JP2004256806A - Fiber-polypropylene resin composite, its pellet and fiber reinforced resin molded product - Google Patents
Fiber-polypropylene resin composite, its pellet and fiber reinforced resin molded product Download PDFInfo
- Publication number
- JP2004256806A JP2004256806A JP2004027767A JP2004027767A JP2004256806A JP 2004256806 A JP2004256806 A JP 2004256806A JP 2004027767 A JP2004027767 A JP 2004027767A JP 2004027767 A JP2004027767 A JP 2004027767A JP 2004256806 A JP2004256806 A JP 2004256806A
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- component
- resin
- weight
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 106
- 239000011347 resin Substances 0.000 title claims abstract description 106
- 239000000835 fiber Substances 0.000 title claims abstract description 72
- 239000008188 pellet Substances 0.000 title claims abstract description 30
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 29
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 29
- 239000000805 composite resin Substances 0.000 title claims abstract description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 68
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 30
- 229920005604 random copolymer Polymers 0.000 claims abstract description 27
- 239000004711 α-olefin Substances 0.000 claims abstract description 25
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 20
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- 229920005672 polyolefin resin Polymers 0.000 claims description 28
- 238000007493 shaping process Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 28
- -1 polypropylene Polymers 0.000 description 20
- 238000005259 measurement Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920001384 propylene homopolymer Polymers 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
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- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000011342 resin composition Substances 0.000 description 4
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- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
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- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
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Abstract
Description
本発明は、繊維−ポリプロピレン樹脂複合体とそのペレット、および、これらを用いて得られる繊維強化樹脂成形体に関する。さらに詳細には、クリープ特性に優れた繊維強化樹脂成形体、およびクリープ特性に優れ、前記繊維強化樹脂成形品の材料として好適な繊維−ポリプロピレン樹脂複合体とそのペレットに関する。 The present invention relates to a fiber-polypropylene resin composite, a pellet thereof, and a fiber-reinforced resin molded product obtained using the composite. More specifically, the present invention relates to a fiber-reinforced resin molded article having excellent creep properties, a fiber-polypropylene resin composite having excellent creep properties and suitable as a material for the fiber-reinforced resin molded article, and a pellet thereof.
従来、ポリプロピレン樹脂の剛性や衝撃強度等の機械的強度を向上させる手段として、フィラーやガラス繊維等を配合することが知られている。
例えば、特開平３−１２１１４６号公報には、ポリオレフィンと、変性ポリオレフィン系重合体と、２ｍｍ以上の長さを有する強化用繊維を含有してなる長繊維強化成形用ポリオレフィン樹脂組成物が記載されている。
Conventionally, it has been known to mix fillers, glass fibers, and the like as means for improving mechanical strength such as rigidity and impact strength of polypropylene resin.
For example, JP-A-3-121146 describes a polyolefin resin composition for long-fiber reinforced molding comprising a polyolefin, a modified polyolefin-based polymer, and a reinforcing fiber having a length of 2 mm or more. I have.
また、特開平４−２９８５５３号公報には、ポリプロピレン系樹脂、低密度ポリエチレン、ガラス繊維および変性ポリオレフィンからなるガラス繊維強化ポリオレフィン樹脂組成物が記載されており、ポリプロピレン系樹脂としてプロピレンとエチレンのブロック共重合体を使用できることが記載されている。 JP-A-4-298553 describes a glass fiber-reinforced polyolefin resin composition comprising a polypropylene resin, low-density polyethylene, glass fiber and a modified polyolefin. It is stated that polymers can be used.
そして、特開平９−１８３８６９号公報には、強化用連続ガラス繊維束を引きながら、前記ガラス繊維束にポリオレフィン樹脂を含浸し、切断して得られる長繊維強化ポリオレフィン樹脂ペレットが記載されており、ポリオレフィン樹脂としてプロピレン単独重合体、プロピレン−エチレンのランダムまたはブロック共重合体を使用できることが記載されている。 Japanese Patent Application Laid-Open No. 9-183869 describes a long fiber reinforced polyolefin resin pellet obtained by impregnating the glass fiber bundle with a polyolefin resin while pulling a continuous glass fiber bundle for reinforcement and cutting the glass fiber bundle. It is described that a propylene homopolymer or a propylene-ethylene random or block copolymer can be used as the polyolefin resin.
しかし、上記の公報に記載されている長繊維強化樹脂組成物とそのペレット、および、それらの樹脂組成物またはペレットからなる成形体は、クリープ特性について更なる改良が求められる。 However, the long fiber reinforced resin composition and its pellets described in the above-mentioned publications, and the molded article made of those resin compositions or pellets, require further improvement in creep properties.
本発明の目的は、クリープ特性に優れた繊維強化樹脂成形品、およびクリープ特性に優れ、前記繊維強化樹脂成形品の材料として好適な繊維−ポリプロピレン樹脂複合体とそのペレットを提供することにある。 An object of the present invention is to provide a fiber-reinforced resin molded article having excellent creep properties, and a fiber-polypropylene resin composite excellent in creep properties and suitable as a material for the fiber-reinforced resin molded article, and a pellet thereof.
本発明者等は、かかる実状に鑑みて鋭意検討を重ねた結果、以下に記す発明を完成した。
［１］ 下に定義する成分（Ａ）２０〜９５重量％と、重量平均繊維長が２〜１００ｍｍの繊維である成分（Ｂ）８０〜５重量％を含有する繊維−ポリプロピレン樹脂複合体（ここで、成分（Ａ）の量と成分（Ｂ）の量は共に、成分（Ａ）と成分（Ｂ）の合計量に対する量である）。
成分（Ａ）：プロピレンとエチレン及びα−オレフィンからなる群から選ばれる少なくとも１種の単量体とを共重合して得られるプロピレン系ランダム共重合体である成分（Ａ−１）を含有し、前記エチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量が０．１〜３重量％のプロピレン系樹脂、または該プロピレン系樹脂を不飽和カルボン酸またはその誘導体で変性して得られる変性プロピレン系樹脂（ただし、前記重合単量体単位の前記含有量は、当該プロピレン系樹脂に含有される全重合単量体単位の量に対する量である）。
以下の説明において、この複合体を「第一（の）複合体」と記すことがある。
The present inventors have conducted intensive studies in view of such circumstances, and as a result, have completed the invention described below.
[1] A fiber-polypropylene resin composite containing 20 to 95% by weight of a component (A) defined below and 80 to 5% by weight of a component (B) having a weight average fiber length of 2 to 100 mm (here Where both the amount of component (A) and the amount of component (B) are relative to the total amount of component (A) and component (B).
Component (A): Component (A-1) which is a propylene-based random copolymer obtained by copolymerizing propylene with at least one monomer selected from the group consisting of ethylene and α-olefin. A propylene-based resin having a total content of monomer units derived from monomers belonging to the group consisting of ethylene and α-olefins of 0.1 to 3% by weight, or a propylene-based resin containing unsaturated carboxylic acid Or a modified propylene resin obtained by modification with a derivative thereof (however, the content of the polymerized monomer unit is an amount based on the total amount of the polymerized monomer units contained in the propylene resin).
In the following description, this complex may be referred to as a “first (complex)”.
［２］ 下に定義する樹脂（Ｄ）、及び該樹脂（Ｄ）１００重量部に対して５〜４００重量部の、重量平均繊維長が２〜１００ｍｍの繊維である成分（Ｂ）を含有する繊維−ポリプロピレン樹脂複合体。
樹脂（Ｄ）：下に定義する成分（Ａ’）６０〜９９．９重量％と、成分（Ｃ）である変性ポリオレフィン樹脂０．１〜４０重量％とからなる樹脂（ここで、成分（Ａ’）の量と成分（Ｃ）の量は共に、当該樹脂の全量に対する量であり、両者の合計は１００重量％である）。
成分（Ａ’）：プロピレンとエチレン及びα−オレフィンからなる群から選ばれる少なくとも１種の単量体とを共重合して得られるプロピレン系ランダム共重合体である成分（Ａ−１）を含有し、前記エチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量が０．１〜３重量％のプロピレン系樹脂（ただし、前記重合単量体単位の前記含有量は、当該プロピレン系樹脂に含有される全重合単量体単位の量に対する量である）。
以下の説明において、この複合体を「第二（の）複合体」と記すことがある。
[2] A resin (D) as defined below, and a component (B) which is a fiber having a weight average fiber length of 2 to 100 mm in an amount of 5 to 400 parts by weight based on 100 parts by weight of the resin (D). Fiber-polypropylene resin composite.
