JP5211658B2 - Composition for automotive interior parts - Google Patents
Composition for automotive interior parts Download PDFInfo
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- JP5211658B2 JP5211658B2 JP2007308590A JP2007308590A JP5211658B2 JP 5211658 B2 JP5211658 B2 JP 5211658B2 JP 2007308590 A JP2007308590 A JP 2007308590A JP 2007308590 A JP2007308590 A JP 2007308590A JP 5211658 B2 JP5211658 B2 JP 5211658B2
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- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、自動車内装部品用組成物に関し、詳しくは、有機長繊維により強化されたプロピレン系樹脂組成物から成るインストルメントパネル・コンソールボックス・ピラー・トリム等の自動車内装部品用組成物に関する。 TECHNICAL FIELD The present invention relates to a composition for automobile interior parts, and more particularly to a composition for automobile interior parts such as instrument panels, console boxes, pillars, trims, and the like made of a propylene-based resin composition reinforced with organic long fibers.
従来、自動車のインストルメントパネル及び安全対応内装材の構造材料として、プロピレン系樹脂にゴム成分とタルクを配合し、前者で耐衝撃性を、後者で剛性を付与することが行われている。この方法によれば原料が比較的安価なため製造される製品も安価であること、常温使用条件において延性破壊し得ること、平滑な成形品外観が得られること、等の利点がある(特許文献1〜6)。 2. Description of the Related Art Conventionally, as a structural material for automobile instrument panels and safety-compliant interior materials, a rubber component and talc are blended in a propylene resin, and the former provides impact resistance and the latter imparts rigidity. According to this method, since the raw material is relatively inexpensive, there are advantages such as that the manufactured product is also inexpensive, can be ductile fractured under normal temperature use conditions, and can obtain a smooth molded product appearance. 1-6).
しかしながら、通常、零下の低温使用条件において脆性破壊が起こること、ゴム成分の組成比が多量になることにより剛性などの物性バランスを取ることが困難であること、経時変化としてゴム成分や相溶化成分などが劣化したり分離したりすること、等の問題がある。 However, usually, brittle fracture occurs under low temperature usage conditions below zero, it is difficult to balance physical properties such as rigidity due to a large composition ratio of rubber components, and rubber components and compatibilizing components as time-dependent changes There are problems such as deterioration or separation.
そこで、低温使用条件でも延性破壊し得るように改良するため、ゴム成分を更に大量に配合する試みが多数なされているが、ゴム成分はマトリクス樹脂に比べて高価であり製造される製品の価格も高価になってしまうこと、耐熱剛性などの物性バランスを補うため更に大量にタルク等を加えることにより成形加工時の流動性が著しく低下すること、比重が重くなること、製品の肉厚化やリブ増強が必要になったり金属部品で裏から補強が必要になったりして設計が非常に煩雑になること、等の問題が引き起こされる。 Therefore, many attempts have been made to add a larger amount of the rubber component in order to improve the ductile fracture under low temperature use conditions, but the rubber component is more expensive than the matrix resin and the price of the manufactured product is also high. Addition of a large amount of talc, etc. to compensate for the balance of physical properties such as heat resistance and rigidity, resulting in significantly reduced fluidity during molding, increased specific gravity, increased product thickness and ribs Problems such as the need for reinforcement or the need for reinforcement from the back with metal parts make the design very complicated.
一方、耐熱剛性を特に向上させるため、プロピレン系樹脂に、タルク、マイカ、ガラスフレーク、ガラス繊維などを配合することも提案されている(特許文献7)。しかしなから、この場合は、剛直なガラス繊維が成形時に配向するため樹脂の収縮に異方性が生じ、成形品に反りや変形が生じる。 On the other hand, in order to particularly improve the heat-resistant rigidity, it has also been proposed to blend propyl, mica, glass flakes, glass fibers and the like with a propylene resin (Patent Document 7). However, in this case, since the rigid glass fibers are oriented at the time of molding, anisotropy occurs in the shrinkage of the resin, and the molded product is warped or deformed.
本発明は、上記実情に鑑みなされたものであり、その目的は、繊維の分散がよく、外観に優れ、剛性や耐衝撃性などの機械的強度に優れ、更に、自動車内装材に要求される耐スクラッチ性が良く、反り変形が少なく、射出成形時の流動性が高い、自動車内装部品用組成物を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is good dispersion of fibers, excellent appearance, excellent mechanical strength such as rigidity and impact resistance, and further required for automobile interior materials. An object of the present invention is to provide a composition for automobile interior parts that has good scratch resistance, little warping deformation, and high fluidity during injection molding.
すなわち、本発明の要旨は、プロピレン系樹脂100重量部に対し有機長繊維10〜200重量部を含有して成り(但し、プロピレン系樹脂100重量部に対し10〜200重量部の割合でタルクを含有する場合を除く)、引き抜き成形法で得られた長繊維強化複合樹脂組成物であって、有機長繊維が表面に極性樹脂を付着させて成る有機長繊維であって極性樹脂の付着量が有機長繊維に対し0.01〜3.5重量%であることを特徴とする自動車内装部品用組成物に存する。 That is, the gist of the present invention comprises 10 to 200 parts by weight of organic long fibers with respect to 100 parts by weight of propylene resin (however, talc is added at a ratio of 10 to 200 parts by weight with respect to 100 parts by weight of propylene resin. except when containing), a fiber-reinforced composite resin composition obtained by the pultrusion method, the adhesion amount of the polar resin is an organic continuous fiber organic filaments are made by attaching the polar resin to the surface It exists in the composition for motor vehicle interior components characterized by being 0.01-3.5 weight% with respect to an organic long fiber .
