JP2011016287A - Fluorine-based resin laminated film and method of manufacturing the same - Google Patents

Abstract

Disclosed is a fluororesin laminated film having a good appearance that can maintain the weather resistance of a fluororesin and that does not peel off even when exposed outdoors for a long time, and a method for producing the same. provide.
A fluororesin laminated film in which a fluororesin layer is laminated on an acrylic resin layer, wherein the fluororesin forming the fluororesin layer contains 5 to 20% by mass of hexafluoropropylene units. The manufacturing method of said fluorine resin laminated | multilayer film with which a certain fluorine resin laminated | multilayer film and acrylic resin layer, and the fluorine resin layer were laminated | stacked by the coextrusion method.
[Selection figure] None

Description

  The present invention relates to a fluororesin laminated film and a method for producing the same.

  Fluorine-based resin film has excellent weather resistance, chemical resistance, and contamination resistance, so it is widely used as a protective film to be laminated on the surface of various substrates such as plastic, glass, slate, rubber, metal plate and wood board. Has been. Moreover, the base material whose surface is protected by a fluorine-based resin film is used in many applications such as interior materials, exterior materials, and furniture of buildings.

  In addition to single-layer films, fluororesin multilayer films coextruded with methacrylic resin compositions are used for the purpose of preventing deterioration of the base material and maintaining aesthetics, for example, plastic, metal, wood, etc. There is a strong interest in the market as protective films for laminating to various materials and coating or plating substitute films for laminating automobile interior and exterior parts.

  As a fluorine resin multilayer film, for example, in Patent Document 1, a laminated film having a surface layer made of a vinylidene fluoride resin having a specific composition and a back layer made of a methacrylate ester resin having a specific composition, and a glycol-modified polyester resin layer There has been proposed a resin laminate having: With this technology, it is possible to improve the weather resistance of laminates obtained by laminating a vinylidene fluoride resin layer on the surface of a glycol-modified polyester resin layer with a manufacturing method that has less environmental impact in terms of equipment and productivity. It is said.

  Patent Document 2 proposes a laminated film in which a surface layer made of a vinylidene fluoride resin having a specific composition containing an antibacterial agent and a back layer made of a methacrylic ester resin having a specific composition containing an ultraviolet absorber are laminated. Has been. With this technology, when this laminated film is laminated on various substrates, the resulting laminate is given the characteristics such as excellent weather resistance, stain resistance, chemical resistance and antibacterial performance that are characteristic of fluororesin. At the same time, it is possible to suppress the peeling between the vinylidene fluoride resin and the various base materials and the back surface printed layer.

  However, in any of the above techniques, when high adhesion is required between the front surface layer and the back surface layer, a resin composition obtained by blending a vinylidene fluoride resin and a methacrylic ester resin is used. There is a problem that the weather resistance, chemical resistance and the like inherently possessed by the vinylidene fluoride resin are reduced.

Japanese Patent Application Laid-Open No. 2004-223,919 Japanese Patent Laid-Open No. 2006-213,885

  The object of the present invention is to maintain the weather resistance of a fluororesin, and to produce a fluororesin laminated film having a good appearance in which the fluororesin layer does not peel even when exposed outdoors for a long time, and its production Is to provide a method.

  The gist of the present invention is a fluororesin laminated film in which a fluororesin layer is laminated on an acrylic resin layer, and the fluororesin that forms the fluororesin layer is 5 to 20% by mass of hexafluoropropylene units. A fluorine-based resin laminated film (hereinafter, referred to as “the present fluorine-based resin laminated film”) containing the above is a first invention.

  Moreover, the place made into the summary of this invention makes the manufacturing method of this fluorine-type resin laminated | multilayer film by which the acrylic resin layer and the fluorine-type resin layer were laminated | stacked by the co-extrusion method to 2nd invention.

  This fluorine-based resin laminated film is resistant to peeling of the fluorine-based resin layer even when exposed outdoors, and has various weather resistance, contamination resistance, chemical resistance, etc. It can be suitably used as various films such as a protective film, a film for laminating automobile interior and exterior parts, and a plating substitute film.

Acrylic resin layer

In the present invention, as the acrylic resin that forms the acrylic resin layer, for example, a main structural unit is a structural unit obtained from at least one alkyl methacrylate selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, A single polymer having a structural unit obtained from another vinyl monomer such as an acrylic ester having an alkyl group having 1 to 8 carbon atoms, vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, or the like Examples thereof include an acrylic rubber-containing polymer having a copolymer and an alkyl (meth) acrylate unit as a main structural unit.

