WO2021117879A1 - Article moulé en résine, composition de résine (méth)acrylique pour matériau de moulage, composition de résine (méth)acrylique, et composition de résine pour matériau de moulage - Google Patents

Article moulé en résine, composition de résine (méth)acrylique pour matériau de moulage, composition de résine (méth)acrylique, et composition de résine pour matériau de moulage Download PDF

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WO2021117879A1
WO2021117879A1 PCT/JP2020/046327 JP2020046327W WO2021117879A1 WO 2021117879 A1 WO2021117879 A1 WO 2021117879A1 JP 2020046327 W JP2020046327 W JP 2020046327W WO 2021117879 A1 WO2021117879 A1 WO 2021117879A1
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meth
resin composition
acrylic resin
mass
fatty acid
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PCT/JP2020/046327
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Japanese (ja)
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祐次朗 濱田
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三菱ケミカル株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16Homopolymers or copolymers or vinylidene fluoride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Definitions

  • the present invention relates to a resin molded product, a (meth) acrylic resin composition for a molding material, a (meth) acrylic resin composition, and a resin composition for a molding material.
  • the present application claims priority based on Japanese Patent Application No. 2019-224164 filed in Japan on December 12, 2019 and Japanese Patent Application No. 2020-185151 filed in Japan on November 5, 2020. The contents are used here.
  • (Meta) Acrylic resin is a material for housing equipment such as vanities, bathtubs, flush toilets, etc.; building materials; vehicle parts such as interior and exterior materials of vehicles, etc. due to its excellent appearance, scratch resistance, and heat resistance. Widely used in many applications.
  • the product may be scratched by contact with a person or an object, and therefore, more excellent scratch resistance is required. In addition, excellent transparency is also required.
  • molding a (meth) acrylic resin using a known melt molding method such as extrusion molding or injection molding, molding obtained depending on molding conditions such as the temperature inside the extruder, the temperature of the mold, and the injection speed. There is a problem that the scratch resistance of the body changes. Therefore, the (meth) acrylic resin is required to have a small dependence on molding conditions.
  • Patent Document 1 discloses an acrylic resin composition for paints containing a polyvinylidene fluoride-based copolymer.
  • Patent Document 2 discloses an acrylic resin film containing a polyvinylidene fluoride-based copolymer.
  • Patent Document 3 discloses a methacrylic resin composition containing a fatty acid amide compound.
  • the acrylic resin composition for coatings disclosed in Patent Document 1 the acrylic resin film disclosed in Patent Document 2, and the methacrylic resin composition disclosed in Patent Document 3 are all scratch resistant. Adhesiveness and dependence on molding conditions were insufficient.
  • the present invention relates to a (meth) acrylic resin composition for a molding material, a (meth) acrylic resin composition, and a resin for a molding material, which can obtain a resin molded product having excellent scratch resistance, molding condition dependence, and transparency. It is an object of the present invention to provide a composition. Another object of the present invention is to provide a resin molded product having excellent scratch resistance, molding condition dependence, and transparency.
  • the present invention has the following aspects.
  • the coefficient of dynamic friction (F) measured in accordance with ISO 8295: 1995 is 0.150 or less.
  • the peak absorbance (P2) in the region of wave number 870 to 890 cm -1 and the peak absorbance in the region of wave number 1710 to 1730 cm -1 ( A resin molded body having an absorbance ratio (P2 / P3) with P3) of 0.0005 or more.
  • [3] [1] or [2] comprising a (meth) acrylic resin composition containing a (meth) acrylic polymer (A), a fluorine-containing olefin polymer (B), and a fatty acid compound (C). Resin molded body.
  • a (meth) acrylic resin composition for a molding material which comprises a fluorine atom-containing compound and a fatty acid compound (C).
  • C a fatty acid compound
  • the fluoroolefin polymer (B) is a homopolymer of vinylidene fluoride, a repeating unit derived from a vinylidene fluoride monomer, and a single amount copolymerizable with vinylidene fluoride.
  • the solubility parameter value of the fatty acid compound (C) is 16.4 (J / cm 3 ) 1/2 or more and 24.6 (J / cm 3 ) 1/2 or less, [6] to [ 9]
  • the (meth) acrylic resin composition for any of the molding materials is 16.4 (J / cm 3 ) 1/2 or more and 24.6 (J / cm 3 ) 1/2 or less.
  • the content ratio of the (meth) acrylic polymer (A) is 60% by mass or more with respect to the total mass of the (meth) acrylic resin composition for the molding material, [14] to [16]. ] (Meta) acrylic resin composition for any of the molding materials.
  • the solubility parameter value of the fatty acid compound (C) is 16.4 (J / cm 3 ) 1/2 or more and 24.6 (J / cm 3 ) 1/2 or less (18).
  • Meta) Acrylic resin composition [20] The (meth) acrylic resin composition of [18] or [19], wherein the fatty acid compound (C) is a fatty acid amide compound (C1).
  • the fluoroolefin polymer (B) is a homopolymer of vinylidene fluoride, or a repeating unit derived from a vinylidene fluoride monomer and a monomer copolymerizable with vinylidene fluoride.
  • the content of the fluorine-containing olefin polymer (B) is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer (A), [23] or [24] (Meta) acrylic resin composition.
  • the content of the fatty acid compound (C) is 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer (A).
  • the (meth) acrylic resin composition according to any one of [25].
  • the (meth) acrylic resin composition [28]
  • a resin composition for a molding material which comprises the (meth) acrylic resin composition according to any one of [18] to [27].
  • the (meth) acrylic resin composition for any of the molding materials of [6] to [17] or the (meth) acrylic resin composition of any of [18] to [27] is molded.
  • the (meth) acrylic resin composition for molding materials According to the (meth) acrylic resin composition for molding materials, the (meth) acrylic resin composition, and the resin composition for molding materials of the present invention, a resin having excellent scratch resistance, molding condition dependence, and transparency. A molded product is obtained.
  • the resin molded product of the present invention is excellent in scratch resistance, molding condition dependence, and transparency.
  • the "(meth) acrylic polymer” means at least one selected from the “acrylic polymer” and the “methacrylic polymer”.
  • “(meth) acrylate” means at least one selected from “acrylate” and “methacrylic acid”
  • “(meth) acrylic acid” is selected from “acrylic acid” and "methacrylic acid”.
  • “(Meta) acrylic resin” means at least one selected from “acrylic resin” and "methacrylic resin”.
  • the "monomer” means an unpolymerized compound
  • the "repeating unit” means a unit derived from the monomer formed by polymerizing the monomer.
  • the repeating unit may be a unit directly formed by a polymerization reaction, or a part of the unit may be converted into another structure by processing a polymer.
  • "% by mass” indicates the content ratio of a predetermined component contained in 100% by mass of the total amount.
  • the "obtained resin molded product” is any one of the (meth) acrylic resin composition for molding materials, the (meth) acrylic resin composition, and the resin composition for molding materials of the present invention. It means a molded product made by molding.
  • the (meth) acrylic resin composition according to the first aspect of the present invention contains the fatty acid compound (C) described later, and the content ratio of fluorine atoms is 0 with respect to the total mass of the (meth) acrylic resin composition. It is 5.5% by mass or more.
  • the "fluorine atom content ratio” is the content of fluorine atoms contained in the (meth) acrylic resin composition of the first aspect of the present invention and contained in the repeating unit constituting the polymer chain. It is defined as the content ratio (unit: mass%) of fluorine atoms to 100% by mass of the total mass of the (meth) acrylic resin composition.
  • the fluorine-containing olefin-based polymer (B) described later contains a fluorine atom in its structure
  • the fluorine-containing olefin-based polymer (B) is based on 100% by mass of the total mass of the (meth) acrylic resin composition. It refers to the content ratio of fluorine atoms in.
