JP5647785B2 - Resin composition for painted molded body - Google Patents

Resin composition for painted molded body Download PDF

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JP5647785B2
JP5647785B2 JP2009286182A JP2009286182A JP5647785B2 JP 5647785 B2 JP5647785 B2 JP 5647785B2 JP 2009286182 A JP2009286182 A JP 2009286182A JP 2009286182 A JP2009286182 A JP 2009286182A JP 5647785 B2 JP5647785 B2 JP 5647785B2
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polyamide
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resin
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carboxylic acid
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JP2011080029A (en
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稔夫 小邦
稔夫 小邦
裕一 大江
裕一 大江
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Daicel Polymer Ltd
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Priority to PCT/JP2010/065387 priority patent/WO2011030778A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions 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
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions 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 carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/18—Homopolymers or copolymers of nitriles
    • C09D133/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D135/00—Coating compositions based on 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 carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/06—Copolymers with vinyl aromatic monomers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Description

本発明は、成形時におけるバリの発生が少なく、外観が美しい成形体が得られる樹脂組成物に関する。   The present invention relates to a resin composition that can produce a molded article with little appearance of burrs during molding and a beautiful appearance.

特許文献１には、ポリアミドとポリオレフィンからなるポリマーアロイ樹脂とテルペン系樹脂を配合したポリアミド系ポリマーアロイ樹脂組成物が記載されている。実施例１では、ナイロン６とポリプロピレンに対して、相溶化剤として無水マレイン酸変性ポリプロピレンを配合し、実施例７では、ナイロン６６に対して無水マレイン酸変性ＥＰＤＭを配合している。この組成物は、流動性が良く、機械的性質や耐熱性が良いことが記載されている（表１）。   Patent Document 1 describes a polyamide polymer alloy resin composition in which a polymer alloy resin composed of polyamide and polyolefin and a terpene resin are blended. In Example 1, maleic anhydride-modified polypropylene is blended as a compatibilizer with nylon 6 and polypropylene. In Example 7, maleic anhydride-modified EPDM is blended with nylon 66. It is described that this composition has good fluidity and good mechanical properties and heat resistance (Table 1).

特許文献２には、ナイロン６、ナイロン６６、ＡＢＳ樹脂、無水マレイン酸をグラフトしたスチレン−マレイミド共重合体等を配合した組成物が記載されている（実施例の表Ｉ、II参照）。この組成物は、機械的性質や耐熱性が良いことが記載されている（表III）。   Patent Document 2 describes a composition in which nylon 6, nylon 66, ABS resin, styrene-maleimide copolymer grafted with maleic anhydride, and the like are blended (see Tables I and II of Examples). This composition is described as having good mechanical properties and heat resistance (Table III).

特許文献３には、ＡＢＳ樹脂、ナイロン６、マレイミド重合体等を配合した組成物が記載されている。この組成物は、耐熱性、機械的性質、成形品の外観、耐薬品性が良いことが記載されている（実施例の表３）。   Patent Document 3 describes a composition containing ABS resin, nylon 6, maleimide polymer, and the like. It is described that this composition has good heat resistance, mechanical properties, appearance of a molded product, and chemical resistance (Table 3 in Examples).

特許文献４には、ナイロン６、ナイロン１２、マレイミド系共重合体、変性ポリオレフィン系共重合体対して、ガラス繊維、カーボン繊維等の繊維状フィラーを配合した組成物が記載されている。この組成物は、流動性（MFR）、機械的性質、耐熱性等が良いことが記載されている（実施例の表−３）。なお、繊維状フィラーは目的によって使い分けることが記載されており、表面状態が問題になるときはウィスカー系を使用することが記載されている（７欄４〜８行）。   Patent Document 4 describes a composition in which fibrous fillers such as glass fibers and carbon fibers are blended with nylon 6, nylon 12, maleimide copolymer, and modified polyolefin copolymer. It is described that this composition has good fluidity (MFR), mechanical properties, heat resistance and the like (Table 3 in Examples). In addition, it is described that the fibrous filler is properly used depending on the purpose, and when the surface state becomes a problem, it is described that a whisker system is used (column 7, lines 4 to 8).

特開２０００−１４３９７３号公報JP 2000-143973 A 特表２００４−５２１９８０号公報JP-T-2004-521980 特許第３３８９６５２号公報Japanese Patent No. 3389852 特許第２７３５６０６号公報Japanese Patent No. 2735606

上記文献中、特許文献３では、成形品の表面外観が良いことが記載されているが、ガラス繊維等の繊維状充填剤を配合することは全く記載されていない。さらに特許文献４では、ガラス繊維等の繊維状フィラーを配合することが記載されているが、表面状態が問題になるときはウィスカーを使用することが記載されている。   Among the above documents, Patent Document 3 describes that the surface appearance of a molded product is good, but does not describe mixing a fibrous filler such as glass fiber. Further, Patent Document 4 describes that a fibrous filler such as glass fiber is blended, but it is described that whiskers are used when the surface condition becomes a problem.

