (F2), the fluororesin (A) is composed of the above-mentioned shear viscosity (SVA) of the acrylic resin (B) and the fluororesin ( The above-mentioned shear viscosity (SVF) of A) is preferably a fluororesin that satisfies the following formula (3).

1.0 ≦ SVA / SVF ≦ 2.0 (3)
[Non-crosslinked acrylic resin (B)]
The solubility parameter (SPA) of the non-crosslinked acrylic resin (B) used in the present invention should be 4.0 J ^1/2 cm ^−3/2 or more higher than the solubility parameter (SPF) of the fluororesin (A). is necessary. By using such a non-crosslinked acrylic resin (B), the resulting fluorine matting film (F1), fluorine matting laminated film (F2), fluorine matting decorative laminate film (F3) and laminate sheet ( F4) is excellent in appearance and matting properties, and can have good solvent resistance.

In the present invention, the solubility parameter means a value (σ) represented by the following Fedors equation.
<Fedors formula>
σ = (E _v / v) ^1/2 = (ΣΔe _i / ΣΔv _i ) ^1/2
σ: Solubility parameter (unit: J ^1/2 cm ^-3/2 )
E _v : Evaporation energy v: Molar volume Δe _i : Evaporation energy of each atom or atomic group Δv _i : Molar volume of each atom or atomic group Evaporation energy and molar volume of each atom or atomic group used in the calculation of the above formula are , “RFFedors, Polym. Eng. Sci., 14, 147 (1974)”.

Further, the difference between SPA and SPF (Δσ: SPA−SPF) needs to be 4.0 J ^1/2 cm ^−3/2 or more. Further, the upper limit of Δσ is not particularly limited, but the matte of the fluorine matte film (F1), the fluorine matte laminate film (F2), the fluorine matte decorative laminate film (F3) and the laminate sheet (F4) of the present invention. In terms of expression and dispersibility of the non-crosslinked acrylic resin (B) in the fluorine matte film (F1), 6.8 or less is preferable, and 6.3 or less is more preferable.

  The “non-crosslinked acrylic resin” refers to an acrylic resin that does not contain a polyfunctional monomer unit such as a crosslinker monomer unit or a graft crossing agent monomer unit. The non-crosslinked acrylic resin (B) used in the present invention may be any one having SPA that satisfies the above conditions, and known acrylic resins can be used.

  As the non-crosslinked acrylic resin (B), for example, a structural unit obtained from at least one kind of methacrylate selected from the group consisting of methyl methacrylate, hydroxyethyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate is used as a main structural unit. A single polymer or copolymer having a structural unit obtained from another vinyl monomer such as an alkyl acrylate having 1 to 8 carbon atoms, vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, etc. A polymer having the above-mentioned SPA can be selected from a polymer and an acrylic polymer having a (meth) acrylate unit as a main constituent unit. These can be used alone or in combination. “(Meth) acrylate” indicates acrylate or methacrylate.

  Examples of the non-crosslinked acrylic resin (B) having SPA include resins comprising a hydroxyl group-containing polymer, a carboxy group-containing polymer, and the like. Among them, the resulting fluorine mat film (F1), fluorine mat In view of improving the matte appearance of the laminated film (F2), the fluorine matted decorative laminated film (F3), and the laminated sheet (F4), a resin made of a hydroxyl group-containing polymer is particularly preferable. As this hydroxyl-containing polymer, the hydroxyl-containing polymer (1) shown below is mentioned, for example. By using this hydroxyl group-containing polymer (1), the elongation of the resulting fluorine matte film (F1) can be hardly lowered as compared with the elongation of the fluororesin. As a result, the fluorine mat film (F1), the fluorine mat laminated film (F2), the fluorine mat decorative laminate film (F3), and the laminate sheet (F4) of the present invention are cut, for example, during secondary processing. And the like are less likely to occur.

  Hydroxyl group-containing polymer (1) is a hydroxyalkyl (meth) acrylate having a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms, and an alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms. It is a polymer obtained by copolymerizing a monomer component containing 0 to 79% by mass of alkyl acrylate having 1% by mass and an alkyl group having 1 to 8 carbon atoms. “(Meth) acrylic acid” refers to acrylic acid or methacrylic acid.

  Examples of the hydroxyalkyl (meth) acrylate having a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms constituting the hydroxyl group-containing polymer (1) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and methacrylic acid. Examples include 2,3-dihydroxypropyl, 2-hydroxyethyl acrylate, and 4-hydroxybutyl acrylate. These can be used alone or in combination of two or more. Among them, 2-hydroxyethyl methacrylate is particularly preferable in terms of matte expression.

  The content of hydroxyalkyl (meth) acrylate having a hydroxyl group-containing alkyl group having 1 to 8 carbon atoms in 100% by mass of the monomer component is preferably 1 to 80% by mass. By setting this content to preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably more than 20% by mass, SPA tends to be within the range defined by the present invention, and the fluorine gloss of the present invention. The matte effect (matteness and appearance) of the matte film (F1), the fluorine matte laminated film (F2), the fluorine matte decorative laminate film (F3) and the laminate sheet (F4) tends to be good. Moreover, by making this content preferably 80% by mass or less, more preferably 50% by mass or less, the dispersibility of the hydroxyl group-containing polymer (1) particles becomes better, and in the fluorine matte film (F1). The presence of undispersed particles of the hydroxyl group-containing polymer (1) is suppressed, and the film forming property tends to be good.

  Examples of the alkyl methacrylate having a C1-C13 alkyl group constituting the hydroxyl group-containing polymer (1) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, and methacrylic acid. Examples include n-butyl, i-butyl methacrylate, and t-butyl methacrylate. These can be used alone or in combination of two or more. Among these, methyl methacrylate is particularly preferable from the viewpoint of weather resistance.

  The content of the alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms in 100% by mass of the monomer component is preferably 20% by mass or more, more preferably 30% by mass or more in terms of weather resistance. Further, the content thereof is preferably 99% by mass or less, more preferably 90% by mass or less, in terms of matte expression.

  Examples of the alkyl acrylate having a C 1-8 alkyl group constituting the hydroxyl group-containing polymer (1) include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, and acrylic acid. Examples include n-butyl, i-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate. These can be used alone or in combination of two or more.

The content of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in 100% by mass of the monomer component may be 0% by mass, preferably in terms of dispersibility of the non-crosslinked acrylic resin (B). It is 0.5 mass% or more, more preferably 5 mass% or more. The content thereof is 79% by mass or less, preferably 40% by mass or less, and more preferably 25% by mass or less in terms of weather resistance and heat resistance.

  The glass transition temperature of the non-crosslinked acrylic resin (B) is the fluorine matte film (F1), the fluorine matte laminated film (F2), the fluorine matted decorative laminate film (F3) and the laminate sheet (F4) of the present invention. Is preferably 90 ° C. or less, and more preferably 80 ° C. or less, from the viewpoint of the matt appearance of the polymer and the dispersibility of the particles of the hydroxyl group-containing polymer (1) in the fluorine mat film (F1). In these cases, the content of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in the monomer component is preferably 0.5 to 30% by mass, and more preferably 0.5 to 20% by mass. The glass transition temperature of the non-crosslinked acrylic resin (B) is described in the Tg value of the homopolymer of each monomer component (polymer handbook [Polymer Handbook, J. Brandrup, Interscience, 1989]. ) To calculate from the FOX equation.

  The intrinsic viscosity of the non-crosslinked acrylic resin (B) is such that the dispersibility of the non-crosslinked acrylic resin (B) in the fluorine matte film (F1) of the present invention is good, By reducing the unmelted components of the hydroxyl group-containing polymer (1), the fluorine-matte film (F1), the fluorine-matte laminated film (F2), the fluorine-matte decorated laminated film (F3) and the laminated sheet ( In view of improving the appearance of F4), 0.3 L / g or less is preferable, and 0.12 L / g or less is more preferable. In addition, the intrinsic viscosity of the fluorine matte film (F1), fluorine matte laminated film (F2), fluorine matte decorative laminate film (F3) and laminate sheet (F4) of the present invention is good. In view of this, 0.01 L / g or more is preferable. In addition, the intrinsic viscosity of the non-crosslinked acrylic resin (B) was measured at 25 ° C. using an AVL-2C automatic viscometer manufactured by Sun Electronics Co., Ltd., using chloroform as a solvent.

  In order to adjust the intrinsic viscosity of the non-crosslinked acrylic resin (B), for example, a polymerization regulator such as mercaptan can be used. Examples of mercaptans include n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan. The mercaptan content is not particularly limited, but is preferably 0.01 parts by mass or more in terms of dispersibility with respect to 100 parts by mass of the monomer constituting the non-crosslinked acrylic resin. Moreover, 1 mass part or less is preferable at the point which makes mat | matte property favorable.