  • the content ratio of fluorine atoms in the (meth) acrylic resin composition is 0.5% by mass or more, the obtained resin molded product has excellent dependence on molding conditions, and the surface friction coefficient tends to decrease. Because it is located in, it has excellent scratch resistance.
  • the content ratio of the fluorine atom is preferably 0.7% by mass or more, more preferably 1.0% by mass or more, based on the total mass of the (meth) acrylic resin composition.
  • the upper limit of the content ratio of fluorine atoms is not particularly limited, but if it is 15% by mass or less, the hardness of the obtained resin molded product is not impaired, so that scratch resistance can be maintained satisfactorily.
  • the content ratio of the fluorine atom is more preferably 12% by mass or less, and further preferably 10% by mass or less, based on the total mass of the (meth) acrylic resin composition.
  • the upper and lower limits of the content ratio of fluorine atoms can be arbitrarily combined.
  • the content ratio of fluorine atoms to the total mass (100% by mass) of the (meth) acrylic resin composition is preferably 0.5% by mass or more and 15% by mass or less, and 0.7% by mass or more and 12% by mass or less. More preferably, it is 1.0% by mass or more and 10% by mass or less.
  • a method for controlling the content ratio of fluorine atoms in the (meth) acrylic resin composition a method of blending the fluorine-containing olefin polymer (B) described later into the (meth) acrylic resin composition or fluorination (meth) Examples thereof include a method of blending a polymer containing a meta) acrylate unit into a (meth) acrylic resin composition. From the viewpoint of excellent scratch resistance of the obtained resin molded product, a method of blending the fluorine-containing olefin polymer (B) with the (meth) acrylic resin composition is preferable.
  • the (meth) acrylic polymer (A) may be contained, and the fluorine-containing olefin polymer (B) described later may be contained.
  • the fluorine-containing olefin polymer (B) described later may be contained.
  • the (meth) acrylic resin composition of the present embodiment may contain an impact reinforcing material (D) described later, a silicone oil (E) described later, and carbon black (F) described later. May include.
  • the (meth) acrylic resin composition of the present embodiment is a (meth) acrylic polymer (A) or a fluorine-containing olefin polymer (as long as the compounding amount does not impair the performance of the resin molded product. Even if components other than B), the fatty acid compound (C), the impact reinforcing material (D), the silicone oil (E), and the carbon black (F) (hereinafter, also referred to as "other additives”) are further contained. Good.
  • the MFR measured under the conditions of a temperature of 230 ° C. and a load of 3.8 kg according to ISO 1133-1: 2011 of the (meth) acrylic resin composition of the present embodiment is not particularly limited, but is usually 0.5 to 50 g. It is about / 10min.
  • the (meth) acrylic polymer (A) is one of the constituents of the (meth) acrylic resin composition of the present embodiment.
  • the (meth) acrylic polymer (A) means a polymer in which at least a part of the constituent units is a constituent unit based on the (meth) acrylic monomer.
  • the (meth) acrylic polymer (A) may further contain a structural unit based on a monomer other than the (meth) acrylic monomer (for example, a vinyl monomer such as styrene).
  • "(Meta) acrylic monomer” means a monomer having at least one of an acryloyl group and a methacryloyl group.
  • the (meth) acrylic polymer (A) preferably contains a structural unit based on a methacrylic monomer, and more preferably contains a repeating unit derived from methyl methacrylate (hereinafter, referred to as “methyl methacrylate unit”). preferable.
  • the content ratio of the methyl methacrylate unit is preferably 70% by mass or more with respect to the total mass of the (meth) acrylic polymer (A).
  • the (meth) acrylic polymer (A) in which the content ratio of the methyl methacrylate unit is 70% by mass or more with respect to the total mass of the (meth) acrylic polymer (A) is particularly "polymer (A1)". Also called.
  • the polymer (A1) is a homopolymer of methyl methacrylate; a methyl methacrylate unit of 70% by mass or more and less than 100% by mass, and more than 0% by mass and 30% by mass or less with respect to the total mass of the polymer (A1).
  • Examples thereof include a copolymer containing a repeating unit derived from another monomer (hereinafter, also referred to as “another monomer unit”).
  • the methyl methacrylate unit is based on the total mass of the polymer (A1).
  • a copolymer having a content of 90% by mass or more or a homopolymer of methyl methacrylate is preferable, and a copolymer having a content ratio of methyl methacrylate units of 95% by mass or more with respect to the total mass of the polymer (A1).
  • a homopolymer of methyl methacrylate is more preferable.
  • the other monomer is a monomer other than methyl methacrylate that can be copolymerized with methyl methacrylate.
  • the other monomer is not particularly limited as long as it can be copolymerized with methyl methacrylate, but for example, methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate.
  • N-butyl (meth) acrylate isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate , Benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenta (Meta) acrylate compounds other than methyl methacrylate such as nyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth)
  • a (meth) acrylate compound other than methyl methacrylate is preferable because the original performance of the (meth) acrylic resin is not easily impaired, and the obtained resin molded product has excellent heat-decomposability. Therefore, methyl acrylate, ethyl acrylate, and n-butyl acrylate are more preferable, and methyl acrylate and ethyl acrylate are even more preferable.
  • These other monomers may be used alone or in combination of two or more.
  • the content ratio of the other monomer units to the total mass of the polymer (A1) does not easily impair the original performance of the (meth) acrylic resin. It is preferably more than 0% by mass and 20% by mass or less, more preferably more than 0% by mass and 10% by mass or less, and further preferably more than 0% by mass and 5% by mass or less.
  • Examples of the method for producing the polymer (A1) include a massive polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method.
  • the massive polymerization method and the suspension polymerization method are preferable, and the massive polymerization method is more preferable, because they are excellent in productivity.
  • the mass average molecular weight of the polymer (A1) is preferably 20,000 to 200,000, more preferably 50,000 to 150,000.
  • the mass average molecular weight of the polymer (A1) is 20,000 or more, the mechanical properties of the obtained resin molded product are excellent. Further, when the mass average molecular weight of the polymer (A1) is 200,000 or less, the fluidity at the time of melt molding is excellent.
  • the mass average molecular weight is a value measured by using standard polystyrene as a standard sample and using gel permeation chromatography.
  • the obtained resin molded product has transparency, heat resistance, weather resistance, etc. From the viewpoint of maintaining the original performance of the (meth) acrylic resin, 60% by mass or more is preferable, 70% by mass or more is more preferable, and 90% by mass or more is further preferable.
  • the content ratio of the (meth) acrylic polymer (A) to the total mass (100% by mass) of the (meth) acrylic resin composition is 99 from the viewpoint of excellent scratch resistance of the obtained resin molded product. It is preferably 9% by mass or less, more preferably 98% by mass or less, and further preferably 97% by mass or less.
  • the upper and lower limits of the content ratio of the (meth) acrylic polymer (A) can be arbitrarily combined.
  • the content ratio of the (meth) acrylic polymer (A) with respect to the total mass (100% by mass) of the (meth) acrylic resin composition is preferably 60% by mass or more and 99% by mass or less, and 70% by mass or more and 98% by mass or more. More preferably, it is 90% by mass or more, and further preferably 97% by mass or less.
  • the fluorine-containing olefin polymer (B) is one of the optional constituents of the (meth) acrylic resin composition of the present embodiment.
  • the content ratio of fluorine atoms can be adjusted with respect to the total mass of the (meth) acrylic resin composition. It can be 0.5% by mass or more.
  • the fluorine-containing olefin-based polymer (B) is not particularly limited as long as it is an olefin-based polymer containing a fluorine atom, and conventionally known fluoroolefin-based copolymers can be used.