  Specific examples of the acrylic resin include JP-A 52-56,150, JP-A 57-140,161, JP-A 58-215,444, and JP-A 63-77,963. JP, 9-263,614, JP 11-228,710, 2003-128,735, 2003-211,446, 2004-2,665. And a multilayer structure polymer as described in JP-A-2005-163,003, JP-A-2006-110,744, JP-A-2006-91,847, and JP-A-2007-91. , 784, and JP 2007-178,514 Acrylic resin.

  In this invention, in order to improve the weather resistance of a base material at the time of laminating and using this fluororesin laminated | multilayer film on a base material, a ultraviolet absorber can be mix | blended in an acrylic resin. Moreover, when mix | blending a ultraviolet absorber, a light stabilizer can be used together as needed.

  As said ultraviolet absorber, the thing of molecular weight 300 or more is preferable, for example, and the thing of molecular weight 400 or more is more preferable.

  Examples of the ultraviolet absorber having a molecular weight of 400 or more include benzotriazole-based and triazine-based ones.

  Specific examples of the benzotriazole ultraviolet absorber include Tinuvin 234 manufactured by Ciba Specialty Chemicals Co., Ltd. and Adeka Stub LA-31 manufactured by ADEKA Co., Ltd. (both are trade names).

  A specific example of the triazine-based ultraviolet absorber is Tinuvin 1577 (trade name) manufactured by Ciba Specialty Chemicals Co., Ltd.

  As a compounding quantity of a ultraviolet absorber, 0.1-10 mass parts is preferable with respect to 100 mass parts of acrylic resins, and 0.2-5 mass parts is more preferable.

  Examples of the light stabilizer include hindered amine radical scavengers.

  Specific examples of the light stabilizer include ADEKA Corporation ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63 and ADK STAB LA-68; and SANOH manufactured by Sankyo Lifetech Co., Ltd. LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114 and Sanol LS-744 (all are trade names).

  As a compounding quantity of a light stabilizer, 0.1-10 mass parts is preferable with respect to 100 mass parts of acrylic resins, and 0.2-5 mass parts is more preferable.

  The ultraviolet absorber and the light stabilizer can be used alone or in combination of two or more.

  In the present invention, the reduced viscosity is 0.15 L / g or more in the acrylic resin layer in order to improve the film forming property of the acrylic resin film for forming the acrylic resin layer when forming the fluororesin laminated film. These processing aids can be blended.

  In the present invention, the reduced viscosity is a value obtained by measuring a polymer 0.1 g dissolved in chloroform 100 mL at 25 ° C.

  Examples of the processing aid include a polymer obtained by polymerizing or copolymerizing 50 to 100% by mass of methyl methacrylate and 0 to 50% by mass of another vinyl monomer copolymerizable therewith. Can be mentioned. Other vinyl monomers copolymerizable with methyl methacrylate can be used alone or in combination of two or more.

  As a compounding quantity of a processing aid, 20 mass parts or less are preferable with respect to 100 mass parts of acrylic resins, and 1-10 mass parts is more preferable at the point of film film forming property.

  In the present invention, if necessary, a heat stabilizer, an antioxidant, a lubricant, a matting agent, a plasticizer, an impact-resistant agent, a foaming agent, a filler, an antibacterial agent, an antifungal agent, and a release agent in an acrylic resin. Various compounding agents such as an antistatic agent, a colorant, an ultraviolet absorber and a flame retardant 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 the flame retardant include bromine flame retardant, phosphorus flame retardant, chlorine flame retardant, nitrogen flame retardant, aluminum flame retardant, antimony flame retardant, magnesium flame retardant, boron flame retardant and zirconium flame retardant. Examples include flame retardants.

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

  Examples of the matting agent include organic matting agents and inorganic matting agents.

  Specific examples of the matting agent include spherical fine particles of a crosslinked resin having a methyl methacrylate unit as a main constituent unit and having a mass average particle diameter of 2 to 15 μm from the viewpoint of transparency of the fluororesin laminated film. Further, as a matting agent, a heavy metal containing a hydroxyl group described in JP-A-2005-139,416 is disclosed in terms of transparency, matting property, film forming property and moldability of the fluororesin laminated film. Examples thereof include at least one polymer selected from the polymer (V) and the polymer (VI).

  By using said polymer, the fall of physical properties, such as an elongation, of this fluorine-type resin laminated | multilayer film can be suppressed. Therefore, a fluororesin laminated film in which the above polymer is blended as a matting agent is preferable because, for example, film breakage does not occur during secondary processing.

  The said compounding agent can be used individually or in combination of 2 or more types.