  The Mw (mass average molecular weight) / Mn (number average molecular weight) of the non-crosslinked acrylic resin (B) is preferably 2.2 or less, and more preferably 2.0 or less. As this Mw / Mn is smaller, the molecular weight distribution of the non-crosslinked acrylic resin (B) becomes closer to monodisperse, so that the high molecular weight component decreases, and the fluorine mat film (F1) and fluorine mat laminated film of the present invention. In (F2), the fluorine mat decorative laminated film (F3) and the laminated sheet (F4), the occurrence of unmelted materials causing appearance defects such as fish eyes is suppressed. In addition, Mw / Mn shows the value obtained by measuring on the following GPC measurement conditions by a gel permeation chromatograph (GPC).

<GPC measurement conditions>
Equipment used: HLC-8320GPC system manufactured by Tosoh Corporation Column: TGKgel SuperHZM-H (trade name, manufactured by Tosoh Corporation) 2 eluents: tetrahydrofuran Column temperature: 40 ° C
Detector: differential refractive index (RI).

The shear viscosity (SVA) of the uncrosslinked acrylic resin (B) at 220 ° C. and a shear rate of 60 sec ⁻¹ is preferably 6,000 Pa · s or less, and more preferably 3,000 Pa · s or less. The smaller this SVA, the poorer the appearance of fish eyes and the like in the fluorine matte film (F1), the fluorine matte laminated film (F2), the fluorine matte laminated film (F3) and the laminate sheet (F4) of the present invention. The occurrence of poor dispersion of the non-crosslinked acrylic resin (B), which causes the above, is suppressed.

  Examples of the method for producing the non-crosslinked acrylic resin (B) include suspension polymerization and emulsion polymerization.

  Examples of the initiator used for suspension polymerization include organic peroxides and azo compounds. Examples of the suspension stabilizer include organic colloidal polymer materials, inorganic colloidal polymer materials, inorganic fine particles, and combinations of these with surfactants. Among them, an organic suspension stabilizer is preferable, for example, a copolymer of methyl methacrylate and potassium methacrylate and methyl methacrylate, potassium methacrylate and methacrylic acid disclosed in JP-A-1-168,702. And a copolymer with 2-sulfoethyl sodium salt. In the case of using an inorganic suspension stabilizer, those that can be removed by post-polymerization treatment such as washing are preferred, and examples thereof include tricalcium phosphate. The amount of the suspension stabilizer used is not particularly limited, but is preferably 0.1 parts by mass or more from the viewpoint of stabilizing the suspension polymerization. Moreover, it is preferable that it is 10 mass parts or less from the point of economical efficiency.

  Usually, suspension polymerization is carried out using an aqueous suspension of a monomer and the like together with a polymerization initiator in the presence of a suspension stabilizer. In addition, a polymer soluble in the monomer can be dissolved in the monomer and polymerized when suspension polymerization is performed as required. After suspension polymerization, it is preferable to remove cullet, which is a component insoluble in chloroform generated during polymerization, which causes poor appearance, from the bead-like material obtained by suspension polymerization. As a sieve used by sieving, in order to ensure a sufficient yield, 150 mesh or less is preferable, and 50 mesh or less is more preferable. Moreover, when removing a cullet sufficiently, 50 mesh or more is preferable and 150 mesh or more is more preferable.

  The uncrosslinked acrylic resin (B) preferably contains no cullet of 300 μm or more, and more preferably contains no cullet of 100 μm or more.

  When polymerizing using an inorganic suspension stabilizer, the resulting fluorine matte film (F1), fluorine matte laminated film (F2), fluorine matte decorative laminate film (F3) and laminate sheet (F4) In order to suppress the occurrence of fisheye in the printing medium and to prevent printing omission, the beads of non-crosslinked acrylic resin (B) obtained by suspension polymerization are washed with water to obtain a non-crosslinked acrylic resin (B It is preferable to reduce the content of inorganic substances in

  As this water washing method, for example, a dispersion washing method in which a washing liquid such as nitric acid is added to a bead-like product of non-crosslinked acrylic resin (B) and dispersed, and then solid-liquid separation, and a non-crosslinked acrylic resin ( There is a passing washing method in which a washing liquid is passed through the bead-like material of B). The washing temperature is preferably 10 to 90 ° C. in terms of washing efficiency.

  In post-treatment such as sieving after the completion of polymerization and water washing as described above, the cullet is efficiently removed by sieving without reducing the product yield, and the inorganic substance is efficiently removed by washing. Therefore, the average particle diameter of the hydroxyl group-containing polymer (1) is preferably 300 μm or less, and more preferably 100 μm or less. Further, the average particle diameter is preferably 10 μm or more from the viewpoint of the handleability of the polymer. In addition, the average particle diameter of a hydroxyl-containing linear polymer (1) can be measured using the laser diffraction scattering type particle size distribution measuring device LA-910 made from HORIBA.

[Fluorine matte film (F1)]
The fluorine matte film (F1) of the present invention contains 100 parts by mass of a fluororesin (A) and 1 to 18 parts by mass of a non-crosslinked acrylic resin (B) (based on 100 parts by mass of the fluororesin (A)). It is preferable. When the blending amount of the non-crosslinked acrylic resin (B) is 1 part by mass or more with respect to 100 parts by mass of the fluororesin (A), the fluorine matte film (F1), the fluorine matte laminated film (F2) of the present invention ), The matte property of the fluorine mat decorative laminated film (F3) and the laminate sheet (F4) is improved. Furthermore, from the viewpoint of upgrading the image, the 60 ° surface gloss of the fluorine mat film (F1), the fluorine mat laminated film (F2), the fluorine mat decorative laminate film (F3) and the laminate sheet (F4) is low. In general, a 60 ° surface glossiness of 45% or less exhibits a high-class feeling. For this reason, as for the compounding quantity of a non-crosslinked acrylic resin (B), 3 mass parts or more are more preferable. In addition, the surface glossiness of the fluorine mat film (F1), the fluorine mat laminated film (F2), the fluorine mat decorative laminate film (F3) and the laminate sheet (F4) of the present invention is measured according to JIS Z8741. It is the value.

  On the other hand, when the blending amount of the non-crosslinked acrylic resin (B) is 18 parts by mass or less with respect to 100 parts by mass of the fluororesin (A), the fluorine mat film (F1) and the fluorine mat laminated film of the present invention are used. The solvent resistance of (F2), the fluorine mat decorative laminated film (F3) and the laminated sheet (F4) becomes good. Furthermore, from a cost-effective viewpoint of blending the non-crosslinked acrylic resin (B), it is more preferably 15 parts by mass or less, and more preferably 13 parts by mass or less.

  The thickness of the fluorine matte film (F1) is preferably 5 to 500 μm, more preferably 15 to 200 μm, and more preferably 30 to 100 μm in terms of the laminate property, film forming property, or secondary processability of the fluorine matte film (F1). Is particularly preferred.

  It is also a preferred embodiment that the surface of the fluorine matte film (F1) [and the fluorine matte laminated film (F2), the fluorine matte decorative laminate film (F3) and the laminate sheet (F4)] are formed with irregularities. . In this case, the average interval (Sm) of the surface irregularities is preferably 30 μm or less. When non-crosslinked acrylic resin (B) is blended and this Sm is 30 μm or less, fluorine matte film (F1), fluorine matte laminate film (F2), fluorine matte decorate laminate film (F3) and laminate sheet The matte state of (F4) is fine and the matte property tends to be very good. In addition, the average space | interval (Sm) of surface unevenness | corrugation is the value measured according to JISB0601.

  For the fluorine matte film (F1), if necessary, an antioxidant, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, a filler, a matting agent, a processing aid, an impact aid, Various additives such as 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. Components other than the fluororesin (A) and the non-crosslinked acrylic resin (B) in the fluorine mat film (F1) are preferably 10% by mass or less.

  As a method of blending the additive into the fluorine matte film (F1), for example, a method of supplying the fluorine matte film (F1) together with a raw material to a molding machine for obtaining a molded product, and fluorine in advance. Examples thereof include a method of kneading a raw material mixture in which an additive is added to the raw material for forming the matte film (F1) with various kneaders. Examples of the kneader used in the latter method include a single screw extruder, a twin screw extruder, a Banbury mixer, and a roll kneader. When melt extrusion is performed, each layer in a molten state is composed of, for example, a screen mesh of 200 mesh or more in order to remove nuclei and foreign matters that cause printing omission and poor appearance when printing on a film. The resin composition to be extruded is preferably extruded while being filtered.

[Method for producing fluorine matte film (F1)]
Examples of the molding method for obtaining the fluorine matte film (F1) include melt extrusion methods such as a T-die method and an inflation method, and among these, the T-die method is preferable in terms of economy. The melt extrusion temperature is, for example, about 150 to 235 ° C. Moreover, as an extruder, a single screw extruder and a twin screw extruder are mentioned, for example.

[Fluorine matte laminated film (F2)]
The fluorine mat layer film (F2) of the present invention is formed by laminating a fluorine mat resin layer (I) and an acrylic resin layer (II). The fluorine mat resin layer (I) is a layer made of the same resin composition as the material constituting the fluorine mat film (F1) described above.