  • the fluorine-containing olefin polymer (B) has good solubility in the (meth) acrylic resin composition, and the obtained resin molded product has excellent scratch resistance. It is preferable to use a polymer having sufficiently high compatibility with the meta) acrylic polymer (A).
  • the state in which the compatibility between the fluoroolefin polymer (B) and the (meth) acrylic polymer (A) is sufficiently high is, for example, in accordance with ISO 3146: 2000, and the heat flow flux differential scanning calorific value.
  • the glass transition point of the (meth) acrylic resin composition was measured using a meter, the glass transition point derived from the (meth) acrylic polymer (A) and the fluorine-containing olefin polymer (B) were obtained. A state in which each of the derived glass transition points is not detected and only one glass transition point is detected can be mentioned.
  • the (meth) acrylic resin composition of the present embodiment has the effect of improving the scratch resistance of both the fluorine-containing olefin polymer (B) and the fatty acid compound (C) described later in combination. Combined with this, the scratch resistance of the obtained molded product can be further improved without increasing the content of the fluorine-containing olefin polymer (B), so that the transparency, heat resistance, weather resistance, etc. (meth) can be further improved. ) It does not easily impair the original performance of acrylic resin.
  • the obtained resin molded product has excellent scratch resistance even with a small blending amount, and the (meth) acrylic resin composition.
  • a vinylidene fluoride-based (co) polymer containing a vinylidene fluoride unit is preferable from the viewpoint that the melting temperature can be prevented from becoming too high and the original performance of the (meth) acrylic resin is not impaired.
  • the vinylidene fluoride-based (co) polymer includes a homopolymer of vinylidene fluoride; a repeating unit derived from a vinylidene fluoride monomer and a repeating unit derived from a monomer copolymerizable with vinylidene fluoride. Examples thereof include vinylidene fluoride-based copolymers.
  • the vinylidene fluoride-based copolymer includes a vinylidene fluoride unit and at least one simple substance selected from hexafluoropropylene, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and ethylene. Examples thereof include vinylidene fluoride-based copolymers containing a repeating unit derived from a metric.
  • vinylidene fluoride-trifluoroethylene copolymer vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexa.
  • fluoropropylene-based copolymers fluoropropylene-based copolymers and vinylidene fluoride-chlorotrifluoroethylene-based copolymers.
  • the obtained resin molded product has excellent scratch resistance
  • the (meth) acrylic resin composition has a low melt viscosity and is easy to mold, so that it is a vinylidene fluoride-based (co) polymer.
  • a homopolymer of vinylidene fluoride, a binary copolymer of vinylidene fluoride unit 60-95% by mass and tetrafluoroethylene unit 5-40% by mass, vinylidene fluoride unit 60-95% by mass and hexafluoropropylene unit A binary copolymer with 5 to 40% by mass is preferable.
  • vinylidene fluoride-based (co) polymer one type can be used alone, or two or more types of polymers can be used in combination. Further, these vinylidene fluoride-based (co) polymers may be copolymers containing other components in the molecular chain, or copolymers in which other components are graft-bonded to the side chains. There may be.
  • the MFR measured under the conditions of a temperature of 230 ° C. and a load of 3.8 kg according to ISO 1133: 2011 of the fluorine-containing olefin polymer (B) is not particularly limited, but is usually about 0.5 to 50 g / 10 min. Is.
  • homopolymer of vinylidene fluoride for example, commercially available products such as KFT # 850 and # 1000 manufactured by Kureha Corporation; Kynar (registered trademark) 705, 721, 761 and 301F manufactured by Arkema Corporation can be used. it can.
  • vinylidene fluoride-based copolymer for example, commercially available products such as KynarFlex2801 manufactured by Arkema Co., Ltd.; VP-50 manufactured by Daikin Industries, Ltd .; Solef (registered trademark) series manufactured by Solvay Co., Ltd. can be used.
  • the content of the fluoroolefin polymer (B) contained in the (meth) acrylic resin composition of the present embodiment is the (meth) acrylic weight from the viewpoint of excellent scratch resistance of the obtained resin molded product. 1 part by mass or more is preferable, and 1.5 parts by mass or more is more preferable with respect to 100 parts by mass of the total mass of the coalescence (A).
  • the content of the fluoroolefin polymer (B) is 100, the total mass of the (meth) acrylic polymer (A), from the viewpoint that the obtained resin molded product does not impair the original performance of the (meth) acrylic resin. It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less with respect to parts by mass.
  • the upper and lower limits of the content of the fluorine-containing olefin polymer (B) can be arbitrarily combined.
  • the content of the fluorine-containing olefin polymer (B) contained in the (meth) acrylic resin composition of the present embodiment is based on 100 parts by mass of the total mass of the (meth) acrylic polymer (A). It is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, and further preferably 1.5 parts by mass or more and 10 parts by mass or less.
  • the fatty acid compound (C) is one of the constituents of the (meth) acrylic resin composition of the present embodiment.
  • the (meth) acrylic resin composition of the first aspect of the present invention contains the fatty acid compound (C)
  • the surface slipperiness of the obtained resin molded product is improved, and the scratch resistance is further improved. it can.
  • the scratch resistance improving effect of both is combined with the fatty acid compound. Since the scratch resistance of the obtained molded product can be further improved without increasing the content of (C), the original performance of the (meth) acrylic resin such as transparency, heat resistance, and weather resistance is impaired. Hateful.
  • the solubility parameter value of the fatty acid compound (C) is preferably 16.4 (J / cm 3 ) 1/2 or more and 24.6 (J / cm 3 ) 1/2 or less.
  • the solubility parameter value (SP value) is a solution parameter, which is a measure of solubility. The larger the SP value, the higher the polarity, and conversely, the smaller the value, the lower the polarity.
  • the SP value is calculated by the method proposed by Fedors et al. Specifically, it can be calculated by referring to "POLYMER ENGINEERING AND SCIENCE, FEBRARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 147 to 154)".
  • solubility parameter value of the fatty acid compound (C) is 16.4 (J / cm 3 ) 1/2 or more, the compatibility with the (meth) acrylic polymer (A) tends to be excellent.
  • the resulting resin molded product has excellent scratch resistance.
  • the solubility parameter value of the fatty acid compound (C) is more preferably 16.8 (J / cm 3 ) 1/2 or more, and further preferably 17.4 (J / cm 3 ) 1/2 or more.
  • the solubility parameter value of the fatty acid compound (C) is 24.6 (J / cm 3 ) 1/2 or less, the compatibility with the (meth) acrylic polymer (A) tends to be excellent.
  • the obtained resin molded product can maintain good scratch resistance.
  • the solubility parameter value of the fatty acid compound (C) is more preferably 23.6 (J / cm 3 ) 1/2 or less, and further preferably 22.6 (J / cm 3 ) 1/2 or less.
  • the upper and lower limits of the solubility parameter value of the fatty acid compound (C) can be arbitrarily combined.
  • the solubility parameter value of the fatty acid compound (C) is preferably 16.4 (J / cm 3 ) 1/2 or more and 24.6 (J / cm 3 ) 1/2 or less, preferably 16.8 (J / cm 3). 3 ) 1/2 or more and 23.6 (J / cm 3 ) 1/2 or less is more preferable, 17.4 (J / cm 3 ) 1/2 or more and 22.6 (J / cm 3 ) 1/2 or less. More preferred.
  • the fatty acid compound (C) at least one selected from a carboxyl group, an amide group, an ester group, or a carbonyl group in the molecule is selected from the viewpoint of easily improving the scratch resistance of the obtained resin molded product.
  • a chain hydrocarbon compound having one is preferable.
  • the chain hydrocarbon compound means a compound in which a carbon atom to which a carboxyl group, an amide group, an ester group, or a carbonyl group is bonded is a constituent atom of the carbon chain.
