WO2021039533A1 - フッ化ビニリデン系樹脂多層フィルム、自動車内外装用フィルム、自動車用部品及び自動車 - Google Patents

フッ化ビニリデン系樹脂多層フィルム、自動車内外装用フィルム、自動車用部品及び自動車 Download PDF

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Publication number
WO2021039533A1
WO2021039533A1 PCT/JP2020/031281 JP2020031281W WO2021039533A1 WO 2021039533 A1 WO2021039533 A1 WO 2021039533A1 JP 2020031281 W JP2020031281 W JP 2020031281W WO 2021039533 A1 WO2021039533 A1 WO 2021039533A1
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Prior art keywords
vinylidene fluoride
surface layer
resin
multilayer film
mass
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Ceased
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PCT/JP2020/031281
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English (en)
French (fr)
Japanese (ja)
Inventor
洪太 永岡
敬司 ▲高▼野
康史 宮村
憲朗 安本
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Denka Co Ltd
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Denka Co Ltd
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Application filed by Denka Co Ltd filed Critical Denka Co Ltd
Priority to EP20856862.6A priority Critical patent/EP4023439B1/en
Priority to CN202080051728.0A priority patent/CN114126866A/zh
Priority to US17/637,489 priority patent/US20220274388A1/en
Priority to JP2021542783A priority patent/JP7627659B2/ja
Publication of WO2021039533A1 publication Critical patent/WO2021039533A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Definitions

  • the present invention relates to vinylidene fluoride-based resin multilayer films, automobile interior / exterior films, automobile parts, and automobiles.
  • the fluorine-based resin multilayer film has been required to withstand harsh conditions and long-term use, and the fluorine-based resin multilayer film having this characteristic is used for various purposes.
  • a fluororesin multilayer film has been used as a back sheet for a solar cell module by taking advantage of its characteristics such as weather resistance (for example, Patent Document 1).
  • a decorative film containing a fluorine-based resin multilayer film and a decorative layer is molded, and the decorative film is applied to, for example, the surface of car interior and exterior parts, electronic devices, miscellaneous goods, and the like.
  • Patent Document 2 has come to be used as an alternative to.
  • an ultraviolet absorber is added to the methacrylic acid ester resin in the back layer thereof.
  • the ultraviolet absorber for example, triazine type, benzotriazole type, oxalic acid type, benzophenone type, hindered amine type and many other types are used.
  • the present inventors have conducted various studies on the weather resistance of a vinylidene fluoride-based resin multilayer film including two layers in which a front surface layer is laminated on a back surface layer. At this time, the present inventors examined discoloration (specifically, whitening of the two-layer film composed of the back surface layer and the front surface layer) and bleed-out of the vinylidene fluoride-based resin multilayer film in the thermal cycle test. , 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol (for example, tinuvin 1577ED), which is often used in triazine-based UV absorbers. ) Did not give satisfactory results for both.
  • a main object of the present invention to provide a vinylidene fluoride resin multilayer film having excellent bleed-out resistance against temperature change, discoloration resistance against temperature change, and ultraviolet ray blocking property.
  • Another object of the present invention is to provide an automobile interior / exterior film, an automobile part, and an automobile using the vinylidene fluoride-based resin multilayer film.
  • the "bleed-out" phenomenon of a film is a phenomenon in which additives contained in the film emerge on the surface of the film over time.
  • the “discoloration" of a multilayer film of the present technology means that a hue change occurs in this multilayer film before and after the start of the test when exposed to a temperature change in a thermal cycle test.
  • the present inventors have made that the raw materials used in the back surface layer and the surface layer of the vinylidene fluoride-based resin multilayer film and their respective formulations with respect to bleed-out resistance against temperature change, discoloration resistance against temperature change, and ultraviolet ray blocking property. We reexamined the amount.
  • the present inventors cut the multilayer film vertically before and after the thermal cycle test, and cut the cut surface vertically with a scanning electron microscope, respectively. It was observed by (SEM). The cut surface before the cold cycle was smooth, but on the cut surface after the cold cycle, needle-shaped crystals were observed in the cross section of the back surface layer portion thereof. As a result of performing energy dispersive X-ray analysis (EDS) on this needle-shaped crystal, N atoms were detected from the crystal.
  • EDS energy dispersive X-ray analysis
  • the present inventors considered that the N atoms are derived from the triazine-based ultraviolet absorber.
  • the present inventors have obtained a vinylidene fluoride resin multilayer film in which the content of the fluororesin is reduced in the back surface layer and the content of the methacrylic acid ester resin is higher than a specific value (for example, in Examples described later). See Comparative Example 3). With this vinylidene fluoride-based resin multilayer film, satisfactory results were obtained in terms of discoloration resistance to temperature changes in a thermal cycle test.
  • the present inventors have found that the powdery foreign matter is 2- (4,6-diphenyl-1,3,5-triazine-2). It was identified as a triazine-based UV absorber of -yl) -5-[(hexyl) oxy] -phenol. This was the same as the UV absorber used for the back layer. From this, the present inventors considered that in the thermal cycle test, this triazine-based ultraviolet absorber was precipitated on the surface portion of the back surface layer and was detected as a powdery foreign substance.
  • the present inventors considered that the causative substance of bleed-out due to temperature change and discoloration due to temperature change is a triazine-based ultraviolet absorber. Then, the present inventors, including the change of the ultraviolet absorber to a system other than the triazine system, include the raw materials used in the back surface layer and the surface layer contained in the vinylidene fluoride resin multilayer film, and the respective compounding amounts. Was further reexamined.
  • the present inventors used a specific amount of a triazine compound having a molecular weight of 500 or more for an ultraviolet absorber in the back layer while increasing the content of the methacrylic acid ester resin in the back layer. By doing so, they have found that it is possible to provide a vinylidene fluoride-based resin multilayer film having excellent bleed-out resistance to temperature changes, discoloration resistance to temperature changes, and ultraviolet ray blocking property, and completed the present invention. That is, the present invention is as follows.
  • the present invention is a vinylidene fluoride-based resin multilayer film including two layers in which a back surface layer and a front surface layer are laminated.
  • the surface layer contains 80% by mass or more of vinylidene fluoride resin based on the total amount of the resin component of the surface layer.
  • the back surface layer contains 85% by mass or more of a methacrylic acid ester resin based on the total amount of the resin component of the back surface layer.
  • the back surface layer contained 7 parts by mass or less of a triazine-based ultraviolet absorber having a molecular weight of 500 or more with respect to 100 parts by mass of the total resin component of the back surface layer.
  • a vinylidene fluoride-based resin multilayer film can be provided.
  • the surface layer may contain 80% by mass or more of vinylidene fluoride-based resin and 20% by mass or less of methacrylic acid ester-based resin, based on the total amount of the resin component of the surface layer.
  • the vinylidene fluoride-based resin of the surface layer may contain a copolymer of vinylidene fluoride and hexafluoropropene and / or polyvinylidene fluoride.