[Acrylic resin layer (II)]
The acrylic resin layer (II) constituting the fluorine mat laminated film (F2) is a layer made of an acrylic resin composition. As this acrylic resin composition, an acrylic resin composition containing a rubber-containing polymer is preferable, and various conventionally known acrylic resin compositions can be used. In particular, when the fluorine-matte laminated film (F2) needs flexibility for building materials and the like, the resin compositions described in JP-B-62-19309 and JP-B-63-8983 are preferable. Further, when the fluorine mat laminated film (F2) needs to have scratch resistance, pencil hardness, heat resistance, and chemical resistance that can be used for vehicles in particular, JP-A-8-323934 and JP-A-11 The resin compositions described in JP-A No. 147237, JP-A No. 2002-80678, JP-A No. 2002-80679, JP-A No. 2005-97351 and the like are preferable. Further, in particular, when molding whitening resistance when insert molding or in-mold molding is required, JP 2004-137298 A, JP 2005-163003 A, JP 2005-139416 A, The resin composition described in Kaikai 2008-106252 and the like is preferable.

  As the acrylic resin composition suitably used for the acrylic resin layer (II), for example, a known rubber-containing multi-stage weight containing at least an alkyl acrylate and / or an alkyl methacrylate and a graft crossing agent as a constituent component of the polymer. Coalescence is mentioned. Among these, a rubber-containing multistage polymer having at least an alkyl acrylate and / or an alkyl methacrylate and a graft crossing agent as constituent components of the polymer is preferable. More specific examples of the preferable rubber-containing multistage polymer include at least an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and / or an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, and a graft crossing agent. An elastic polymer (S) as a constituent component of the polymer, and a hard polymer (H) having at least an alkyl methacrylate having a C 1-4 alkyl group as a constituent component of the polymer are polymerized in this order. And a rubber-containing multistage polymer. The terms “alkyl acrylate” and “alkyl methacrylate” mean alkyl esters of acrylic acid and methacrylic acid, respectively.

  Said elastic polymer (S) is, for example, an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and / or an alkyl methacrylate (S1) having an alkyl group having 1 to 4 carbon atoms (hereinafter referred to as “component ( S1) "), another monomer having a copolymerizable double bond (S2) (hereinafter referred to as component (S2)"), which is used as necessary, and a multifunctional monomer used as necessary. A polymer comprising a monomer (S3) (hereinafter referred to as “component (S3)”) and a graft crossing agent (S4) (hereinafter referred to as “component (S4)”) as constituent components, comprising a rubber-containing multistage It is polymerized first when polymerizing the polymer.

  Of the component (S1) constituting the elastic polymer (S), the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms may be either linear or branched. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and the like. These can be used alone or in admixture of two or more. Among these, those having a low glass transition temperature (Tg) are more preferable, and butyl acrylate is preferable. In addition, among the components (S1), the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms may be either linear or branched. Specific examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like. These can be used alone or in admixture of two or more.

  The alkyl (meth) acrylate (S1) is preferably used in the range of 60 to 100% by mass with respect to 100% by mass of the total amount of the components (S1) to (S3). Further, it is most preferable to use the same kind of alkyl (meth) acrylate used in the elastic polymer (A) even when the subsequent hard polymer is polymerized. However, in each polymer of components (S) and (H), two or more types of alkyl (meth) acrylates may be mixed, or another type of alkyl (meth) acrylate may be used. “Alkyl (meth) acrylate” means alkyl acrylate and / or alkyl methacrylate.

  What is necessary is just to use the component (S2) which comprises an elastic polymer (S) as needed. Specific examples thereof include higher alkyl acrylate having an alkyl group having 9 or more carbon atoms, lower alkoxy having an alkoxy group having 4 or less carbon atoms, alkyl acrylate monomers such as cyanoethyl acrylate, acrylamide, and acrylic acid. Methacrylic acid, styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile and the like. It is preferable to use a component (S2) within the range of 0-40 mass% with respect to 100 mass% of components (S1)-(S3) total.

  What is necessary is just to use the polyfunctional monomer (S3) which comprises an elastic polymer (S) as needed. As specific examples, it is preferable to use alkylene glycol dimethacrylate such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate. Further, polyvinyl benzene such as divinyl benzene and trivinyl benzene can also be used. Moreover, even when the polyfunctional monomer (S3) does not act at all, a rubber-containing multistage polymer is obtained which is considerably stable as long as the graft crossing agent is present. For example, when heat resistance or the like is strictly required, it may be arbitrarily used depending on the purpose of addition. It is preferable to use a component (S3) within the range of 0-10 mass% with respect to 100 mass% of components (S1)-(S3) total.

  Examples of the component (S4) constituting the elastic polymer (S) include copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid allyl, methallyl or crotyl ester. Particularly preferred are allyl esters of acrylic acid, methacrylic acid, maleic acid or fumaric acid. Among these, particularly allyl methacrylate has an excellent effect. In addition, triallyl cyanurate, triallyl isocyanurate and the like are also effective. In component (A4), the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group or crotyl group, and is chemically bonded.

  0.1-5 mass parts is preferable with respect to 100 mass parts of total amounts of component (S1)-(S3), and, as for the usage-amount of a component (S4), 0.5-2 mass parts is more preferable. The lower limit of these ranges is significant in terms of the effective amount of graft bonds. Further, the upper limit value is significant in that the amount of reaction with the polymer to be subsequently polymerized is moderately suppressed and the elasticity of the rubber elastic body is prevented from being lowered.

  The content of the elastic polymer (S) in the rubber-containing multistage polymer is preferably 5 to 70% by mass, and more preferably 5 to 50% by mass.

  The elastic polymer (S) in the rubber-containing multistage polymer may be polymerized 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 is a component involved in the moldability, mechanical properties, etc. of the rubber-containing multistage polymer, and an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms ( H1) (hereinafter referred to as “component (H1)”) and another monomer (H2) having a copolymerizable double bond (hereinafter referred to as “component (H2)”) used as necessary. A polymer as a constituent component, which is polymerized at the end of the rubber-containing multistage polymer.

  Preferred specific examples of the components (H1) and (H2) are the same as those described for the components (S1) and (S2) of the elastic polymer (S), respectively. As for the usage-amount of a component (H1), 51-100 mass% is preferable with respect to a total of 100 mass% of a component (H1) and a component (H2).

  The Tg of the hard polymer (H) alone is preferably 60 ° C. or higher, more preferably 80 ° C. or higher. The content of the hard polymer (H) in the rubber-containing multistage polymer is preferably 30 to 95% by mass, and more preferably 40 to 70% by mass.

  A preferable rubber-containing multistage polymer has the elastic polymer (S) and the hard polymer (H) described above as basic structures. In addition, after the elastic polymer (S) is polymerized and before the hard polymer (H) is polymerized, the intermediate polymer (M) may be polymerized in one stage or two or more stages.

  This intermediate polymer (M) uses alkyl acrylate (M1) having an alkyl group having 1 to 8 carbon atoms, alkyl methacrylate (M2) having an alkyl group having 1 to 4 carbon atoms, if necessary. A polymer comprising another monomer (M3) having a copolymerizable double bond, a polyfunctional monomer (M4) used if necessary, and a graft crossing agent (M5) used if necessary And the amount of the alkyl acrylate component monotonously decreases from the elastic polymer (S) toward the hard polymer (H). Here, monotonically decreasing means that the intermediate polymer (M) has a composition at one point between the composition of the elastic polymer (S) and the composition of the hard polymer (H), and is hard from the elastic polymer (S). It means that the composition approaches the polymer (H) gradually or continuously. In particular, what has an intermediate composition at one point may be the transparency of the resulting fluorine mat laminated film (F2).

  Preferred specific examples of the components (M1) to (M5) are the same as those described for the components (S1) to (S4) of the elastic polymer (S). In particular, the graft crossing agent (M5) used for the intermediate polymer (M) is preferably used in order to bind each polymer closely and obtain excellent properties.

  The amount of the component (M1) used is preferably 10 to 90% by mass in the intermediate polymer (M). The amount of the component (M2) used is preferably 10 to 90% by mass. As for the usage-amount of a component (M3), 0-20 mass% is preferable. The amount of the component (M4) used is preferably 0 to 10% by mass. The amount of component (M5) used is preferably 0.1 to 5% by mass.

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

  The average particle size of the rubber-containing multistage polymer produced by the emulsion polymerization method is 0.08 to 0.3 μm in consideration of the mechanical properties and transparency of the fluorine mat laminated film (F2) containing this as a main component. A range is preferred.

  A method for obtaining a rubber-containing multistage polymer includes, for example, emulsion polymerization, but is not particularly limited. For example, an emulsion prepared by mixing a monomer or a monomer mixture that gives the elastic polymer (S) with water and a surfactant is supplied to the reactor for polymerization, and then an intermediate polymer ( M) and a monomer or monomer mixture that gives the hard polymer (H) are respectively supplied to the reactor in order and polymerized.

  As the surfactant used in preparing the emulsion, anionic, cationic, and nonionic surfactants can be used. An anionic surfactant is particularly preferable.