本願発明は、成形時におけるバリの発生が少なく、成形品の外観が美しく、さらに成形品の塗装性も良い樹脂組成物を提供することを課題とする。   An object of the present invention is to provide a resin composition in which the occurrence of burrs during molding is small, the appearance of the molded product is beautiful, and the paintability of the molded product is also good.

本発明は、課題の解決手段として、
（Ａ）ポリアミド系樹脂混合物であり、前記ポリアミド系樹脂混合物が下記の（A-1）〜（A-5）から選ばれるいずれか１つのもの５０〜９５質量％
（A-1）ポリアミド６とポリアミド６６の共重合体、ポリアミド６及びポリアミド６６の混合物
（A-2）ポリアミド６とポリアミド６６の共重合体とポリアミド６の混合物、
（A-3）ポリアミド６とポリアミド６６の混合物、
（A-4）ポリアミド６とポリアミド６６の共重合体とポリアミド６６の混合物、
（A-5）ポリアミド６とポリアミド６６の共重合体
（Ｂ）カルボン酸無水物変性オレフィン樹脂、カルボン酸変性ＡＳ樹脂、カルボン酸変性アクリル樹脂、カルボン酸無水物変性マレイミド樹脂、カルボン酸変性ＡＢＳ樹脂、カルボン酸無水物変性ＳＥＢＳ樹脂、カルボン酸無水物変性ＥＰＤＭ、ＡＳ樹脂から選ばれる１種以上を５〜５０質量％
（Ｃ）ガラス繊維及び／又は炭素繊維を（Ａ）及び（Ｂ）成分の合計１００質量部に対して１０〜１５０質量部含有する、樹脂組成物を提供する。 As a means for solving the problems, the present invention
(A) A polyamide-based resin mixture, and the polyamide-based resin mixture is any one selected from the following (A-1) to (A-5): 50 to 95% by mass
(A-1) a copolymer of polyamide 6 and polyamide 66, a mixture of polyamide 6 and polyamide 66 (A-2) a mixture of a copolymer of polyamide 6 and polyamide 66 and polyamide 6;
(A-3) A mixture of polyamide 6 and polyamide 66,
(A-4) A mixture of polyamide 6 and polyamide 66 copolymer and polyamide 66,
(A-5) Copolymer of polyamide 6 and polyamide 66 (B) Carboxylic acid modified olefin resin, carboxylic acid modified AS resin, carboxylic acid modified acrylic resin, carboxylic acid modified maleimide resin, carboxylic acid modified ABS resin 5 to 50% by mass of one or more selected from carboxylic acid anhydride-modified SEBS resin, carboxylic acid anhydride-modified EPDM, and AS resin
(C) The resin composition which contains 10-150 mass parts of glass fiber and / or carbon fiber with respect to a total of 100 mass parts of (A) and (B) component is provided.

本発明の樹脂組成物は、成形時におけるバリの発生が少ない。さらに本発明の樹脂組成物は、ガラス繊維等を含有しているにも拘わらず外観が良いほか、塗装性の良い成形品を得ることができ、ガラス繊維を含有しているため、機械的性質も良い成形品を得ることができる。   The resin composition of the present invention is less likely to generate burrs during molding. Furthermore, the resin composition of the present invention has a good appearance in spite of containing glass fibers and the like, and can obtain a molded article with good paintability. A good molded product can be obtained.

実施例で使用したガラス繊維の長軸長さ／短軸長さの比率と断面形状を示す図。The figure which shows the ratio of long-axis length / short-axis length of glass fiber used in the Example, and cross-sectional shape.

＜（Ａ）成分＞
（Ａ）成分のポリアミド系樹脂混合物は、（A-1）〜（A-5）から選ばれるいずれか１つのものである。
（A-1）ポリアミド６とポリアミド６６の共重合体、ポリアミド６及びポリアミド６６の混合物
（A-2）ポリアミド６とポリアミド６６の共重合体とポリアミド６の混合物
（A-3）ポリアミド６とポリアミド６６の混合物
（A-4）ポリアミド６とポリアミド６６の共重合体とポリアミド６６の混合物
（A-5）ポリアミド６とポリアミド６６の共重合体 <(A) component>
The polyamide-based resin mixture as the component (A) is any one selected from (A-1) to (A-5).
(A-1) Copolymer of polyamide 6 and polyamide 66, mixture of polyamide 6 and polyamide 66 (A-2) Mixture of copolymer of polyamide 6 and polyamide 66 and polyamide 6 (A-3) Polyamide 6 and polyamide 6 Mixture of 66 (A-4) Copolymer of polyamide 6 and polyamide 66 and polyamide 66 (A-5) Copolymer of polyamide 6 and polyamide 66