プロピレン系樹脂に有機長繊維を含有させた本発明の自動車内装部品用組成物(以下「樹脂組性物」と略記する)は、長繊維が網目状に分散して補強していることと、繊維とマトリクス樹脂との界面接着を弱くさせていることにより、従来公知の樹脂組性物では成し得ない耐衝撃性、耐熱剛性などの機械特性のバランスを容易にとることが出来る。 The composition for automobile interior parts of the present invention containing organic long fibers in a propylene-based resin (hereinafter abbreviated as “resin composition”) has long fibers dispersed and reinforced, and By weakening the interfacial adhesion between the fiber and the matrix resin, it is possible to easily balance mechanical properties such as impact resistance and heat-resistant rigidity that cannot be achieved by a conventionally known resin composition.
更に、本発明の樹脂組成物は、耐熱剛性、耐衝撃性、機械的強度を所望の性能で得るために、多量のゴム成分、タルク、ガラス成分などを配合する必要が無いため、自動車内装材に要求される耐スクラッチ性がよいこと、反り変形が少ないこと、射出成形時の流動性が高いことといった、自動車内装材に要求される性能を満たすことが出来る。しかも、本発明の樹脂組成物によれば、成形品に衝撃が加わって破壊が起きた際に、破壊点が脆性破壊にならず、かつシャープエッジにもならないため、製品近傍に人体があっても切傷などの二次被害を引き起こすこともない。 Furthermore, since the resin composition of the present invention does not need to contain a large amount of rubber component, talc, glass component, etc. in order to obtain heat-resistant rigidity, impact resistance, and mechanical strength with desired performance, it is an automobile interior material. Therefore, it is possible to satisfy the performance required for automobile interior materials, such as good scratch resistance, low warpage deformation, and high fluidity during injection molding. Moreover, according to the resin composition of the present invention, when the impact is applied to the molded product and the fracture occurs, the fracture point does not become brittle fracture and does not become a sharp edge. There is no secondary damage such as cuts.
本発明で使用するプロピレン系樹脂は、特に制限されず、例えば、プロピレンの単独重合体、プロピレンを主成分とした、エチレン、1−ブテン等の他のα−オレフィンの1種または2種以上との共重合体などが挙げられる。共重合体は、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。なお、上記の「主成分」とは、プロピレン系樹脂中に50重量%以上、好ましくは60重量%以上含まれるものを指す。 The propylene-based resin used in the present invention is not particularly limited. For example, a propylene homopolymer, one or more of other α-olefins such as ethylene and 1-butene having propylene as a main component, and And the like. The copolymer may be a random copolymer or a block copolymer. In addition, said "main component" refers to what is contained in a propylene-type resin 50weight% or more, Preferably it is 60weight% or more.
プロピレン系樹脂の重合様式は、樹脂状物が得られる限り、如何なる重合様式を採用しても差し支えないが、気相法、溶液法であるものが特に好ましい。 As a polymerization mode of the propylene-based resin, any polymerization mode may be adopted as long as a resinous material can be obtained, but a gas phase method or a solution method is particularly preferable.
プロピレン系樹脂のメルトフローレート(JIS K7210に準拠し、温度230℃、荷重21.18Nで測定した値)は、通常0.05〜200g/10分、好ましくは0.1〜100g/10分である。メルトフローレートが0.05g/10分未満の場合は、成形加工性が低下し、得られる成形品の表面外観が不良になり易い傾向にあり、200g/10分を超える場合は、成形品の機械的強度と有機長繊維の分散が不良になり易い傾向にある。 The melt flow rate of propylene resin (based on JIS K7210, measured at a temperature of 230 ° C. and a load of 21.18 N) is usually 0.05 to 200 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes. is there. When the melt flow rate is less than 0.05 g / 10 minutes, the moldability tends to be deteriorated, and the surface appearance of the resulting molded product tends to be poor, and when it exceeds 200 g / 10 minutes, Mechanical strength and dispersion of organic long fibers tend to be poor.
本発明の樹脂組成物において、プロピレン系樹脂は2種以上を併用してもよく、更に、本発明の効果を損なわない範囲で、熱可塑性樹脂、ゴム、充填材、添加剤など従来公知の成分を配合させることが出来る。 In the resin composition of the present invention, two or more types of propylene-based resins may be used in combination, and further, conventionally known components such as thermoplastic resins, rubbers, fillers, additives and the like within the range not impairing the effects of the present invention. Can be blended.
本発明で使用する有機長繊維は、その表面に極性樹脂を付着させておくことが出来る。ここで、極性樹脂とは、非極性であるプロピレン系樹脂より極性の高い樹脂を指す。斯かる極性樹脂としては、例えば、不飽和ポリエステル、ビニルエステル樹脂、エポキシ樹脂(エポキシ化合物を含む)、フェノール(レゾール型)樹脂、ユリア・メラミン樹脂、ポリイミド、ウレタン樹脂、これらの共重合体、変性体などの熱硬化性樹脂が挙げられる。また、飽和ポリエステル、ポリアミド、アクリル系樹脂、これらの共重合体、変性体などの熱可塑性樹脂も挙げられる。極性樹脂としては、特に、取扱・加工性や力学特性の観点から、熱硬化性樹脂のエポキシ樹脂またはウレタン樹脂が好ましく、特にエポキシ樹脂が好ましい。エポキシ樹脂の具体例としては、次の化合物が挙げられる。 The organic long fiber used in the present invention can have a polar resin attached to its surface. Here, the polar resin refers to a resin having a higher polarity than a non-polar propylene resin. Examples of such polar resins include unsaturated polyesters, vinyl ester resins, epoxy resins (including epoxy compounds), phenol (resole type) resins, urea / melamine resins, polyimides, urethane resins, copolymers thereof, and modified And thermosetting resins such as body. Moreover, thermoplastic resins, such as saturated polyester, polyamide, acrylic resin, these copolymers, and a modified body, are also mentioned. As the polar resin, a thermosetting resin epoxy resin or urethane resin is particularly preferable from the viewpoint of handling / workability and mechanical properties, and an epoxy resin is particularly preferable. Specific examples of the epoxy resin include the following compounds.