  • the vinylidene fluoride-based resin multilayer film may have a HAZE of less than 10% as measured based on JIS K7136.
  • the vinylidene fluoride-based resin multilayer film may be a vinylidene fluoride-based resin multilayer film for a decorative film.
  • the present invention can also provide an automobile interior / exterior film formed by using the vinylidene fluoride-based resin multilayer film.
  • the present invention can also provide an automobile in which the above-mentioned automobile interior / exterior film is adhered to the surface.
  • the present invention can also provide an automobile part in which the automobile interior / exterior film is adhered to the surface.
  • the present invention it is possible to provide a vinylidene fluoride-based resin multilayer film having excellent bleed-out resistance against temperature change, discoloration resistance against temperature change, and ultraviolet ray blocking property. Further, according to the present invention, it is possible to provide an automobile interior / exterior film, an automobile part, and an automobile using the vinylidene fluoride-based resin multilayer film.
  • the effects described here are not necessarily limited, and may be any of the effects described in the present technology.
  • FIG. 1 is a schematic view showing a structure used for each evaluation of bleed-out resistance to temperature change, discoloration resistance to temperature change, and the like.
  • FIG. 2 is a diagram showing a structure used for evaluating the ultraviolet ray blocking property.
  • the vinylidene fluoride-based resin multilayer film of the present invention may consist of two layers in which a back surface layer and a front surface layer are laminated, or another layer may be laminated on one side or both sides of the two layers.
  • the vinylidene fluoride resin multilayer film of the present invention is a vinylidene fluoride resin multilayer film containing two layers in which a back surface layer and a front surface layer are laminated, and the surface layer contains a high content of vinylidene fluoride resin.
  • the back surface layer is a layer containing (hereinafter, also referred to as “fluorine-rich resin layer”)
  • the back surface layer is a layer containing a high content of methacrylic acid ester resin (hereinafter, also referred to as “methacryl-rich resin layer”).
  • the present invention provides a vinylidene fluoride-based resin multilayer film in which a predetermined amount of a triazine-based ultraviolet absorber having a molecular weight of 500 or more is contained in the back surface layer with respect to 100 parts by mass of the total resin component of the back surface layer. can do.
  • the vinylidene fluoride-based resin multilayer film of the present invention can be applied to a film having a wide range of applications such as a decorative film and a film for interior and exterior of automobiles. Further, it is possible to provide an automobile or an automobile part to which the film is adhered.
  • the surface layer is a fluorine-rich resin layer containing 80% by mass or more of vinylidene fluoride-based resin based on the total amount of the resin component of the surface layer (100% by mass). Further, the surface layer may contain 20% by mass or less of the methacrylic acid ester resin based on the total amount of the resin component of the surface layer, or may not contain the methacrylic acid ester resin.
  • the fluorine-rich resin layer preferably contains 80% by mass or more of the vinylidene fluoride resin and 20% by mass or less of the methacrylic acid ester resin.
  • the total amount of the vinylidene fluoride resin and the methacrylic acid ester resin is 100% by mass in the surface layer.
  • the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the vinylidene fluoride-based resin multilayer film can be further improved.
  • the methacrylic acid ester resin has excellent compatibility with the vinylidene fluoride resin, improves workability by lowering the extrusion temperature during film extrusion molding, and has adhesiveness when laminated with other materials. Can be improved. If the surface layer contains too much methacrylic acid ester resin component, the component is oxidized and the discoloration of the film becomes large. Therefore, by setting the content of the methacrylic acid ester resin to 20% by mass or less, such a film Discoloration can be suppressed.
  • the surface layer is preferably 85% by mass or more of vinylidene fluoride resin, more preferably 88% by mass or more of vinylidene fluoride resin, and even more preferably fluorine, based on the total amount of the resin component of the surface layer. It is a fluorine-rich resin layer containing 90% by mass or more of vinylidene resin.
  • the content of the methacrylic acid ester resin in the surface layer is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the resin component of the surface layer. ..
  • the surface layer may be a fluorine-rich resin layer substantially made of vinylidene fluoride-based resin, and is a fluorine-rich resin layer containing 100% by mass of vinylidene fluoride-based resin based on the total amount of resin components of the surface layer.
  • “Substantially” means that the methacrylic acid ester resin can be contained within a range that does not impair the effects of the present invention, and may be contained, for example, about 0.5% by mass or less.
  • Vinylidene fluoride resin used in the surface layer of the present invention can be used for the surface layer of the present invention.
  • the vinylidene fluoride resin can also be appropriately applied to the back surface layer described later.
  • the vinylidene fluoride-based resin used in the surface layer of the present invention is not particularly limited as long as it is a vinylidene fluoride-based polymer, and is, for example, a homopolymer of vinylidene fluoride monomer or a vinylidene fluoride monomer. It is a copolymer with another monomer copolymerizable with this.
  • the vinylidene fluoride-based copolymer is not particularly limited, and examples thereof include a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene-based copolymer and a vinylidene fluoride-hexafluoropropylene-based copolymer.
  • a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene-based copolymer and a vinylidene fluoride-hexafluoropropylene-based copolymer.
  • One kind or two or more kinds selected from the group consisting of these polymers and copolymers can be used.
  • the vinylidene fluoride-based resin is a copolymer of a vinylidene fluoride monomer and another vinyl compound monomer
  • the vinyl compound copolymerizing with the vinylidene fluoride monomer is, for example, vinyl fluoride.
  • vinyl fluoride examples thereof include fluorinated vinyl compounds such as ethylene tetrafluoride, ethylene trifluoride, and propylene hexafluoride, and known vinyl monomers such as styrene, ethylene, butadiene, and propylene.
  • the copolymer one kind or two or more kinds selected from the group consisting of these monomers can be used.
  • the vinylidene fluoride-based resin is preferably polyvinylidene fluoride, vinylidene fluoride-6 propylene fluoride copolymer, vinylidene fluoride-6 propylene fluoride-4 ethylene copolymer fluoride, ethylene-trifluorinated ethylene. It is possible that one or two or more types of vinylidene fluoride-based resins selected from the group consisting of ethylene copolymers and ethylene-4 ethylene fluoride copolymers.
  • the vinylidene fluoride resin used for the surface layer of the present invention contains a copolymer of vinylidene fluoride and hexafluoropropene and / or polyvinylidene fluoride from the viewpoint of compatibility with the methacrylate ester resin. It is preferable, and it is more preferable to contain at least polyvinylidene fluoride. As a result, the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the vinylidene fluoride-based resin multilayer film can be further improved.
  • Methacrylic acid ester resin used in the surface layer of the present invention As described above, a methacrylic acid ester resin can be used for the surface layer of the present invention. The methacrylic acid ester resin can also be appropriately applied to the back surface layer described later.