As a blending method of the above compounding agent in an acrylic resin, for example, a method of supplying an extruder when forming an acrylic resin film for forming an acrylic resin layer, or a compounding agent in an acrylic resin in advance. A method of kneading and mixing the blended mixture with a kneader can be mentioned. Examples of the kneader used in the latter method include a single screw extruder, a twin screw extruder, a Banbury mixer, and a roll kneader.

Fluorine resin layer

In the present invention, the fluororesin forming the fluororesin layer contains 5 to 20% by mass of hexafluoropropylene units.

  When the hexafluoropropylene unit in the fluororesin is 5 to 20% by mass, peeling of the fluororesin layer hardly occurs when the fluororesin laminated film of the present invention is exposed outdoors, and the weather resistance and appearance are improved. Can be good.

  Examples of the fluororesin containing 5 to 20% by mass of hexafluoropropylene unit (hereinafter referred to as “the present fluororesin”) include, for example, Kyner Superflex 2500-20 and Kyner Flex 2800-20 manufactured by Arkema Co., Ltd. Can be mentioned.

  Moreover, in this invention, the monomer unit which can be copolymerized with vinylidene fluoride can be contained in this fluororesin as needed.

  Examples of the monomer copolymerizable with vinylidene fluoride, which is a raw material for constituting a monomer unit copolymerizable with vinylidene fluoride, include, for example, ethylene tetrafluoride, ethylene trifluoride, and vinyl fluoride. Is mentioned.

  In the present invention, polyvinylidene fluoride can be blended with the fluororesin containing a large amount of hexafluoropropylene units so that the hexafluoropropylene units contained in the fluororesin are 5 to 20% by mass.

  Examples of the polyvinylidene fluoride include Kyner 720 and Kyner 740 manufactured by Arkema Co., Ltd.

  In this invention, various compounding agents can be mix | blended with this fluororesin as needed.

  As a compounding agent, the thing similar to what is mix | blended in an acrylic resin is mentioned.

As a blending method of the compounding agent in the fluororesin, the same method as in blending in the acrylic resin can be mentioned.

This fluorine resin laminated film

This fluororesin laminated film is obtained by laminating a fluororesin layer on an acrylic resin layer.

  In this invention, this fluorine-type resin laminated | multilayer film contains a sheet-like thing, and 50-500 micrometers is preferable as the thickness.

  As the thickness of the fluororesin layer and the acrylic resin layer in the present fluororesin laminated film, the ratio of the thickness of the fluororesin layer and the acrylic resin layer (the thickness of the fluororesin layer / the thickness of the acrylic resin layer) is 1 / 25-1. / 3 is preferable, 1/20 to 1/4 is more preferable, and 1/15 to 1/9 is particularly preferable. When the ratio of the thickness of the fluororesin layer and the acrylic resin layer is 1/25 or more, the surface appearance of the fluororesin laminated film tends to be good. Moreover, the ratio of the thickness of the fluororesin layer and the acrylic resin layer is 1/3 or less, and the transparency of the fluororesin laminated film tends to be good.

  In the present invention, in terms of the peel resistance of the fluororesin layer after the exposure of the fluororesin laminate film, the acrylic resin layer and the fluororesin layer in the fluororesin laminate film are not It is preferable to have an interface that can be recognized as a layer different from the acrylic resin layer and the fluorine resin layer when the cross-sectional structure of the fluorine resin laminate film is observed with a transmission electron microscope. Further, the thickness of the interface is preferably 300 nm or more, more preferably 400 nm or more, and particularly preferably 500 nm or more.

  The upper limit of the interface thickness is not particularly limited as long as it does not deactivate properties such as weather resistance, stain resistance, and chemical resistance of the acrylic resin layer and the fluorine resin layer.

  By laminating this fluororesin laminated film on the surface of various substrates such as resin molded products, woodwork products, metal molded products, etc., a laminated molded body having a fluororesin layer on the surface can be produced.

  In addition, in order to impart design properties to the laminated molded body, the present fluororesin laminated film can be printed by an appropriate printing method.

  In this case, what was printed on one side to this fluorine resin laminated film is preferable. Moreover, as a printing surface of this fluorine-type resin laminated film, the surface which contacts a base material is preferable at the point of protection of a printing surface, or provision of a high-class feeling.

  In addition, when using the color tone of a base material and using it as an alternative of a low gloss coating, this fluorine-type resin laminated film can be used as it is. In particular, when using this fluororesin laminated film for applications that take advantage of the color tone of the base material, the resulting laminated molded product is more transparent and deeper than when using a polyvinyl chloride film or a polyester film. And excellent in terms of luxury.