＜（Ｂ）成分＞
（Ｂ）カルボン酸無水物変性オレフィン樹脂、カルボン酸変性ＡＳ樹脂、カルボン酸変性アクリル樹脂、カルボン酸無水物変性マレイミド樹脂、カルボン酸変性ＡＢＳ樹脂、カルボン酸無水物変性ＳＥＢＳ樹脂、カルボン酸無水物変性ＥＰＤＭ、ＡＳ樹脂から選ばれる１種以上である。（Ｂ）成分としては、さらに必要に応じてＡＢＳ樹脂を含有することもできる。（Ｂ）成分は２種以上を組み合わせることが好ましい。 <(B) component>
(B) Carboxylic acid anhydride-modified olefin resin, carboxylic acid-modified AS resin, carboxylic acid-modified acrylic resin, carboxylic acid anhydride-modified maleimide resin, carboxylic acid-modified ABS resin, carboxylic acid anhydride-modified SEBS resin, carboxylic acid anhydride-modified One or more selected from EPDM and AS resin. As the component (B), an ABS resin can be further contained as necessary. (B) It is preferable to combine 2 or more types of components.

（Ｂ）成分は、下記の（B-1）成分から選ばれるもの、下記の（B-1）成分と（B-2）成分の組み合わせからなるものが好ましい。   The component (B) is preferably one selected from the following components (B-1) or a combination of the following components (B-1) and (B-2).

（B-1）成分としては、カルボン酸変性ＡＳ樹脂、カルボン酸変性ＡＢＳ樹脂、カルボン酸又はその無水物変性オレフィン樹脂、カルボン酸又はその無水物変性ＥＰＤＭ、マレイミド系モノマーを４０質量％以上含むモノマー混合物から得られたカルボン酸又はその無水物変性マレイミド樹脂を挙げることができる。
（B-1）成分として更に好ましくは、カルボン酸変性ＡＳ樹脂、カルボン酸無水物変性ＥＰＤＭ、マレイミド系モノマーを４０質量％以上含むモノマー混合物から得られたカルボン酸無水物変性マレイミド樹脂を挙げることができる。 (B-1) Component includes carboxylic acid-modified AS resin, carboxylic acid-modified ABS resin, carboxylic acid or anhydride-modified olefin resin, carboxylic acid or anhydride-modified EPDM, monomer containing 40% by mass or more of maleimide monomer Mention may be made of carboxylic acids obtained from the mixtures or their anhydride-modified maleimide resins.
More preferably, the component (B-1) includes a carboxylic acid modified AS resin, a carboxylic acid anhydride modified EPDM, and a carboxylic acid anhydride modified maleimide resin obtained from a monomer mixture containing 40% by mass or more of a maleimide monomer. it can.

カルボン酸変性ＡＳ樹脂は公知のものであり、ＡＳ樹脂にアクリル酸、メタクリル酸、マレイン酸等から選ばれるカルボン酸が共重合したものを挙げることができる。   The carboxylic acid-modified AS resin is a known one, and examples include those obtained by copolymerizing an AS resin with a carboxylic acid selected from acrylic acid, methacrylic acid, maleic acid and the like.

カルボン酸変性ＡＢＳ樹脂は公知のものであり、ＡＢＳ樹脂にアクリル酸、メタクリル酸、マレイン酸等から選ばれるカルボン酸が共重合したものを挙げることができる。   The carboxylic acid-modified ABS resin is a known one, and examples thereof include those obtained by copolymerizing an ABS resin with a carboxylic acid selected from acrylic acid, methacrylic acid, maleic acid and the like.

カルボン酸無水物変性オレフィン樹脂とカルボン酸又はその無水物変性ＥＰＤＭは公知のものであり、いずれも末端に無水マレイン酸等が結合したものを挙げることができる。（B-1）成分としてカルボン酸又はその無水物変性ＥＰＤＭを含有すると、成形時のバリの発生を抑制する効果が高められる。   The carboxylic acid anhydride-modified olefin resin and the carboxylic acid or its anhydride-modified EPDM are known ones, and any of them may include those having maleic anhydride or the like bonded to the terminal. When carboxylic acid or its anhydride-modified EPDM is contained as the component (B-1), the effect of suppressing the generation of burrs during molding is enhanced.