  A well-known thing can be used for the polymerization initiator used for superposition | polymerization. As the addition method, a method of adding to one or both of the aqueous phase and the monomer phase can be used. Preferred initiators include peroxides, azo initiators, or redox initiators in which an oxidizing agent / reducing agent is combined. Among these, a redox initiator is more preferable, and a sulfoxylate initiator combined with ferrous sulfate / ethylenediaminetetraacetic acid disodium salt / longalite / hydroperoxide is particularly 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 polymer latex containing the rubber-containing multistage polymer can be treated using a filtration device provided with a filter medium as necessary. The rubber-containing multistage polymer is recovered in powder form from this latex by a method such as salting out, acid precipitation coagulation, spray drying, or freeze drying.

  The acrylic resin layer (II) contains, for example, a compounding agent such as a stabilizer, a lubricant, a processing aid, a plasticizer, an impact resistance aid, a foaming agent, a filler, a colorant, and an ultraviolet absorber as necessary. Can do.

  In particular, in terms of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. The type of the UV absorber is not particularly limited, but a benzotriazole UV absorber having a molecular weight of 400 or more and a triazine UV absorber having a molecular weight of 400 or more are particularly preferable. As the former commercial product, for example, trade name Tinuvin 234 of Ciba Specialty Chemicals, Asahi Denka Kogyo Co., Ltd., product name Adeka Stub LA-31 Asahi Denka Kogyo Co., Ltd. trade name ADK STAB LA-46 and the like.

  As for the addition amount of a ultraviolet absorber, 0.1-10 mass parts is preferable with respect to 100 mass parts of resin which comprises acrylic resin layer (II). From the viewpoint of weather resistance, the amount is more preferably 0.5 parts by mass, particularly preferably 1 part by mass or more. On the other hand, 5 parts by mass or less is more preferable, and 3 parts by mass or less is particularly preferable from the viewpoints of process contamination, solvent resistance, and transparency during film formation of the fluorine mat laminated film (F2).

  In particular, it is preferable that a light stabilizer is added to the acrylic resin layer (II). Known light stabilizers can be used, and radical scavengers such as hindered amine light stabilizers are particularly preferred. Examples of such commercially available light stabilizers include ADK STAB LA-57, ADK STAB LA-67, SANOL LS-770, etc. (trade names) (Asahi Denka Kogyo Co., Ltd.).

  The addition amount of the hindered amine light stabilizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin constituting the acrylic resin layer (II). From the viewpoint of light resistance, the amount is more preferably 0.2 parts by mass or more. On the other hand, it is more preferably 2 parts by mass or less, particularly preferably 1 part by mass or less, from the viewpoint of preventing process contamination during the film formation of the fluorine mat laminated film (F2).

  As a method for adding these compounding agents, for example, a method for supplying an acrylic resin layer (II) together with an acrylic resin composition to an extruder for forming an acrylic resin layer (II), and various kneaders prepared by adding a compounding agent to an acrylic resin composition in advance. The method of mixing and mixing is mentioned. Examples of the kneader used in the latter method include ordinary single screw extruders, twin screw extruders, Banbury mixers, roll kneaders, and the like. In the case of melt extrusion, each layer in a molten state is composed of a screen mesh of 200 mesh or more in order to remove cores and foreign matters that cause printing omission and poor appearance when printing on a film. The resin composition is preferably extruded while being filtered.

  The thickness of the fluorine mat laminated film (F2) is preferably 300 μm or less. In the case of a film used for a laminated molded product, the thickness is preferably 50 μm to 300 μm. When this thickness is 50 μm or more, a sufficient depth can be obtained in the appearance of the molded product. In particular, when molding into a complicated shape, a sufficient thickness can be obtained by stretching. On the other hand, when the thickness is 300 μm or less, since it has appropriate rigidity, laminating property, secondary workability and the like are improved. In addition, it is economically advantageous in terms of mass per unit area. Furthermore, the film forming property is stable and the production of the film becomes easy.

  The ratio of the layer thickness of the fluorine matting resin layer (I) and the acrylic resin layer (II) (hereinafter simply referred to as “(I) / (II)”) is not particularly limited. However, from the viewpoints of solvent resistance, cost, surface hardness, transparency, matte appearance and printability of the fluorine mat laminated film (F2), (I) / (II) = 1/99 to 20/80 is preferable. (I) / (II) = 2/98 to 10/90 is more preferable. In the present invention, the thickness of each of the fluorine matting resin layer (I) and the acrylic resin layer (II) is a transmission type sample obtained by cutting the fluorine matting laminated film (F2) into a thickness of 70 nm in the cross-sectional direction. It observes with an electron microscope, measures each thickness in five places, and calculates by averaging them. An example of a commercially available transmission electron microscope is J100S (trade name) manufactured by JEOL Ltd.

  Regarding the surface hardness of the fluorine mat laminated film (F2), the pencil hardness (JIS K5400) is preferably higher than B. Further, HB or more is more preferable, and F or more is most preferable. When the fluorine mat laminated film (F2) having a pencil hardness higher than B is used, it is difficult to be scratched during the process of insert molding or in-mold molding described below, and the scratch resistance of the molded product is also good. When used for vehicle applications, the pencil hardness of the fluorine mat laminated film (F2) is more preferably HB or higher. When the pencil hardness of the fluorinated matte laminated film (F2) is HB or higher, the resulting laminate is suitable for use in various vehicle components such as door waist garnish, front control panel, power window switch panel, airbag cover, etc. I can do it. Furthermore, when the pencil hardness is higher than F, the scratches are hardly noticeable even when scratched with a cloth having a rough surface such as gauze, so that the industrial utility value is increased. As described above, the surface hardness of the fluorine mat layered film (F2) is the ratio of the layer thickness of the fluorine mat resin layer (I) and the acrylic resin layer (II) ((I) / (II)) or acrylic resin. What is necessary is just to adjust by selecting the acrylic resin composition which comprises layer (II).

[Production method of fluorine mat laminated film (F2)]
As a method for producing the fluorine mat laminated film (F2) of the present invention, various conventionally known methods can be used. For example, a method of forming a laminated structure of a fluorine mat resin layer (I) and an acrylic resin layer (II) by a coextrusion molding method through a feed block die or a multi-manifold die, or a fluorine mat resin layer (I) And the acrylic resin layer (II) are formed into a film by a melt extrusion method using a T die, and the two types of films are laminated by a thermal laminating method. Further, an extrusion lamination method in which the fluorine mat resin layer (I) is formed into a film and then the acrylic resin layer (II) is laminated by a melt extrusion method may be used. In this case, the fluorine mat resin layer (I) and the acrylic resin layer (II) may be exchanged. In particular, from the viewpoint of economy and process simplification, it is preferable to form a laminated structure of the fluorine mat resin layer (I) and the acrylic resin layer (II) by a coextrusion molding method. Specifically, for example, a coextrusion molding method through a feed block die or a multi-manifold die as described above is particularly preferable.

  Further, for example, as described in JP-A-2002-361712, a fluorine mat resin layer (I) and an acrylic resin layer (II) by a co-extrusion molding method through a feed block die or a multi-manifold die or the like. When forming this laminated structure, a method of manufacturing by sandwiching between a mirror roll and a rubber roll is also preferable. When the acrylic resin layer (II) side constituting the fluorine mat layered film (F2) is in contact with the mirror roll, the mirror smoothness on the side where the acrylic resin layer (II) is laminated is even better, and as a result It is preferable because the printability can be imparted. The fluorine matting resin layer (I) side is preferably in contact with the rubber roll. In this case, it is possible to improve the mirror smoothness on the acrylic resin layer (II) side without increasing the surface glossiness of the fluorine matting resin layer (I) (that is, while maintaining a good matting degree). High utility value.

  The rubber roll to be used is not particularly limited, but a silicone rubber roll is preferable from the viewpoint of heat resistance. A known processing method can be used for the surface finishing of the silicone rubber roll. However, from the viewpoint of consistency between the surface appearance of the fluorine mat laminated film (F2) and the surface appearance of the laminate finally obtained by insert molding or in-mold molding, room temperature curable silicone rubber is applied to the outermost surface. A rubber roll produced by finishing is preferred.

  Each of the fluorine mat resin layer (I) and the acrylic resin layer (II) constituting the fluorine mat laminated film (F2) may be composed of a plurality of layers.

  In addition, when performing melt extrusion, in order to remove nuclei and foreign matters that may cause printing loss, extrusion is performed while filtering the resin composition constituting each layer in a molten state with a screen mesh of 200 mesh or more. Is preferred.

[Fluorine matte decorative laminated film (F3)]
The fluorine mat decorative laminated film (F3) of the present invention has a pattern layer (III) on at least one side of the fluorine mat laminated film (F2). In particular, those having a pattern layer (III) on the acrylic resin layer (II) side are preferable from the viewpoint of printability.

  Further, at the time of manufacturing a laminated sheet (F4) or a laminated molded product to be described later, it is possible to arrange the pattern layer (III) on the adhesive surface side with the thermoplastic resin layer (IV) or the base material (V). It is preferable from the viewpoint of protection of the film and imparting a high-class feeling.

[Picture layer (III)]
The pattern layer (III) constituting the fluorine mat decorative laminated film (F3) can be formed by a known method. In particular, one or both of a printing layer formed by a printing method and a vapor deposition layer formed by a vapor deposition method is preferably used as the pattern layer (III). This printed layer becomes a pattern or characters on the surface of the laminate obtained by insert or in-mold molding described later. Examples of the print pattern include a pattern made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, letters, full-face solid, metallic and the like.