  • the carbon chain in the chain hydrocarbon compound may be saturated or unsaturated, and may be linear or branched.
  • Examples of such a fatty acid compound (C) include fatty acids and derivatives thereof as chain hydrocarbon compounds having a carboxyl group in the molecule.
  • Examples of the chain hydrocarbon compound having an amide group in the molecule include fatty acid amides and derivatives thereof.
  • Examples of the chain hydrocarbon compound having an ester group or a carbonyl group in the molecule include a fatty acid alkyl ester and its derivative, or a fatty acid glyceride and its derivative.
  • the hydrogen atom in the chain hydrocarbon compound or a part or all of the side chain was replaced with another organic group. It is a compound of structure.
  • organic group examples include a polyether group, a polyalkyl group, an aralkyl group, and a polyester group, which may be used alone or in combination of two or more.
  • fatty acid amide derivative it can be appropriately selected and used from various compounds including, for example, monoamide and bisamide, depending on various situations. These fatty acid compounds (C) may be used alone or in combination of two or more.
  • fatty acid compound (C1) a fatty acid amide and a derivative thereof (hereinafter, these are collectively referred to as "fatty acid amide compound (C1)") are preferable.
  • Examples of the fatty acid amide compound (C1) include saturated fatty acid amide compounds, unsaturated fatty acid amide compounds, and bis fatty acid amide compounds.
  • One of these fatty acid amide compounds (C1) may be used alone, or two or more thereof may be used in combination.
  • saturated fatty acid amide compounds and unsaturated fatty acid amides are preferable, and saturated fatty acid amide compounds are more preferable, because the obtained resin molded product is excellent in scratch resistance.
  • fatty acid amide compound (C1) a compound represented by the following general formula (i) (hereinafter, also referred to as “compound (i)”) can be used.
  • Compound (i) is preferable from the viewpoint that the obtained resin molded product has excellent scratch resistance even with a small blending amount and the original performance of the (meth) acrylic resin is not impaired.
  • R-CONH 2 ... (i) (In the general formula (i), R is a hydrocarbon group having 10 to 25 carbon atoms which may have a substituent.)
  • the carbon number of R in the formula (i) of the fatty acid amide compound (C1) is excellent in compatibility with the (meth) acrylic polymer (A), and the obtained resin molded product is excellent in scratch resistance. 10 or more is preferable, 15 or more is more preferable, and 17 or more is further preferable.
  • the carbon number of R in the formula (i) of the fatty acid amide compound (C1) is such that the fatty acid amide compound (C1) has good dispersibility in the (meth) acrylic resin composition, and the obtained resin molded product is scratch resistant. From the viewpoint of maintaining good adhesion, 25 or less is preferable, 24 or less is more preferable, and 23 or less is further preferable.
  • the upper and lower limits of the carbon number of R in the formula (i) of the fatty acid amide compound (C1) can be arbitrarily combined.
  • the carbon number of R in the formula (i) of the fatty acid amide compound (C1) is preferably 10 to 25, more preferably 15 to 24, and even more preferably 17 to 23.
  • saturated fatty acid amide compound examples include lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide. These saturated fatty acid amide compounds may be used alone or in combination of two or more. Among these saturated fatty acid amide compounds, stearic acid amide, palmitic acid amide, and behenic acid amide are preferable because they are excellent in scratch resistance of the molded product.
  • unsaturated fatty acid amides examples include erucic acid amides, oleic acid amides, brassic acid amides, and elaidic acid amides. These unsaturated fatty acid amide compounds may be used alone or in combination of two or more. Among these unsaturated fatty acid amide compounds, erucic acid amide and oleic acid amide are preferable, and erucic acid amide is more preferable, because the obtained resin molded product is excellent in scratch resistance.
  • the bis fatty acid amide compound examples include bis fatty acid amides such as methylene bisstearic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide; Acid amides can be mentioned.
  • bis fatty acid amide compounds may be used alone, or two or more thereof may be used in combination.
  • the content of the fatty acid compound (C) contained in the (meth) acrylic resin composition of the present embodiment is the (meth) acrylic polymer (A) from the viewpoint of excellent scratch resistance of the obtained resin molded product. 0.5 parts by mass or more is preferable, and 1.0 part by mass or more is more preferable with respect to 100 parts by mass of the total mass.
  • the content of the fatty acid compound (C) is based on 100 parts by mass of the total mass of the (meth) acrylic polymer (A) from the viewpoint that the obtained resin molded product does not impair the original performance of the (meth) acrylic resin. It is preferably 10 parts by mass or less, and more preferably 5 parts by mass.
  • the upper and lower limits of the content of the fatty acid compound (C) can be arbitrarily combined.
  • the content of the fatty acid compound (C) contained in the (meth) acrylic resin composition of the present embodiment is 0.5 mass by mass with respect to 100 parts by mass of the total mass of the (meth) acrylic polymer (A). 10 parts by mass or more is preferable, and 1.0 part by mass or more and 5.0 parts by mass or less is more preferable.
  • the impact reinforcing material (D) can be blended in the (meth) acrylic resin composition of the present embodiment. By blending the impact reinforcing material (D), the impact resistance of the obtained resin molded product becomes good.
  • the impact reinforcing material (D) a known impact resistance improving agent can be used, and for example, the impact reinforcing material (D) disclosed in the specification of International Publication No. 2018/016473 is used. Can be done.
  • Silicone oil (E) can be added to the (meth) acrylic resin composition of the present embodiment. By blending the silicone oil (E), the surface slipperiness of the obtained resin molded product can be improved, and the scratch resistance of the resin molded product can be made more excellent.
  • Silicone oil (E) is a polymer having a linear structure having a bifunctional siloxane unit as a main skeleton.
  • the silicone oil (E) a polymer having a molecular weight of 2000 or less is preferable.
  • the silicone oil (E) may be an unmodified silicone oil or a modified silicone oil.
  • Examples of the unmodified silicone oil include dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone.
  • the modified silicone oil include organically modified silicone.
  • Examples of the organically modified silicone include reactive organically modified silicones and non-reactive organically modified silicones.
  • silicone oils a silicone oil containing at least one selected from the group consisting of dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone because the obtained resin molded product tends to have excellent scratch resistance. Is preferable.
  • Carbon black (F) can be added to the (meth) acrylic resin composition of the present embodiment.
  • Carbon black (F) can be added to the (meth) acrylic resin composition of the present embodiment.
  • the jet-blackness of the obtained resin molded product can be made more excellent.
  • the carbon black (F) for example, the compatibility with the (meth) acrylic polymer (A) is improved, and the dispersibility of the carbon black (F) in the (meth) acrylic resin composition is enhanced. From the viewpoint that the obtained resin molded product can exhibit a deeper jet-blackness, carbon black coated with a surface coating agent is preferable.
  • the surface coating agent is not particularly limited, and is, for example, a group consisting of zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitate amide, methylene bisstearyl amide, and ethylene bisstearyl amide.
  • zinc stearate, magnesium stearate, calcium stearate, oleic acid amide, stearic acid amide, palmitate amide, methylene bisstearyl amide, and ethylene bisstearyl amide One or more selected from the above is preferable.
  • These surface coating agents may be used alone or in combination of two or more.
  • additives include, for example, UV absorbers, anti-aging agents, light stabilizers, plasticizers, light diffusers, matting agents, lubricants, mold release agents, antistatic agents, fluidity modifiers, sliding Examples include sex-imparting agents and colorants such as pigments and dyes. These other additives may be used alone or in combination of two or more.
  • the (meth) acrylic resin composition of the present embodiment includes, for example, a (meth) acrylic polymer (A), a fatty acid compound (C), and, if necessary, a fluorine-containing olefin polymer (B).