Resin (D): a resin composed of 60 to 99.9% by weight of component (A ′) defined below and 0.1 to 40% by weight of modified polyolefin resin as component (C) (here, component (A) Both the amount of ') and the amount of component (C) are relative to the total amount of the resin, the sum of both being 100% by weight).
Component (A ′): contains component (A-1), which is a propylene-based random copolymer obtained by copolymerizing propylene with at least one monomer selected from the group consisting of ethylene and α-olefin. A propylene-based resin having a content of all the polymerizable monomer units derived from the monomers belonging to the group consisting of the ethylene and the α-olefin of 0.1 to 3% by weight (however, The content is an amount based on the total amount of polymerized monomer units contained in the propylene-based resin).
In the following description, this complex may be referred to as “second (complex) complex”.
［３］ 上記［１］又は［２］に記載の繊維−ポリプロピレン樹脂複合体からなるペレットであって、該ペレット中において、成分（Ｂ）の個々の繊維が互いに平行に配列しているペレット。 [3] A pellet comprising the fiber-polypropylene resin composite according to the above [1] or [2], wherein the individual fibers of the component (B) are arranged parallel to each other in the pellet.
［４］ 上記［１］又は［２］に記載の繊維−ポリプロピレン樹脂複合体を溶融混練し、得られた混練物を賦形してなる繊維強化樹脂成形体であって、該成形体中において、成分（Ｂ）に由来する繊維の重量平均繊維長が１ｍｍ以上である成形体。 [4] A fiber-reinforced resin molded product obtained by melting and kneading the fiber-polypropylene resin composite according to [1] or [2], and shaping the obtained kneaded product. A molded article in which the fiber derived from the component (B) has a weight average fiber length of 1 mm or more.
本発明によれば、クリープ特性に優れた、すなわち、引張クリ−プ測定での破断時間が充分に長い繊維強化樹脂成形品、およびその材料として好適な繊維−ポリプロピレン樹脂複合体とそのペレットを得ることができる。 According to the present invention, a fiber-reinforced resin molded article having excellent creep properties, that is, a sufficiently long breaking time in tensile creep measurement, and a fiber-polypropylene resin composite and pellets suitable as the material are obtained. be able to.
第一複合体に成分（Ａ）として含まれ、または第一複合体の成分（Ａ）の原料として用いられ、また第二複合体に成分（Ａ‘）として含まれる前記プロピレン系樹脂は、プロピレンとエチレン及びα−オレフィンからなる群から選ばれる少なくとも１種の単量体とを共重合して得られるプロピレン系ランダム共重合体である成分（Ａ−１）を含有する樹脂である。 The propylene-based resin contained as the component (A) in the first composite or used as a raw material of the component (A) of the first composite, and contained as the component (A ′) in the second composite, is propylene. And a component (A-1), which is a propylene-based random copolymer obtained by copolymerizing a polymer with at least one monomer selected from the group consisting of ethylene and α-olefins.
成分（Ａ−１）であるプロピレン系ランダム共重合体は、プロピレンとエチレン及びα−オレフィンからなる群から選ばれる少なくとも１種の単量体とを共重合して得られる共重合体である。具体的には、プロピレン−エチレンランダム共重合体、プロピレン−α−オレフィンランダム共重合体、プロピレン−エチレン−α−オレフィンランダム共重合体等が挙げられる。 The propylene-based random copolymer as the component (A-1) is a copolymer obtained by copolymerizing propylene with at least one monomer selected from the group consisting of ethylene and α-olefin. Specific examples include a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer, and a propylene-ethylene-α-olefin random copolymer.
また、上記プロピレン系樹脂は、前記プロピレン系ランダム共重合体のみで構成されてもよく、また前記プロピレン系ランダム共重合体とプロピレン単独重合体（以下、成分（Ａ−２）と記すことがある）との混合物であってもよい。上記プロピレン系樹脂が成分（Ａ−１）と成分（Ａ−２）との混合物である場合、これに含有される成分（Ａ−１）の重量比率は通常、１０重量％以上１００重量％未満であり、好ましくは２０重量％以上１００重量％未満であり、より好ましくは２５重量％以上１００重量％未満である。成分（Ａ−１）の具体的な重量比率は、成分（Ａ−１）であるプロピレン系ランダム共重合体の共重合組成（すなわち、当該プロピレン系ランダム共重合体における各種重合単量体単位の比率）と、所望のプロピレン系樹脂に含まれるべき、エチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量に応じて適宜決定される。 Further, the propylene-based resin may be composed of only the propylene-based random copolymer, or the propylene-based random copolymer and a propylene homopolymer (hereinafter sometimes referred to as component (A-2)). )). When the propylene-based resin is a mixture of the component (A-1) and the component (A-2), the weight ratio of the component (A-1) contained therein is usually 10% by weight or more and less than 100% by weight. , Preferably from 20% by weight to less than 100% by weight, more preferably from 25% by weight to less than 100% by weight. The specific weight ratio of the component (A-1) is determined based on the copolymer composition of the propylene random copolymer as the component (A-1) (that is, the various polymerizable monomer units in the propylene random copolymer). Ratio) and the content of all polymerized monomer units derived from monomers belonging to the group consisting of ethylene and α-olefin to be contained in the desired propylene-based resin.
上記プロピレン系樹脂に含有されるエチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量は０．１〜３重量％である。ここで、前記重合単量体単位の含有量は、当該プロピレン系樹脂に含有される全重合単量体単位の量に対する量である。 The content of all polymerized monomer units derived from monomers belonging to the group consisting of ethylene and α-olefin contained in the propylene-based resin is 0.1 to 3% by weight. Here, the content of the polymerized monomer unit is an amount based on the total amount of the polymerized monomer units contained in the propylene-based resin.
上記プロピレン系樹脂が成分（Ａ−１）であるプロピレン系ランダム共重合体のみで構成されている場合、成分（Ａ−１）は、エチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量が０．１〜３重量％であるランダム共重合体である。繊維強化樹脂成形品の剛性や衝撃強度、またはクリープ特性の観点から、成分（Ａ−１）に含有されるエチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量は、好ましくは０．２〜２．５重量％であり、より好ましくは０．４〜２重量％である。
成分（Ａ−１）に含まれるエチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量は、“新版 高分子分析ハンドブック”（日本化学会、高分子分析研究懇談会編 紀伊国屋書店（１９９５））に記載されているＩＲ法またはＮＭＲ法を用いて測定する。
When the propylene-based resin is composed of only the propylene-based random copolymer that is the component (A-1), the component (A-1) is derived from a monomer belonging to the group consisting of ethylene and α-olefin. Is a random copolymer having a content of all the polymerizable monomer units of 0.1 to 3% by weight. From the viewpoint of rigidity, impact strength, or creep properties of the fiber-reinforced resin molded article, all polymerized monomer units derived from monomers belonging to the group consisting of ethylene and α-olefin contained in the component (A-1) Is preferably 0.2 to 2.5% by weight, more preferably 0.4 to 2% by weight.
The content of all polymerized monomer units derived from the monomers belonging to the group consisting of ethylene and α-olefin contained in the component (A-1) is described in “New Edition Polymer Analysis Handbook” (The Chemical Society of Japan, It is measured using the IR method or the NMR method described in Analytical Research Roundtable, Kinokuniya Shoten (1995).