すなわち、ジグリシジルエーテル化合物では、エチレングリコールジグリシジルエーテル及びポリエチレングリコールジグリシジルエーテル類、プロピレングリコールジグリシジルエーテル及びポリプロピレングリコールジグリシジルエーテル類、1,4−ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル類などが挙げられる。また、ポリグリシジルエーテル化合物では、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル類、ソルビトールポリグリシジルエーテル類、アラビトールポリグリシジルエーテル類、トリメチロールプロパンポリグリシジルエーテル類、ペンタエリスリトールポリグリシジルエーテル類、脂肪族多価アルコールのポリグリシジルエーテル類などが挙げられる。好ましくは、反応性の高いグリシジル基を有する脂肪族のポリグリシジルエーテル化合物である。更に好ましくは、ポリエチレングリコールジグリシジルエーテル類、ポリプロピレングリコールジグリシジルエーテル類、アルカンジオールジグリシジルエーテル類である。 That is, in the diglycidyl ether compound, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether , Polytetramethylene glycol diglycidyl ether, polyalkylene glycol diglycidyl ether, and the like. Polyglycidyl ether compounds include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ethers, arabitol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, pentaerythritol poly Examples thereof include glycidyl ethers and polyglycidyl ethers of aliphatic polyhydric alcohols. Preferably, it is an aliphatic polyglycidyl ether compound having a highly reactive glycidyl group. More preferred are polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, and alkanediol diglycidyl ethers.
ところで、本発明において、前記のプロピレン系樹脂としては、例えば、無水マレイン酸で変性された酸変性プロピレン系樹脂樹脂などは除くのが好ましい。また、後述する有機長繊維においても酸変性オレフィン系樹脂で表面処理されたものを除くのが好ましい。更に、有機長繊維に付着させる上記の極性樹脂としても酸変性オレフィン系樹脂は除くのが好ましい。斯かる条件を満足することにより、マトリクス樹脂であるプロピレン系樹脂と有機長繊維との界面強度を一層弱くすることが出来、引張破断伸びや耐衝撃性を一層高めることが出来る。 By the way, in the present invention, as the propylene-based resin, for example, an acid-modified propylene-based resin resin modified with maleic anhydride is preferably excluded. Moreover, it is preferable to remove the organic long fiber described later from the surface treated with the acid-modified olefin resin. Furthermore, it is preferable to exclude the acid-modified olefin resin as the polar resin to be attached to the organic long fiber. By satisfying such conditions, the interface strength between the propylene-based resin as the matrix resin and the organic long fiber can be further reduced, and the tensile breaking elongation and impact resistance can be further enhanced.
上記の酸変性オレフィン系樹脂としては、(A)オレフィンの単独重合体または2種以上のオレフィンの共重合体、例えば、ポリオレフィンに不飽和カルボン酸またはその誘導体をグラフト重合したもの、(B)ポリオレフィンの重合原料モノマーである1種または2種以上のオレフィンと1種または2種以上の不飽和カルボン酸またはその誘導体を共重合したもの、(C)上記(B)で得られたものに更に不飽和カルボン酸またはその誘導体をグラフト重合したもの等が挙げられる。 Examples of the acid-modified olefin resin include (A) an olefin homopolymer or a copolymer of two or more olefins, for example, a polyolefin obtained by graft polymerization of an unsaturated carboxylic acid or a derivative thereof, and (B) a polyolefin. A copolymer of one or more olefins and one or two or more unsaturated carboxylic acids or derivatives thereof, which is a polymerization raw material monomer of (C), and (C) those obtained in (B) above. Examples include those obtained by graft polymerization of saturated carboxylic acids or derivatives thereof.
有機長繊維としては、例えば、ポリエステル系繊維、ポリアミド系繊維、ポリウレタン系繊維、ポリアクリロニトリル系繊維、ケナフ、セルロース系繊維などが挙げられる。これらの有機長繊維は2種以上を併用してもよい。これらの中では、取扱・加工性や力学特性の観点から、ポリエステル系繊維またはポリアミド系繊維が好ましく、特に、ポリエチレンテレフタレート(PET)繊維(融点260℃、ガラス転移温度67℃)、ポリエチレンナフタレート(PEN)繊維(融点272℃、ガラス転移温度113℃)が好ましい。ポリエステル系繊維は、射出成形品中の分散が良く、繊維としての物性も高いため、良好な機械物性の射出成形品が得られる。 Examples of the organic long fibers include polyester fibers, polyamide fibers, polyurethane fibers, polyacrylonitrile fibers, kenaf, and cellulose fibers. These organic long fibers may be used in combination of two or more. Among these, polyester fiber or polyamide fiber is preferable from the viewpoint of handling / workability and mechanical properties, and in particular, polyethylene terephthalate (PET) fiber (melting point 260 ° C., glass transition temperature 67 ° C.), polyethylene naphthalate ( PEN) fibers (melting point 272 ° C., glass transition temperature 113 ° C.) are preferred. Since the polyester fiber is well dispersed in the injection molded product and has high physical properties as a fiber, an injection molded product having good mechanical properties can be obtained.