マレイミド系モノマーを４０質量％以上（好ましくは４５質量％以上、より好ましくは５０質量％以上）含むモノマー混合物から得られたカルボン酸無水物変性マレイミド樹脂は、マレイミド系モノマー、不飽和ジカルボン酸無水物、その他芳香族ビニルモノマー等の共重合可能なモノマーから得られたものを挙げることができる。   Carboxylic acid anhydride-modified maleimide resin obtained from a monomer mixture containing 40% by weight or more (preferably 45% by weight or more, more preferably 50% by weight or more) of maleimide monomer is a maleimide monomer or unsaturated dicarboxylic acid anhydride. Other examples include those obtained from copolymerizable monomers such as aromatic vinyl monomers.

上記樹脂の製造方法は、個々のモノマー成分を重合することにより、目的組成の共重合体を製造する方法や、不飽和ジカルボン酸無水物と芳香族ビニルモノマー成分等を共重合した後、得られた共重合体とアンモニア又はメチルアミン、エチルアミン、アニリン等の第1級アミンを反応させて無水カルボン酸残基をイミド化することにより目的組成の共重合体を製造する方法があり、いずれを採用しても良い。   The resin production method is obtained by polymerizing individual monomer components to produce a copolymer having a target composition or after copolymerizing an unsaturated dicarboxylic acid anhydride and an aromatic vinyl monomer component. There is a method of producing a copolymer of the desired composition by reacting a copolymer with ammonia or a primary amine such as methylamine, ethylamine, aniline and imidizing a carboxylic anhydride residue. You may do it.

前記モノマー混合物は、マレイミド、Ｎ−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−プロピルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−フェニルマレイミド、Ｎ−トルイルマレイミド、Ｎ−キシリールマレイミド、Ｎ−ナフチルマレイミド、Ｎ−ｔ−ブチルマレイミド、Ｎ−オルトクロルフェニルマレイミド、Ｎ−オルトメトキシフェニルマレイミドから選ばれるマレイミド系単量体と、前記単量体と共重合できる他の単量体単位からなるものを挙げることができる。   The monomer mixture is maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-toluylmaleimide, N-xylylmaleimide, N- Consists of a maleimide monomer selected from naphthylmaleimide, Nt-butylmaleimide, N-orthochlorophenylmaleimide, N-orthomethoxyphenylmaleimide, and other monomer units copolymerizable with the monomer. Can be mentioned.

（B-2）成分はＡＳ樹脂であるが、必要に応じて（B-2）成分としてＡＢＳ樹脂も含有することができる。（B-2）成分としてＡＳ樹脂を含有すると、特に塗装性の向上に効果があり、ＡＢＳ樹脂を含有すると、成形時のバリの発生を抑制する効果が高められる。   The component (B-2) is an AS resin, but an ABS resin can also be contained as the component (B-2) as necessary. When an AS resin is contained as the component (B-2), the effect of improving paintability is particularly improved, and when an ABS resin is contained, the effect of suppressing the generation of burrs during molding is enhanced.

（Ｂ）成分として（B-1）成分と（B-2）成分を含有するときは、
（Ｂ）成分中の（B-1）成分の含有量は１０〜１００質量％が好ましく、１５〜１００質量％がより好ましく、１５〜８０質量％がさらに好ましく、２０〜７０質量％が特に好ましく、
（Ｂ）成分中の（B-2）成分の含有量は９０〜０質量％が好ましく、８５〜０質量％がより好ましく、８５〜２０質量％がさらに好ましく、８０〜３０質量％が特に好ましい。 When (B) component (B-1) and (B-2) component are included,
The content of the component (B-1) in the component (B) is preferably 10 to 100% by mass, more preferably 15 to 100% by mass, further preferably 15 to 80% by mass, and particularly preferably 20 to 70% by mass. ,
The content of the component (B-2) in the component (B) is preferably 90 to 0% by mass, more preferably 85 to 0% by mass, further preferably 85 to 20% by mass, and particularly preferably 80 to 30% by mass. .

なお、（B-2）成分としてＡＢＳ樹脂を含有するときには、組成物中のＡＢＳ樹脂の含有量は５質量％以下である。   In addition, when it contains ABS resin as (B-2) component, content of ABS resin in a composition is 5 mass% or less.

＜（Ｃ）成分＞
（Ｃ）成分は、ガラス繊維及び炭素繊維のいずれか一方を使用するか、ガラス繊維と炭素繊維を併用する。 <(C) component>
As the component (C), either one of glass fiber and carbon fiber is used, or glass fiber and carbon fiber are used in combination.

ガラス繊維は、Ｅ−ガラス、Ｄ−ガラスからなるガラス繊維を挙げることができ、炭素繊維は、ポリアクリロニトリル系、ピッチ系、レーヨン系等からなるものを挙げることができる。   Examples of the glass fiber include glass fibers made of E-glass and D-glass, and examples of the carbon fiber include those made of polyacrylonitrile, pitch, rayon, and the like.