  For the formation of the printing layer as the picture layer (III), a colored ink containing a binder and an appropriate color pigment or dye may be used. Examples of binders 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 ester resins. And resins such as alkyd resins and chlorinated polyolefin resins. Various known pigments can be used as the pigment. For example, examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as yellow lead. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as petals. Examples of the blue pigment include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue. Examples of the black pigment include organic pigments such as aniline black. Examples of the white pigment include inorganic pigments such as titanium dioxide. Various known dyes can be used as the dye.

  Examples of the method for forming the printing layer include known printing methods such as offset printing, gravure rotary printing, and screen printing, known coating methods such as roll coating and spray coating, flexographic printing, and the like. The thickness of the printing layer may be appropriately determined as necessary, and is usually about 0.5 to 30 μm. The thickness of the printed layer may be appropriately selected according to the degree of elongation at the time of molding so that a desired surface appearance can be obtained in a laminate obtained by insert or in-mold molding described later.

  The vapor deposition layer as the pattern layer (III) is, for example, at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead and zinc, or these These alloys or metal compounds can be used. Examples of the method for forming the vapor deposition layer include vacuum vapor deposition, sputtering, ion plating, and plating. The thickness of the vapor-deposited layer may be appropriately selected according to the degree of expansion at the time of molding so that a desired surface appearance can be obtained in a laminated molded body obtained by insert or in-mold molding described later.

[Laminated sheet (F4)]
The laminated sheet (F4) of the present invention is a film and a thermoplastic resin selected from the group consisting of a fluorine mat film (F1), a fluorine mat film (F2), and a fluorine mat decorative film (F3). The sheet is formed by laminating the layer (IV). The thermoplastic resin layer (IV) may be laminated on at least one surface of the film. In particular, the surface on the acrylic resin layer (II) side having excellent smoothness of the film surface is disposed on the thermoplastic resin layer (IV). It is preferable to laminate so as to.

[Thermoplastic resin layer (IV)]
The thermoplastic resin layer (IV) constituting the laminated sheet (F4) is preferably made of a material having compatibility with the base material (V) for the purpose of improving adhesion with the base material (V) described later. . In particular, those made of the same material as the substrate (V) are more preferred.

  As the thermoplastic resin layer (IV), a known thermoplastic resin film or sheet can be used. Specific examples thereof include acrylic resins, ABS resins, AS resins, chlorinated resins such as polyvinyl chloride and polyvinylidene chloride, polyolefin resins such as polyethylene, polypropylene, polybutene and polymethylpentene, ethylene-vinyl acetate copolymers or Saponified products, polyolefin copolymers such as ethylene- (meth) acrylic acid ester copolymers, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, copolymer polyester, Polyamide resins such as nylon, 6,6-nylon, 6,10-nylon, 12-nylon, polystyrene resins, cellulose derivatives, fibrous derivatives such as nitrocellulose, polyvinyl fluoride, polyvinylidene fluoride, Li tetrafluoroethylene, ethylene - fluorocarbon resin such as tetrafluoroethylene copolymers, or two or more copolymers, or a mixture selected from these, complexes, laminates, and the like. Among these, the formability of the pattern layer (III) (the pattern layer (III) is not formed on the fluorine matte film (F1) or the fluorine matte decorative film (F2), but the thermoplastic resin layer (IV)). From the viewpoint of secondary formability of the laminated sheet (F4), acrylic resin, ABS resin, vinyl chloride resin, polyolefin, and polycarbonate are preferable.

  For the thermoplastic resin layer (IV), for example, stabilizers, antioxidants, lubricants, processing aids, plasticizers, impact agents, foaming agents, fillers, antibacterial agents, antifungal agents, You may mix | blend compounding agents, such as a mold release agent, an antistatic agent, a coloring agent, a ultraviolet absorber, a light stabilizer, a heat stabilizer, a flame retardant.

  The thickness of the thermoplastic resin layer (IV) may be appropriately determined as necessary. Usually, it is preferably about 20 to 500 μm. The thermoplastic resin layer (IV) may have a thickness such that the appearance of the laminated sheet (F4) has a completely smooth upper surface, absorbs surface defects of the base material, or the pattern layer does not disappear during injection molding. preferable.

  Examples of the method for obtaining the laminated sheet (F4) include known methods such as thermal lamination, dry lamination, wet lamination, hot melt lamination and the like. Further, the fluorine mat film (F1) or the fluorine mat laminated film (F2) and the thermoplastic resin layer (IV) can be laminated by extrusion lamination.

  The laminated sheet (F4) exhibits sufficient strength for handling against external forces such as impact and deformation. For example, after film is vacuum formed by insert molding, which will be described later, it is removed from the mold, or when the vacuum molded product is mounted on an injection mold, cracks, etc. are incurred. It is difficult to occur and the handleability is good.

[Heat seal layer]
The heat seal layer is a case where the fluorine mat film (F1), the fluorine mat laminated film (F2), the fluorine mat decorative laminate film (F3) and the thermoplastic resin layer (IV) of the present invention are firmly bonded. Use as appropriate. When the fluorine matting film (F1), the fluorine matting laminated film (F2), the fluorine matting decorative laminate film (F3) and the thermoplastic resin layer (IV) of the present invention have adhesiveness Although not necessary, it is preferable to use it in order to increase the interlayer strength. As the heat sealant used for the heat seal layer, acrylic-polyester-vinyl acetate resin is suitable, but it is not particularly limited thereto.

[Laminated molded products]
The laminate molded product of the present invention is a film selected from the group consisting of a fluorine mat film (F1), a fluorine mat laminate film (F2), a fluorine mat decorating laminate film (F3), and a laminate sheet (F4). Alternatively, the sheet is laminated on the substrate (V). In particular, it is preferable to laminate so that the surface on the acrylic resin layer (II) side having excellent smoothness of the film surface is in contact with the substrate (V).

  Examples of the material of the substrate (V) include resin, wood veneer, wood plywood, particle board, medium density fiber board (MDF) and other wood boards, wood fiber board and other water quality boards, and metals such as iron and aluminum. Etc.

  Examples of the resin constituting the substrate (V) include polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, polyolefin resins such as olefin thermoplastic elastomer, polystyrene General-purpose thermoplastic or thermosetting resins such as resins, ABS resins, AS resins, acrylic resins, urethane resins, unsaturated polyester resins, epoxy resins, polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetals, polycarbonate modified polyphenylene ethers General-purpose engineering resins such as polyethylene terephthalate, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyetherimide, polyimide, liquid crystal polyester, poly Super engineering resins such as rill-based heat-resistant resins, reinforcing materials such as glass fibers or inorganic fillers (talc, calcium carbonate, silica, mica, etc.), composite resins added with modifiers such as rubber components, or various modified resins Can be mentioned.

  Among these, resins capable of being melt-bonded are preferable, and for example, ABS resins, AS resins, polystyrene resins, polycarbonate resins, vinyl chloride resins, acrylic resins, polyester resins, or resins containing these as main components are preferable. In terms of adhesiveness, an ABS resin, an AS resin, a polycarbonate resin, a vinyl chloride resin, or a resin containing these as a main component is preferable, and an ABS resin, a polycarbonate resin, or a resin containing these as a main component is more preferable. Moreover, even if it is resin which is not heat-sealed, such as polyolefin resin, it is possible to make it adhere | attach at the time of shaping | molding by providing an contact bonding layer.

  As a manufacturing method of a laminated body, when it is a two-dimensionally shaped laminated body and the substrate can be heat-sealed, a known method such as thermal lamination can be used. For example, for wood substrates such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), water quality boards such as wood fiber board, metals such as iron and aluminum, etc. It is possible to bond them through an adhesive layer.

  In the case of a three-dimensional laminated product, as a manufacturing method thereof, for example, an insert molding method, an in-mold molding method, or a vacuum molding apparatus is used to laminate a molding object on the surface of a mold prepared in advance. And a method (hereinafter referred to as “three-dimensional overlay laminate molding method”).

  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 vacuum forming or the like, and unnecessary film or sheet portions are removed by trimming, and then an injection mold. This is a method for obtaining a molded product (laminate) by integrating the resin as a base material by injection molding.

  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 a resin as a base material in the same mold This is a method of obtaining a molded product (laminated body) by integrating them.

  In the three-dimensional overlay laminate molding method, first, two sealed spaces partitioned by a sheet are formed, a molded body is disposed on one space side, and only the space in which both 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 this 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 a curved surface or the like, the sheet can be satisfactorily adhered to the molded body. Can do. As an apparatus to be used, for example, “TOM (trade name)” manufactured by Fuse Vacuum Co., Ltd. may be mentioned.

  Since the fluorine matting film (F1), the fluorine matting laminated film (F2), the fluorine matting decorative laminated film (F3), and the laminated sheet (F4) of the present invention are rich in elongation at high temperatures, This is very advantageous when a three-dimensional shape is imparted by molding.