一方、上記プロピレン系樹脂が成分（Ａ−１）であるプロピレン系ランダム共重合体と成分（Ａ−２）であるプロピレン単独重合体との混合物である場合には通常、成分（Ａ−１）に含有されるエチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量が０．１重量％を超え５重量％以下であるプロピレン系ランダム共重合体が成分（Ａ−１）として用いられる。この場合、上記プロピレン系樹脂に含有されるエチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量が０．１〜３重量％になるように、成分（Ａ−１）及び（Ａ−２）の量が決定される。前記重合単量体単位の含有量は、繊維強化樹脂成形品の剛性、衝撃強度、クリープ特性などの観点から、好ましくは０．２〜２．５重量％であり、より好ましくは０．４〜２重量％である。
上記プロピレン系樹脂が成分（Ａ−１）と成分（Ａ−２）との混合物である場合にも、当該プロピレン系樹脂に含まれるエチレン及びα−オレフィンからなる群に属する単量体に由来する全重合単量体単位の含有量は、“新版 高分子分析ハンドブック”（日本化学会、高分子分析研究懇談会編 紀伊国屋書店（１９９５））に記載されているＩＲ法またはＮＭＲ法を用いて測定する。
On the other hand, when the propylene resin is a mixture of a propylene random copolymer as the component (A-1) and a propylene homopolymer as the component (A-2), the component (A-1) is usually used. A propylene random copolymer in which the content of all polymerized monomer units derived from monomers belonging to the group consisting of ethylene and α-olefin contained in the propylene-based random copolymer is more than 0.1% by weight and 5% by weight or less Used as component (A-1). In this case, the components are adjusted so that the content of all the polymerized monomer units derived from the monomers belonging to the group consisting of ethylene and α-olefin contained in the propylene-based resin is 0.1 to 3% by weight. The amounts of (A-1) and (A-2) are determined. The content of the polymerized monomer unit is preferably from 0.2 to 2.5% by weight, more preferably from 0.4 to 2.5% by weight, from the viewpoints of rigidity, impact strength, creep characteristics and the like of the fiber-reinforced resin molded product. 2% by weight.
Even when the propylene-based resin is a mixture of the component (A-1) and the component (A-2), the propylene-based resin is derived from a monomer belonging to the group consisting of ethylene and α-olefin contained in the propylene-based resin. The content of all the polymerized monomer units is determined by using the IR method or the NMR method described in "New Edition Polymer Analysis Handbook" (edited by The Chemical Society of Japan, edited by Kinokuniya Shoten (1995)). Measure.
成分（Ａ−１）であるプロピレン系ランダム共重合体におけるα−オレフィンは、炭素数４〜２０のα−オレフィンであり、例えば１−ブテン、２−メチル−１−プロペン、２−メチル−１−ブテン、３−メチル−１−ブテン、１−ヘキセン、２−エチル−１−ブテン、２，３−ジメチル−１−ブテン、２−メチル−１−ペンテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、３，３−ジメチル−１−ブテン、１−ヘプテン、メチル−１−ヘキセン、ジメチル−１−ペンテン、エチル−１−ペンテン、トリメチル−１−ブテン、メチルエチル−１−ブテン、１−オクテン、メチル−１−ペンテン、エチル−１−ヘキセン、ジメチル−１−ヘキセン、プロピル−１−ヘプテン、メチルエチル−１−ヘプテン、トリメチル−１−ペンテン、プロピル−１−ペンテン、ジエチル−１−ブテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン等が挙げられる。好ましくは、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテンである。 The α-olefin in the propylene random copolymer as the component (A-1) is an α-olefin having 4 to 20 carbon atoms, such as 1-butene, 2-methyl-1-propene, and 2-methyl-1. -Butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4 -Methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1- Butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene And propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like. Preferably, they are 1-butene, 1-pentene, 1-hexene, and 1-octene.
成分（Ａ−１）であるプロピレン系ランダム共重合体のメルトフローレート（以下、ＭＦＲと略記する）は、繊維強化樹脂成形品中における繊維の分散性や、繊維強化樹脂成形品の外観や衝撃強度などの観点から、好ましくは５〜１５０ｇ／１０分であり、より好ましくは１０〜１００ｇ／１０分である。なお、ＭＦＲは、Ａ．Ｓ．Ｔ．Ｍ．Ｄ１２３８に従い、２３０℃、２１．２Ｎ荷重で測定した値である。 The melt flow rate (hereinafter abbreviated as MFR) of the propylene random copolymer as the component (A-1) is determined by the dispersibility of the fibers in the fiber-reinforced resin molded product, and the appearance and impact of the fiber-reinforced resin molded product. From the viewpoint of strength and the like, the amount is preferably 5 to 150 g / 10 minutes, and more preferably 10 to 100 g / 10 minutes. In addition, MFR is A. S. T. M. It is a value measured at 230 ° C and 21.2N load according to D1238.
成分（Ａ−２）であるプロピレン単独重合体のＭＦＲは、繊維強化樹脂成形品中における繊維の分散性や、繊維強化樹脂成形品の外観や曲げ強度などの観点から、好ましくは５〜３００ｇ／１０分であり、より好ましくは５〜１５０ｇ／１０分であり、特に好ましくは１０〜１００ｇ／１０分である。なお、ＭＦＲは、Ａ．Ｓ．Ｔ．Ｍ．Ｄ１２３８に従い、２３０℃、２１．２Ｎ荷重で測定した値である。 The MFR of the propylene homopolymer as the component (A-2) is preferably from 5 to 300 g / m from the viewpoints of fiber dispersibility in the fiber-reinforced resin molded product, appearance and bending strength of the fiber-reinforced resin molded product. It is 10 minutes, more preferably 5 to 150 g / 10 minutes, and particularly preferably 10 to 100 g / 10 minutes. In addition, MFR is A. S. T. M. It is a value measured at 230 ° C and 21.2N load according to D1238.
上記変性プロピレン系樹脂は、未変性プロピレン系樹脂を原料として用い、“実用 ポリマーアロイ設計”（井出文雄著、工業調査会（１９９６））、Ｐｒｏｇ． Ｐｏｌｙｍ． Ｓｃｉ．，２４，８１−１４２（１９９９）、特開２００２−３０８９４７号公報等に記載されている溶融混練法によって製造する。
上記変性プロピレン系樹脂の調製に用いられる不飽和カルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、アクリル酸、メタクリル酸等が挙げられる。また、不飽和カルボン酸の誘導体としては、前記の不飽和カルボン酸から誘導される酸無水物、エステル化合物、アミド化合物、イミド化合物、金属塩等が挙げられ、その具体例としては、無水マレイン酸、無水イタコン酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸グリシジル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸グリシジル、マレイン酸モノエチルエステル、マレイン酸ジエチルエステル、フマル酸モノメチルエステル、フマル酸ジメチルエステル、アクリルアミド、メタクリルアミド、マレイン酸モノアミド、マレイン酸ジアミド、フマル酸モノアミド、マレイミド、Ｎ−ブチルマレイミド、メタクリル酸ナトリウム等が挙げられる。また、クエン酸やリンゴ酸のように、プロピレン系樹脂にグラフト重合する工程で脱水して不飽和カルボン酸を生じる化合物を用いてもよい。
不飽和カルボン酸またはその誘導体として、好ましくはアクリル酸、メタクリル酸のグリシジルエステル、無水マレイン酸である。
また、繊維強化樹脂成形品の衝撃強度、疲労特性、剛性等の機械的強度の観点から、上記変性プロピレン系樹脂として好ましくは、不飽和カルボン酸およびその誘導体に由来する重合単量体単位を０．０１〜１０重量％、より好ましくは０．０５〜１０重量％、特に好ましくは０．１〜５重量％含有する変性プロピレン系樹脂である。
The modified propylene-based resin uses an unmodified propylene-based resin as a raw material and is described in “Practical Polymer Alloy Design” (by Fumio Ide, Industrial Research Institute (1996)), Prog. Polym. Sci. , 24, 81-142 (1999), JP-A-2002-308947, and the like.