  • the melt-kneaded product may be pelletized using a pelletizer or the like.
  • Each component may be melt-kneaded directly by a melt-kneader without using the pre-mixing means.
  • the melt kneader include a twin-screw extruder such as a vent type twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more shafts.
  • the (meth) acrylic resin composition of the first aspect of the present invention contains the fatty acid compound (C), the obtained resin molded product has excellent scratch resistance. Further, since the (meth) acrylic resin composition of the first aspect of the present invention has a fluorine atom content of 0.5% by mass or more and further contains a fatty acid compound (C), the obtained resin molding The scratch resistance of the body and the dependence on molding conditions are excellent. In particular, if the (meth) acrylic resin composition contains the fatty acid compound (C) and further contains the fluorine-containing olefin polymer (B), the scratch resistance of the obtained resin molded product and the dependence on the molding conditions can be obtained. It will be better.
  • the (meth) acrylic resin composition according to the first aspect of the present invention is a resin obtained as compared with the case where the fluorine-containing olefin polymer (B) and the fatty acid compound (C) are contained alone.
  • the scratch resistance of the molded product is remarkably excellent. The reason is not clear, but the fluorine-containing olefin polymer (B) and the fatty acid compound (C) can interact with each other so that they can be present at a higher concentration on the surface of the obtained resin molded product and its vicinity. It is presumed that this is because the dynamic friction coefficient of the surface of the resin molded product is reduced.
  • the (meth) acrylic resin composition of the first aspect of the present invention is excellent in scratch resistance, it is not necessary to increase the content of the fluorine-containing olefin polymer (B), and the transparency is improved. It does not easily impair the original performance of (meth) acrylic resin such as heat resistance and weather resistance. Therefore, according to the (meth) acrylic resin composition of the first aspect of the present invention, a resin molded product having excellent scratch resistance, molding condition dependence, and transparency can be obtained.
  • the resin composition for a molding material according to the second aspect of the present invention includes the (meth) acrylic resin composition according to the first aspect of the present invention described above.
  • the content ratio of the (meth) acrylic resin composition according to the first aspect of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass, based on the total mass of the resin composition for molding materials. % Or more is more preferable.
  • the content ratio of the (meth) acrylic resin composition according to the first aspect of the present invention may be 100% by mass with respect to the total mass of the resin composition for molding materials.
  • the resin composition for a molding material may consist of the (meth) acrylic resin composition of the first aspect of the present invention, or may be a component other than the (meth) acrylic resin composition of the first aspect of the present invention. (Hereinafter, also referred to as "other components") may be contained.
  • other components contained in the resin composition for molding materials for example, (meth) acrylic polymer (A) and fluorine-containing olefin polymer (B) are excluded as long as the effects of the present invention are not impaired. Examples thereof include other thermoplastic resins such as polycarbonate-based resins and polystyrene-based resins.
  • the resin composition for molding material of the second aspect of the present invention contains the (meth) acrylic resin composition of the first aspect of the present invention, it is excellent in scratch resistance, molding condition dependence, and transparency. A resin molded product is obtained.
  • the (meth) acrylic resin composition for a molding material according to the third aspect of the present invention contains a fluorine atom-containing compound and a fatty acid compound (C), which will be described later.
  • the content ratio of fluorine atoms derived from the fluorine atom-containing compound is the total mass of the (meth) acrylic resin composition for molding materials. On the other hand, it is preferably 0.5% by mass or more.
  • the "content ratio of fluorine atoms" is defined as fluorine contained in the (meth) acrylic resin composition for a molding material according to the third aspect of the present invention and contained in a repeating unit constituting a polymer chain. It is the content ratio of atoms, and is defined as the content ratio of fluorine atoms (unit: mass%) with respect to the total mass of 100% by mass of the (meth) acrylic resin composition for molding materials. Specifically, it refers to the content ratio of fluorine atoms derived from the fluorine atom-containing compound to 100% by mass of the total mass of the (meth) acrylic resin composition for molding materials.
  • the method is similar to the first aspect of the present invention.
  • the (meth) acrylic resin composition for a molding material according to the third aspect of the present invention for example, a fluorine atom-containing compound, a (meth) acrylic polymer (A), and a fatty acid compound (C), which will be described later, are used. ) Is included.
  • the (meth) acrylic polymer (A) contained in the (meth) acrylic resin composition for molding material of the present embodiment and its content ratio are the (meth) acrylic resin composition of the first aspect of the present invention. This is the same as the (meth) acrylic polymer (A) exemplified above and its content ratio.
  • the fatty acid compound (C) and its content contained in the (meth) acrylic resin composition for molding material of the present embodiment are described first in the description of the (meth) acrylic resin composition of the first aspect of the present invention. It is the same as the example fatty acid compound (C) and its content.
  • the (meth) acrylic resin composition for a molding material of the present embodiment may further contain an impact reinforcing material (D), a silicone oil (E), and carbon black (F).
  • the (meth) acrylic resin composition for the molding material of the present embodiment is a (meth) acrylic polymer (A) or a fluorine atom-containing compound as long as the blending amount does not impair the performance of the resin molded product.
  • Fatty compound (C), impact reinforcing material (D), silicone oil (E), and components other than carbon black (F) hereinafter, also referred to as “other additives” may be further contained.
  • the impact reinforcing material (D), silicone oil (E), carbon black (F), and other additives contained in the (meth) acrylic resin composition for molding materials of the present embodiment are the first of the present invention, respectively. This is the same as the impact reinforcing material (D), the silicone oil (E), the carbon black (F), and other additives exemplified above in the description of the (meth) acrylic resin composition according to the above embodiment.
  • the MFR measured under the conditions of a temperature of 230 ° C. and a load of 3.8 kg according to ISO 1133-1: 2011 of the (meth) acrylic resin composition for molding materials of the present embodiment is not particularly limited, but is usually 0. It is about 5 to 50 g / 10 min.
  • the fluorine atom-containing compound is one of the constituents of the (meth) acrylic resin composition for a molding material of the present embodiment.
  • the fluorine atom-containing compound include a fluorine-containing olefin polymer (B) and a polymer containing a fluorinated (meth) acrylate unit. These fluorine atom-containing compounds may be used alone or in combination of two or more. Among these fluorine atom-containing compounds, the fluorine-containing olefin polymer (B) is more preferable from the viewpoint of excellent scratch resistance of the obtained resin molded product.
  • the fluorine-containing olefin-based polymer (B) is the same as the fluorine-containing olefin-based polymer (B) exemplified above in the description of the (meth) acrylic resin composition of the first aspect of the present invention.
  • the content of the fluorine atom-containing compound contained in the (meth) acrylic resin composition for a molding material of the present embodiment has been exemplified above in the description of the (meth) acrylic resin composition of the first aspect of the present invention.
  • the content is the same as that of the fluorine-containing olefin polymer (B).
  • the (meth) acrylic resin composition for a molding material of the present embodiment includes, for example, a (meth) acrylic polymer (A), a fluorine atom-containing compound, a fatty acid compound (C), and impact reinforcement as required.
  • a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer. It is produced by sufficiently mixing the mixture, granulating it with an extrusion granulator, a briquetting machine, or the like, and then melt-kneading it with a melt-kneader.
  • the melt-kneaded product may be pelletized using a pelletizer or the like.
  • Each component may be melt-kneaded directly by a melt-kneader without using the pre-mixing means.
  • the melt kneader include a twin-screw extruder such as a vent type twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more shafts.