  As a base material (V) used for injection molding, the shrinkage rate after injection molding is the fluorine matting film (F1), the fluorine matting laminated film (F2), the fluorine matting decorative laminated film (F3) of the present invention. ), A resin approximate to the shrinkage rate of the laminated sheet (F4) is preferable. When the shrinkage ratios of the two are approximate, problems such as warpage of the laminate obtained by in-mold molding, insert molding and three-dimensional overlay lamination, or peeling of the film or sheet are less likely to occur.

Hereinafter, the present invention will be described with reference to examples and comparative examples. In the following description, “part” represents “part by mass”. Moreover, evaluation of each film, sheet | seat, and laminated molded product was performed with the following method. 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“ LPO ”: lauryl peroxide“ t-BH ”: t-butyl hydroperoxide“ EDTA ”: disodium ethylenediaminetetraacetate“ HEMA ”: 2-hydroxyethyl methacrylate“ MEK ”: methyl ethyl ketone.

(1) Mass average particle diameter of non-crosslinked acrylic resin (B):
The mass average particle diameter of the non-crosslinked acrylic resin (B) was measured using a laser diffraction scattering type particle size distribution analyzer LA-910 manufactured by HORIBA.

(2) Mass average particle diameter of acrylic resin compositions (2-1) and (2-2):
Using a light scattering photometer DLS-700 (trade name) manufactured by Otsuka Electronics Co., Ltd., the mass average particle diameters of the acrylic resin compositions (2-1) and (2-2) were measured by a dynamic light scattering method. .

(3) Intrinsic viscosity of the non-crosslinked acrylic resin (B):
The intrinsic viscosity of the non-crosslinked acrylic resin (B) was measured with an AVL-2C automatic viscometer manufactured by Sun Electronics Co., Ltd. at 25 ° C. in a chloroform solvent.

(4) Gel content of acrylic resin compositions (2-1) and (2-2):
A predetermined amount (mass before extraction) of the acrylic resin composition (2-1) and (2-2) powder is extracted under reflux in an 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
(5) Appearance:
The A4 size fluorine matte film (F1) or fluorine matte resin layer (I) side was visually observed, and the appearance was evaluated according to the following criteria.
“◯”: 0 to 3 fish eyes due to poor dispersion of non-crosslinked acrylic resin.
“Δ”: 4 to 10 fish eyes due to poor dispersion of non-crosslinked acrylic resin.
“X”: 11 or more fish eyes due to poor dispersion of non-crosslinked acrylic resin.

(6) 60 degree surface glossiness:
In accordance with JIS Z8741, a portable gloss meter (trade name: GM-268, manufactured by Konica Minolta Sensing Co., Ltd.) is used, and the 60 ° surface glossiness on the fluorine matting film (F1) or fluorine matting resin layer (I) side Was measured.

(7) Matting property:
The surface on the fluorine matting film (F1) or fluorine matting resin layer (I) side was visually observed, and matting properties were evaluated according to the following criteria.
“◎”: It has a very fine matte state.
“O”: A fine matte state.
"X": It has a rough matte state.

(8) Average interval (Sm) of film surface irregularities:
Using a shape measurement laser microscope VK-8500 (trade name) manufactured by Keyence Co., Ltd., an average interval (Sm) of surface irregularities formed on the surface of the fluorine matte film (F1) was measured at a magnification of 200 times.

(9) Solvent resistance 1:
One drop of a solvent (acetone or MEK) was dropped on the surface of the fluorine matte film (F1) or the fluorine matting resin layer (I) and left to dry at room temperature. The sample surface after drying was visually observed, and the solvent resistance was evaluated according to the following criteria.
“◯”: There is no change on the sample surface.
“Δ”: A slight trace of 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.

(10) Solvent resistance 2:
A gauze was placed on the surface of the fluorine matting film (F1) or the fluorine matting resin layer (I), a drop of suntan lotion (trade name: Coppertone Waterbabies 30SPF) was dropped thereon, and an aluminum plate was further included thereon. A load of 500 g was applied and left at 74 ° C. for 1 hour. The sample surface after the test was visually observed, and the solvent resistance was evaluated according to the following criteria.
“◯”: There is no change on the sample surface.
“Δ”: A slight trace of solvent remains on the sample surface.
"X": The trace of the solvent or gauze remains clearly on the sample surface, or the surface of the sample surface in contact with the solvent is cloudy.

(11) Solvent resistance 3:
One drop of 10% lactic acid aqueous solution was dropped on the surface of the fluorine matte film (F1) or the fluorine matting resin layer (I) and left at 80 ° C. for 24 hours. The sample surface after the test was visually observed, and the solvent resistance was evaluated according to the following criteria.
“◯”: There is no change on the sample surface.
“Δ”: A slight trace of 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) 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 fluorine matting film (F1) or fluorine matting resin layer (I), and is firmly attached to the test piece with a crimping device, and the air freshener for automobiles in the opening (5 ml of Grace Mate Poppy Citrus, manufactured by Dia Chemical Co., Ltd.) 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 then air-dried, and the whitening state of the surface of the test part was observed.
“◯”: There is no change on the sample surface.
“Δ”: A slight trace of 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.

(13) 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 fluorine matting film (F1) or fluorine matting resin layer (I), and is firmly attached to the test piece with a crimping machine, and a plasticizer for plastics in the opening. 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 crimper was removed, the test piece was washed with water and then air-dried, and the whitening state of the surface of the test part was observed.
“◯”: There is no change on the sample surface.
“Δ”: A slight trace of 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.

(14) Solvent resistance 6:
One drop of N, N-diethyl-m-toluamide was dropped on the surface of the fluorine matting film (F1) or the fluorine matting resin layer (I) and left at 80 ° C. for 24 hours. The sample surface after the test was visually observed, and the solvent resistance was evaluated according to the following criteria.
“◯”: There is no change on the sample surface.
“Δ”: A slight trace of 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.

(15) Fluorine matte resin layer (I) and acrylic resin layer (II) thickness of each layer:
A sample obtained by cutting the fluorine matte resin laminated film (F2) to a thickness of 70 nm in the cross-sectional direction is observed with a transmission electron microscope (trade name J100S, manufactured by JEOL Ltd.). It was calculated and determined by measuring and averaging them.

(16) Printability of fluorine mat laminated film (F2):
A silver metallic pattern was provided as a pattern layer on the acrylic resin layer (II) side by gravure printing. The number of missing prints was counted and evaluated as follows.
“◯”: The number of missing prints is less than 1 / m ² .
“×”: The number of missing prints is 10 / m ² or more.

(17) Surface hardness of laminated molded product:
The surface hardness was measured according to JIS K5400 using the fluorine mat resin layer (I) surface of the laminated molded product.

[Preparation Example 1] (Production of hydroxyl group-containing polymer (1-1) as non-crosslinked acrylic resin (B))
The following monomer mixture (1) was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like. Next, after sufficiently replacing the inside of the container with nitrogen gas, the monomer mixture (1) in the reaction container was heated to 75 ° C. with stirring, and reacted in a nitrogen gas stream for 3 hours. Thereafter, the temperature in the reaction vessel is raised to 90 ° C., and is further maintained for 45 minutes to complete the polymerization, followed by sieving under conditions of 150 mesh (aperture 100 μm), and the passed beads are dehydrated. And dried to obtain a hydroxyl group-containing polymer (1-1).

SPA obtained hydroxyl group-containing polymer (1-1) was 22.6J ^1/2 cm ^-3/2. Moreover, Tg of the polymer was 77 ° C., the intrinsic viscosity was 0.06 L / g, Mw / Mn was 2.1, and the mass average particle diameter was 70 μm. The shear viscosity (SVA) under the conditions of 220 ° C. and a shear rate of 60 sec ⁻¹ was 1662.3 Pa · s.

<Monomer mixture (1)>
MA: 10 parts MMA: 60 parts HEMA: 30 parts n-octyl mercaptan: 0.18 parts LPO: 1 part Tricalcium phosphate: 1.8 parts Water: 250 parts.

[Preparation Example 2] (Production of acrylic resin composition (2-1) as acrylic resin layer (II))
<Rubber-containing polymer (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 together with 0.025 part of CHP, and stirred and mixed at room temperature. Subsequently, 1.3 parts of an emulsifier (manufactured by Toho Chemical Co., Ltd., trade name Phosphanol RS610NA) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.
(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 charged into the polymerization vessel at once. Next, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the 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 CHP 0.016 part, and then the reaction was continued for 60 minutes to obtain the monomer mixture (a-A). ) Of the second stage of polymerization was completed.
(A-A-2)
MMA: 1.5 parts n-BA: 22.5 parts 1,3-BD: 1.0 part AMA: 0.25 part FOX for the monomer mixture (a-A-1) used in 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 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 (a-B) was 20 degreeC.
(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 n-OM 0.19 parts and t-BH 0.08 parts over 140 minutes. After dripping into the polymerization vessel, the reaction was continued for 60 minutes to obtain a polymer latex of the rubber-containing polymer (a).
(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. Moreover, the mass average particle diameter of the rubber-containing polymer (a) measured after polymerization was 0.12 μm.