Examples of the unsaturated carboxylic acid used for preparing the modified propylene-based resin include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and the like. Examples of the unsaturated carboxylic acid derivative include acid anhydrides, ester compounds, amide compounds, imide compounds, and metal salts derived from the unsaturated carboxylic acids. Specific examples thereof include maleic anhydride. , Itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, fumaric acid Monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, sodium methacrylate and the like can be mentioned. Further, a compound such as citric acid or malic acid which generates an unsaturated carboxylic acid by dehydration in a step of graft polymerization to a propylene-based resin may be used.
As the unsaturated carboxylic acid or derivative thereof, acrylic acid, glycidyl ester of methacrylic acid, and maleic anhydride are preferable.
Further, from the viewpoint of mechanical strength such as impact strength, fatigue properties, and rigidity of the fiber-reinforced resin molded product, the modified propylene-based resin is preferably a polymer monomer unit derived from an unsaturated carboxylic acid and a derivative thereof in an amount of 0%. The modified propylene-based resin contains 0.01 to 10% by weight, more preferably 0.05 to 10% by weight, and particularly preferably 0.1 to 5% by weight.
本発明における成分（Ｂ）は、重量平均繊維長が２〜１００ｍｍの繊維である。成分（Ｂ）である繊維の重量平均繊維長は、繊維強化樹脂成形品の剛性や衝撃強度等の機械的強度、繊維−樹脂複合体の製造及び成形のしやすさの観点から、好ましくは３〜５０ｍｍである。なお、前記重量平均繊維長は、特開２００２−５９２４号公報に記載されている方法によって測定することができる。 The component (B) in the present invention is a fiber having a weight average fiber length of 2 to 100 mm. The weight average fiber length of the fiber as the component (B) is preferably 3 from the viewpoint of mechanical strength such as rigidity and impact strength of the fiber-reinforced resin molded product, and ease of production and molding of the fiber-resin composite. ５０50 mm. The weight average fiber length can be measured by a method described in JP-A-2002-5924.
成分（Ｂ）として用いられる繊維としては、無機繊維、有機繊維、天然繊維が挙げられ、例えば、ガラス繊維、炭素繊維、金属繊維、芳香族ポリアミド繊維、ケナフ繊維、竹繊維、ポリエステル繊維、ナイロン繊維、ジュート繊維、セルロース繊維、ラミー繊維等が挙げられる。好ましくはガラス繊維である。 Examples of the fibers used as the component (B) include inorganic fibers, organic fibers, and natural fibers. For example, glass fibers, carbon fibers, metal fibers, aromatic polyamide fibers, kenaf fibers, bamboo fibers, polyester fibers, and nylon fibers , Jute fiber, cellulose fiber, ramie fiber and the like. Preferably, it is glass fiber.
成分（Ｂ）として用いられる繊維は、収束剤で収束された繊維であってもよい。収束剤としては、例えば、ポリオレフィン樹脂、ポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂、エポキシ樹脂、澱粉、植物油等が挙げられる。また、成分（Ｂ）として用いられる繊維の収束剤には、酸変性ポリオレフィン樹脂、表面処理剤、パラフィンワックス等の潤滑剤を配合してもよい。 The fiber used as the component (B) may be a fiber converged with a sizing agent. Examples of the sizing agent include polyolefin resin, polyurethane resin, polyester resin, acrylic resin, epoxy resin, starch, and vegetable oil. Further, a lubricant such as an acid-modified polyolefin resin, a surface treating agent, and a paraffin wax may be blended with the fiber sizing agent used as the component (B).
プロピレン系樹脂との濡れ性や接着性等の改良のために、成分（Ｂ）用の繊維は表面処理剤で処理されていても良い。この表面処理剤としては、例えばシラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤、クロム系カップリング剤、ジルコニウム系カップリング剤、ボラン系カップリング剤等が挙げられ、好ましくはシラン系カップリング剤またはチタネート系カップリング剤であり、特に好ましくはシラン系カップリング剤である。 The fiber for component (B) may be treated with a surface treating agent to improve the wettability and adhesion with the propylene-based resin. Examples of the surface treatment agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a chromium coupling agent, a zirconium coupling agent, and a borane coupling agent. It is a silane coupling agent or a titanate coupling agent, and particularly preferably a silane coupling agent.
前記のシラン系カップリング剤としては、例えば、トリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン等が挙げられ、好ましくはγ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン等のアミノシラン類である。 Examples of the silane coupling agent include, for example, triethoxysilane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane , N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like, and preferably γ-aminopropyltriethoxysilane, N-β- (aminoethyl ) -Γ-Aminopropyl trime It is an aminosilane such as Kishishiran.
繊維を表面処理剤で処理する方法としては、従来から慣用されている方法、例えば、水溶液法、有機溶媒法、スプレー法等が挙げられる。 As a method of treating the fiber with the surface treatment agent, a conventionally used method, for example, an aqueous solution method, an organic solvent method, a spray method and the like can be mentioned.
本発明の第二の複合体は、下に定義する樹脂（Ｄ）、及び重量平均繊維長が２〜１００ｍｍの繊維である成分（Ｂ）を含有する繊維−ポリプロピレン樹脂複合体である。
樹脂（Ｄ）：下に定義する成分（Ａ’）６０〜９９．９重量％と、成分（Ｃ）である変性ポリオレフィン樹脂０．１〜４０重量％とからなる樹脂（ここで、成分（Ａ’）の量と成分（Ｃ）の量は共に、当該樹脂の全量に対する量であり、両者の合計は１００重量％である）。
成分（Ａ’）：前記プロピレン系ランダム共重合体である成分（Ａ−１）を含有し、前記エチレン及びα−オレフィンからなる群に属する単量体に由来する重合単量体単位の含有量が０．１〜３重量％のプロピレン系樹脂（ただし、前記重合単量体単位の前記含有量は、当該プロピレン系樹脂に含有される全重合単量体単位の量に対する量である）。
The second composite of the present invention is a fiber-polypropylene resin composite containing a resin (D) defined below and a component (B) having a weight average fiber length of 2 to 100 mm.
Resin (D): a resin composed of 60 to 99.9% by weight of component (A ′) defined below and 0.1 to 40% by weight of modified polyolefin resin as component (C) (here, component (A) Both the amount of ') and the amount of component (C) are relative to the total amount of the resin, the sum of both being 100% by weight).
Component (A ′): The content of the polymerized monomer unit containing the component (A-1) that is the propylene-based random copolymer and derived from the monomer belonging to the group consisting of the ethylene and the α-olefin. Is a propylene-based resin of 0.1 to 3% by weight (however, the content of the polymerized monomer unit is an amount based on the total amount of the polymerized monomer units contained in the propylene-based resin).
成分（Ｃ）である変性ポリオレフィン樹脂は、以下の（１）〜（４）のいずれかである。
（１）オレフィンの単独重合体に、不飽和カルボン酸および／またはその誘導体をグラフト重合して得られる変性ポリオレフィン樹脂、
（２）少なくとも２種のオレフィンの共重合体に、不飽和カルボン酸および／またはその誘導体をグラフト重合して得られる変性ポリオレフィン樹脂、
（３）オレフィンを単独重合した後に少なくとも２種のオレフィンを共重合して得られるブロック共重合体に、不飽和カルボン酸および／またはその誘導体をグラフト重合して得られる変性ポリオレフィン樹脂。
（４）少なくとも１種のオレフィンと、不飽和カルボン酸および／またはその誘導体をランダム共重合あるいはブロック共重合して得られる変性ポリオレフィン樹脂。
The modified polyolefin resin as the component (C) is any of the following (1) to (4).
(1) a modified polyolefin resin obtained by graft-polymerizing an unsaturated carboxylic acid and / or a derivative thereof to an olefin homopolymer,
(2) a modified polyolefin resin obtained by graft-polymerizing an unsaturated carboxylic acid and / or a derivative thereof to a copolymer of at least two olefins;
(3) A modified polyolefin resin obtained by graft-polymerizing an unsaturated carboxylic acid and / or a derivative thereof to a block copolymer obtained by homopolymerizing an olefin and then copolymerizing at least two types of olefins.
(4) A modified polyolefin resin obtained by random or block copolymerization of at least one olefin and an unsaturated carboxylic acid and / or a derivative thereof.