  • the methacrylic acid ester-based resin used in the surface layer of the present invention is not particularly limited as long as it is a methacrylic acid ester-based polymer containing a methacrylic acid ester monomer unit as a main component, and for example, methacrylic ester (for example, methacrylic).
  • the methacrylic acid ester-based polymer may be a homopolymer of one kind of methacrylic acid ester monomer, may be a copolymer of two or more kinds of methacrylic acid ester monomers, or may be a copolymer. It may be a copolymer of one or more kinds of methacrylic acid esters and other monomers.
  • the methacrylic acid ester-based polymer used in the surface layer of the present invention is preferably a methacrylic acid ester-based copolymer, and more preferably a methacrylic acid ester-based copolymer containing no rubber component.
  • the methacrylic acid ester-based polymer used in the back layer of the present invention which will be described later, is preferably a methacrylic acid ester-based copolymer, and more preferably a methacrylic acid ester-based copolymer containing a rubber component.
  • the methacrylic acid ester is not particularly limited, and examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, and hexyl methacrylate, and at least methyl methacrylate is used. Is preferable.
  • the alkyl group of the alkyl ester portion of the methacrylic acid ester may be linear, branched chain, or cyclic, but linear or branched chain is preferable.
  • the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 2 carbon atoms.
  • One or more selected from the group consisting of these methacrylic acid ester monomers can be used.
  • the other monomer copolymerizable with the above methacrylic acid ester is not particularly limited, but is, for example, acrylic acid ester, acrylic acid, methacrylic acid, styrene, ⁇ -methylstyrene, acrylonitrile, and other ethylenic non-formylates.
  • examples include saturated monomers. One or more selected from the group consisting of these monomers can be used.
  • the acrylic acid ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate (for example, n-butyl, etc.), pentyl acrylate, and hexyl acrylate. Be done.
  • the alkyl group of the alkyl ester portion of the acrylic acid ester the same group as the alkyl group of the methacrylic acid ester is preferable.
  • One or more selected from the group consisting of these acrylic acid ester monomers can be used.
  • the methacrylic acid ester-based copolymer is preferably a methacrylic acid ester-based copolymer having 1 to 4 carbon atoms and an acrylic acid ester having 1 to 8 carbon atoms.
  • the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the vinylidene fluoride-based resin multilayer film can be improved.
  • the methacrylic acid esters preferably one, two or three selected from the group consisting of methyl methacrylate, ethyl methacrylate, and propyl methacrylate is used, and more preferably methyl methacrylate. Is to use one of.
  • the methacrylic acid ester-based copolymer used in the surface layer of the present invention is more preferably a methacrylic acid ester-based copolymer of methyl methacrylate and an acrylic acid ester having 1 to 8 carbon atoms. More preferably, it is a methyl methacrylate copolymer containing butyl acrylate or methyl acrylate as a comonomer.
  • methacrylic acid ester and the acrylic acid ester for example, "methacrylic acid ester having 1 to 4 carbon atoms and acrylic acid ester having 1 to 8 carbon atoms” and “carbon number 1 to 4" and “carbon number”. "1 to 8" and the like mean the number of carbon atoms of the alkyl group of the alkyl ester moiety.
  • the crystallinity of the surface layer is preferably 45% or more.
  • oxidation of the methacrylic acid ester resin in the back surface layer can be reduced, and discoloration of the film can be suppressed.
  • the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the vinylidene fluoride-based resin multilayer film can be further improved.
  • the crystallinity can be calculated from the X-ray diffraction profile using an X-ray diffractometer.
  • the ratio of ⁇ crystals to the total crystal components of the vinylidene fluoride resin is 60% or more.
  • the ratio of ⁇ crystals is 60% or more, oxidation of the methacrylic acid ester resin in the back surface layer can be reduced, discoloration of the film can be suppressed, and acid rain can be easily prevented from penetrating into the back surface layer.
  • the crystallinity of the surface layer and the high ratio of ⁇ -crystals are combined to improve the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the vinylidene fluoride-based resin multilayer film. Can be done.
  • Hanada et al. As a method for measuring the peak intensity ratio of ⁇ crystals, Hanada et al. (Tomomi Hanada, Yutaka Ando, “Crystallization of polyvinylidene fluoride and polyvinylidene fluoride and polyvinylidene fluoride in a polymethylmethacrylate blend system”, Tokyo Kasei Gakuin It is calculated as follows by the method described in the university bulletin, July 1992, No. 32, paragraph 5-12).
  • the component ratio of the ⁇ -type crystal ( %) is represented by ((the absorption intensity at 765cm -1) / (absorption intensity at the absorption intensity + 840 cm -1 at 765cm -1)) ⁇ 100 (% ).
  • the film is formed so that this value is preferably 60% or more, more preferably 70% or more, and further preferably 70 to 90%.
  • this value is preferably 60% or more, more preferably 70% or more, and further preferably 70 to 90%.
  • the resin component in the present invention and the resin component in the method of Hanada et al. are not the same, the absorption characteristics of the crystal in the infrared absorption spectrum do not change, so that the above relational expression can be used as it is in the composition system in the present invention. ..
  • the thickness of the surface layer is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more as its lower limit value, and preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less as its upper limit value, and more preferably. It is 10 to 200 ⁇ m, more preferably 15 to 150 ⁇ m.
  • the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the vinylidene fluoride-based resin multilayer film can be further improved.
  • by reducing the thickness of the surface layer to 100 ⁇ m or less it is preferable in terms of handleability as an automobile exterior film and also in terms of suppressing the cost of vinylidene fluoride resin.
  • the back surface layer is a methacrylic acid-rich resin layer containing more than 80% by mass of a methacrylic acid ester-based resin based on the total amount of the resin component of the back surface layer (100% by mass).
  • the methacrylic acid ester-based resin layer is preferably 85% by mass or more of the methacrylic acid ester-based resin, more preferably 90% by mass or more of the methacrylic acid ester-based resin, still more preferably 95% by mass or more of the methacrylic acid ester-based resin, and even more preferably methacrylic acid.
  • the back surface layer is a methacrylic rich resin layer which may contain less than 20% by mass of vinylidene fluoride resin based on the total amount of the resin component of the back surface layer, but is not limited thereto.
  • the content of the vinylidene fluoride resin in the methacrylic rich resin layer is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 2% by mass or less.
  • the composition of the resin component contained in the back surface layer is preferably 90% by mass or more of the methacrylic acid ester resin and 10% by mass or less of the vinylidene fluoride resin, more preferably methacrylic acid ester type, based on the total amount of the resin component of the back surface layer.
  • the resin is 95% by mass or more and the vinylidene fluoride resin is 5% by mass or less.
  • the total amount of the vinylidene fluoride resin and the methacrylic ester resin is 100% by mass based on the total amount of the resin components of the back surface layer.