ところで、本発明の樹脂組成物を、射出成形によって成形する場合、プロピレン系樹脂の融点以上の温度で成形するため、有機長繊維としては射出成形の際に溶融しないものを使用するのが好ましい。すなわち、プロピレン系樹脂の融点は、通常70〜170℃、成形温度(成形機の出口温度とする)は通常150〜210℃の範囲から選択される。有機長繊維の融点は、成形温度より、通常10℃以上、好ましくは20℃以上高いことが好ましい。従って、有機長繊維の融点は通常200℃以上の範囲から選択される。 By the way, when the resin composition of the present invention is molded by injection molding, it is preferable to use organic long fibers that do not melt during the injection molding because they are molded at a temperature higher than the melting point of the propylene resin. That is, the melting point of the propylene-based resin is usually selected from the range of 70 to 170 ° C., and the molding temperature (the outlet temperature of the molding machine) is usually selected from the range of 150 to 210 ° C. The melting point of the organic long fiber is preferably higher than the molding temperature by usually 10 ° C. or more, preferably 20 ° C. or more. Therefore, the melting point of the organic long fiber is usually selected from a range of 200 ° C. or higher.
また、有機長繊維の繊維径が太すぎると成形品のアイゾット衝撃強度が低下する。一方、繊維径が細すぎても何ら問題はなく、ナノサイズの繊維まで使用可能と思われ、成形品の用途によっては良好な結果をもたらす。このように繊維径が広範に亘るため、有機長繊維の使用本数は一義的に規定できない。しかしながら、繊維の束の断面積で考えると、通常は、ペレットの繊維と略直行する方向の断面積中5〜60%程度を有機長繊維の断面積が占める程の本数が好ましい。有機長繊維の単糸繊度は、通常1〜20dtex、好ましくは2〜15dtexである。また、有機長繊維の総繊度は、通常150〜3,000dtex、好ましくは250〜2000dtexである。さらに、有機長繊維のフィラメント数は、通常10〜1,000フィラメント、好ましくは50〜500フィラメントである。 Moreover, if the fiber diameter of the organic long fiber is too large, the Izod impact strength of the molded product is lowered. On the other hand, there is no problem even if the fiber diameter is too thin, and it seems that nano-sized fibers can be used, and good results are obtained depending on the application of the molded product. Thus, since the fiber diameter covers a wide range, the number of organic long fibers used cannot be uniquely defined. However, considering the cross-sectional area of the bundle of fibers, the number of the organic long fibers is preferably about 5 to 60% of the cross-sectional area in the direction substantially perpendicular to the pellet fibers. The single yarn fineness of the organic long fiber is usually 1 to 20 dtex, preferably 2 to 15 dtex. The total fineness of the organic long fibers is usually 150 to 3,000 dtex, preferably 250 to 2000 dtex. Furthermore, the number of filaments of the organic long fiber is usually 10 to 1,000 filaments, preferably 50 to 500 filaments.
有機長繊維に極性樹脂を付着させる方法としては、(A)有機長繊維を製造する工程においてチーズ状に巻き取る前に、プロピレン系樹脂と相溶または反応しない、極性のある化合物を付与する方法、(B)有機長繊維を一旦巻取った後に、プロピレン系樹脂と相溶または反応しない、極性のある化合物を有機長繊維に含浸付与し熱処理する方法が挙げられる。 As a method of attaching a polar resin to an organic long fiber, (A) a method of providing a polar compound that is not compatible with or reacts with a propylene-based resin before being wound into a cheese shape in the step of producing the organic long fiber (B) A method of once winding an organic long fiber and then impregnating the organic long fiber with a polar compound that does not dissolve or react with the propylene-based resin and heat-treats the organic long fiber.
有機長繊維への極性樹脂の付着量は、通常0.01〜5重量%、好ましくは0.03〜3.5重量%である。極性樹脂の付着量が0.01重量%未満の場合は、有機長繊維とマトリクス樹脂の界面接着を弱くさせる効果が得にくく、また、成形中に繊維同士が絡み合うため、有機長繊維の分散が悪くなり、その結果、外観品位が低下する。一方、極性樹脂の付着量が5重量%を超える場合は、有機長繊維が硬くなりすぎるため、加工性が低下し、有機長繊維との複合化が困難になる。 The adhesion amount of the polar resin to the organic long fiber is usually 0.01 to 5% by weight, preferably 0.03 to 3.5% by weight. When the adhesion amount of the polar resin is less than 0.01% by weight, it is difficult to obtain the effect of weakening the interfacial adhesion between the organic long fibers and the matrix resin, and the fibers are entangled with each other during molding. As a result, appearance quality deteriorates. On the other hand, when the adhesion amount of the polar resin exceeds 5% by weight, the organic long fiber becomes too hard, so that the processability is lowered and it is difficult to combine with the organic long fiber.
本発明の樹脂組性物においてペレット中の有機長繊維の長さは、ペレットの長さに相当する。プロピレン系樹脂より成るペレット中に含有された有機長繊維の平均繊維長は、通常4〜50mm、好ましくは4〜20mm、更に好ましくは4〜10mmである。有機長繊維の平均繊維長が4mm未満の場合は耐衝撃性の向上効果が十分に得られず、一方、平均繊維長が50mmを超える場合は成形が困難になる。 In the resin composition of the present invention, the length of the organic long fiber in the pellet corresponds to the length of the pellet. The average fiber length of the organic long fibers contained in the pellet made of propylene-based resin is usually 4 to 50 mm, preferably 4 to 20 mm, and more preferably 4 to 10 mm. When the average fiber length of the organic long fibers is less than 4 mm, the effect of improving the impact resistance is not sufficiently obtained. On the other hand, when the average fiber length exceeds 50 mm, molding becomes difficult.