（Ｃ）成分のガラス繊維又は炭素繊維は、長軸長さと短軸長さの比率（長軸長さ／短軸長さ）が１．０〜５．０の範囲のものが好ましく、１．２〜５．０の範囲のものがより好ましく、２．０〜５．０の範囲のものがさらに好ましく、３．０〜５．０の範囲のものが特に好ましい。なお、長軸長さと短軸長さの比率が１．０の場合は、断面が円形であることを意味する。   The glass fiber or carbon fiber of component (C) preferably has a ratio of major axis length to minor axis length (major axis length / minor axis length) in the range of 1.0 to 5.0. The thing of the range of 2-5.0 is more preferable, The thing of the range of 2.0-5.0 is further more preferable, The thing of the range of 3.0-5.0 is especially preferable. In addition, when the ratio of the major axis length to the minor axis length is 1.0, it means that the cross section is circular.

（Ｄ）成分のガラス繊維又は炭素繊維は、幅方向の断面形状が円形（図１に示すガラス繊維１）のもの、楕円形、多角形（二等辺三角形、正三角形、長方形、正方形、六角形、台形、菱形等）又は前記の多角形で角のみに丸みが付けられているものでもよいが、略繭玉形（図１に示すガラス繊維２）、略長円形（図１に示すガラス繊維３）のものが特に好ましい。   The glass fiber or carbon fiber of component (D) has a cross-sectional shape in the width direction of a circle (glass fiber 1 shown in FIG. 1), oval, polygon (isosceles triangle, equilateral triangle, rectangle, square, hexagon) , Trapezoid, rhombus, etc.) or the above-mentioned polygonal shape with rounded corners only, but it is generally jade-shaped (glass fiber 2 shown in FIG. 1), substantially oval (glass fiber 3 shown in FIG. ) Is particularly preferred.

なお、略繭玉形は、長さ方向及び幅方向の２つの中心軸からみて、左右対称のものでもよいし、非対称（但し、近似した形状）のものでもよいことを意味し、略長円形は、長さ方向及び幅方向の２つの中心軸からみて、左右対称（但し、近似した形状）のものでもよいし、非対称のものでもよいことを意味する。   Note that the substantially jade shape means that it may be bilaterally symmetric or asymmetrical (but approximated) when viewed from the two central axes in the length direction and the width direction. This means that it may be bilaterally symmetric (however, approximated shape) or asymmetrical when viewed from the two central axes in the length direction and the width direction.

本発明の組成物中、（Ａ）、（Ｂ）、（Ｃ）成分の含有量は、以下のとおりである。   In the composition of the present invention, the contents of the components (A), (B), and (C) are as follows.

（Ａ）成分の含有量は５０〜９５質量％、好ましくは６０〜９０質量％、より好ましくは６０〜８５質量％、さらに好ましくは６５〜８０質量％である。   (A) Content of a component is 50-95 mass%, Preferably it is 60-90 mass%, More preferably, it is 60-85 mass%, More preferably, it is 65-80 mass%.

（Ｂ）成分の含有量は５〜５０質量％、好ましくは４０〜１０質量％、より好ましくは４０〜１５質量％、さらに好ましくは３５〜２０質量％である。   (B) Content of a component is 5-50 mass%, Preferably it is 40-10 mass%, More preferably, it is 40-15 mass%, More preferably, it is 35-20 mass%.

（Ｃ）成分の含有量は、（Ａ）及び（Ｂ）成分の合計１００質量部に対して１０〜１５０質量部であり、好ましくは２０〜１３０質量部、より好ましくは３０〜１００質量部である。   (C) Content of a component is 10-150 mass parts with respect to a total of 100 mass parts of (A) and (B) component, Preferably it is 20-130 mass parts, More preferably, it is 30-100 mass parts. is there.

本発明の組成物は、上記課題を解決できる範囲内にて、必要に応じて、紫外線吸収剤、光安定剤、帯電防止剤、酸化防止剤、滑剤、可塑剤、難燃剤、離型剤等を含有することができる。   The composition of the present invention is, as necessary, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antioxidant, a lubricant, a plasticizer, a flame retardant, a release agent, etc. Can be contained.

実施例及び比較例
表１に示す各成分を用い、日本製鋼社製の二軸押出機TEX30α（スクリュー径３２mm）にて、２７０℃で溶融混練し、ストランド状に押し出した後に冷却し、切断してペレットを得た（スクリュー回転数：２５０rpm、投入量：３０ｋｇ／時間）。ガラス繊維は、サイドフィードを用いて、途中から投入した。各例の組成物について、下記の各試験をした。結果を表１に示す。 Examples and Comparative Examples Using each of the components shown in Table 1, it was melt-kneaded at 270 ° C. in a twin-screw extruder TEX30α (screw diameter 32 mm) manufactured by Nippon Steel Co., Ltd., extruded into a strand, cooled, and cut. Thus, pellets were obtained (screw rotation speed: 250 rpm, input amount: 30 kg / hour). The glass fiber was introduced from the middle using a side feed. Each composition described below was subjected to the following tests. The results are shown in Table 1.