  • the back surface layer is more preferably a methacrylic acid ester-based resin substantially composed of a methacrylic acid ester-based resin, and more preferably a methacrylic acid containing 100% by mass of the methacrylic acid ester-based resin based on the total amount of the resin component of the back surface layer. It is a rich resin layer. “Substantially” means that the vinylidene fluoride resin can be contained within a range that does not impair the effects of the present invention, and may be contained, for example, about 0.5% by mass or less. By increasing the content of the methacrylic acid ester resin in the back layer, in the present invention, the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the vinylidene fluoride-based resin multilayer film can be further improved.
  • the hindered amine light stabilizer contained in the decorative layer is transferred to the back surface layer, and the hindered amine light stabilizer causes the skeleton of the vinylidene fluoride resin contained in a small amount in the back surface layer.
  • a polyene structure may be formed inside. The polyene structure absorbs light, making the film look yellow. From this point as well, it is preferable that the back surface layer is a methacrylic rich resin layer with less vinylidene fluoride resin.
  • the compositions of the methacrylic acid ester resin and vinylidene fluoride resin used for the back surface layer of the present invention include the above-mentioned ⁇ vinylidene fluoride resin used in the surface layer of the present invention> and ⁇ methacrylic acid used in the surface layer of the present invention.
  • the methacrylic acid ester-based copolymer used in the back surface layer of the present invention is more preferably a methacrylic acid ester-based copolymer of methyl methacrylate and an acrylic acid ester having 1 to 8 carbon atoms.
  • the vinylidene fluoride-based resin multilayer film is a methyl methacrylate copolymer containing butyl acrylate or methyl acrylate as a comonomer.
  • the methacrylic rich resin layer which is the back surface layer, preferably contains less than 8 parts by mass of a triazine-based ultraviolet absorber having a molecular weight of 500 or more with respect to 100 parts by mass of the resin component.
  • the amount of the ultraviolet absorber is less than 8 parts by mass, it is preferable from the viewpoint that the transparency of the vinylidene fluoride-based resin multilayer film is not impaired and the film surface is less contaminated by bleeding out.
  • the triazine-based ultraviolet absorber is preferably 7 parts by mass or less, more preferably 6 parts by mass or less, more preferably 6 parts by mass or less, with the triazine-based ultraviolet absorber as the upper limit value with respect to 100 parts by mass of the total resin component of the methacryl-rich resin layer. Is contained in 5 parts by mass or less, more preferably 4 parts by mass or less, particularly preferably 3.5 parts by mass or less, extremely preferably 3 parts by mass or less, and preferably as the lower limit value thereof. 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, particularly preferably 1 part by mass or more. contains.
  • the numerical range is more preferably 0.01 to 10 parts by mass, further preferably 0.1 to 5 parts by mass, still more preferably 0.1 to 4 parts by mass, and particularly preferably 0.5 to 0.5 parts. 3.5 parts by mass.
  • an ultraviolet absorber is used for the back surface layer from the viewpoint of sustaining the ultraviolet absorbing effect.
  • the ultraviolet absorber of the present invention is a triazine-based compound having a molecular weight of at least 500 or more, whereby vinyllidene fluoride is used. It is possible to improve the bleed-out resistance, discoloration resistance, and ultraviolet ray blocking property of the based resin multilayer film.
  • the upper limit of the molecular weight of the triazine compound is preferably 5000 or less, more preferably 3000 or less, further preferably 2000 or less, still more preferably 1000 or less, particularly preferably 900 or less, which is extremely preferable. 800 or less, most preferably 700 or less, and the lower limit thereof is preferably 510 or more, more preferably 550 or more, still more preferably 600 or more, and even more preferably 605 or more.
  • the molecular weight range is preferably a molecular weight of 500 to 2000, more preferably a molecular weight of 500 to 1000, and even more preferably a molecular weight of 510 to 700.
  • the triazine compound can be measured in molecular weight by GC-TOFMS analysis and can be identified by IR analysis or NMR analysis.
  • the triazine-based compound refers to a compound having at least a triazine skeleton, preferably a compound having a 1,3,5-triazine skeleton, and more preferably 2- (2-hydroxyphenyl) -1,3,5-triazine. It is a compound having a skeleton.
  • the triazine-based compound is more preferably a compound having a triazine skeleton represented by the following formula (1).
  • the above formula (1) represents the main skeleton of a suitable triazine-based compound of the present invention, and may have a substituent 2- (2-hydroxyphenyl) -1,3,5-triazine-based. Also called a compound. It is preferable that the triazine compound of the above formula (1) has a 2-hydroxyphenyl group at the 2-position.
  • the 2-hydroxyphenyl group preferably has at least an alkoxy group of C1 to 18 which may have a substituent, and at this time, the alkoxy group is bonded to the 4-position of the 2-hydroxyphenyl group. Is preferable.
  • the alkoxy groups C1 to 18 may have a substituent or may be an unsubstituted group. Further, the 2-hydroxyphenyl group may have one or more substituents (for example, methyl group) other than the alkoxy group of C1-18.
  • the alkoxy group of the 2-hydroxyphenyl group is not particularly limited, but for example, 2-ethylhexanoyloxy group, n-octyloxy group, n-hexyloxy group, (2-hydroxy-3-dodecyloxypropyl) oxy.
  • Groups, (2-hydroxy-3-dodecyloxypropyl) oxy group, (2-hydroxy-3-tridecyloxypropyl) oxy group, 2-hydroxy-4-iso-octyloxy group, etc. are mentioned and consist of these.
  • One or more selected from the group can be used.
  • the 4-position and the 6-position of the triazine-based compound of the above formula (1) have the same or separate aryl groups which may have a substituent, and the aryl groups are the same. More suitable.
  • the number of substituents of the aryl groups at the 4- and 6-positions may be 0, 1, 2, 3, 4, or 5, and if it is 0, it is an unsubstituted aryl group.
  • the aryl group may be either a monocyclic aromatic hydrocarbon group or a polycyclic aromatic hydrocarbon group, but a monocyclic aromatic hydrocarbon group (preferably a phenyl group) is preferable.
  • the substituent in the above formula (1) is preferably a hydroxyl group, a halogen atom, a substituted or unsubstituted monovalent or divalent organic group, and more preferably a hydroxyl group, a substituted or unsubstituted monovalent organic. It is a group. One, two, or three or more selected from the group consisting of these substituents is preferable.
  • the organic group of the triazine-based compound of the present invention has an alkyl group moiety (an unsubstituted alkyl group moiety or a substituted alkyl group moiety (for example, an ethylene group moiety))
  • the alkyl group moiety is a linear or branched chain. It may be in the form of a ring or a ring, but a linear or branched chain is preferable.
  • the alkyl group portion of the organic group is preferably C1 to 18, for example, methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Examples thereof include, but are not limited to, one or more selected from the group consisting of these groups.
  • organic groups preferably substituted or unsubstituted C1-18 alkyl groups, substituted or unsubstituted C1-18 alkoxy groups, substituted or unsubstituted C5-18 aryl groups (preferably phenyl). Groups), or substituted or unsubstituted C1-18 acyloxy groups, and one, two, or three or more selected from the group consisting of these organic groups is preferable.
