JP2008036932A - Two-layer resin molding having contamination resistance and low linear expansion properties and method for producing the molding - Google Patents
Two-layer resin molding having contamination resistance and low linear expansion properties and method for producing the molding Download PDFInfo
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- JP2008036932A JP2008036932A JP2006213022A JP2006213022A JP2008036932A JP 2008036932 A JP2008036932 A JP 2008036932A JP 2006213022 A JP2006213022 A JP 2006213022A JP 2006213022 A JP2006213022 A JP 2006213022A JP 2008036932 A JP2008036932 A JP 2008036932A
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- polypropylene resin
- resin composition
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- weight
- molded
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 6
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Images
Abstract
Description
本発明は、ポリプロピレン系樹脂による二層樹脂成形体及びその製造方法に関し、特に、表面塗装を施さなくても屋外等で長期間使用可能な耐汚染性、耐傷付き性に優れた性能を有し、且つ自動車の大型外装部品などに必要な寸法安定性（低線膨張性、低反り変形性）に優れた二層樹脂成形体及びその製造方法に関する。 The present invention relates to a two-layer resin molded body using a polypropylene resin and a method for producing the same, and in particular, has excellent performance of stain resistance and scratch resistance that can be used outdoors for a long time without surface coating. In addition, the present invention relates to a two-layer resin molded article excellent in dimensional stability (low linear expansion property, low warpage deformability) necessary for large exterior parts of automobiles, and a method for producing the same.
自動車の外装部品として、バンパー、サイドロッカーカバー、サイドモール、バックドアなどは、軽量化やデザイン自由度の観点から樹脂化が進んでいるが、高光沢、高艶感といった見栄え性や耐傷付き性などを得るために、塗装が施されることが多く、この塗装により、高外観な見栄え性を長期間保つことができている。
しかしながら、ポリプロピレン系樹脂に塗装を行なうには、一般に、前洗浄→プライマー塗布→ベース塗料塗布→トップコート塗布→焼付乾燥の複数工程が必要であり、設備費や運転費などを合わせると、塗装に要する費用は大きく、部品のコストを高めることになる。
また、塗料成分の有機溶剤による環境負荷や廃製品をリサイクルした時の塗膜混入によるリサイクル製品の品質低下などの問題があり、塗装廃止を目的とした高外観部品の技術検討が多く行われている。例えば、使用する材料として、高硬度、高光沢の特性をもつ高結晶性ホモポリプロピレン樹脂を選定して着色を施せば、無塗装品でも塗装品並みの見栄え性は得られるが、衝撃強度が低いために自動車などの外装用途には適用できないなどの用途に制約がある。
さらに、衝撃強度を改善するために、高結晶ホモポリプロピレン樹脂にゴム成分を添加した場合には、表面光沢や耐傷付き性が低下し、塗装並みの外観品質が得られない。
As automotive exterior parts, bumpers, side rocker covers, side moldings, back doors, etc. are being made of resin from the viewpoint of weight reduction and design freedom, but they have high gloss and high gloss appearance and scratch resistance. In order to obtain the above, painting is often performed, and this painting can maintain the appearance of high appearance for a long period of time.
However, in order to paint on polypropylene resin, in general, multiple steps of pre-cleaning → primer application → base paint application → top coat application → baking drying are required. The cost required is large and the cost of the parts is increased.
In addition, there are problems such as environmental impact due to the organic solvent of paint components and deterioration of the quality of recycled products due to coating film coating when recycling waste products. Yes. For example, if a highly crystalline homopolypropylene resin with high hardness and high gloss properties is selected as the material to be used and colored, the appearance of the unpainted product is as good as the painted product, but the impact strength is low. For this reason, there are restrictions on applications that cannot be applied to exterior applications such as automobiles.
Further, when a rubber component is added to the high crystal homopolypropylene resin in order to improve the impact strength, the surface gloss and scratch resistance are lowered, and the appearance quality equivalent to the coating cannot be obtained.
そこで、二層射出成形やサンドイッチ射出成形法などにより、高硬度・高光沢樹脂を用いたスキン層と、耐衝撃強度を持つ樹脂を用いたコア層からなる二層樹脂成形体を得、自動車などの外装用途への適用検討が行われている（例えば、特許文献１、２参照。）。
例えば、特許文献１には、多層射出成形法を用いポリオレフィン樹脂組成物からなるコア層の上に着色された高光沢樹脂からなるスキン層を積層する無塗装部品の製造方法が開示されている。また、特許文献２には、サンドイッチ射出成形法を用いポリプロピレン系樹脂材料の基材表面に着色された高硬度（ロックウエル硬度が８５以上）のポリプロピレン樹脂を被覆成形することにより塗装と同程度の高光沢感を得、更に耐傷付き性にも優れることが開示されている。
これらの技術を用いれば、衝撃強度が要求される外装用途に適した無塗装の射出成形体を得ることができる。
Therefore, by using a two-layer injection molding or sandwich injection molding method, etc., a two-layer resin molded body consisting of a skin layer using a high-hardness, high-gloss resin and a core layer using a resin with impact strength is obtained, such as an automobile. (See, for example, Patent Documents 1 and 2).