（１）バリの評価
縦120mm×横120mm×厚み3mmの成形品を金型温度120℃で射出成形した時のバリの幅をキーエンス社製デジタルマイクロスコープYHX-200により測定し評価した。
○：バリの幅が30μm未満
△：バリの幅が30μm以上、50μm未満
×：バリの幅が50μm以上 (1) Evaluation of burrs The width of burrs when a molded product having a length of 120 mm, a width of 120 mm and a thickness of 3 mm was injection-molded at a mold temperature of 120 ° C. was measured and evaluated with a digital microscope YHX-200 manufactured by Keyence Corporation.
○: Burr width is less than 30μm △: Burr width is 30μm or more, less than 50μm ×: Burr width is 50μm or more

（２）成形品外観の評価
縦120mm×横120mm×厚み3mmの成形品を金型温度120℃で射出成形した時の外観を目視評価した。
○：フィラー浮きが無く、平滑で外観が良い。
△：一部にフィラー浮きが見られる。
×：全体にフィラー浮きが見られ、平滑性にも劣る。 (2) Evaluation of appearance of molded product The appearance when a molded product having a length of 120 mm, a width of 120 mm and a thickness of 3 mm was injection-molded at a mold temperature of 120 ° C. was visually evaluated.
○: No filler floating, smooth and good appearance.
(Triangle | delta): The filler float is seen in part.
X: The filler float is seen in the whole and it is inferior to smoothness.

（３）塗装性の評価
射出成形で作製した平板（100×100×２mm）の表面をイソプロパノールで脱脂し、２液型アクリルウレタン塗料（カシュー（株）製，ストロン100）で塗装し、乾燥（80℃×２時間）後、JIS K5400-1990の碁盤目テスト法で100マスの残目を数えて、塗装性を評価した。○表示は、100/100を示している。 (3) Evaluation of paintability The surface of a flat plate (100 x 100 x 2 mm) produced by injection molding is degreased with isopropanol, painted with a two-part acrylic urethane paint (Cashew Co., Ltd., Stron 100), and dried ( After 2 hours at 80 ° C., the paintability was evaluated by counting the remainder of 100 squares by the cross-cut test method of JIS K5400-1990. ○ The display shows 100/100.

（４）そりの評価
縦120mm×横120mm×厚み2mmのサイズに成形した平板を、平らな水平面の上に、開いたの中央部が水平面と接触するように（そりが生じている場合には各コーナー部が浮き上がるように）載置した。次に、各コーナー部を水平面に固定した後、固定したコーナー部に対して対角線上にあるコーナー部の水平面に対する高さ（持ち上がり高さ）を測定した。これを各コーナー部についても測定し、もっとも大きい持ち上がり高さについて、以下の基準で評価した。
◎：5mm未満
○：5mm以上8mm未満
△：8mm以上10mm未満
×：10mm以上 (4) Evaluation of the sled A flat plate molded into a size of 120mm in length x 120mm in width x 2mm in thickness is placed on a flat horizontal surface so that the center of the open part is in contact with the horizontal surface. It was placed so that each corner was raised. Next, after fixing each corner part to a horizontal plane, the height (lifting height) of the corner part on the diagonal with respect to the fixed corner part was measured. This was also measured for each corner, and the largest lifting height was evaluated according to the following criteria.
◎: Less than 5mm ○: 5mm or more and less than 8mm △: 8mm or more and less than 10mm ×: 10mm or more

（５）荷重たわみ温度
ＩＳＯ７５に準拠して測定した。 (5) Deflection temperature under load Measured according to ISO75.

（６）曲げ弾性率
ＩＳＯ１７８に準拠して測定した。 (6) Flexural modulus Measured according to ISO178.