  • the aryl groups (preferably phenyl groups) at the 4- and 6-positions in the above formula (1) may be unsubstituted or have a substituent.
  • the substituent is preferably a hydroxyl group, a substituted or unsubstituted monovalent organic group.
  • One kind, two kinds or three or more kinds selected from the group consisting of these are preferable.
  • the phenyl group bonded to the 4- or 6-position of the triazine-based compound may be either a substituent or a non-substituent, and the substituent is not particularly limited, but for example, a phenyl group, a hydroxyl group, a methyl group, or a hexyloxy group. And the like, and one kind, two kinds or three or more kinds selected from the group consisting of these are preferable. When a methyl group is selected at this time, dimethyl having two methyl groups may be used.
  • the triazine-based compound of the present invention is more preferably a 2- (2-hydroxyphenyl) -4,6-diphenyl-1,3,5-triazine-based compound represented by the following formula (2).
  • the compound may have a substituent.
  • n (number of substituents) of (Ra ) n is the same or different, and is any one of 1, 2, 3 or 4, preferably any one of 1 to 3, more preferably. Is 1 or 2. Further, in the above formula (2), n (number of substituents) of (R b ) n and (R c ) n is the same or different, and is either 0, 1, 2, 3, 4, or 5. , Preferably any of 0 to 3, and more preferably any of 1 to 3. Incidentally, a (R b) when n and (R c) n n of 0, unsubstituted phenyl group.
  • Ra , R b , and R c are the same or separate hydroxyl groups, halogen atoms, substituted or unsubstituted mono-divalent organic groups, and more preferably of these substituents. , Hydroxyl group, substituted or unsubstituted monovalent organic group, and one or more selected from the group consisting of these substituents is preferable.
  • acyloxy group is represented by RCOO-, preferably R is an alkyl group, and examples thereof include an ethylhexanoyloxy group.
  • Ra in the above formula (2) is preferably an alkoxy group of C1 to 18 and an alkyl group of C1 to 3 (preferably a methyl group), and more preferably at least an alkoxy group of C1 to 18.
  • the alkoxy group of C1 to 18 is preferably held at the 4-position of the 2-hydroxyphenyl group.
  • R b and R c in the above formula (2) are preferably hydroxyl groups, substituted or unsubstituted monovalent organic groups, and among the organic groups, C1 to 18 alkyl groups (more preferably C1 to 3), Alkoxy groups of C1 to 18 (more preferably C3 to 18) or phenyl groups of C6 to 18 are preferable.
  • R b and R c are one or more selected from the group consisting of these substituents.
  • the substituents of R b and R c may be the same, different, and may be singular or plural.
  • the substituent for example, two methyl groups may be used.
  • it may have one hydroxyl group, one methyl group, and one hexyloxy group.
  • R b and R c are the same.
  • triazine-based compound examples include (a) 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol ( Mw512) (eg, Adecastab LA-46), (b) 2- [4,6-di (4-biphenylyl) -1,3,5-triazine-2-yl] -5- (2-ethylhexyloxy) phenol (Mw606) (eg, thynubin 1600), (c) 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenol) -1,3,5-triazine (Mw640) (for example, contained in thynubin 400), (d) 2- [4-[(2-hydroxy-3-tridecyloxypropyl) -5
  • the method for synthesizing the above-mentioned triazine-based compound is not particularly limited, and a synthetic method usually used for synthesizing a compound having a triazine structure can be applied (for example, Reference 1: JP-A-2004-160883, References). 2: Japanese Patent Application Laid-Open No. 2010-270336, Reference 3: Japanese Patent Application Laid-Open No. 11-503112, etc.).
  • a desired derivative such as a phenol derivative or a resorcinol (1,3-dihydroxybenzene) derivative is added to cyanuric chloride (a structure in which 1,3,5-triazine is chlorinated) using aluminum trichloride. The method can be mentioned.
  • Each substituent may be introduced after forming the 1,3,5-triazine skeleton compound, or may be introduced into the phenol derivative or resorcinol derivative before forming the 1,3,5-triazine skeleton compound. May be good. Further, for example, a desired substituent may be further introduced into the compound obtained with 2- (4-biphenyl) -4H-1,3-benzoxazine-4-one and benzamidine hydrochloride or 4-biphenylamidine hydrochloride. Good.
  • the vinylidene fluoride-based resin multilayer film of the present invention is a multilayer film containing at least two layers in which a back surface layer (methacrylic rich resin layer) and a front surface layer (fluorine rich resin layer) are laminated.
  • the thickness of the back surface layer is not particularly limited, but is preferably 10 to 180 ⁇ m, more preferably 15 to 150 ⁇ m from the viewpoint of cost reduction and film strength, and the upper limit of the thickness of the back surface layer is cost reduction and components. From the viewpoint of flexible compatibility with the shape, it is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the total thickness including the front surface layer and the back surface layer is not particularly limited, but is preferably 20 to 200 ⁇ m, more preferably 30 to 200 ⁇ m from the viewpoint of cost reduction and film strength. Further, the upper limit of the total thickness including the front surface layer and the back surface layer is more preferably 150 ⁇ m or less, still more preferably 100 ⁇ m or less, from the viewpoint of cost reduction and flexible compatibility with the component shape.
  • another layer may be laminated on the front surface layer and / or the back surface layer.
  • Other layers include, for example, a decorative layer, a protective layer, an adhesive layer, a printing layer, a metal vapor deposition layer, and the like, but are not particularly limited.
  • the total thickness including these layers is preferably 20 to 500 ⁇ m (more preferably 400 to 500 ⁇ m), and for example, in the case of three layers of the front surface layer, the back surface layer and the decorative layer, the total thickness is 20 to 200 ⁇ m (more preferably). More preferably, it is 30 to 200 ⁇ m), which is preferable in terms of workability and cost of adhesion to automobile exterior and interior parts.
  • the vinylidene fluoride-based resin multilayer film of the present invention may have a two-layer structure composed of a back surface layer and a front surface layer, and in the case of this two-layer structure film, the "vinylidene fluoride resin film alone" or “this Also referred to as "the film of the invention". Further, the vinylidene fluoride-based resin multilayer film of the present invention is also referred to as a "decorative film" when at least a decorative layer is laminated on the front surface layer and / or the back surface layer. An adhesive layer for adhering to parts or the like may be laminated on the decorative film.
  • an acrylic resin, a polycarbonate resin, a vinyl chloride resin, a polyester resin, or a resin composition containing these resins can be used as the decorative layer.
  • additives such as pigments can be added as appropriate.
  • Polyester-based resins are used for panel parts such as automobiles and mobile phones by plating or metallic printing because of their good surface gloss and excellent printability. Since the acrylic resin sheet has excellent weather resistance and excellent adhesion to the acrylonitrile-butadiene-styrene copolymer resin, it is suitable for surface decoration of a molded product using this resin as a base material.