For example, Patent Document 1 discloses a method for producing an unpainted part in which a skin layer made of a colored high gloss resin is laminated on a core layer made of a polyolefin resin composition using a multilayer injection molding method. Further, Patent Document 2 discloses a sandwich resin molding method in which a polypropylene resin having a high hardness (Rockwell hardness of 85 or more) is coated and molded on the surface of the base material of the polypropylene resin material. It is disclosed that a glossy feeling is obtained and that the scratch resistance is also excellent.
By using these techniques, it is possible to obtain a non-painted injection-molded article suitable for exterior applications that require impact strength.
しかしながら、自動車の外装用途など長期での屋外使用を考えると、前記材料系では、太陽光や雨水、油、埃、ダスト、排気ガス、虫などの汚れ性（又は汚染性）への考慮が無いため、長期屋外使用における成形品表面への雨だれなどによる黒いしみが発生するといった問題が想定され、外観品質を長期維持するという観点では、塗装品より劣るという問題がある。
実際に、前記技術に用いられる材料にて、使用態様を想定した汚れ試験を行なうと、付着した汚れが落ちにくいという結果であった。
また、積層体の製造方法や材料の選定によっては、成形後に反り変形を生じたり、或いはヒートサイクル試験において寸法変動が大きい場合もあり、大型製品への適用に、難点があった。
Actually, when the soil test assuming the use mode was performed on the material used in the above technique, the adhered soil was difficult to be removed.
In addition, depending on the method of manufacturing the laminate and the selection of materials, warpage deformation may occur after molding, or there may be large dimensional fluctuations in the heat cycle test, which has been difficult to apply to large products.
本発明の目的は、上記問題点に鑑み、塗装品並みの外観品質を有し、屋外でも長期使用が可能な耐汚染性（又は耐汚れ性）に優れた無塗装成形体及びその製造方法を提供することにあり、特に、自動車の外装用途などに必要な寸法安定性（低線膨張性、低反り変形性）をも兼ね備えた二層樹脂成形体及びその製造方法を提供することにある。 In view of the above problems, an object of the present invention is to provide an uncoated molded article having an appearance quality equivalent to that of a coated product and excellent in stain resistance (or stain resistance) that can be used for a long time even outdoors, and a method for producing the same. In particular, it is an object to provide a two-layer resin molded article that also has dimensional stability (low linear expansion property, low warpage deformability) necessary for automotive exterior applications and the like, and a method for producing the same.
本発明者等は、上記課題を解決するため、種々の研究を重ねた結果、ポリプロピレン樹脂に、必須成分として、特定のエチレン・エチルアクリレート共重合体（ＥＥＡ）及び脂肪酸アミド類を組み合わせた樹脂組成物とすることにより、従来材料に比べて耐汚染性が格段に向上することを見出し、さらに、該樹脂組成物を二層樹脂成形体のスキン層（衣装外面）として用いると、塗装品並みの外観品質を有し、屋外でも長期使用が可能な耐汚染性に優れたものとなり、一方、コア層（内面）として、ポリプロピレン樹脂に、必須成分として、無機フィラーを組み合わせた樹脂組成物とすることにより、二層樹脂成形体として線膨張係数を小さくでき、その結果、優れた耐汚染性と寸法安定性を有する無塗装二層樹脂成形体が得られることを見出し、これらの知見に基き、本発明を完成するに至った。 In order to solve the above problems, the present inventors have made various studies, and as a result, a resin composition in which a specific ethylene / ethyl acrylate copolymer (EEA) and fatty acid amides are combined as an essential component with polypropylene resin. When it is made into a product, it is found that the stain resistance is remarkably improved as compared with conventional materials. Furthermore, when the resin composition is used as a skin layer (outer surface of a costume) of a two-layer resin molded product, Appearance quality and excellent anti-contamination that can be used for a long time outdoors. On the other hand, as a core layer (inner surface), a polypropylene resin and a resin composition combining an inorganic filler as an essential component. As a result, the linear expansion coefficient can be reduced as a two-layer resin molded product, and as a result, an uncoated two-layer resin molded product having excellent stain resistance and dimensional stability can be obtained. And, based on these findings, the present invention has been completed.