＜（Ａ）成分＞
PA-1：ポリアミド６／６６共重合体，宇部興産（株）のUBEナイロン5013B（温度25℃、９６重量％硫酸中に樹脂濃度を 1g／100mlとして測定したときの相対粘度が２．５のポリアミド６／６６共重合体）
PA-2：ポリアミド６／６６共重合体，宇部興産（株）のUBEナイロン5023B（温度25℃、９６重量％硫酸中に樹脂濃度を 1g／100mlとして測定したときの相対粘度が３．０のポリアミド６／６６共重合体
PA-3：ポリアミド６６，宇部興産（株）のUBEナイロン2015B（温度25℃、９６重量％硫酸中に樹脂濃度を 1g／100mlとして測定したときの相対粘度が２．５のポリアミド６６）
PA-4：ポリアミド６，宇部興産（株）のUBEナイロン1013B（温度25℃、９６重量％硫酸中に樹脂濃度を 1g／100mlとして測定したときの相対粘度が２．５のポリアミド６）
＜（Ｂ）成分＞
酸変性マレイミド樹脂：スチレン４７質量％−Nフェニルマレイミド５１質量％−無水マレイン酸２質量％の共重合体，ガラス転移温度１９６℃，重量平均分子量１２万，265℃10ｋｇでのメルトフローレート:4
酸変性AS:スチレン71質量％，アクリロニトリル24質量％メタクリル酸5質量％
酸変性EPDM：Shanghai SUNNY New Technology Development CMG9802
AS樹脂：ダイセルポリマー（株）のセビアンN 050SF
ABS樹脂：日本エイアンドエル（株）のサンタック AT-08
＜（Ｃ）成分＞
ガラス繊維：日本電気硝子（株）製のECS-03-T-120，長軸長さ／短軸長さ＝1.0（断面が円形）（図１参照）
ガラス繊維２：日東紡績（株），CSH 3PA-870S，長軸長さ／短軸長さ＝2.0（断面が略繭玉形）（図１参照）
ガラス繊維３：日東紡績（株），CSG 3PA-820S，長軸長さ／短軸長さ＝4.0（断面が略長円形）（図１参照） <(A) component>
PA-1: Polyamide 6/66 copolymer, UBE nylon 5013B from Ube Industries, Ltd. (temperature 25 ° C., relative viscosity 2.5 when measured at 96% by weight sulfuric acid at a resin concentration of 1 g / 100 ml) Polyamide 6/66 copolymer)
PA-2: Polyamide 6/66 copolymer, UBE nylon 5023B from Ube Industries, Ltd. (temperature 25 ° C., 96 wt% sulfuric acid with a resin concentration of 1 g / 100 ml and a relative viscosity of 3.0) Polyamide 6/66 copolymer
PA-3: polyamide 66, UBE nylon 2015B from Ube Industries, Ltd. (polyamide 66 with a relative viscosity of 2.5 when measured at a temperature of 25 ° C. and a resin concentration of 1 g / 100 ml in 96 wt% sulfuric acid)
PA-4: Polyamide 6, UBE nylon 1013B from Ube Industries, Ltd. (polyamide 6 with a relative viscosity of 2.5 when measured at a temperature of 25 ° C. and a resin concentration of 1 g / 100 ml in 96% by weight sulfuric acid)
<(B) component>
Acid-modified maleimide resin: 47% by mass of styrene-51% by mass of N-phenylmaleimide-2% by mass of maleic anhydride, glass transition temperature 196 ° C., weight average molecular weight 120,000, 265 ° C. Melt flow rate at 10 kg: 4
Acid-modified AS: 71% by mass of styrene, 24% by mass of acrylonitrile, 5% by mass of methacrylic acid
Acid-modified EPDM: Shanghai SUNNY New Technology Development CMG9802
AS resin: Sebian N 050SF from Daicel Polymer Co., Ltd.
ABS plastic: Nippon A & L Co., Ltd. Santac AT-08
<(C) component>
Glass fiber: ECS-03-T-120 manufactured by Nippon Electric Glass Co., Ltd., major axis length / minor axis length = 1.0 (circular cross section) (see Fig. 1)
Glass fiber 2: Nitto Boseki Co., Ltd., CSH 3PA-870S, major axis length / minor axis length = 2.0 (the cross section is approximately jade-shaped) (see Fig. 1)
Glass fiber 3: Nitto Boseki Co., Ltd., CSG 3PA-820S, major axis length / minor axis length = 4.0 (section is substantially oval) (see FIG. 1)

Figure 0005647785
Figure 0005647785

（Ｃ）成分のガラス繊維としてガラス繊維２、３を配合した実施例１７〜１９は、そりが小さく、特に実施例１８、１９はそりが小さかった。
表１の結果から、本発明の組成物は、各種成形品の成形材料として適していることが確認され、特にそりの小さい実施例１７〜１９の組成物は、薄肉成形品（例えば、厚さ０．４〜２．０ｍｍ）の成形材料として適していることが確認された。 In Examples 17 to 19 in which glass fibers 2 and 3 were blended as the glass fiber of component (C), the warp was small, and in particular, Examples 18 and 19 had a small warp.
From the results shown in Table 1, it was confirmed that the composition of the present invention was suitable as a molding material for various molded articles. The compositions of Examples 17 to 19 having a small warp were particularly thin molded articles (for example, thickness It was confirmed that it was suitable as a molding material of 0.4 to 2.0 mm.