  • the vinyl chloride resin sheet Since the vinyl chloride resin sheet has a high tensile elongation when heated and has moldability to follow a shape having a high degree of deep drawing, it is laminated with the vinylidene fluoride resin multilayer film of the present invention. , Can be suitably used for surface decoration of a molded product having a complicated shape.
  • the decorative layer may contain a hindered amine-based light stabilizer (HALS, etc.), and HALS is a basic substance that prevents deterioration due to light.
  • HALS hindered amine-based light stabilizer
  • the crystallinity of the surface layer is 45% or more and ⁇ crystals. Since the ratio of the above can be 60% or more, the formation of the polyene structure can be suppressed, and discoloration can be suppressed for a longer period of time.
  • any other additive component may be added to the front surface layer and / or the back surface layer as long as the effects of the present invention are not impaired.
  • pigments or fillers, stabilizers, dispersants, antioxidants, matting agents, surfactants, antistatic agents, fluorine-based surface modifiers, processing aids and the like can be added.
  • a multi-layer with a film such as isotropic or syndiotactic polypropylene, high density polyethylene, low density polyethylene, polystyrene, polyethylene terephthalate, ethylene-vinyl acetate copolymer (EVA). It is also possible to perform various decoration treatments such as embossing.
  • HAZE Transparency of vinylidene fluoride resin multilayer film
  • the transparency can be expressed by HAZE, and HAZE of the present invention is a value obtained by measuring a vinylidene fluoride resin film alone.
  • the HAZE of the vinylidene fluoride-based resin multilayer film of the present invention is preferably 15% or less, more preferably less than 10%, still more preferably 2% or less, still more preferably 1.7% or less.
  • the total light transmittance of the vinylidene fluoride-based resin multilayer film is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more.
  • the total light transmittance and HAZE can be measured under the following conditions according to JISK-7361-1 and JISK-7136.
  • the vinylidene fluoride-based resin multilayer film of the present invention has excellent UV-blocking properties, and thus has good substrate protection.
  • the vinylidene fluoride-based resin multilayer film of the present invention is laminated on a decorative layer as a base, and an ultraviolet ray irradiation is performed to perform a weather resistance promotion test, and the change ⁇ b of the yellowness of the sample before and after the test can be evaluated. Details will be described in Examples. Discoloration can be prevented by containing the ultraviolet absorber in the vinylidene fluoride-based resin multilayer film of the present invention.
  • the vinylidene fluoride-based resin multilayer film of the present invention has excellent discoloration resistance to temperature changes because the film is less discolored even when the temperature of cold heat changes cyclically.
  • the conventional vinylidene fluoride resin film alone may be whitened by a temperature change.
  • the vinylidene fluoride-based resin film of the present invention is excellent in whitening resistance against temperature changes. Therefore, when the decorative layer is laminated on the film alone of the present invention, the decorative film has excellent discoloration resistance against temperature changes.
  • the decorative film of the present invention containing a red-based decorative layer has an advantage that the color is less likely to change to pink or pale red due to changes over time.
  • the discoloration resistance of the present invention can be expressed by ⁇ E, and ⁇ E is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less.
  • ⁇ E of the present invention is a value obtained by laminating a specific decorative layer on the vinylidene fluoride resin film of the present invention and measuring the decorative film.
  • the vinylidene fluoride-based resin multilayer film of the present invention has excellent bleed-out resistance against temperature changes.
  • the vinylidene fluoride resin film of the present invention has good bleed-out resistance against temperature changes. Therefore, the precipitation and adhesion of powdery foreign matter can be suppressed on the surface of the front surface layer or the back surface layer of the film alone of the present invention.
  • the evaluation of the bleed-out resistance of the present invention will be described in detail in Examples, but after a predetermined cooling / heating cycle is performed on the vinylidene fluoride resin film alone, powdery foreign matter is found on the surface of the back surface layer.
  • MFR Melt mass flow rate of front layer and back layer
  • MFR Absolute difference in melt mass flow rate measured by applying a load of 2.16 kgf at 240 ° C. between the front surface layer and the back surface layer of the vinylidene fluoride resin multilayer film of the present invention.
  • the value is preferably 0.5 to 5.0 g / 10 min, more preferably 1.0 to 2.0 g / 10 min.
  • the MFRs of the front surface layer and the back surface layer are preferably 0.5 to 25.0 g / 10 min and 0.5 to 25.0 g / 10 min, respectively, but are not particularly limited.
  • MFR melt mass flow rate
  • the method for producing the vinylidene fluoride-based resin multilayer film of the present invention is not particularly limited, but it can be easily produced by a conventionally used melt extrusion molding method. Specifically, there are a T-die method in which a film is formed using a T-type die and a method in which a film is formed using an inflation die. Extrusion conditions are not particularly limited, and it is generally used for forming a vinylidene fluoride-based resin multilayer film. You can use the conditions that are used in the above.
  • the T-die method a metal cooling roll and a rubber roll are arranged under the T-shaped die, and the molten resin extruded from the lip opening of the T-shaped die is pinched between the rolls to cool and solidify the film.
  • Either the method of cooling and solidifying with a metal cooling roll without using a pinch roll and the method of forming a film can be adopted.
  • the amount of heat converted per unit time when cooling the molten resin is a calculation formula represented by the following formula, and is preferably 70 to 180 kW per 1 kg of the molten resin.
  • Heat conversion specific heat of resin composition (J / kg ⁇ ° C) ⁇ ⁇ T / cooling time (sec)
  • ⁇ T molten resin temperature ⁇ temperature after cooling.
  • the amount of heat converted per 1 kg of the molten resin is preferably 94 kW. is there. If the amount of heat converted is less than 70 kW, the releasability from the cooling roll may deteriorate due to insufficient cooling, and if it exceeds 180 kW, the vinylidene fluoride-based resin multilayer film having the crystal structure of the present invention cannot be obtained.
  • the extruded film is preferably cooled and solidified to a thickness of 30 to 100 ⁇ m.
  • the vinylidene fluoride resin multilayer film of the present invention is excellent in bleed-out resistance against temperature change, discoloration resistance against temperature change, and ultraviolet ray blocking property. Therefore, the vinylidene fluoride-based resin multilayer film is preferably laminated on the decorative layer. By laminating the decorative layers, it is possible to provide a decorative film having an excellent decorative effect. Further, by using the vinylidene fluoride resin multilayer film of the present invention, it is possible to provide a film for automobile interior / exterior parts and an automobile or automobile interior / exterior parts using the same.
  • the vinylidene fluoride resin multilayer film of the present invention to an exterior film, it is possible to impart further scratch resistance and water repellency by laminating a protective layer or the like on the surface layer.
  • a protective layer or the like on the surface layer.
  • the film for interior and exterior of automobiles is excellent in handleability, it can be used for large parts such as bonnets and roofs, and small parts such as internal holders, panels and gauges.