  • the (meth) acrylic resin composition for a molding material according to the third aspect of the present invention contains a fluorine atom-containing compound and a fatty acid compound (C), the obtained resin molded product has scratch resistance and molding conditions. The dependency becomes excellent. Further, the (meth) acrylic resin composition for a molding material of the third aspect has scratch resistance of the obtained resin molded product as compared with the case where the fluorine atom-containing compound and the fatty acid compound (C) are contained alone. The sex is remarkably excellent.
  • the fluorine-containing olefin polymer (B) and the fatty acid compound (C) interact with each other and are present in a higher concentration on the surface of the obtained resin molded product and in the vicinity thereof. It is presumed that this is possible because the dynamic friction coefficient on the surface of the resin molded product is reduced.
  • the (meth) acrylic resin composition for a molding material according to the third aspect of the present invention has excellent scratch resistance, it is not necessary to increase the content of the fluorine atom-containing compound, and the transparency and heat resistance do not need to be increased. , And the original performance of (meth) acrylic resin such as weather resistance is not easily impaired. Therefore, according to the (meth) acrylic resin composition for a molding material of the third aspect, a resin molded product having excellent scratch resistance, molding condition dependence, and transparency can be obtained.
  • the dynamic friction coefficient (F) measured in accordance with ISO 8295: 1995 is 0.150 or less, and the surface of the resin molded body is infrared.
  • the peak absorbance refers to the absorbance at the top of the peak at the peak including the corresponding wave number.
  • the coefficient of kinetic friction (F) is 0.150 or less and the absorbance ratio (P2 / P3) is 0.0005 or more, the scratch resistance, molding condition dependence, and transparency of the resin molded product (1) are all all. It will be excellent.
  • the upper limit of the dynamic friction coefficient (F) is preferably 0.140 or less, more preferably 0.110 or less.
  • the lower limit of the dynamic friction coefficient (F) is preferably 0.010 or more, more preferably 0.020 or more, and even more preferably 0.030 or more.
  • the upper and lower limits of the dynamic friction coefficient (F) can be arbitrarily combined.
  • the dynamic friction coefficient (F) is preferably 0.010 or more and 0.150 or less, more preferably 0.020 or more and 0.140 or less, and further preferably 0.030 or more and 0.110 or less.
  • the coefficient of kinetic friction (F) is measured by the method described in Examples described later.
  • the lower limit of the absorbance ratio (P2 / P3) is preferably 0.0010 or more, more preferably 0.0020 or more.
  • the upper limit of the absorbance ratio (P2 / P3) is not particularly limited, but is preferably 0.1200 or less, more preferably 0.0500 or less, and even more preferably 0.0300 or less.
  • P2 / P3 is 0.02 or less, the content of the fluorine atom-containing compound such as the fluorine-containing olefin polymer (B) does not become too high on the surface of the resin molded product and in the vicinity of the surface, and the resin molded product does not become too high. The mechanical strength of the resin molded product is unlikely to decrease, and the scratch resistance of the resin molded product can be sufficiently improved.
  • the upper and lower limits of the absorbance ratio (P2 / P3) can be arbitrarily combined.
  • the absorbance ratio (P2 / P3) is preferably 0.0005 or more and 0.1200 or less, more preferably 0.0010 or more and 0.0500 or less, and further preferably 0.0020 or more and 0.0300 or less.
  • the absorbance ratio (P2 / P3) is a numerical value that is an index of the abundance of a fluorine atom-containing compound such as a fluorine-containing olefin polymer (B) on the surface of the resin molded product (1) and in the vicinity of the surface.
  • the absorbance ratio (P2 / P3) is measured by the method described in Examples described later.
  • the values of P2 / P3 are the blending amount of the fluorine atom-containing compound such as the fluorine-containing olefin polymer (B), various molding temperatures, and molding pressures in the production of the resin molded product of the present invention during injection molding. It can be controlled by adjusting the molding conditions including.
  • the resin molded body (1) a region having a wave number of 1630 to 1650 cm -1 in the infrared absorption spectrum measured by the single reflection ATR surface reflection method using an infrared spectrophotometer on the surface of the resin molded body (1).
  • the absorbance ratio (P1 / P3) between the peak absorbance (P1) and the peak absorbance (P3) is 0.0005 or more and 0.0120 or less, and the absorbance ratio (P1 / P3) and the dynamic friction coefficient (F) are It is preferable to satisfy the following general formula (1).
  • the absorbance ratio (P1 / P3) is 0.0005 or more and 0.0120 or less, and the absorbance ratio (P1 / P3) and the dynamic friction coefficient (F) satisfy the general formula (1), the resin molded product The scratch resistance, molding condition dependence, and transparency of (1) become more excellent.
  • the lower limit of the absorbance ratio (P1 / P3) is preferably 0.0010 or more, more preferably 0.0030 or more, and even more preferably 0.0070 or more.
  • the upper limit of the absorbance ratio (P1 / P3) is preferably 0.0110 or less, more preferably 0.0105 or less, and even more preferably 0.0100 or less.
  • the upper and lower limits of the absorbance ratio (P1 / P3) can be arbitrarily combined.
  • the absorbance ratio (P1 / P3) is preferably 0.0010 or more and 0.0110 or less, more preferably 0.0030 or more and 0.0105 or less, and further preferably 0.0070 or more and 0.0100 or less.
  • the absorbance ratio (P1 / P3) is a numerical value that is an index of the abundance of the fatty acid compound (C) on the surface of the resin molded product (1) and in the vicinity of the surface.
  • the general formula (1) defines the dynamic friction coefficient (F) according to the value of the absorbance ratio (P1 / P3), and the upper limit of the dynamic friction coefficient (F) is defined according to the abundance of the fatty acid compound (C). There is a value. If the absorbance ratio (P1 / P3) and the dynamic friction coefficient (F) satisfy the general formula (1), the molding condition dependence and transparency of the resin molded product (1) become more excellent.
  • the absorbance ratio (P1 / P3) is measured by the method described in Examples described later.
  • the value of P1 / P3 is controlled by adjusting the compounding amount of the fatty acid compound (C), various molding temperatures, and molding conditions including molding pressure when injection molding the resin molded product of the present invention. it can.
  • the resin molded product (1) is preferably composed of a (meth) acrylic resin composition containing a (meth) acrylic polymer (A), a fluorine-containing olefin polymer (B), and a fatty acid compound (C). ..
  • the resin molded product (1) contains the fatty acid compound (C), and the content ratio of fluorine atoms is 0.5% by mass or more with respect to the total mass of the (meth) acrylic resin composition.
  • It is preferably composed of a (meth) acrylic resin composition.
  • examples of such a (meth) acrylic resin composition include the (meth) acrylic resin composition of the first aspect of the present invention described above.
  • the resin molded product (1) preferably comprises a (meth) acrylic resin composition for a molding material containing a fluorine atom-containing compound and a fatty acid compound (C).
  • a (meth) acrylic resin composition for a molding material of the second aspect of the present invention or the (meth) acrylic resin composition for a molding material of the third aspect of the present invention can be used. Can be mentioned.
  • the resin molded product (1) As a method for producing the resin molded product (1), a known molding method for a resin composition can be adopted, and examples thereof include injection molding, extrusion molding, and pressure molding. Further, the obtained resin molded body (1) may be further subjected to, for example, secondary molding of compressed air molding or vacuum forming. Molding conditions including molding temperature and molding pressure may be appropriately set.
  • the resin molded product of the fourth aspect of the present invention for example, a resin molded product obtained by molding the (meth) acrylic resin composition of the first aspect of the present invention described above (2).
  • the manufacturing method of the resin molded body (2), the resin molded body (3), and the resin molded body (4) is the same as the manufacturing method of the resin molded body (1).