  The polymer latex of the rubber-containing polymer (a) thus obtained was filtered using a vibration type filtration device equipped with a SUS mesh (average opening: 62 μm) as a filter medium, and then 3.5 parts of calcium acetate was added. Salting out was carried out in an aqueous solution containing, recovered by washing with water, 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 the rubber-containing polymer (a) obtained by the above procedure, and further 1.4 parts of an ultraviolet absorber (trade name: Tinuvin 234, manufactured by Ciba Specialty Chemicals Co., Ltd.), an antioxidant (Asahi Denka Kogyo Co., Ltd.) 0.1 parts manufactured and trade name ADK STAB AO-50) and 0.3 parts light stabilizer (Asahi Denka Kogyo Co., Ltd. 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., kneaded, and extruded with an extruder while removing foreign matters with a 300 mesh screen mesh. Pelletized to obtain an acrylic resin composition (2-1) constituting the acrylic resin layer (II).

[Preparation Example 3] (Production of acrylic resin composition (2-2) as acrylic resin layer (II))
<Rubber-containing polymer (b)>
An emulsion was prepared in the same manner as in Preparation Example 2, except that the amount of deionized water charged in the container in advance was changed to 10.8 parts. Next, the amount of deionized water to be added is changed to 139.2 parts, and the temperature of the temperature rise is changed to 75 ° C. The first stage of the monomer mixture (aA) of Preparation Example 2 In the same manner as the polymerization, the first stage polymerization of the monomer mixture (b-A) was completed.

Subsequently, the monomer mixture (a-) of Preparation Example 2 was used except that the monomer component (b-A-2) shown below was used instead of the monomer component (a-A-2). In the same manner as in the second stage polymerization of A), the second stage polymerization of the monomer mixture (b-A) was completed.
(B-A-2)
MMA: 9.6 parts n-BA: 14.4 parts 1,3-BD: 1.0 part AMA: 0.25 part FOX for 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 polymerization of the monomer mixture (a-B) of Preparation Example 2 except that the monomer mixture (b-B) shown below was used instead of the monomer mixture (a-B). Polymerization was carried out in the same manner as described above.
(B-B)
MMA: 6 parts MA: 4 parts AMA: 0.075 part The Tg determined from the FOX equation for the monomer mixture (b-B) was 60 ° C.

Subsequently, instead of the monomer mixture (a-C), the monomer mixture (b-C) shown below was used, except that the amount of n-OM was changed to 0.264 part. Polymerization was carried out in the same manner as in the polymerization of the monomer mixture (a-C) in Example 2 to obtain a polymer latex of a rubber-containing polymer (b).
(B-C)
MMA: 57 parts MA: 3 parts The Tg determined from the FOX equation for the monomer mixture (b-C) was 99 ° C. Moreover, the mass average particle diameter of the rubber-containing polymer (b) measured after polymerization was 0.11 μm.

  The polymer latex of the obtained rubber-containing polymer (b) was filtered and collected in the same manner as in Preparation Example 2, and dried to obtain a powdery rubber-containing polymer (b). The gel content of the rubber-containing polymer (b) was 70% by mass.

  Then, instead of 100 parts of rubber-containing polymer (a), 45 parts of rubber-containing polymer (b) and thermoplastic polymer [MMA / MA copolymer (MMA / MA = 99/1 (mass ratio), reduced Viscosity ηsp / c = 0.06 L / g) Except that 55 parts were used, each additive was mixed in the same manner as in Preparation Example 2, extruded with an extruder while removing foreign matters with a 300 mesh screen mesh, and pellets And an acrylic resin composition (2-2) constituting the acrylic resin layer (II) was obtained.

<Example 1>
As the “(a)” of the fluororesin (A), polyvinylidene fluoride (manufactured by Arkema Co., Ltd., trade name: KYNAR740, 220 ° C., shear rate (SVF) at a shear rate of 60 sec ⁻¹ ) = 996.7 Pa · s for solubility parameter ^{(SPF) = 17.1J 1/2 cm -3/2} ) 100 parts of a hydroxyl group-containing polymer obtained in Preparation example 1 (1-1) 5 parts were blended, using a Henschel mixer For 30 seconds, using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., trade name: TEM45, L / D = 32), cylinder temperature 180-200 ° C, die head temperature 220 ° C, screw rotation speed (Ns) Extruding while removing foreign matters with a 300 mesh screen mesh under two conditions of 250 rpm and extrusion rate (Q) 80 kg / hr or 50 kg / hr, and cutting into pellets.

  After the obtained pellets were dried, each film was formed using a 40φ film forming machine (manufactured by Musashinokikai Co., Ltd.) while removing foreign matter with a 300 mesh screen mesh by the T-die method, and a fluorine film (F1) having a thickness of about 50 μm. ) In the film formation, the cylinder temperature was set to 180 to 220 ° C., and the temperature of the T-die was set to 230 ° C. Table 1 shows the evaluation results of 60 ° surface gloss, matteness, appearance, Sm and solvent resistance of the obtained film.

<Examples 2-3 and Comparative Examples 1-2>
In Example 1, it implemented like Example 1 except having mix | blended the fluororesin (A) shown in Table 1, and the non-crosslinked acrylic resin (B).

Abbreviations and abbreviations in the table are as follows.
Fluorine resin (A) "(a)": polyvinylidene fluoride (Arkema Co., Ltd. under the trade name KYNAR740, SVF = 996.7Pa · s, SPF = 17.1J 1/2 cm -3/2)
Fluorine resin (A) "(b)": polyvinylidene fluoride (Kureha Co., Ltd. under the trade name KF-T1000, SVF = 1173.0Pa · s, SPF = 17.1J 1/2 cm -3/2 )
Fluorine resin (A) "(c)": polyvinylidene fluoride (Arkema Co., Ltd. under the trade name KYNAR760, SVF = 2139.3Pa · s, SPF = 17.1J 1/2 cm -3/2)
Fluorine resin (A) "(d)": polyvinylidene fluoride (Arkema Co., Ltd. under the trade name KYNAR720, SVF = 700.8Pa · s, SPF = 17.1J 1/2 cm -3/2)
· "Hydroxyl group-containing polymer (1-1)": hydroxyl group-containing polymer obtained in Preparation Example 1 (SVA = 1662.3Pa · s, SPA = 22.6J 1/2 cm -3/2)
"Thermoplastic polymer": Methyl methacrylate (MMA) -methyl acrylate (MA) copolymer (MMA / MA = 87/13 (mass ratio), reduced viscosity ηsp / c = 0.06 L / g, SVA = 1443 ^{.0Pa · s, SPA = 20.3J 1/2} cm -3/2)
“Δσ”: SPA-SPF (J ^1/2 cm ^−3/2 ).

  From the examples and comparative examples described above, the following became clear.

  In Examples 1 to 3, even if the raw material pelletized under any conditions of the extrusion rate (Q) of 80 kg / hr and 50 kg / hr is used, the fluororesin originally has the solvent resistance and has a fine texture. A matte film having a matte state was obtained. However, in Example 3, since the SVA / SVF was low, a matte film having a good appearance was obtained, but a cut occurred in the width direction from the end portion in some places. That is, the film forming property was slightly inferior to Examples 1 and 2.

On the other hand, in Comparative Example 1, since SVA / SVF is too large, when a raw material pelletized under a high production condition with an extrusion rate (Q) of 80 kg / hr is used, fish eyes are generated due to poor dispersion, and the appearance is A good matte film could not be obtained. In Comparative Example 2, Δσ (SP
Since (A-SPF) is too low, the matte property was insufficient.

<Example 4>
The fluorine resin composition pellets obtained in Example 1 constituting the fluorine mat resin layer (I) and the acrylic resin composition (2-1) obtained in Preparation Example 2 constituting the acrylic resin layer (II) The pellets were dried at 80 ° C. overnight. The acrylic resin composition (2-1) is plasticized using a non-vent screw type 65 mmφ extruder provided with a 500 mesh screen mesh set at a cylinder temperature of 240 ° C., while the cylinder temperature is also increased to 180 to 220 ° C. The fluororesin composition is plasticized using a 25 mmφ extruder provided with a set 500 mesh screen mesh, and then set to 240 ° C for a two-kind, two-layer multimanifold die, with the acrylic resin layer (II) side having a mirror surface A fluorine mat laminated film (F2) having a thickness of 50 μm was produced so as to be in contact with the cooling roll.

  When the cross section of the fluorine mat layered film (F2) was observed, the thickness of the fluorine mat resin layer (I) was 5 μm, and the thickness of the acrylic resin layer (II) was 45 μm.

  On the other hand, as a thermoplastic resin layer (IV), a 90 μm-thick film (RIKEN TECHNOS) containing a hindered phenolic antioxidant, a UV absorber, a hindered amine light stabilizer, and iron oxide (pigment) in a randomly polymerized polypropylene resin. Co., Ltd., trade name: Ribest TPO) was used. On the surface of this thermoplastic resin layer (IV), as a pattern layer (III), the binder resin is an acrylic resin and vinyl chloride resin, the pigment is at least one of isoindoline, diketopyrrolopyrrole, carbon black, phthalocyanine blue The pattern was printed by the gravure printing method using the following ink. The pattern layer (III) was arranged so that the acrylic resin layer (II) side of the fluorine mat laminated film (F2) was in contact, and these were thermally laminated to obtain a laminated sheet (F4).