  • the automobile interior / exterior parts to which the present invention is applied are, for example, instrument panel parts, console parts, or pillar parts for automobile interiors, or side mirror covers or bumpers for automobile exteriors, but are not limited thereto.
  • the vinylidene fluoride resin film simple substance 1 shown in FIG. 1 is composed of a front surface layer 2 and a back surface layer 3, and is the smallest unit of the vinylidene fluoride resin multilayer film of the present invention. Further, in the vinylidene fluoride resin multilayer film of the present invention, the front surface layer 2, the back surface layer 3, and the decorative layer 4 can be sequentially laminated to obtain a vinylidene fluoride resin multilayer film laminated on the decorative layer. it can. When the decorative layer 4 is included in this way, it is also referred to as a decorative film in the present invention.
  • the back surface layer 3 of the vinylidene fluoride-based resin multilayer film may contain a phenol-based antioxidant as an antioxidant in an amount of about 0.1% by mass (for example, 0.05 to 0.2% by mass). ..
  • the decorative layer 4 may be the same as that of the constituent used in the above evaluation method, but is not particularly limited.
  • the decorative layer 4 may be a white vinyl chloride sheet.
  • the white vinyl chloride sheet contains DEHA (bis (2-ethylhexyl adipate)), DEHP (bis (2-ethylhexyl phthalate)), 2-hydroxy-4-n-octyloxybenzophenone, and DINP (diisononyl phthalate). It may be contained, and HALS may be contained in an amount of about 0.5% by mass (for example, 0.1 to 1% by mass).
  • the adhesive layer 5 of the vinylidene fluoride-based resin multilayer film shown in FIG. 1 is used for adhering the film alone or the decorative film of the present invention to an automobile or an automobile part (for example, an automobile interior / exterior part). It is preferable to do so.
  • the adhesive layer 5 may be the same as that of the constituent used in the evaluation method of the present invention, or is preferably made of an acrylic pressure-sensitive adhesive, but is not particularly limited.
  • reference numeral 11 may be an iron plate 11 or an ABS resin plate 11, and is not particularly limited.
  • FIG. 1 may be an example of a cross-sectional view of a part of an automobile or an automobile part using the vinylidene fluoride-based resin multilayer film of the present invention, but the present invention is not limited thereto.
  • UV absorber Triazine-based ultraviolet absorber
  • Tnuvin 1577ED 2- (4,6-diphenyl-1,3,5-triazine-2-yl)- 5-[(Hexyl) oxy] -phenol triazine-based ultraviolet absorber: Compound A (Mw606): 2- [4,6-di (4-biphenylyl) -1,3,5-triazine-2-yl]- 5- (2-Ethylhexyloxy) phenol (manufactured by BASF Japan Co., Ltd .: tinuvin 1600 may be used) -Triazine-based UV absorber: Compound B (Mw510): 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazin
  • PVC resin Polyvinyl chloride (PVC) S1008C manufactured by Kaneka Corporation
  • each raw material is premixed in an unmelted state, then melted in a melting and mixing facility, and uniformly mixed. Then, it was extruded into a strand shape, cooled, and then cut into a pellet shape and used as a raw material (see Tables 1 to 3).
  • the fluorine-based resin layer (front surface layer) and the acrylic resin layer (back surface layer) were laminated by laminating each of the above compounds as follows to obtain a laminated film having a predetermined thickness.
  • the production of the vinylidene fluoride-based resin multilayer film (single film composed of the front surface layer and the back surface layer) of each of the present example and the comparative example was in accordance with the conditions shown in Table 3.
  • the draft ratio defined by the value obtained by dividing the lip opening, which represents the width of the lip gap of the T-die, by the film thickness was set to 15.
  • the surface temperature of the first cooling roll that is cooled by contacting the resin extruded from the T die was set to 50 ° C.
  • the draw ratio defined by the value obtained by dividing the film winding speed by the rotation speed of the first cooling roll was set to 1.1.
  • the front surface of the back surface layer was heat-laminated to obtain each component (thickness 150 ⁇ m).
  • the back surface of the vinylidene fluoride resin film alone is laminated so that the decorative film is in contact with each other, sandwiched between a metal roll heated to 140 ° C. and a rubber roll, and each roll is sandwiched at a speed of 1 m / min.
  • the method was performed by rotating and heat-pressing.
  • each of these components is adhered to an ABS sheet (Morino Kako Co., Ltd., Emron) with a base material-less double-sided tape (MHM-FWV25: Niei Kako Co., Ltd., thickness 25 ⁇ m), and each test sheet (length 50 mm ⁇ ). A width of 50 mm and a thickness of 400 to 500 ⁇ m) were produced.
  • This test plate is subjected to a 120-hour cooling cycle "(80 ° C x 3h ⁇ 23 ° C x 1h ⁇ -30 ° C x 3h) using a low temperature constant temperature / humidity controller (low temperature constant temperature / humidity controller PL-3J manufactured by Espec Co., Ltd.). ⁇ 23 ° C. ⁇ 1h ⁇ 50 ° C. ⁇ 95% RH ⁇ 15h ⁇ 23 ° C. ⁇ 1h) ⁇ 5 cycles ”, and the hue change ⁇ E before and after the injection was measured.
  • ⁇ Color difference ⁇ E measurement> The E value was calculated in accordance with JIS Z8729 using a color difference meter (ZE6000) manufactured by Nippon Denshoku Kogyo Co., Ltd., and the value obtained by subtracting the E value before the test from the E value after the test was defined as the ⁇ E value.
  • ZE6000 color difference meter
  • ⁇ E value was evaluated as the color change resistance ( ⁇ E) with respect to the cold cycle.
  • a ⁇ E value of 3 or less was set as the pass level.
  • ⁇ Measurement of change in yellowness ⁇ b> For the above structure, a colorimetric color difference meter (ZE6000) manufactured by Nippon Denshoku Kogyo Co., Ltd. was used to calculate the b value in accordance with JIS Z8729, and the value obtained by subtracting the b value before the test from the b value after the test was calculated. The ⁇ b value was used as the evaluation of the ultraviolet ray blocking performance. A ⁇ b value of 2.0 or less was set as the pass level.
  • X-ray source Cu sealed tube Applied voltage / current: 40kV / 40mA Measurement range: 10 ° ⁇ 2 ⁇ ⁇ 50 ° Exposure time: 20 minutes Measurement step: 0.02 ° Scan speed: 1 ° / min
  • Unit configuration CBO unit, PB0.3 selection slit Solar slit open, PB collimator holder ⁇ 0.1mm
  • Pinhole collimator Detector Semiconductor detector (HyPit-3000) Measurement stage: The 2D transmission attachment data was converted into one-dimensional data using XRD data analysis software 2DP (2D data processing), and the profile fitting function of XRD data analysis software PDXL (Power diffraction analysis) was used.