すなわち、本発明の第１の発明によれば、スキン層（Ｓ）とコア層（Ｃ）とからなるポリプロピレン系樹脂二層成形体であって、スキン層（Ｓ）は、下記ポリプロピレン樹脂組成物（Ａ）からなり、及びコア層（Ｃ）は、下記ポリプロピレン樹脂組成物（Ｂ）からなることを特徴とするポリプロピレン系樹脂二層成形体が提供される。
ポリプロピレン樹脂組成物（Ａ）：
（ａ）ポリプロピレン樹脂：１００重量部
（ｂ）エチルアクリレート重合単位の比率が５〜５０重量％であるエチレン・エチルアクリレート共重合体：０．５〜１５重量部
（ｃ）脂肪酸アミドまたはその誘導体：０．０５〜２．５重量部
（ｄ）熱可塑性エラストマー：０〜３５重量部
（ｅ）無機フィラー：０〜３５重量部
（ｆ）着色剤：０〜５０重量部
ポリプロピレン樹脂組成物（Ｂ）：
（α）ポリプロピレン樹脂：１０〜９９重量％
（β）無機フィラー：１〜３５重量％
（γ）熱可塑性エラストマー：０〜５０重量％
（δ）着色剤：０〜５重量％
また、本発明の第２の発明によれば、第１の発明において、ポリプロピレン樹脂組成物（Ａ、Ｂ）に配合されるポリプロピレン樹脂（ａ、α）は、プロピレン単独重合体、又はプロピレン・α−オレフィンランダム共重合体若しくはプロピレン・α−オレフィンブロック共重合体であり、メルトフローレート（ＭＦＲ）（試験条件：２３０℃、２．１６ｋｇ荷重）が１０〜２００ｇ／１０分であることを特徴とするポリプロピレン系樹脂二層成形体が提供される。
さらに、本発明の第３の発明によれば、第１の発明において、ポリプロピレン樹脂組成物（Ｂ）に配合される無機フィラー（β）は、炭素繊維単体または炭素繊維とタルクの併用系であることを特徴とするポリプロピレン系樹脂二層成形体が提供される。
That is, according to the first invention of the present invention, a polypropylene resin bilayer molded body comprising a skin layer (S) and a core layer (C), wherein the skin layer (S) comprises the following polypropylene resin composition: There is provided a polypropylene resin two-layer molded body comprising (A) and the core layer (C) comprising the following polypropylene resin composition (B).
Polypropylene resin composition (A):
(A) Polypropylene resin: 100 parts by weight (b) Ethylene / ethyl acrylate copolymer having a ratio of ethyl acrylate polymer units of 5 to 50% by weight: 0.5 to 15 parts by weight (c) Fatty acid amide or derivative thereof: 0.05 to 2.5 parts by weight (d) Thermoplastic elastomer: 0 to 35 parts by weight (e) Inorganic filler: 0 to 35 parts by weight (f) Colorant: 0 to 50 parts by weight Polypropylene resin composition (B) :
(Α) Polypropylene resin: 10 to 99% by weight
(Β) Inorganic filler: 1 to 35% by weight
(Γ) Thermoplastic elastomer: 0 to 50% by weight
(Δ) Colorant: 0 to 5% by weight
According to the second invention of the present invention, in the first invention, the polypropylene resin (a, α) blended in the polypropylene resin composition (A, B) is a propylene homopolymer or propylene · α. -Olefin random copolymer or propylene / α-olefin block copolymer, characterized in that melt flow rate (MFR) (test conditions: 230 ° C, 2.16 kg load) is 10 to 200 g / 10 min. A polypropylene-based resin bilayer molded body is provided.
Furthermore, according to the third invention of the present invention, in the first invention, the inorganic filler (β) blended in the polypropylene resin composition (B) is a carbon fiber alone or a combined system of carbon fiber and talc. A polypropylene resin two-layer molded product is provided.
また、本発明の第４の発明によれば、第１の発明において、ポリプロピレン樹脂組成物（Ｂ）の２３℃から８０℃までにおける線膨張係数が６×１０−５ｃｍ／（ｃｍ・℃）以下であり、及び二層成形体の２３℃から８０℃までにおける線膨張係数が１０×１０−５ｃｍ／（ｃｍ・℃）以下である低線膨張性を有することを特徴するポリプロピレン系樹脂二層成形体が提供される。
さらに、本発明の第５の発明によれば、第１の発明において、スキン層（Ｓ）となるポリプロピレン樹脂組成物（Ａ）を射出成形又は射出圧縮成形し、得た成形体の表面上に、コア層（Ｃ）となるポリプロピレン樹脂組成物（Ｂ）を射出成形又は射出圧縮成形する、二層射出成形法により得られることを特徴とするポリプロピレン系樹脂二層成形体が提供される。
According to the fourth invention of the present invention, in the first invention, the linear expansion coefficient of the polypropylene resin composition (B) at 23 ° C. to 80 ° C. is 6 × 10 −5 cm / (cm · ° C.). A polypropylene resin resin having a low linear expansion property, wherein the linear expansion coefficient at 23 ° C. to 80 ° C. of the two-layer molded body is 10 × 10 −5 cm / (cm · ° C.) or less. A layered compact is provided.