変性ポリオレフィン樹脂の製造には、例えば、“実用 ポリマーアロイ設計”（井出文雄著、工業調査会（１９９６））、Ｐｒｏｇ． Ｐｏｌｙｍ． Ｓｃｉ．，２４，８１−１４２（１９９９）、特開２００２−３０８９４７号公報等に記載されている方法など、種々の方法を用いることができる。すなわち、溶液法、バルク法、溶融混練法のいずれの方法を用いてもよい。また、これらの方法を組み合わせて用いてもよい。 The production of the modified polyolefin resin is described in, for example, "Practical Polymer Alloy Design" (by Fumio Ide, Industrial Research Council (1996)), Prog. Polym. Sci. , 24, 81-142 (1999), JP-A-2002-308947, and the like. That is, any of a solution method, a bulk method, and a melt-kneading method may be used. Further, these methods may be used in combination.
上記変性ポリオレフィン樹脂の調製に用いられる不飽和カルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、アクリル酸、メタクリル酸等が挙げられる。また、不飽和カルボン酸の誘導体としては、前記の不飽和カルボン酸から誘導される酸無水物、エステル化合物、アミド化合物、イミド化合物、金属塩等が挙げられ、その具体例としては、無水マレイン酸、無水イタコン酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸グリシジル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸グリシジル、マレイン酸モノエチルエステル、マレイン酸ジエチルエステル、フマル酸モノメチルエステル、フマル酸ジメチルエステル、アクリルアミド、メタクリルアミド、マレイン酸モノアミド、マレイン酸ジアミド、フマル酸モノアミド、マレイミド、Ｎ−ブチルマレイミド、メタクリル酸ナトリウム等が挙げられる。また、クエン酸やリンゴ酸のように、ポリオレフィンにグラフト重合する工程で脱水して不飽和カルボン酸を生じる化合物を用いてもよい。
不飽和カルボン酸および／またはその誘導体として、好ましくはアクリル酸、メタクリル酸のグリシジルエステル、無水マレイン酸である。
Examples of the unsaturated carboxylic acid used for preparing the modified polyolefin resin include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, and the like. Examples of the unsaturated carboxylic acid derivative include acid anhydrides, ester compounds, amide compounds, imide compounds, and metal salts derived from the unsaturated carboxylic acids. Specific examples thereof include maleic anhydride. , Itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, fumaric acid Monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, sodium methacrylate and the like can be mentioned. Further, a compound such as citric acid or malic acid which generates an unsaturated carboxylic acid by dehydration in a step of graft polymerization to a polyolefin may be used.
As the unsaturated carboxylic acid and / or derivative thereof, acrylic acid, glycidyl ester of methacrylic acid, and maleic anhydride are preferable.
好ましい成分（Ｃ）として、
（１）エチレンとプロピレンとから選ばれる少なくとも１種の単量体に由来する単位を主な構成単位とするポリオレフィン樹脂に、無水マレイン酸をグラフト重合することによって得られる変性ポリオレフィン樹脂、
（２）エチレンとプロピレンとから選ばれる少なくとも１種の単量体を主な成分とするオレフィンと、メタクリル酸グリシジルエステルまたは無水マレイン酸とを共重合することによって得られる変性ポリオレフィン樹脂
が挙げられる。
As a preferred component (C),
(1) a modified polyolefin resin obtained by graft-polymerizing maleic anhydride onto a polyolefin resin having a unit derived from at least one monomer selected from ethylene and propylene as a main constituent unit;
(2) Modified polyolefin resins obtained by copolymerizing an olefin mainly composed of at least one monomer selected from ethylene and propylene with glycidyl methacrylate or maleic anhydride.
また、繊維強化樹脂成形品の衝撃強度、疲労特性、剛性等の機械的強度の観点から、成分（Ｃ）の変性ポリオレフィン樹脂として好ましくは、不飽和カルボン酸および／またはその誘導体に由来する重合単量体単位を０．１〜１０重量％含有する変性ポリオレフィン樹脂である。特に、不飽和カルボン酸および／またはその誘導体を用いて、ランダム共重合あるいはブロック共重合によって得られる変性ポリオレフィン樹脂の場合には、不飽和カルボン酸および／またはその誘導体に由来する重合単量体単位の含有量は３〜１０重量％が好ましく、グラフト重合によって得られる変性ポリオレフィン樹脂の場合には、不飽和カルボン酸および／またはその誘導体に由来する重合単量体単位の含有量は０．１〜１０重量％が好ましい。 Further, from the viewpoint of mechanical strength such as impact strength, fatigue properties and rigidity of the fiber-reinforced resin molded product, the modified polyolefin resin of the component (C) is preferably a polymerized monomer derived from an unsaturated carboxylic acid and / or a derivative thereof. It is a modified polyolefin resin containing 0.1 to 10% by weight of a monomer unit. Particularly, in the case of a modified polyolefin resin obtained by random copolymerization or block copolymerization using an unsaturated carboxylic acid and / or a derivative thereof, a polymerized monomer unit derived from the unsaturated carboxylic acid and / or a derivative thereof Is preferably 3 to 10% by weight. In the case of a modified polyolefin resin obtained by graft polymerization, the content of a polymerized monomer unit derived from an unsaturated carboxylic acid and / or a derivative thereof is 0.1 to 10% by weight. 10% by weight is preferred.
本発明の第一複合体における成分（Ａ）と成分（Ｂ）の配合割合は、成分（Ａ）が２０〜９５重量％であり、成分（Ｂ）が８０〜５重量％である。ここに記載の成分（Ａ）の量と成分（Ｂ）の量は、共に、成分（Ａ）と成分（Ｂ）の合計量に対する量である。 The compounding ratio of the component (A) and the component (B) in the first composite of the present invention is such that the component (A) is 20 to 95% by weight and the component (B) is 80 to 5% by weight. The amounts of component (A) and component (B) described herein are both based on the total amount of component (A) and component (B).
繊維強化樹脂成形品の剛性や衝撃強度等の機械的強度や、繊維−樹脂複合体の製造および成形のしやすさの観点から、成分（Ａ）と成分（Ｂ）の配合割合は、好ましくは、成分（Ａ）が３０〜９０重量％であり、成分（Ｂ）が７０〜１０重量％である。 In view of the mechanical strength such as the rigidity and impact strength of the fiber-reinforced resin molded product, and the ease of manufacturing and molding the fiber-resin composite, the mixing ratio of the component (A) and the component (B) is preferably The component (A) is 30 to 90% by weight, and the component (B) is 70 to 10% by weight.
本発明の第二複合体において、樹脂（Ｄ）における成分（Ａ’）と成分（Ｃ）の配合割合は、成分（Ａ’）が９９．９〜６０重量％であり、成分（Ｃ）が０．１〜４０重量％である。ただし、ここに記載した成分（Ａ’）の量と成分（Ｃ）の量は、共に、樹脂（Ｄ）の全量に対する量であり、両者の合計は１００重量％である。 In the second composite of the present invention, the mixing ratio of the component (A ′) to the component (C) in the resin (D) is 99.9 to 60% by weight for the component (A ′), and 0.1 to 40% by weight. However, the amount of the component (A ') and the amount of the component (C) described herein are both based on the total amount of the resin (D), and the total of both is 100% by weight.
繊維強化樹脂成形品の剛性や衝撃強度等の機械的強度、及び疲労特性の観点から、樹脂（Ｄ）中の成分（Ａ’）と成分（Ｃ）の配合割合は、好ましくは、成分（Ａ’）が９９．５〜７０重量％であり、成分（Ｃ）が０．５〜３０重量％であり、より好ましくは、成分（Ａ’）が９９〜８０重量％であり、成分（Ｃ）が１〜２０重量％である。 From the viewpoints of mechanical strength such as rigidity and impact strength of the fiber-reinforced resin molded product and fatigue characteristics, the mixing ratio of the component (A ′) to the component (C) in the resin (D) is preferably the component (A). ') Is 99.5 to 70% by weight, component (C) is 0.5 to 30% by weight, more preferably component (A') is 99 to 80% by weight, and component (C) Is 1 to 20% by weight.