  As a method for producing the present fluororesin laminated film, for example, a coextrusion method in which an acrylic resin and a fluororesin are laminated simultaneously with melt extrusion in that the production process of the present fluororesin laminated film can be reduced. Is a preferred method.

  Specific examples of the coextrusion method of laminating acrylic resin and fluororesin simultaneously with melt extrusion include a method of laminating before passing a die such as a feed block method, a method of laminating in a die such as a multi-manifold method, and multi-slot And a method of laminating after passing through a die.

  When the acrylic resin and the fluororesin are laminated simultaneously while melting, the acrylic resin layer may be melt-extruded so as to be in contact with the cooling roll, or the fluororesin layer may be melt-extruded so as to be in contact with the cooling roll. Also good.

Hereinafter, the present invention will be described with reference to examples and comparative examples. In the following, “part” and “%” represent “part by mass” and “% by mass”, respectively. Moreover, the symbol in an Example shows the following compounds.
MMA: methyl methacrylate n-BA: n-butyl acrylate 1,3BD: 1,3-butylene glycol dimethacrylate AMA: allyl methacrylate CHP: cumene hydroperoxide emulsifier (I): Phosphanol RS manufactured by Toho Chemical Co., Ltd. -610NA (trade name)
SFS: sodium formaldehyde sulfoxylate EDTA: disodium ethylenediaminetetraacetate n-OM: n-octyl mercaptan tBH: t-butyl hydroperoxide emulsifier (b): Latemul ASK (trade name) manufactured by Kao Corporation
In Examples and Comparative Examples, the weight average particle diameter of polymer particles in the polymer latex, the glass transition temperature of the polymer (hereinafter referred to as “Tg”), the thickness of the interface in the fluororesin laminated film, and the weather resistance Evaluation was made by the following method.
(1) Mass average particle diameter The mass average particle diameter of the polymer particles in the polymer latex was determined by an absorbance method.
(2) Tg
The Tg of the polymer was calculated from the FOX equation using the values described in Polymer HandBook (J. Brandrup, Interscience, 1989).
(3) Interfacial thickness A cross section of the fluororesin laminated film was cut out with a LEICA ultramicrotome (EM-ULTRACUTCT, product name), and a transmission electron microscope (model: JEM-1011) manufactured by JEOL Ltd. was used. The interface thickness was measured.
(4) Weather resistance Fluorine-based resin laminated film laminated on a polycarbonate plate using Daipla Wintes Co., Ltd., Daipura Metal Weather KU-R4CI-A (trade name), after implementation of accelerated exposure under the following test conditions A cross-cut test of the fluororesin laminated film was conducted, the exposure time until the surface fluororesin peeled off was measured, and the weather resistance was evaluated according to the following criteria.
○: Even if exposed for 100 hours or more, the surface layer does not peel off.
X: The surface layer peels off by exposure for less than 100 hours.
<Test conditions>
L (light): 53 ° C., 50% RH, 20 hours D (condensation): 30 ° C., 98% RH, 4 hours R (rest): 30 ° C., 98% RH, 0.01 hours Shower (spray): D Illuminance 30 seconds before and after: 65mW / cm ² (Ushio Electric Co., Ltd. illuminance meter used)
Filter: Daifura Wintes KF-1 (trade name, opening 295-780 nm)
[Preparation Example 1] Production of acrylic resin (1) After charging 8.5 parts of ion-exchanged water into a container equipped with a stirrer, 0.3 part of MMA, 4.5 parts of n-BA, 0.2 part of 1,3-BD , A mixture containing 0.05 part of AMA and 0.025 part of CHP was added and stirred and mixed at room temperature. Thereafter, 1.1 parts of emulsifier (I) was charged into the container while stirring, and stirring was continued for 20 minutes to prepare an emulsion.

  Next, 186.5 parts of ion-exchanged water was put into a polymerization vessel equipped with a cooler, and the temperature was raised to 70 ° C. Further, a mixture prepared by adding 0.20 part of SFS, 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. Further, while stirring under nitrogen, the prepared emulsion was dropped into the polymerization vessel over 8 minutes, and then the reaction was continued for 15 minutes to complete the polymerization of the first elastic polymer (A-1).

  Subsequently, a mixture containing 1.5 parts of MMA, 22.5 parts of n-BA, 1.0 part of 1,3-BD and 0.25 part of AMA was dropped into the polymerization vessel over 90 minutes together with 0.016 part of CHP. The reaction was continued for a minute to obtain an elastic polymer (A) containing the second elastic polymer (A-2). The Tg of the first elastic polymer (A-1) alone was −48 ° C., and the Tg of the second elastic polymer (A-2) alone was −48 ° C.