本発明で使用するタルクの平均粒径は、通常15μm以下、好ましくは12mμ以下、更に好ましくは10μm以下であり、その下限は通常0.5μmである。平均粒径が15μmを超える場合は製品の耐衝撃性が低下する傾向がある。また、平均粒径が0.5μmの場合は、タルク自体が高価となり、更に、樹脂組成物の流動性が著しく低下する。ここでいう平均粒径は液相沈降式光透過法で測定し、粒度累積分布曲線から読み取った累積量50重量%の粒径値である。なお、上記の様な平均粒径のタルクは、一般に乾式粉砕後に乾式分級して製造される。 The average particle diameter of talc used in the present invention is usually 15 μm or less, preferably 12 μm or less, more preferably 10 μm or less, and its lower limit is usually 0.5 μm. When the average particle size exceeds 15 μm, the impact resistance of the product tends to decrease. When the average particle size is 0.5 μm, talc itself is expensive, and the fluidity of the resin composition is significantly reduced. The average particle size referred to here is a particle size value measured by a liquid phase precipitation type light transmission method and having a cumulative amount of 50% by weight read from a cumulative particle size distribution curve. The talc having an average particle diameter as described above is generally produced by dry classification after dry pulverization.
タルクの比表面積は、通常1.5m2/g以上、好ましくは2.0m2/g以上、更に好ましくは3.0m2/g以上であり、その上限は通常20m2/gである。比表面積が1.5m2/g未満の場合は、製品の耐衝撃性が不足する傾向がある。また、比表面積が20m2/gを超える場合は、タルク自体が高価となり、しかも、樹脂組成物の流動性が低下する傾向にある。ここでいう比表面積は空気透過法により測定した値である。 The specific surface area of talc is usually 1.5 m 2 / g or more, preferably 2.0 m 2 / g or more, more preferably 3.0 m 2 / g or more, and the upper limit is usually 20 m 2 / g. When the specific surface area is less than 1.5 m 2 / g, the impact resistance of the product tends to be insufficient. On the other hand, when the specific surface area exceeds 20 m 2 / g, talc itself is expensive, and the fluidity of the resin composition tends to decrease. The specific surface area here is a value measured by an air permeation method.
本発明の樹脂組成物は、必須成分としてプロピレン系樹脂と有機長繊維を含有する。そして、プロピレン系樹脂100重量部に対する割合として、有機長繊維の割合は、10〜200重量部、好ましくは20〜180重量部である。有機長繊維の割合が上記の範囲未満の場合は、補強効果が不十分となる傾向にあり、上記の範囲より多い場合は、成形が困難になり成形品外観も悪くなる傾向にある。本発明の樹脂組成物がタルクを含有する場合、その割合は、プロピレン系樹脂100重量部に対する割合として、10〜200重量部、好ましくは20〜180重量部である。タルクの割合が上記の範囲より少ない場合は、所望の剛性を付与できない傾向にあり、上記の範囲より多い場合は、流動性が著しく低下し成形が困難になり成形品外観も悪くなる傾向にあり、また、比重が重くなる傾向にある。 The resin composition of the present invention contains a propylene-based resin and organic long fibers as essential components. And as a ratio with respect to 100 weight part of propylene-type resin, the ratio of an organic long fiber is 10-200 weight part, Preferably it is 20-180 weight part. When the ratio of the organic long fibers is less than the above range, the reinforcing effect tends to be insufficient, and when it is more than the above range, molding tends to be difficult and the appearance of the molded product tends to deteriorate. When the resin composition of this invention contains a talc, the ratio is 10-200 weight part as a ratio with respect to 100 weight part of propylene-type resin, Preferably it is 20-180 weight part. When the ratio of talc is less than the above range, the desired rigidity tends not to be imparted, and when it is more than the above range, the fluidity is remarkably lowered and molding becomes difficult, and the appearance of the molded product tends to deteriorate. Also, the specific gravity tends to increase.
本発明の樹脂組成物(ペレット)は、連続した有機長繊維をクロスヘッドダイを通して引きながら溶融樹脂で含浸する方法(引き抜き成形法)により得られる。例えば、プロピレン系樹脂に必要に応じて樹脂添加剤を加え、有機長繊維をクロスヘッドダイに通して引き抜きながら、プロピレン系樹脂を押出機から溶融状態でクロスヘッドダイに供給し、有機長繊維にプロピレン系樹脂を含浸被覆させ、溶融含浸物を加熱し、冷却後、引き抜き方向と直角に切断して得られる。この方法によれば、有機長繊維の損傷を起こすことなく、得られるペレットの長さ方向に有機長繊維が同一長さで平行配列している樹脂組成物(ペレット)が得られる。 The resin composition (pellet) of the present invention is obtained by a method (pulling molding method) in which continuous organic long fibers are impregnated with a molten resin while being drawn through a crosshead die. For example, if necessary, a resin additive is added to the propylene resin and the propylene resin is supplied from the extruder to the crosshead die in a molten state while being drawn through the crosshead die. It is obtained by impregnating with a propylene-based resin, heating the melt-impregnated product, cooling, and cutting it at right angles to the drawing direction. According to this method, a resin composition (pellet) in which organic long fibers are arranged in parallel with the same length in the length direction of the obtained pellet can be obtained without causing damage to the organic long fibers.