<Example 5>
As the acrylic resin layer (II), the acrylic resin layer (2-2) obtained in Preparation Example 3 was used in place of the acrylic resin composition (2-1) obtained in Preparation Example 2, and the fluorine-matte laminated film was used. A fluorine mat laminated film (F2) was obtained in the same manner as in Example 4 except that the thickness was changed to 125 μm.

  When the cross section of the fluorine mat layered film (F2) was observed, the thickness of the fluorine mat resin layer (I) was 5 μm, and the thickness of the acrylic resin layer (II) was 120 μm.

  A silver metallic pattern as a pattern layer (III) was provided by gravure printing on the acrylic resin layer (II) side of the obtained fluorine mat laminated film (F2) to obtain a fluorine mat decorating laminated film (F3). The printability evaluation was “◯”.

  Further, an ABS sheet having a thickness of 0.35 mm having an adhesive layer as the thermoplastic resin layer (IV) was laminated by thermal lamination so that the adhesive layer and the silver metallic pattern layer were in contact with each other, to obtain a laminated sheet (F4). It was. Molding was performed using this laminated sheet (F4). Specifically, this laminated sheet (F4) is placed in a mold having a vacuuming function so that the fluorine mat laminated film (F2) side becomes the cavity side, and the laminated sheet (F4) is kept at 190 ° C. After heating with a heater until it reached, vacuum forming was performed.

  Unnecessary portions of the vacuum-formed laminated sheet (F4) (portions that do not adhere to the substrate (V) in the final laminated body) were trimmed from the fluorine mat laminated film (F2) side using a Thomson punching die.

The laminated sheet (F4) after trimming the unnecessary part is a mold having a recess of 1 cm ² and a depth of 1 mm at a position 3 cm laterally from the bottom of the mold on the cavity side and the central gate. Was placed so that the fluorine mat laminated film (F2) side of the laminated sheet (F4) was the cavity side. Next, ABS resin (UMG ABS Co., Ltd., trade name Diapet ABS Bulk Sum TM25) serving as the base material (V) is injection-molded on the thermoplastic resin layer (IV) of the laminated sheet (F4) and laminated by insert molding. A body (laminated molded product) was obtained.

  The shape of the laminated body is a box shape with a length of 150 mm × width of 120 mm × thickness of 2 mm and a depth of 10 mm. The gate position of the mold is one in the middle of the laminated body, and 40 mm above and below the central gate (stacked body longitudinal direction). The gate shape is a pinpoint gate having a diameter of 1 mm. The corner corner R connecting the bottom surface and the side surface on the cavity side of the mold is about 3. The corner R was measured with RADIUS GAGE (trade name) manufactured by FUJI TOOL. This injection molding was performed using a J85 ELII type injection molding machine (trade name) manufactured by Nippon Steel Works, Ltd. under the conditions of a cylinder temperature of 250 ° C., an injection speed of 30%, an injection pressure of 43%, and a mold temperature of 60 ° C. . Various evaluations of the laminated molded product were performed. The results are shown in Table 2.

<Examples 6 to 7>
Except that the fluorine matte resin layer (I) and acrylic resin layer (II) layer thickness and ratio [(I) / (II)] were changed as shown in Table 2, the same procedure as in Example 5 was performed. A laminated molded product was produced and evaluated. The results are shown in Table 2.

  The fluorine-matte film (F1), fluorine-matte laminated film (F2), fluorine-matte decorative laminated film (F3), laminated sheet (F4) and laminated molded product of the present invention are particularly suitable for vehicle applications and building material applications. ing. Specific examples include instrument panels, console boxes, meter covers, door lock pezels, steering wheels, power window switch bases, center clusters, dashboards and other automotive interior applications, 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, etc., automotive exterior applications such as windows, headlamp covers, tail lamp covers, windshield parts, AV equipment and furniture products Applications such as front panels, buttons, emblems, surface cosmetics, housings for mobile phones, display windows, buttons, etc. Building interior materials such as surfaces, ceilings, floors, exterior walls such as siding, exterior materials for buildings such as fences, roofs, gates, and windbreak boards, surfaces of furniture such as window frames, doors, handrails, sills, and duck Cosmetic materials, various displays, lenses, mirrors, goggles, window glass and other optical components, trains, airplanes, ships and other vehicles other than automobiles, interior and exterior applications, bottles, cosmetic containers, various packaging such as accessories It can be suitably used for various other uses such as containers and materials, miscellaneous goods such as prizes and accessories.

Claims (15)

It contains a fluororesin (A) and a non-crosslinked acrylic resin (B). The solubility parameter (SPF) of the fluororesin (A) and the solubility parameter (SPA) of the noncrosslinked acrylic resin (B) are expressed by the following formula (1) satisfied, 220 ° C., shear viscosity (SVA) and 220 ° C. uncrosslinked acrylic resin under conditions of shear rate of 60sec ^-1 (B), the shear of the fluororesin (a) under conditions of shear rate of 60 sec ^-1 A fluorine matte film (F1) having a viscosity (SVF) satisfying the following formula (2).
SPA-SPF ≧ 4.0J ^1/2 cm ^-3/2 (1)
SVA / SVF ≦ 2.0 (2) 220 ° C., the shear viscosity of the shear viscosity (SVA) and 220 ° C. uncrosslinked acrylic resin under conditions of shear rate of 60sec ^-1 (B), fluorine resin under conditions of shear rate of 60sec ^-1 (A) (SVF) The fluorine mat film (F1) according to claim 1, which satisfies the following formula (3).
1.0 ≦ SVA / SVF ≦ 2.0 (3)   The fluorine mat | matte film (F1) of Claim 1 or 2 containing 1-18 mass parts of non-crosslinked acrylic resins (B) with respect to 100 mass parts of fluororesins (A). 220 ° C., erase fluorine gloss of any one of claims 1 to 3 shear viscosity (SVA) is not more than 6,000 Pa · s for the non-crosslinked acrylic resin under conditions of shear rate of 60 sec ^-1 (B) Film (F1).   The fluorine matte film (F1) according to any one of claims 1 to 4, wherein the non-crosslinked acrylic resin (B) is a hydroxyl group-containing polymer.   The fluorine matte film (F1) according to claim 5, wherein the hydroxyl group-containing polymer has a glass transition temperature of 90 ° C or lower. It contains a fluororesin (A) and a non-crosslinked acrylic resin (B). The solubility parameter (SPF) of the fluororesin (A) and the solubility parameter (SPA) of the noncrosslinked acrylic resin (B) are expressed by the following formula (1) satisfied, 220 ° C., shear viscosity (SVA) and 220 ° C. uncrosslinked acrylic resin under conditions of shear rate of 60sec ^-1 (B), the shear of the fluororesin (a) under conditions of shear rate of 60 sec ^-1 A fluorine-matte laminated film (F2) obtained by laminating a fluorine-matte resin layer (I) having a viscosity (SVF) satisfying the following formula (2) and an acrylic resin layer (II).
SPA-SPF ≧ 4.0J ^1/2 cm ^-3/2 (1)
SVA / SVF ≦ 2.0 (2) 220 ° C., the shear viscosity of the shear viscosity (SVA) and 220 ° C. uncrosslinked acrylic resin under conditions of shear rate of 60sec ^-1 (B), fluorine resin under conditions of shear rate of 60sec ^-1 (A) (SVF) The fluorine mat laminated film (F2) according to claim 7, which satisfies the following formula (3).
1.0 ≦ SVA / SVF ≦ 2.0 (3)   The fluorine mat laminated film (F2) according to claim 7 or 8, comprising 1 to 18 parts by mass of a non-crosslinked acrylic resin (B) with respect to 100 parts by mass of the fluororesin (A). 220 ° C., erase fluorine gloss of any one of claims 7-9 shear viscosity (SVA) is not more than 6,000 Pa · s for the non-crosslinked acrylic resin under conditions of shear rate of 60 sec ^-1 (B) Laminated film (F2).   The fluorine mat laminated film (F2) according to any one of claims 7 to 10, wherein the non-crosslinked acrylic resin (B) is a hydroxyl group-containing polymer.   The fluorine mat laminated film (F2) according to claim 11, wherein the hydroxyl group-containing polymer has a glass transition temperature of 90 ° C or lower.   A fluorine mat decorative laminated film (F3) further comprising a picture layer (III) on at least one side of the fluorine mat laminated film (F2) according to claim 7.   The fluorine mat film (F1) according to claim 1, the fluorine mat layer film (F2) according to claim 7, and the fluorine mat layer film (F3) according to claim 13. A laminated sheet (F4) obtained by laminating a film and a thermoplastic resin layer (IV).   The fluorine-matte decorative film (F1) according to claim 1, the fluorine-matte laminated film (F2) according to claim 7, the fluorine-matte decorative laminated film (F3) according to claim 13, and the claim 14. A laminated molded article obtained by laminating a film or sheet selected from the group consisting of laminated sheets (F4) on a substrate (V).