本発明の樹脂組成物は、携帯電話の外装部材、自動車の内装部品及び外装部品等の成形用材料として利用することができる。   The resin composition of the present invention can be used as a molding material for mobile phone exterior members, automobile interior parts, exterior parts, and the like.

Claims (5)

（Ａ）ポリアミド系樹脂混合物であり、前記ポリアミド系樹脂混合物が下記の（A-1）、（A-2）、（A-4）から選ばれるいずれか１つのもの５０〜９５質量％
（A-1）ポリアミド６とポリアミド６６の共重合体、ポリアミド６及びポリアミド６６
の混合物
（A-2）ポリアミド６とポリアミド６６の共重合体とポリアミド６の混合物、
（A-4）ポリアミド６とポリアミド６６の共重合体とポリアミド６６の混合物、
（Ｂ）（B-1）成分と（B-2）成分の組み合わせからなるものを５〜５０質量％
前記（B-1）成分が、カルボン酸変性ＡＳ樹脂、カルボン酸変性ＡＢＳ樹脂、カルボン
酸又はその無水物変性オレフィン樹脂、マレイミド系モノマーを４０質量％以上含むモノマー混合物から得られたカルボン酸又はその無水物変性マレイミド樹脂、カルボン酸又はその無水物変性ＥＰＤＭから選ばれる２種または３種からなるものであり、前記（B-2）成分がＡＳ樹脂であり、（Ｂ）成分中、（B-1）成分が１５〜８０質量％、（B-2）成分が８５〜２０質量％である。
（Ｃ）ガラス繊維及び／又は炭素繊維を（Ａ）及び（Ｂ）成分の合計１００質量部に対して１０〜１５０質量部含有する、樹脂組成物。 (A) A polyamide-based resin mixture, and the polyamide-based resin mixture is any one selected from the following (A-1) , (A-2), and (A-4) : 50 to 95% by mass
(A-1) Copolymer of polyamide 6 and polyamide 66, polyamide 6 and polyamide 66
(A-2) A mixture of polyamide 6 and polyamide 66 copolymer and polyamide 6 ;
(A-4) A mixture of polyamide 6 and polyamide 66 copolymer and polyamide 66 ,
(B) 5 to 50% by mass of a combination of component (B-1) and component (B-2)
The component (B-1) is a carboxylic acid-modified AS resin, a carboxylic acid-modified ABS resin, a carboxylic acid
Two or three kinds selected from acid or anhydride-modified olefin resin, carboxylic acid obtained from a monomer mixture containing 40% by mass or more of maleimide monomer, or anhydride-modified maleimide resin thereof, carboxylic acid or anhydride-modified EPDM The component (B-2) is an AS resin. In the component (B), the component (B-1) is 15 to 80% by mass, and the component (B-2) is 85 to 20% by mass. It is.
(C) The resin composition which contains 10-150 mass parts of glass fiber and / or carbon fiber with respect to a total of 100 mass parts of (A) and (B) component. さらに（Ｂ）成分としてＡＢＳ樹脂を含んでおり、組成物中のＡＢＳ樹脂の含有量は５質量％以下である、請求項１記載の樹脂組成物。 Further (B) contains an ABS resin as a component, the content of the ABS resin in the composition is less than 5 wt%, claim 1 resin composition. （Ｃ）成分のガラス繊維又は炭素繊維が、幅方向の断面の長軸長さと短軸長さの比率（長軸長さ／短軸長さ）が１．２〜５．０の範囲のものである、請求項１又は２記載の樹脂組成物。 (C) The glass fiber or carbon fiber of the component has a ratio of major axis length to minor axis length (major axis length / minor axis length) in the range of 1.2 to 5.0 in the cross section in the width direction. The resin composition according to claim 1 or 2, wherein （Ｃ）成分のガラス繊維又は炭素繊維が、幅方向の断面の長軸長さと短軸長さの比率（長軸長さ／短軸長さ）が２．０〜５．０の範囲のものである、請求項１又は２記載の樹脂組成物。 (C) Component glass fiber or carbon fiber has a ratio of major axis length to minor axis length (major axis length / minor axis length) of the cross section in the width direction in the range of 2.0 to 5.0 The resin composition according to claim 1 or 2, wherein （Ｃ）成分のガラス繊維又は炭素繊維が、幅方向の断面形状が略繭玉形又は略長円形のものである、請求項１〜４のいずれか１項記載の樹脂組成物。 (C) a glass fiber or carbon fiber components are those in the width direction of the cross-sectional shape of substantially cocoon-shaped cakes shaped or oblong, any one resin composition as claimed in claim 1-4.
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