引き抜き成形法は、基本的には、連続した強化用繊維束を引き抜きながら樹脂を含浸する方法である。そして、その態様として、クロスヘッドの中に繊維束を通しながら押出機などからクロスヘッドに樹脂を供給して含浸する方法の他、樹脂のエマルジョン、サスペンジョン又は溶液を入れた含浸浴の中に繊維束を通して含浸する方法、樹脂の粉末を繊維束に吹きつけるか又は粉末を入れた槽の中に繊維束を通して繊維に樹脂粉末を付着させた後に樹脂を溶融して含浸する方法などが知られており、本発明では何れの態様も利用できる。特に好ましいのはクロスヘッド方法である。また、これらの引き抜き成形法における樹脂の含浸操作は1段で行うのが一般的であるが、2段以上に分けてもよく、更に、含浸方法を異にして行ってもよい。 The pultrusion method is basically a method of impregnating a resin while drawing a continuous reinforcing fiber bundle. In addition to the method of supplying and impregnating the resin to the crosshead from an extruder or the like while passing the fiber bundle through the crosshead, as an aspect thereof, the fiber is contained in an impregnation bath containing a resin emulsion, suspension or solution. There are known methods of impregnating through bundles, methods of spraying resin powder onto fiber bundles, or attaching resin powder to fibers through fiber bundles in a tank containing the powder, and then melting and impregnating the resin. Therefore, any aspect can be used in the present invention. Particularly preferred is the crosshead method. Further, the resin impregnation operation in these pultrusion methods is generally performed in one stage, but it may be divided into two or more stages, and may be performed by different impregnation methods.
なお、プロピレン系樹脂に必要に応じて他の熱可塑性樹脂やゴムの1種または2種以上を補助的に少量併用することも可能である。また、目的に応じ、所望の特性を付与するため、一般に熱可塑性樹脂に添加される公知の物質、例えば、酸化防止剤、耐熱安定剤、紫外線吸収剤などの安定剤、帯電防止剤、難燃剤、難燃助剤、着色剤(染料や顔料)、潤滑剤、可塑剤、結晶化促進剤、結晶核剤などを更に配合することも可能である。 In addition, it is possible to supplementarily use a small amount of one or more other thermoplastic resins and rubbers as needed in combination with the propylene resin. In addition, in order to impart desired properties according to the purpose, known substances generally added to thermoplastic resins, for example, stabilizers such as antioxidants, heat stabilizers, UV absorbers, antistatic agents, flame retardants, etc. In addition, flame retardant aids, colorants (dyes and pigments), lubricants, plasticizers, crystallization accelerators, crystal nucleating agents, and the like can be further blended.
上記の含浸操作は、通常150〜300℃、好ましくは170〜260℃、更に好ましくは190〜230℃で行われる。また、上記の含浸物は上記の温度で加熱される。加熱温度が低すぎる場合は含浸が不十分になり、高すぎる場合はプロピレン系樹脂の分解が起こる。 The above impregnation operation is usually performed at 150 to 300 ° C, preferably 170 to 260 ° C, more preferably 190 to 230 ° C. The impregnated material is heated at the above temperature. When the heating temperature is too low, impregnation is insufficient, and when it is too high, the propylene-based resin is decomposed.
溶融含浸物は、加熱反応後、押出されてストランドとなり、切断可能な温度まで冷却され、カッターで切断されてペレットとされる。ペレットの形状としては、円柱状、角柱状、板状、さいころ状などが挙げられる。このようにして得られたペレットでは、有機長繊維が実質的に同じ長さで且つ各繊維の方向が押し出された方向(すなわちペレットの長さ方向)に揃っている。また、上記のペレットは、種類や濃度の異なる2種類以上の有機長繊維を使用したもの、プロピレン系樹脂の混合物を使用したものでもよい。なお、本発明において、「ペレット」は、上記の狭義のペレットの他に、ストランド状、シート状、平板状なども含む広義の意味で使用される。 The melt impregnated product is extruded to a strand after the heating reaction, cooled to a temperature capable of being cut, and cut by a cutter into pellets. Examples of the shape of the pellet include a columnar shape, a prismatic shape, a plate shape, and a die shape. In the pellet thus obtained, the organic long fibers have substantially the same length, and the direction of each fiber is aligned in the extruded direction (that is, the length direction of the pellet). Further, the above pellets may be those using two or more types of organic long fibers having different types and concentrations, and those using a mixture of propylene resins. In the present invention, “pellet” is used in a broad sense including strand shape, sheet shape, flat plate shape and the like in addition to the above-mentioned narrowly defined pellets.
本発明の樹脂組成物から成るペレットの寸法は、有機長繊維の長さとなり、通常4〜50mm、好ましくは4〜20mm、更に好ましくは4〜10mmである。ペレット中の有機長繊維の長さが短すぎる場合は複合材料としての所望の機械的強度が得られず、一方、長すぎる場合はペレットの射出成形機などへの供給が困難となる。 The size of the pellet made of the resin composition of the present invention is the length of the organic long fiber, and is usually 4 to 50 mm, preferably 4 to 20 mm, and more preferably 4 to 10 mm. When the length of the organic long fiber in the pellet is too short, the desired mechanical strength as a composite material cannot be obtained. On the other hand, when the length is too long, it becomes difficult to supply the pellet to an injection molding machine or the like.
上記の様にして得られたペレットは、単独で又は他の熱可塑性樹脂、好ましくはプロピレン系樹脂と同じタイプの樹脂で希釈し、射出成形などの原料として使用される。希釈する樹脂の種類および比率は、所望の成形品の物性値により定められる。本発明の樹脂組成物(ペレット)を使用し、射出成形により得られた成形品は、有機長繊維の射出成形時に折損が少なく、有機長繊維が均一に分散している。 The pellets obtained as described above are used alone or diluted with another thermoplastic resin, preferably a resin of the same type as the propylene resin, and used as a raw material for injection molding or the like. The kind and ratio of the resin to be diluted are determined by the physical property values of the desired molded product. A molded product obtained by injection molding using the resin composition (pellet) of the present invention has little breakage during the injection molding of organic long fibers, and the organic long fibers are uniformly dispersed.