  Furthermore, after dropping a mixture containing 6 parts of MMA, 4 parts of n-BA and 0.075 part of AMA together with 0.0125 part of CHP over 45 minutes into the polymerization vessel having the elastic polymer (A), the reaction is continued for 60 minutes. An intermediate polymer (B) was formed. The Tg of the intermediate polymer (B) alone was 20 ° C.

  Subsequently, a mixture containing MMA 55.2 parts, n-BA 4.8 parts, n-OM 0.19 parts and t-BH 0.08 parts was dropped into the polymerization vessel over 140 minutes, and then the reaction was continued for 60 minutes. A hard polymer (C) was formed to obtain an acrylic resin (1) latex. The Tg of the hard polymer (C) alone was 84 ° C. Moreover, the mass average particle diameter of the acrylic resin (1) was 0.12 μm.

The resulting latex of the acrylic resin (1) was filtered using a vibration type filtration device equipped with a SUS average mesh 62 μm mesh as a filter medium, and then salted out in an aqueous solution containing 3 parts of calcium acetate. After washing with water and collecting, it was dried to obtain a powdery acrylic resin (1).
[Adjustment Example 2] Production of processing aid (A) 200 parts of ion-exchanged water substituted with nitrogen were charged in a reaction vessel, and further 1 part of emulsifier (b) and 0.15 part of potassium persulfate were charged.

  Subsequently, 40 parts of MMA, 2 parts of n-BA and 0.004 part of n-OM were charged in the reaction vessel, and the mixture was stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization.

  Subsequently, a mixture containing 44 parts of MMA and 14 parts of n-BA was added dropwise over 2 hours, and then held for 2 hours to complete the polymerization to obtain a latex of a processing aid (A).

The obtained latex of processing aid (a) was put into a 0.25% aqueous sulfuric acid solution for acid precipitation, and then dehydrated, washed with water and dried to obtain a powdery processing aid (a). The reduced viscosity of the processing aid (A) was 0.38 L / g.
[Production Example 1]
Acrylic resin (1) 100 parts, ADEKA LA-31RG (trade name) 2.1 parts, ADEKA LA-57 (trade name) 0.45 parts, Ciba Specialty Chemicals Irganox 1076 (trade name) 0.1 part and 2 parts of processing aid (A) were mixed with a Henschel mixer to obtain a resin composition. This resin composition was melt-kneaded at a cylinder temperature of 200 to 240 ° C. and a die temperature of 240 ° C. using a degassing extruder (manufactured by Ikekai Kogyo Co., Ltd., trade name: PCM-30) to obtain pellets (α). It was.

(Examples 1-4 and Comparative Examples 1-3)
The pellet (α) obtained in Production Example 1 is supplied to a 40φ single-screw extruder having a cylinder temperature of 230 to 240 ° C., and the fluorine-based resin shown in Table 1 is 30φ single-screw extrusion having a cylinder temperature of 200 to 230 ° C. The melt-plasticized materials that were individually supplied to the machine were molded using a multi-manifold die heated to 250 ° C., so that the fluorine resin layer thickness was 5 μm and the acrylic resin layer thickness was 45 μm. A fluororesin-based laminated film having a layer structure was obtained. In addition, as a fluorine-type resin, what blended Akema Co., Ltd. Kyner 720 and Kyner superflex 2500-20 by the ratio shown in Table 1 was used. Moreover, the film was cooled so that the layer of the acrylic resin (1) was in contact with a cooling roll at 85 ° C. to obtain a fluororesin-based laminated film. Table 2 shows the evaluation results of the interface thickness and weather resistance of the obtained fluororesin-based laminated film.

As is clear from the evaluation results, the fluorine-based resin laminated films of Examples 1 to 4 show good weather resistance even when exposed for a long time. However, in the case of the fluororesin laminated films of Comparative Examples 1 to 3, the weather resistance is poor even when exposed for a short time.

Claims (4)

  Fluorine resin laminated film in which a fluorine resin layer is laminated on an acrylic resin layer, wherein the fluorine resin forming the fluorine resin layer contains 5 to 20% by mass of hexafluoropropylene units Laminated film.   The fluorine-based resin laminated film according to claim 1, wherein the acrylic resin layer contains an ultraviolet absorber and a light stabilizer.   The fluorine resin laminated film according to claim 1 or 2, wherein the interface formed between the acrylic resin layer and the fluorine resin layer has a thickness of 300 nm or more.   The manufacturing method of the fluorine resin laminated | multilayer film in any one of Claims 1-3 with which the acrylic resin layer and the fluorine resin layer were laminated | stacked by the coextrusion method.