  • the crystallinity of the surface layer was calculated by the following formula.
  • Ic weight of the vinylidene fluoride resin in a crystalline state on the surface layer of the PVDF crystal structure halo peak area
  • M Weight of surface layer in 100 g of film
  • Crystallinity (%) of surface layer M FC / M x 100
  • M FC Ic / (Ic + Ia) ⁇ 100.
  • M was calculated from the specific gravity and layer composition ratio (thickness of each layer) of each layer of the sample for which the crystallinity was measured. The specific gravity of each layer was calculated from the mixing ratio of the raw materials. The layer composition ratio of the film was measured as follows.
  • the film was sandwiched and fixed in a small metal vise, and cut with a single-edged knife so that the cross section of the film was smooth.
  • a confocal laser scanning microscope VK-X110 manufactured by KEYENCE CORPORATION
  • the layer composition ratio was calculated from the result.
  • ⁇ Crystal ratio (%) in total crystal components The ⁇ crystal ratio was determined by measuring the infrared absorption spectrum using an ATR unit (UMA-500) of FT-IR (main body: FTS-135) manufactured by Bio-Rad Laboratories Co., Ltd. From the obtained spectra, the absorption intensity (peak height (A)) of wave number 840 cm -1 , which is the characteristic absorption of ⁇ -type crystal, and the absorption intensity (peak height (peak height (A)) of wave number 765 cm -1 , which is the characteristic absorption of ⁇ -type crystal. B)) was obtained, and the component ratio (%) of the ⁇ -type crystal was calculated from the following formula. (B) / ((A) + (B)) x 100 (%)
  • MFR melt mass flow rate
  • the vinylidene fluoride-based resin multilayer film of Comparative Example 5 is a vinylidene fluoride-based resin multilayer film obtained by a triazine-based ultraviolet absorber having a molecular weight of less than 500, but the film changes color with respect to temperature change and with respect to temperature change. Bleedout occurred, and the UV cut performance was also poor.
  • the vinylidene fluoride-based resin multilayer film using the triazine-based ultraviolet absorber having a molecular weight of less than 500 has a back surface layer of 20% by mass or less of the vinylidene fluoride-based resin.
  • vinylidene fluoride-based resin multilayer films using compounds for triazine-based ultraviolet absorbers having a molecular weight of 500 or more have discoloration resistance to temperature changes, bleed-out resistance to temperature changes, and ultraviolet rays.
  • the cutting performance was very good.
  • the molecular weight of the compound for the triazine-based ultraviolet absorber is in the range of 510 to 800 (preferably compounds A, B, C)
  • the vinylidene fluoride-based resin multilayer film using the compound is resistant to temperature changes. It has much better discoloration resistance, bleed-out resistance to temperature changes, and UV blocking performance.
  • Comparative Example 3 when the vinylidene fluoride-based resin in the back surface layer was 20% by mass or more, the discoloration resistance against temperature change and the bleed-out resistance against temperature change were poor. From this, even when a compound for a triazine-based ultraviolet absorber having a molecular weight of 500 or more is used, in order to improve the three properties of discoloration resistance against temperature change, bleed-out resistance against temperature change, and ultraviolet ray blocking performance. Needed to reduce the amount of vinylidene fluoride-based resin in the back surface layer to less than 20% by mass.
  • the content of the vinylidene fluoride-based resin in the back surface layer is 0 to 10% by mass (based on the total amount of the resin component in the back surface layer), the resistance to temperature changes. It has much better discoloration, bleed-out resistance to temperature changes, and UV protection. More preferably, the content of the vinylidene fluoride resin in the back surface layer is 0 to 5% by mass, and more preferably, the content of the vinylidene fluoride resin in the back surface layer is substantially 0% by mass, that is, the back surface layer. It is preferable that the content of the methacrylic acid ester-based resin is substantially 100% by mass. As a result, the discoloration resistance to temperature changes, the bleed-out resistance to temperature changes, and the ultraviolet ray blocking performance of the vinylidene fluoride-based resin multilayer film are further improved.
  • Example 1 Example 4, Example 5, Comparative Example 2, and Comparative Example 4, even when a compound for a triazine-based ultraviolet absorber having a molecular weight of 500 or more is used, the amount used is the back surface. It had to be less than 8 parts by mass with respect to 100 parts by mass of the resin in the layer. Then, as shown in Examples 1, 4 and 5, the amount of the compound for the triazine-based ultraviolet absorber having a molecular weight of 500 or more is 0.1 to 5 with respect to 100 parts by mass of the resin in the back layer. In terms of mass, the vinylidene fluoride-based resin multilayer film had three good properties: discoloration resistance against temperature change, bleed-out resistance against temperature change, and ultraviolet ray blocking performance.
  • each surface layer is 45% or more
  • each vinylidene fluoride resin is obtained by the above-mentioned method for measuring the degree of crystallinity and the method for measuring the peak intensity ratio of ⁇ -type crystals.
  • the ratio of ⁇ crystals to the total crystal components of the above was 60% or more, and the peak intensity ratio of each ⁇ type crystal was in the range of 70 to 90%.
  • the absolute value of the difference between the melt mass flow rates (MFR) is in the range of 1.0 to 2.0 g / 10 min according to the above-mentioned MFR measurement method, and the front surface layer and the back surface are also covered.
  • the MFRs of the layers were 0.5-25.0 g / 10 min and 0.5-25.0 g / 10 min, respectively.
  • the total light transmittance was 90% or more.
  • the back surface layers of Examples 1 to 7 can contain 0.1% by mass of a phenolic antioxidant as an antioxidant.
  • the vinylidene fluoride resin multilayer film of the present invention is suitable for automobile interiors such as instrument panels, dashboards and doors, and automobile exterior applications such as bodies, front bumpers and rear bumpers. It can also be used for interior / exterior films for infrastructure, various buildings, and interior / exterior films for railway vehicles, aircraft, ships, spacecraft, and the like.

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PCT/JP2020/031281 2019-08-26 2020-08-19 フッ化ビニリデン系樹脂多層フィルム、自動車内外装用フィルム、自動車用部品及び自動車 Ceased WO2021039533A1 (ja)

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EP20856862.6A EP4023439B1 (en) 2019-08-26 2020-08-19 Vinylidene fluoride resin multilayer film, automobile interior/exterior film, automobile component, and automobile
CN202080051728.0A CN114126866A (zh) 2019-08-26 2020-08-19 偏氟乙烯系树脂多层膜、汽车内外装饰用膜、汽车用部件及汽车
US17/637,489 US20220274388A1 (en) 2019-08-26 2020-08-19 Vinylidene fluoride resin multilayer film, automobile interior/exterior film, automobile component, and automobile
JP2021542783A JP7627659B2 (ja) 2019-08-26 2020-08-19 フッ化ビニリデン系樹脂多層フィルム、自動車内外装用フィルム、自動車用部品及び自動車

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See also references of EP4023439A4

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