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例により限定されるものではない。以下の諸例で使用した材料および評価方法は以下に示すとおりである。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by a following example, unless the summary is exceeded. The materials and evaluation methods used in the following examples are as shown below.
<使用材料> <Materials used>
(1)ポリプロピレン:
日本ポリプロ(株)製「ノバテックPP BC10AHA」(メルトフローレート100g/10分(230℃、21.2N荷重)
(1) Polypropylene:
“NOVATEC PP BC10AHA” manufactured by Nippon Polypro Co., Ltd. (melt flow rate 100 g / 10 min (230 ° C., 21.2 N load)
(2)PET長繊維1(ポリグリシジルエーテル系エポキシ樹脂を付着品):
帝人ファイバー(株)製「P903AL BHT1670T250」(平均繊維径24μm、エポキシ樹脂付着量=0.2重量%)
(2) PET long fiber 1 (adhesive product with polyglycidyl ether epoxy resin):
“P903AL BHT1670T250” manufactured by Teijin Fibers Limited (average fiber diameter: 24 μm, epoxy resin adhesion amount: 0.2% by weight)
(3)PET長繊維2:
帝人ファイバー(株)製「P900M BHT1670T250」(平均繊維径24μm)
(3) PET long fiber 2:
“P900M BHT1670T250” manufactured by Teijin Fibers Limited (average fiber diameter: 24 μm)
(4)タルク:
日本タルク(株)製「K−1」(平均粒径7.4μm、比表面積7.0m2/g)
(4) Talc:
“K-1” manufactured by Nippon Talc Co., Ltd. (average particle size 7.4 μm, specific surface area 7.0 m 2 / g)
(5)比較材料1(ガラス長繊維強化ポリプロピレン):
日本ポリプロ(株)製「ファンクスターLR23C」(ガラス含量30重量%)
(5) Comparative material 1 (long glass fiber reinforced polypropylene):
“Funkster LR23C” manufactured by Nippon Polypro Co., Ltd. (glass content 30% by weight)
(6)比較材料2(自動車内装材向けPP/ゴム/タルク複合材):
MFR40g/10分のPP単独重合体を含んだMFR25g/10分のエチレンプロピレンブロック共重合体:65wt%、PP含量22wt%で融解温度40℃のエチレンプロピレン共重合ゴム:5wt%、1ブテンをコモノマーとした融解温度80℃のエチレンαオレフィン共重合体:10wt%、比表面積4.0m2/gで平均粒径2.8μmのタルク:20wt%の配合物を二軸押出機(日本製鋼所製「TEX30」)にて210℃で溶融混練して調製した。
(6) Comparative material 2 (PP / rubber / talc composite material for automobile interior materials):
MFR 25 g / 10 min ethylene propylene block copolymer containing 40 g / 10 min PP homopolymer: 65 wt%, ethylene propylene copolymer rubber with PP content 22 wt% and melting temperature 40 ° C .: 5 wt%, 1 butene as comonomer An ethylene α-olefin copolymer having a melting temperature of 80 ° C .: 10 wt%, a specific surface area of 4.0 m 2 / g and an average particle size of 2.8 μm talc: 20 wt% It was prepared by melt-kneading at "TEX30") at 210 ° C.
<評価方法> <Evaluation method>
(1)最大曲げ応力および曲げ弾性率:
成形により得られた厚み4mm×幅10mm×長さ80mmのバーについて、JIS−K7171に準拠して下記条件で測定を行った。試験速度は2mm/min、支点間距離は64mmとした。
(1) Maximum bending stress and flexural modulus:
A bar having a thickness of 4 mm, a width of 10 mm, and a length of 80 mm obtained by molding was measured in accordance with JIS-K7171 under the following conditions. The test speed was 2 mm / min, and the distance between fulcrums was 64 mm.
(2)アイゾット衝撃強度:
成形により得られた厚み4mm×幅12.7mm×長さ63.5mmのバーについて、JIS−K7110に準拠して下記条件で測定を行った。ノッチ加工の回転数は400rpm、ノッチ加工の送り速度は120mm/min、ハンマー容量は5.5J、測定温度は23℃と−40℃とした。
(2) Izod impact strength:
A bar having a thickness of 4 mm, a width of 12.7 mm, and a length of 63.5 mm obtained by molding was measured according to JIS-K7110 under the following conditions. The rotation speed of notch processing was 400 rpm, the feed speed of notch processing was 120 mm / min, the hammer capacity was 5.5 J, and the measurement temperatures were 23 ° C. and −40 ° C.
(3)引張破断強度および引張破断伸び:
成形により得られた厚み3.2mm×幅10mmのダンベル型バーについて、JIS−K7161に準拠して試験速度50mm/minで測定を行った。
(3) Tensile breaking strength and tensile breaking elongation:
A dumbbell bar having a thickness of 3.2 mm and a width of 10 mm obtained by molding was measured at a test speed of 50 mm / min in accordance with JIS-K7161.
(4)外観:
成形により得られた100mm×100mm×厚さ3mmの平板の表面を目視にて観察し、分散性と繊維開繊性について以下の基準で評価した。
(4) Appearance:
The surface of a flat plate of 100 mm × 100 mm × thickness 3 mm obtained by molding was visually observed, and the dispersibility and fiber opening property were evaluated according to the following criteria.
○:繊維分散が良好で、開繊していない繊維の束が殆ど無く、シボ転写も良好である。
△:開繊していない繊維の束が少し見られ、シボ転写が不十分またはムラがある。
×:開繊していない繊維の束が多数見られ、平板表面が荒れている。
○: Good fiber dispersion, almost no bundle of unopened fibers, and good texture transfer.