第二複合体における、成分（Ｂ）の含有量は、繊維強化樹脂成形品の剛性や衝撃強度等の機械的強度や、繊維−樹脂複合体の製造及び成形のしやすさの観点から、樹脂（Ｄ）１００重量部に対して、５〜４００重量部であり、好ましくは、１０〜３００重量部である。 The content of the component (B) in the second composite is determined from the viewpoint of the mechanical strength such as the rigidity and impact strength of the fiber-reinforced resin molded product, and the ease of production and molding of the fiber-resin composite. (D) The amount is 5 to 400 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight.
本発明の第一及び第二の複合体は、プロピレンを単独重合した後にエチレン−プロピレン共重合部を重合して得られるプロピレンブロック共重合体等のオレフィンを単独重合した後に少なくとも２種のオレフィンの共重合部を重合して得られるブロック共重合体や他のポリオレフィン樹脂など、１種以上の樹脂を含有してもよい。また、造核剤や結晶化促進剤を含有してもよい。 The first and second composites of the present invention are obtained by homopolymerizing propylene and then homopolymerizing an olefin such as a propylene block copolymer obtained by polymerizing an ethylene-propylene copolymer part. It may contain one or more resins such as a block copolymer obtained by polymerizing a copolymer part and other polyolefin resins. Further, a nucleating agent and a crystallization accelerator may be contained.
また、ポリオレフィン樹脂に一般的に添加される添加剤、例えば、酸化防止剤、耐熱安定剤、中和剤、紫外線吸収剤等の安定剤、気泡防止剤、難燃剤、難燃助剤、分散剤、帯電防止剤、滑剤、シリカ等のアンチブロッキング剤、染料や顔料等の着色剤、可塑剤等を含有しても良い。 In addition, additives generally added to polyolefin resins, for example, stabilizers such as antioxidants, heat stabilizers, neutralizers, and ultraviolet absorbers, air bubble inhibitors, flame retardants, flame retardant assistants, and dispersants. , An antistatic agent, a lubricant, an antiblocking agent such as silica, a coloring agent such as a dye or a pigment, and a plasticizer.
また、ガラスフレーク、マイカ、ガラス粉、ガラスビーズ、タルク、クレー、アルミナ、カーボンブラック、ウォルスナイト等の板状や粉粒状の無機化合物や、ウィスカー等を配合してもよい。 Further, plate-like or powder-like inorganic compounds such as glass flakes, mica, glass powder, glass beads, talc, clay, alumina, carbon black, and wolsnite, or whiskers may be blended.
本発明の繊維−ポリプロピレン樹脂複合体の製造方法としては、プルトルージョン法を好ましく適用することができる。プルトルージョン法は、基本的には、連続した繊維束を引きながら樹脂を含浸させる方法であり、例えば、
（１）樹脂のエマルジョン、サスペンジョンあるいは溶液を入れた含浸槽の中に繊維束を通し、繊維束に樹脂を含浸させる方法、
（２）樹脂の粉末を繊維束に吹き付け、または、粉末を入れた槽の中に繊維束を通して繊維束に樹脂を付着させたのち、付着した樹脂を溶融して繊維束に含浸させる方法、
（３）クロスヘッドの中に繊維束を通しながら、押出機等から前記クロスヘッドに樹脂を供給し繊維束に含浸させる方法
等が挙げられ、好ましくは、上記（３）のクロスヘッドを用いる方法であり、特に好ましくは、特開平３−２７２８３０号公報等に記載されている型のクロスヘッドを用いる方法である。
As a method for producing the fiber-polypropylene resin composite of the present invention, a pultrusion method can be preferably applied. The pultrusion method is basically a method of impregnating a resin while pulling a continuous fiber bundle.
(1) A method in which a fiber bundle is passed through an impregnation tank containing a resin emulsion, suspension or solution, and the fiber bundle is impregnated with the resin.
(2) a method in which a resin powder is sprayed on the fiber bundle, or the resin is attached to the fiber bundle by passing the fiber bundle into a tank containing the powder, and then the attached resin is melted to impregnate the fiber bundle;
(3) A method in which a resin is supplied to the crosshead from an extruder or the like while the fiber bundle is passed through the crosshead and the fiber bundle is impregnated, and the method using the crosshead of (3) above is preferable. Particularly preferred is a method using a crosshead of the type described in JP-A-3-272830 and the like.
また、上記のプルトルージョン法において、繊維束への樹脂の含浸操作は１段で行なってもよく、２段以上に分けて行ってもよい。 In the above-described pultrusion method, the operation of impregnating the fiber bundle with the resin may be performed in one stage, or may be performed in two or more stages.
本発明の繊維−ポリプロピレン樹脂複合体の形態としては、例えば、ストランド、シート、平板、およびこれらを２〜１００ｍｍの範囲内の長さに裁断してなるペレットが挙げられる。繊維−ポリプロピレン樹脂複合体からなるペレットにおいて、成分（Ｂ）の個々の繊維は、互いに平行に配列していることが好ましい。射出成形へ適用の容易さの観点から好ましくは、長さ２〜５０ｍｍのペレットである。特に、成分（Ｂ）の個々の繊維が互いに平行に配列しており、繊維の配向おける複合体の長さと繊維の長さとが等しく２〜５０ｍｍの範囲にある形態が好ましい。 Examples of the form of the fiber-polypropylene resin composite of the present invention include strands, sheets, flat plates, and pellets obtained by cutting these into lengths in the range of 2 to 100 mm. In the pellet made of the fiber-polypropylene resin composite, the individual fibers of the component (B) are preferably arranged parallel to each other. Pellets having a length of 2 to 50 mm are preferable from the viewpoint of ease of application to injection molding. In particular, it is preferable that the individual fibers of the component (B) are arranged in parallel with each other, and the length of the composite and the length of the fibers in the fiber orientation are equal and in the range of 2 to 50 mm.
本発明の繊維−ポリプロピレン樹脂複合体またはそのペレットは、その溶融混練と、得られた溶融混練物の所望の形状への賦形を経て、繊維強化樹脂成形品に加工することができる。本発明の繊維強化樹脂成形品において、成分（Ｂ）に由来する繊維の重量平均繊維長は１ｍｍ以上であり、好ましくは１ｍｍ以上１００ｍｍ以下である。溶融混練物の賦形方法は特に限定されず、例えば射出成形法を適用することができる。重量平均繊維長が１ｍｍ以上である繊維を含有していることにより、本発明の繊維強化樹脂成形品は機械的強度に優れる。本発明の繊維−ポリプロピレン樹脂複合体、またはそのペレットから繊維強化樹脂成形品を製造する際の溶融混練条件および成形条件は、当業者の通常の知識に基づいて決定することができる。成形品中の繊維の重量平均繊維長は、特開２００２−５９２４号公報に記載されている方法によって測定することができる。なお、繊維−ポリプロピレン樹脂複合体またはそのペレットを用いて繊維強化樹脂成形品を製造する際の溶融混練時に、追加的な樹脂材料や添加剤を前記複合体やそのペレットに配合してもよい。 The fiber-polypropylene resin composite or the pellet thereof of the present invention can be processed into a fiber-reinforced resin molded product through melt-kneading and shaping the obtained melt-kneaded product into a desired shape. In the fiber-reinforced resin molded article of the present invention, the weight average fiber length of the fiber derived from the component (B) is 1 mm or more, preferably 1 mm or more and 100 mm or less. The method for shaping the melt-kneaded product is not particularly limited, and for example, an injection molding method can be applied. By containing fibers having a weight average fiber length of 1 mm or more, the fiber-reinforced resin molded article of the present invention has excellent mechanical strength. Melt kneading conditions and molding conditions for producing a fiber-reinforced resin molded product from the fiber-polypropylene resin composite of the present invention or pellets thereof can be determined based on ordinary knowledge of those skilled in the art. The weight average fiber length of the fibers in the molded article can be measured by the method described in JP-A-2002-5924. In addition, at the time of melt-kneading when producing a fiber-reinforced resin molded product using a fiber-polypropylene resin composite or a pellet thereof, an additional resin material or additive may be added to the composite or a pellet thereof.