  • the resin molded product (2) is formed by molding the (meth) acrylic resin composition according to the first aspect of the present invention, it is excellent in scratch resistance, molding condition dependence, and transparency. Since the resin molded product (3) is formed by molding the resin composition for a molding material according to the second aspect of the present invention, it is excellent in scratch resistance, molding condition dependence, and transparency. Since the resin molded product (4) is formed by molding the (meth) acrylic resin composition for a molding material according to the third aspect of the present invention, it is excellent in scratch resistance, molding condition dependence, and transparency.
  • the resin molded body (1), the resin molded body (2), the resin molded body (3), and the resin molded body (4) are collectively referred to as a "resin molded body".
  • the (meth) acrylic resin composition of the first aspect of the present invention, the resin composition for a molding material of the second aspect of the present invention, and the (meth) acrylic type for a molding material of the third aspect of the present invention are generically also referred to simply as "resin composition".
  • the resin molded body of the fourth aspect of the present invention is excellent in scratch resistance, molding condition dependence, and transparency, for example, a material for housing equipment such as a vanity, a bathtub, and a flush toilet; a building material; It is used as a vehicle member such as an interior / exterior material of a vehicle, and is particularly suitable as a vehicle member.
  • vehicle exterior materials include meter covers, door mirror housings, pillar covers (sash covers), licensed garnishes, front grilles, fog garnishes, emblems and the like.
  • the injection rate is defined by the injection resin volume / resin filling time (unit: cm 3 / sec).
  • the resin filling time is the change in distance according to the increase in injection time when plotting the distance from the screw to the nozzle while increasing the injection time with the injection time on the horizontal axis and the distance from the screw head to the nozzle head on the vertical axis. Refers to the injection time when is no longer recognized.
  • the content ratio of fluorine atoms in the resin composition was measured by the following method A or method B.
  • Method A When the fluorine-containing olefin-based polymer (B) is a homopolymer of vinylidene fluoride (polyvinylidene fluoride), the content ratio of fluorine atoms in the homopolymer of vinylidene fluoride is set to the homopolymer of vinylidene fluoride.
  • the content ratio of the fluorine-containing olefin polymer (B) contained in the resin composition is calculated by a simple desk calculation as 59.4% by mass with respect to the total mass of Calculated.
  • the fluorine-containing olefin-based polymer (B) is a (co) polymer containing at least one selected from vinylidene fluoride units, tetrafluoroethylene units, and hexafluoropropylene units as a constituent unit in the polymer.
  • the content ratio of fluorine atoms in vinylidene fluoride units is 59.4% by mass, the content ratio of fluorine atoms in tetrafluoroethylene units is 76.0% by mass, and hexafluoropropylene units with respect to the total mass of each constituent unit.
  • the content ratio of fluorine atoms in the fluorine-containing olefin-based polymer (B) is based on the content ratio of each structural unit contained in the fluorine-containing olefin-based polymer (B). Was calculated by a simple desktop calculation.
  • the content ratio of each structural unit contained in the fluorine-containing olefin polymer (B) was measured by using an NMR method.
  • the fluoroolefin-containing polymer (B) is a (co) polymer containing a monomer unit other than vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene described above as a constituent unit in the polymer. It is also possible to measure by the following method B, and it is possible to obtain a measured value having substantially the same numerical value as the measured value calculated by the above-mentioned method A.
  • the fluorine atom-containing polymer (B) can be elementally analyzed by using known combustion ion chromatography to calculate the content ratio of fluorine atoms in the resin composition.
  • the fluorine-containing olefin-based polymer (B) contained in the resin composition using the fluorine atom content ratio calculated by elemental analysis using known combustion ion chromatography. From the content ratio of the polymer (B), the content ratio of fluorine atoms in the resin composition can be calculated by a simple desk calculation. It is also possible to directly perform elemental analysis of the resin composition using known combustion ion chromatography to measure the content ratio of fluorine atoms in the resin composition, which was obtained by the method described above. It is possible to obtain a measured value that is almost the same as the measured value.
  • the position of the peak in the wave number region of 880 ⁇ 900 cm -1 indicates the minimum absorbance and (x 2-1), a peak in the wave number region of 850 ⁇ 880 cm -1 is the minimum absorbance
  • a baseline was drawn between the indicated position (x 2-2 ), and the absorbance of the wave number at which the peak showed the maximum absorbance in the region of wave number 870 to 890 cm -1 was calculated as the peak absorbance (P2).
  • P2 peak absorbance
  • the coefficient of dynamic friction (F) was measured by the following method as an index of scratch resistance of the resin molded product. Using a scratch tester KK01 (manufactured by Kato Tech Co., Ltd.), a spherical indenter with a diameter of 1 mm is pressed against the surface of the resin molded product X1 in accordance with ISO 8295: 1995 to keep the horizontal load of the indenter constant (5. While maintaining 0N), the moving speed of the indenter was 100 mm / sec, the moving distance of the indenter was 70 mm, and the vertical load (unit: N) when the resin molded body X1 was moved on the surface was measured.
  • the coefficient of dynamic friction was defined as the value obtained by dividing the horizontal load (5.0 N) by the average value of the vertical load measured in the section of 10 to 60 mm starting from the starting point of the moving distance (70 mm). Using the three resin molded bodies X1, measurements were performed once for each resin molded body X1 to calculate the dynamic friction coefficient, and the average value was taken as the dynamic friction coefficient (F) of the resin molded body X1.
  • ⁇ Evaluation of scratch resistance> As an index of the scratch resistance of the resin molded product, the difference in haze value ( ⁇ haze) before and after the scratch resistance test was measured by the following method.
  • a friction tester for the scratch resistance test, a friction tester (friction tester S type for dyeing fastness, friction tester type II described in JIS L 0849: 2103 modified to a flat type, Toyo Seiki Seisakusho Co., Ltd.) was used.
  • As the friction element a flat friction element (length 20 mm, width 20 mm) and five pieces of gauze (trade name, medical gauze, 100% earth dragonfly cotton, manufactured by Yamato Factory Co., Ltd.) were used.
  • the resin molded body X1 is placed on a flat table, and as shown in FIG.
  • a haze meter (model name: NDH4000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used, and the central portion 3 of the resin molded body X1 (in the case of after the scratch resistance test).
  • the central portion of the surface on which the friction and wear processing portion 2 is formed) a light beam is incident in a direction parallel to the direction in which the friction element is reciprocated, and the haze of the resin molded body X1 is in accordance with ISO 14782: 1999. The value was measured.
  • the difference in haze value ( ⁇ haze) is calculated by subtracting the haze value (H1) before the scratch resistance test from the haze value (H2) after the scratch resistance test, and the ⁇ haze is 0.
  • a case of 5 or less was judged as "A”
  • a case of ⁇ haze exceeding 0.5 and 0.8 or less was judged as “B”
  • a case of ⁇ haze exceeding 0.8 was judged as “C”.
  • the smaller the ⁇ haze the better the scratch resistance.
  • ⁇ Haze Haze value of the resin molded product X1 after the scratch resistance test (H2) -Haze value of the resin molded product X1 before the scratch resistance test (H1) ...
  • the difference in haze value ( ⁇ haze) after the scratch resistance test for the resin molded product X1 and the resin molded product X2 obtained by changing the injection speed is determined by the following method. Measured in. In the same manner as the scratch resistance evaluation method described above, the surfaces of the resin molded body X1 and the resin molded body X2 are abraded using a friction element, and the surfaces of the resin molded body X1 and the resin molded body X2 are rubbed. A wear-treated part was formed.
  • the haze values of the resin molded body X1 and the resin molded body X2 after the scratch resistance test were measured in the same manner as in the scratch resistance evaluation method described above.