(Triangle | delta): The bundle | flux of the fiber which is not opened is seen for a while, and a wrinkle transfer is inadequate or uneven.
X: Many bundles of unopened fibers are seen, and the flat plate surface is rough.
(5)流動性:
成形により得られた100mm×100mm×厚さ3mmの平板の表面を目視にて観察し、ジェッティング、フローマーク、充填ムラについて、以下の基準で評価した。
○:ジェッティング、フローマークが観察されず、均一に充填されている。
△:ジェッティング又はフローマークが僅かに見られ、充填ムラがでることがある。
×:成形が困難で、フル充填できないことが多い。
(5) Fluidity:
The surface of a 100 mm × 100 mm × 3 mm thick flat plate obtained by molding was visually observed, and jetting, flow marks, and filling unevenness were evaluated according to the following criteria.
○: Jetting and flow marks are not observed, and are filled uniformly.
(Triangle | delta): Jetting or a flow mark is seen slightly and filling irregularity may appear.
X: Molding is difficult and often cannot be fully filled.
(6)耐スクラッチ性:
成形により得られた100mm×100mm×厚さ3mmの平板の中心部80mm×80mm×厚さ3mmを切り出した平板について、全自動傷つき試験機(自社製)を使用し、ケガキ針を垂直に当て規定荷重で試験片を移動させる方法で傷つき試験を行った。条件は、ピッチ0.75mm、本数30本、ストローク50mm、速度500mm/分、移動1方向片道のみ、荷重200g、先端形状タングステン鋼R無しとした。結果を目視にて下記基準で評価した。傷つき前後の明度の差・Lも付記した。
(6) Scratch resistance:
100 mm x 100 mm x 3 mm thick flat plate obtained by molding, using a fully automatic scratch testing machine (manufactured in-house), and applying a marking needle vertically. A scratch test was conducted by moving the test piece under load. The conditions were a pitch of 0.75 mm, a number of 30, a stroke of 50 mm, a speed of 500 mm / min, only one direction of movement, a load of 200 g, and no tip-shaped tungsten steel R. The results were visually evaluated according to the following criteria. The difference in brightness before and after damage, L, is also noted.
○:傷端部のほころびやフィラー成分の滑落がなく、目視で傷が目立たない。
△:傷端部のほころびやフィラー成分の滑落が僅かに見られ、傷跡が白く見える。
×:傷端部のほころびやフィラー成分の滑落が著しく、傷跡がはっきり残っている。
◯: No scratches at the scratched edge and no sliding of filler components, and scratches are not noticeable visually.
(Triangle | delta): The crack of a crack edge part and sliding of a filler component are seen slightly, and a scar looks white.
X: Scattering of the scratched edge and sliding of the filler component is remarkable, and the scar remains clearly.
(7)反り変形:
成形により得られた100mm×350mm×厚さ3mmの平板のゲート側端を基盤に固定し、エンド側端の最も基盤の離れた高さを計測した。
(7) Warpage deformation:
The gate side end of a 100 mm × 350 mm × 3 mm thick flat plate obtained by molding was fixed to the base, and the height of the end side end farthest from the base was measured.
実施例1〜12、参考例1及び比較例1〜2:
ポリプロピレンとPET長繊維とタルクとを表1に示す配合で使用し、引き抜き成形を行い、長繊維強化ポリプロピレンペレットを製造した。製造装置としては、クロスヘッドダイを有する二軸押出機(日本製鋼所(株)製「TEX30」、L/D=42、シリンダー径30mm、シリンダー温度:190〜220℃、クロスダイヘッド温度:220℃)を使用した。なお、ペレット長は8mmとなるように調節した。次いで、得られた長繊維含有ポリプロピレンペレットを、射出成形機に供し、シリンダー温度210℃、金型温度70℃、背圧10kg/cm2、スクリュー回転数50rpmにて、平板およびバーを成形した。評価結果を表1〜表3に示す。
Examples 1 to 12 , Reference Example 1 and Comparative Examples 1 to 2:
Polypropylene, PET long fibers and talc were used in the formulation shown in Table 1, and pultrusion molding was performed to produce long fiber reinforced polypropylene pellets. As a manufacturing apparatus, a twin screw extruder having a crosshead die (“TEX30” manufactured by Nippon Steel Works Co., Ltd., L / D = 42, cylinder diameter 30 mm, cylinder temperature: 190 to 220 ° C., cross die head temperature: 220 ° C. )It was used. The pellet length was adjusted to 8 mm. Next, the obtained long fiber-containing polypropylene pellets were subjected to an injection molding machine, and flat plates and bars were molded at a cylinder temperature of 210 ° C., a mold temperature of 70 ° C., a back pressure of 10 kg / cm 2 , and a screw rotation speed of 50 rpm. The evaluation results are shown in Tables 1 to 3.
表1及び表2より、本発明の組成物は、繊維の分散がよく、外観に優れ、剛性や耐衝撃性などの機械的強度に優れ、更に、自動車内装材に要求される耐スクラッチ性が良く、反り変形が少なく、射出成形時の流動性が高い。従って、本発明の樹脂組成物から得られる成形品は自動車内装部品に極めて有用である。 From Tables 1 and 2, the composition of the present invention has good fiber dispersion, excellent appearance, excellent mechanical strength such as rigidity and impact resistance, and scratch resistance required for automotive interior materials. Good, less warping deformation and high fluidity during injection molding. Therefore, the molded product obtained from the resin composition of the present invention is extremely useful for automobile interior parts.
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