以下、実施例および比較例によって本発明を説明するが、本発明はこれらの実施例に限定されるものではない。
実施例または比較例で用いた評価用サンプルの製造方法を以下に示した。
（１）長繊維含有樹脂ペレットの製造方法
特開平３−１２１１４６号公報に記載されている方法に従って、含浸温度２７０℃、引取速度１３ｍ／分で長繊維含有樹脂ペレットを製造した。なお、用いたガラス繊維の繊維径は１６μｍであった。
Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The method for producing the evaluation sample used in the examples or comparative examples is shown below.
(1) Production method of long fiber-containing resin pellets According to the method described in JP-A-3-121146, long fiber-containing resin pellets were produced at an impregnation temperature of 270 ° C and a take-up speed of 13 m / min. The glass fiber used had a fiber diameter of 16 μm.
（２）評価用サンプルの製造方法
上記（１）で得られた長繊維含有樹脂ペレットを用い、下記の成形機により下記の条件で射出成形して、評価用サンプルを製造した。
成形機（日本製鋼所製）
型締力 ：１５０ｔ
スクリュー ：深溝スクリュー
スクリュー径 ：４６ｍｍ
スクリューＬ／Ｄ：２０．３
成形条件
シリンダー温度：２５０℃
金型温度 ：５０℃
背圧 ：０ＭＰａ
(2) Production method of evaluation sample Using the long fiber-containing resin pellet obtained in the above (1), injection molding was performed by the following molding machine under the following conditions to produce an evaluation sample.
Molding machine (made by Japan Steel Works)
Mold clamping force: 150t
Screw: Deep groove screw Screw diameter: 46mm
Screw L / D: 20.3
Molding conditions Cylinder temperature: 250 ° C
Mold temperature: 50 ° C
Back pressure: 0MPa
実施例および比較例における評価方法を以下に示す。
（１）曲げ強度（単位：ＭＰａ）
曲げ強度は、Ａ．Ｓ．Ｔ．Ｍ Ｄ７９０に従って、下記条件で測定した。
Evaluation methods in Examples and Comparative Examples are shown below.
(1) Flexural strength (unit: MPa)
The bending strength is as follows: S. T. It was measured under the following conditions according to MD790.
測定温度 ：２３℃
サンプル厚み：６．４ｍｍ
スパン ：１００ｍｍ
引張速度 ：２ｍｍ／分
Measurement temperature: 23 ° C
Sample thickness: 6.4 mm
Span: 100mm
Tensile speed: 2 mm / min
（２）引張強度（単位：ＭＰａ）
引張強度は、Ａ．Ｓ．Ｔ．Ｍ Ｄ６３８に従って、下記条件で測定した。
測定温度 ：２３℃
サンプル厚み：３．２ｍｍ
引張速度 ：１０ｍｍ／分
(2) Tensile strength (unit: MPa)
The tensile strength is as follows: S. T. It was measured under the following conditions according to MD638.
Measurement temperature: 23 ° C
Sample thickness: 3.2mm
Tensile speed: 10 mm / min
（３）ＩＺＯＤ衝撃強度（単位：ＫＪ／ｍ2）
ＩＺＯＤ衝撃強度は、Ａ．Ｓ．Ｔ．Ｍ Ｄ２５６に従って、下記条件で測定した。
測定温度 ：２３℃
サンプル厚み：６．４ｍｍ［Ｖノッチあり］
(3) IZOD impact strength (unit: KJ / m 2 )
The IZOD impact strength was measured according to A.I. S. T. It was measured under the following conditions according to MD256.
Measurement temperature: 23 ° C
Sample thickness: 6.4 mm [with V notch]
（４）重合コモノマー単位の含有量（単位：重量％）
樹脂に含まれる重合コモノマー単位の含有量は、“新版 高分子ハンドブック”（日本化学会、高分子分析研究懇談会編 紀伊国屋書店（１９９５））に記載された方法に従って、ＩＲ法によって求めた。
(4) Content of polymerized comonomer unit (unit: wt%)
The content of the polymerized comonomer units contained in the resin was determined by the IR method according to the method described in “New Edition Polymer Handbook” (edited by The Chemical Society of Japan, Polymer Analysis Research Council, Kinokuniya Bookstore (1995)).
（５）引張クリープ測定での破断時間（単位：時間）
引張クリープ測定での破断時間は、下記条件によって測定した。測定には、図１に示した形状のサンプルを用いた。
測定器 ： ボールドウイン株式会社製 クリープ試験機 型式ＣＰ−６Ｐ−１００
温度 ： ８０℃
サンプル厚み ： ２．５ｍｍ
負荷応力 ： ４７ＭＰａ
チャック間距離 ： １００ｍｍ
(5) Breaking time in tensile creep measurement (unit: hours)
The breaking time in the tensile creep measurement was measured under the following conditions. For the measurement, a sample having the shape shown in FIG. 1 was used.
Measuring instrument: Boldwin Co., Ltd. Creep tester Model CP-6P-100
Temperature: 80 ° C
Sample thickness: 2.5mm
Load stress: 47MPa
Distance between chucks: 100mm
実施例１
プロピレン系樹脂、繊維及び変性ポリオレフィン樹脂を用い、特開平３−１２１１４６号公報に記載されている方法により、表１に記載した組成で、繊維含有樹脂ペレットを作成した。ペレット中の繊維の含有量は４０重量％であり、ペレット長は９ｍｍであった。得られたペレットを射出成形して、図１に示すような物性測定用のサンプルを得た。得られたサンプルの引張強度、曲げ強度、ＩＺＯＤ衝撃強度、引張クリープ測定での破断時間を表１に示す。
なお、用いたプロピレン系樹脂は、プロピレン−エチレンランダム共重合体（エチレン含量＝１．０重量%、ＭＦＲ＝２５ｇ／１０分）であった。一方、用いた変性ポリオレフィン樹脂は、無水マレイン酸変性ポリプロピレン樹脂（ＭＦＲ＝６０ｇ／１０分、無水マレイン酸グラフト量＝０．６重量％）であり、これは、エチレン−プロピレンブロック共重合体（極限粘度［η］＝２．８（ｄｌ／ｇ）、エチレン−プロピレン共重合体含量＝２１重量％）１００重量部に、無水マレイン酸１．０重量部、ジセチル パーオキシジカルボネート０．５０重量部、１，３−ビス（ｔ−ブチルパーオキシジイソプロピル）ベンゼン０．１５重量部、ステアリン酸カルシウム０．０５重量部、酸化防止剤テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン０．３重量部を添加してヘンシェルミキサーで十分に予備混合し、得られた混合物を単軸押出機に供給して混練を行うことにより調製した。押出機は、いすず加工機製単軸押出機 ＥＸＴ−９０（Ｌ／Ｄ＝３６，シリンダー径＝９０ｍｍ）であった。押出機のシリンダーは上流側半分を１８０℃に、下流側半分を２５０℃に設定し、スクリュー回転数は１３３ｒｐｍであった。
Example 1
Using propylene resin, fiber and modified polyolefin resin, fiber-containing resin pellets were prepared by the method described in JP-A-3-121146 with the composition shown in Table 1. The fiber content in the pellet was 40% by weight, and the pellet length was 9 mm. The obtained pellet was injection-molded to obtain a sample for measuring physical properties as shown in FIG. Table 1 shows the tensile strength, bending strength, IZOD impact strength, and rupture time in tensile creep measurement of the obtained sample.