  • the haze value difference ( ⁇ haze) is obtained by subtracting the haze value (H3) of the resin molded body X1 after the scratch resistance test from the haze value (H4) of the resin molded body X2 after the scratch resistance test. ) Is calculated, "A” when ⁇ haze is 1.5 or less, “B” when ⁇ haze is more than 1.5 and 2.3 or less, and "B” when ⁇ haze is more than 2.3. It was judged as "C".
  • ⁇ Haze Haze value of the resin molded product X2 after the scratch resistance test (H4) -Haze value of the resin molded product X1 after the scratch resistance test (H3) ... (3)
  • fatty acid compound (C) The following compounds were used as the fatty acid compound (C).
  • -C-1 Fatty acid amide containing stearic acid amide as a main component (trade name: IncroMax (registered trademark) PS, manufactured by CRODA).
  • -C-2 Fatty acid amide containing stearic acid amide as a main component (trade name: fatty acid amide S, manufactured by Kao Corporation).
  • -C-3 Fatty acid amide containing behenic acid amide as a main component (trade name: BNT-22H, manufactured by Nippon Fine Chemical Co., Ltd.).
  • -C-4 Fatty acid amide containing erucic acid amide as a main component (trade name: Diamid (registered trademark) L, manufactured by Mitsubishi Chemical Corporation).
  • -C-5 Fatty acid amide containing methylene bisstearic acid amide as a main component (trade name: Bisamide LA, manufactured by Mitsubishi Chemical Corporation).
  • -S-1 Silicone compound (trade name: TEGOMER® H-Si 6441 P, manufactured by Ebonic, polyester-modified silicone in which a polyester group is added to the side chain of polydimethylsiloxane).
  • Example 1 A twin-screw extruder (model name:) containing 100 parts by mass of methacrylic resin (A-1), 2.0 parts by mass of fluoroolefin polymer (B-1), and 2.0 parts by mass of fatty acid amide (C-1). It was supplied to PCM30, manufactured by Ikegai Co., Ltd.) and kneaded at 250 ° C. to obtain a pellet-shaped resin composition. The content ratio of fluorine atoms in the obtained resin composition was determined. In addition, a resin molded product was prepared using the obtained resin composition, and various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
  • Examples 2 to 10 Comparative Examples 1 to 10
  • a pellet-shaped resin composition was produced in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1, a resin molded product was prepared, and various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
  • the fatty acid compound (C) was not blended in Reference Example A, and the pellets of the methacrylic resin (A-1) did not contain fluorine atoms, so that the obtained resin molding was obtained.
  • the body was inferior in scratch resistance and molding condition dependence.
  • the resin molded product obtained by molding the resin compositions obtained in Examples 1 to 10 was excellent in scratch resistance, molding condition dependence, and transparency. Since the resin composition obtained in Comparative Example 1 did not contain the fatty acid compound (C), the obtained resin molded product was inferior in scratch resistance and molding condition dependence. Since the resin compositions obtained in Comparative Examples 2 and 3 did not contain fluorine atoms, the obtained resin molded product was inferior in scratch resistance and molding condition dependence.
  • the obtained resin molded product is inferior in scratch resistance and transparency.
  • the resin compositions obtained in Comparative Examples 5 to 6 did not contain fluorine atoms, the obtained resin molded product was inferior in scratch resistance and molding condition dependence.
  • the resin compositions obtained in Comparative Examples 7 to 8 did not contain the fatty acid compound (C)
  • the obtained resin molded product was inferior in scratch resistance.
  • the resin composition obtained in Comparative Example 9 contained a small proportion of fluorine atoms, the obtained resin molded product was inferior in scratch resistance and dependence on molding conditions.
  • the resin composition obtained in Comparative Example 10 did not contain the fatty acid compound (C), the obtained resin molded product was inferior in scratch resistance and molding condition dependence.
  • the (meth) acrylic resin composition for molding materials According to the (meth) acrylic resin composition for molding materials, the (meth) acrylic resin composition, and the resin composition for molding materials of the present invention, a resin having excellent scratch resistance, molding condition dependence, and transparency. A molded product is obtained. Since the resin molded body of the present invention is excellent in scratch resistance, molding condition dependence, and transparency, for example, materials for housing equipment such as vanities, bathtubs, flush toilets; building materials; vehicle interior / exterior materials. It is used for vehicle members such as, and is particularly suitable as a vehicle member. Examples of vehicle exterior materials include meter covers, door mirror housings, pillar covers (sash covers), licensed garnishes, front grilles, fog garnishes, emblems and the like.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne : une composition de résine (méth)acrylique pour un matériau de moulage, une composition de résine (méth)acrylique, et une composition de résine pour un matériau de moulage, qui sont utilisées pour obtenir un article moulé en résine ayant d'excellentes résistance aux égratignures, dépendance aux états de moulage, et transparence; et un article moulé en résine ayant d'excellentes résistance aux égratignures, dépendance aux états de moulage, et transparence. Pour l'article moulé en résine selon la présente invention, son coefficient (F) de frottement cinétique est de 0,150 ou moins tel que mesuré selon la norme ISO 8295:1995, et le rapport d'absorbance (P2/P3) d'une absorbance pic (P2) dans une région ayant un nombre d'onde de 870 à 890 cm-1 et une absorbance pic (P3) dans une région ayant son nombre d'onde de 1 710 à 1 730 cm-1 est de 0,0005 ou plus dans un spectre d'absorption infrarouge tel que mesuré à la surface de l'article moulé en résine par un procédé de réflexion de surface ATR à réflexion unique utilisant un spectrophotomètre infrarouge. La composition de résine (méth)acrylique pour un matériau de moulage selon la présente invention contient un composé contenant un atome de fluor et un composé acide gras (C). La composition de résine (méth)acrylique selon la présente invention contient le composé acide gras (C), et présente un rapport de la teneur en atome de fluor de 0,5 % en masse ou plus.
PCT/JP2020/046327 2019-12-12 2020-12-11 Article moulé en résine, composition de résine (méth)acrylique pour matériau de moulage, composition de résine (méth)acrylique, et composition de résine pour matériau de moulage WO2021117879A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH107866A (ja) * 1996-06-25 1998-01-13 Daikin Ind Ltd フッ化ビニリデン系共重合体組成物
JP2003327772A (ja) * 2002-05-13 2003-11-19 Asahi Glass Co Ltd ゴム組成物
JP2005042066A (ja) * 2003-07-25 2005-02-17 Daikin Ind Ltd フッ化ビニリデン系共重合体樹脂フィルム
JP2013189655A (ja) * 2013-07-04 2013-09-26 Asahi Glass Co Ltd 架橋ゴム物品
JP2015131948A (ja) * 2013-12-11 2015-07-23 日油株式会社 表面物性改良剤組成物、アクリル樹脂組成物、及びアクリル樹脂成形体
WO2018230336A1 (fr) * 2017-06-12 2018-12-20 Nok株式会社 Composition de caoutchouc fluoré et matériau d'étanchéité à base de caoutchouc fluoré

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH107866A (ja) * 1996-06-25 1998-01-13 Daikin Ind Ltd フッ化ビニリデン系共重合体組成物
JP2003327772A (ja) * 2002-05-13 2003-11-19 Asahi Glass Co Ltd ゴム組成物
JP2005042066A (ja) * 2003-07-25 2005-02-17 Daikin Ind Ltd フッ化ビニリデン系共重合体樹脂フィルム
JP2013189655A (ja) * 2013-07-04 2013-09-26 Asahi Glass Co Ltd 架橋ゴム物品
JP2015131948A (ja) * 2013-12-11 2015-07-23 日油株式会社 表面物性改良剤組成物、アクリル樹脂組成物、及びアクリル樹脂成形体
WO2018230336A1 (fr) * 2017-06-12 2018-12-20 Nok株式会社 Composition de caoutchouc fluoré et matériau d'étanchéité à base de caoutchouc fluoré

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