The propylene resin used was a propylene-ethylene random copolymer (ethylene content = 1.0% by weight, MFR = 25 g / 10 minutes). On the other hand, the modified polyolefin resin used was a maleic anhydride-modified polypropylene resin (MFR = 60 g / 10 min, maleic anhydride graft amount = 0.6% by weight), which was an ethylene-propylene block copolymer (extremely limited). (Viscosity [η] = 2.8 (dl / g), ethylene-propylene copolymer content = 21% by weight), 100 parts by weight, 1.0 part by weight of maleic anhydride, 0.50 part by weight of dicetyl peroxydicarbonate 0.15 parts by weight of 1,3-bis (t-butylperoxydiisopropyl) benzene, 0.05 parts by weight of calcium stearate, tetrakis [methylene-3- (3,5-di-t-butyl-4) antioxidant -Hydroxyphenyl) propionate] methane (0.3 parts by weight) and sufficiently premixed with a Henschel mixer. It was prepared by carrying out the kneading and fed into the extruder. The extruder was a single screw extruder EXT-90 (L / D = 36, cylinder diameter = 90 mm) manufactured by Isuzu Machine. The cylinder of the extruder was set at 180 ° C. on the upstream half and 250 ° C. on the downstream half, and the screw rotation speed was 133 rpm.
比較例１
実施例１において用いたプロピレン系樹脂を、プロピレン−エチレンランダム共重合体（エチレン含量＝４．０重量%、ＭＦＲ＝２５ｇ／１０分）に変更した以外は、実施例１と同様にして繊維含有樹脂ペレットの調製、射出成形、及び物性の評価を行った。
Comparative Example 1
Except that the propylene-based resin used in Example 1 was changed to a propylene-ethylene random copolymer (ethylene content = 4.0% by weight, MFR = 25 g / 10 min), the fiber content was changed in the same manner as in Example 1. Preparation of resin pellets, injection molding, and evaluation of physical properties were performed.
比較例２
実施例１において用いたプロピレン系樹脂を、プロピレン単独重合体（エチレン含量＝０重量％、ＭＦＲ＝２５ｇ／１０分）に変更した以外は、実施例１と同様にして繊維含有樹脂ペレットの調製、射出成形、及び物性の評価を行った。
Comparative Example 2
Preparation of fiber-containing resin pellets in the same manner as in Example 1 except that the propylene resin used in Example 1 was changed to a propylene homopolymer (ethylene content = 0% by weight, MFR = 25 g / 10 minutes), Injection molding and evaluation of physical properties were performed.
ａ−２：プロピレン−エチレンランダム共重合体（エチレン含量＝４．０重量％、ＭＦＲ＝２５ｇ／１０分）
ａ−３：プロピレン単独重合体（エチレン含量＝０重量％、ＭＦＲ＝２５ｇ／１０分）
ｂ−１：ガラス繊維(繊維径１６μｍ)
ｃ−１：無水マレイン酸変性ポリプロピレン樹脂（ＭＦＲ＝６０ｇ／１０分、無水マレイン酸グラフト量＝０．６重量％）
a-2: Propylene-ethylene random copolymer (ethylene content = 4.0% by weight, MFR = 25 g / 10 min)
a-3: propylene homopolymer (ethylene content = 0% by weight, MFR = 25 g / 10 min)
b-1: glass fiber (fiber diameter 16 μm)
c-1: Maleic anhydride-modified polypropylene resin (MFR = 60 g / 10 min, maleic anhydride graft amount = 0.6% by weight)
本発明の要件を満足する実施例１の製品は、クリープ特性に優れている（引張クリ−プ測定での破断時間が充分に長い）。
これに対して、ポリプロピレン系樹脂のエチレン含量が本発明に定める要件を満足しない比較例１および２の製品は、クリープ特性が不充分である（引張クリ−プ測定での破断時間が短い）。
The product of Example 1, which satisfies the requirements of the present invention, has excellent creep properties (sufficiently long rupture time in tensile creep measurement).
On the other hand, the products of Comparative Examples 1 and 2 in which the ethylene content of the polypropylene resin does not satisfy the requirements defined in the present invention have insufficient creep properties (short break time in tensile creep measurement).
Claims (4)
成分（Ａ）：プロピレンとエチレン及びα−オレフィンからなる群から選ばれる少なくとも１種の単量体とを共重合して得られるプロピレン系ランダム共重合体である成分（Ａ−１）を含有し、前記前記エチレン及びα−オレフィンからなる群に属する単量体に由来する重合単量体単位の含有量が０．１〜３重量％のプロピレン系樹脂、または該プロピレン系樹脂を不飽和カルボン酸またはその誘導体で変性して得られる変性プロピレン系樹脂（ただし、前記重合単量体単位の前記含有量は、当該プロピレン系樹脂に含有される全重合単量体単位の量に対する量である）。 A fiber-polypropylene resin composite (herein, component (A)) containing 20 to 95% by weight of a component (A) defined below and 80 to 5% by weight of a component (B) having a weight average fiber length of 2 to 100 mm. (Amounts of (A) and (B) are both relative to the total amount of (A) and (B).)
Component (A): Component (A-1) which is a propylene-based random copolymer obtained by copolymerizing propylene with at least one monomer selected from the group consisting of ethylene and α-olefin. A propylene-based resin containing 0.1 to 3% by weight of a polymerized monomer unit derived from a monomer belonging to the group consisting of the ethylene and the α-olefin, or an unsaturated carboxylic acid Or a modified propylene-based resin obtained by modification with a derivative thereof (provided that the content of the polymerized monomer unit is based on the total amount of the polymerized monomer units contained in the propylene-based resin).
樹脂（Ｄ）：下に定義する成分（Ａ’）６０〜９９．９重量％と、成分（Ｃ）である変性ポリオレフィン樹脂０．１〜４０重量％とからなる樹脂（ここで、成分（Ａ’）の量と成分（Ｃ）の量は共に、当該樹脂の全量に対する量であり、両者の合計は１００重量％である）。
成分（Ａ’）：プロピレンとエチレン及びα−オレフィンからなる群から選ばれる少なくとも１種の単量体とを共重合して得られるプロピレン系ランダム共重合体である成分（Ａ−１）を含有し、前記エチレン及びα−オレフィンからなる群に属する単量体に由来する重合単量体単位の含有量が０．１〜３重量％のプロピレン系樹脂（ただし、前記重合単量体単位の前記含有量は、当該プロピレン系樹脂に含有される全重合単量体単位の量に対する量である）。 Fiber-polypropylene containing resin (D) as defined below, and component (B) having a weight average fiber length of 2 to 100 mm, based on 100 parts by weight of the resin (D). Resin composite.
Resin (D): a resin composed of 60 to 99.9% by weight of component (A ′) defined below and 0.1 to 40% by weight of modified polyolefin resin as component (C) (here, component (A) Both the amount of ') and the amount of component (C) are relative to the total amount of the resin, the sum of both being 100% by weight).
Component (A ′): contains component (A-1), which is a propylene-based random copolymer obtained by copolymerizing propylene with at least one monomer selected from the group consisting of ethylene and α-olefin. A propylene-based resin having a content of polymerized monomer units derived from monomers belonging to the group consisting of ethylene and α-olefin of 0.1 to 3% by weight (provided that The content is the amount based on the total amount of the polymerized monomer units contained in the propylene-based resin).
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| JP2006124534A (en) * | 2004-10-29 | 2006-05-18 | Sumitomo Chemical Co Ltd | Glass fiber-reinforced polypropylene resin pellet and vehicle front end structure and tank disposed in vehicle engine room obtained therefrom |
| JP2019536856A (en) * | 2016-11-23 | 2019-12-19 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | Filled polyolefin composition |
| CN112654674A (en) * | 2018-10-03 | 2021-04-13 | 古河电气工业株式会社 | Resin molded body and resin composition |
| CN112752639A (en) * | 2018-12-05 | 2021-05-04 | 古河电气工业株式会社 | Cellulose fiber-dispersed resin composite material, molded article, and composite member |
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| JP2006124534A (en) * | 2004-10-29 | 2006-05-18 | Sumitomo Chemical Co Ltd | Glass fiber-reinforced polypropylene resin pellet and vehicle front end structure and tank disposed in vehicle engine room obtained therefrom |
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| CN112752639B (en) * | 2018-12-05 | 2023-03-17 | 古河电气工业株式会社 | Cellulose fiber-dispersed resin composite material, molded article, and composite member |
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