Furthermore, according to the fifth invention of the present invention, in the first invention, the polypropylene resin composition (A) to be the skin layer (S) is injection molded or injection compression molded, and is obtained on the surface of the obtained molded body. A polypropylene resin two-layer molded article obtained by a two-layer injection molding method in which a polypropylene resin composition (B) to be a core layer (C) is injection molded or injection compression molded is provided.
一方、本発明の第６の発明によれば、スキン層（Ｓ）となるポリプロピレン樹脂組成物（Ａ）を射出成形又は射出圧縮成形し、次いで、得られた成形体の表面上に、コア層（Ｃ）となるポリプロピレン樹脂組成物（Ｂ）を射出成形又は射出圧縮成形することを特徴とする、第５の発明に係るポリプロピレン系樹脂二層成形体の製造方法が提供される。
また、本発明の第７の発明によれば、第６の発明において、ポリプロピレン樹脂組成物（Ａ、Ｂ）に配合されるポリプロピレン樹脂（ａ、α）は、プロピレン単独重合体、又はプロピレン・α−オレフィンランダム共重合体若しくはプロピレン・α−オレフィンブロック共重合体であり、メルトフローレート（ＭＦＲ）（試験条件：２３０℃、２．１６ｋｇ荷重）が１０〜２００ｇ／１０分であることを特徴とするポリプロピレン系樹脂二層成形体の製造方法が提供される。
さらに、本発明の第８の発明によれば、第６の発明において、ポリプロピレン樹脂組成物（Ｂ）に配合される無機フィラー（β）は、炭素繊維単体または炭素繊維とタルクの併用系であることを特徴とするポリプロピレン系樹脂二層成形体の製造方法が提供される。
On the other hand, according to the sixth invention of the present invention, the polypropylene resin composition (A) to be the skin layer (S) is injection molded or injection compression molded, and then the core layer is formed on the surface of the obtained molded body. There is provided a method for producing a polypropylene resin two-layer molded article according to the fifth invention, wherein the polypropylene resin composition (B) to be (C) is injection molded or injection compression molded.
According to the seventh aspect of the present invention, in the sixth aspect, the polypropylene resin (a, α) blended in the polypropylene resin composition (A, B) is a propylene homopolymer or propylene / α. -Olefin random copolymer or propylene / α-olefin block copolymer, characterized in that melt flow rate (MFR) (test conditions: 230 ° C, 2.16 kg load) is 10 to 200 g / 10 min. There is provided a method for producing a polypropylene-based resin bilayer molded body.
Furthermore, according to the eighth invention of the present invention, in the sixth invention, the inorganic filler (β) blended in the polypropylene resin composition (B) is a carbon fiber alone or a combined system of carbon fiber and talc. A method for producing a polypropylene resin two-layer molded article is provided.
本発明のポリプロピレン系樹脂二層成形体は、耐汚染性に優れ、且つ寸法安定性（低線膨張性、低反り変形性）に優れたものであり、そのため、自動車の外装内装部品や家電用部品、住設部品などの各種工業部品へ、好適に用いることができる無塗装の二層樹脂成形体である。 The polypropylene resin two-layer molded article of the present invention is excellent in stain resistance and excellent in dimensional stability (low linear expansion property, low warpage deformation property). It is an unpainted two-layer resin molded article that can be suitably used for various industrial parts such as parts and housing parts.
本発明のポリプロピレン系樹脂二層成形体は、スキン層（Ｓ）とコア層（Ｃ）とからなるポリプロピレン系樹脂二層成形体であって、スキン層（Ｓ）は、（ａ）ポリプロピレン樹脂、（ｂ）エチレン・エチルアクリレート共重合体及び（ｃ）脂肪酸アミドまたはその誘導体を含有し、さらに必要に応じて、（ｄ）熱可塑性エラストマー、（ｅ）無機フィラー及び（ｆ）着色剤を含有するポリプロピレン樹脂組成物（Ａ）からなり、及びコア層（Ｃ）は、（α）ポリプロピレン樹脂及び（β）無機フィラーを含有し、さらに必要に応じて、（γ）熱可塑性エラストマー及び（δ）着色剤を含有するポリプロピレン樹脂組成物（Ｂ）からなることを特徴とするものである。
以下に、Ｉ．ポリプロピレン系樹脂二層成形体の構成、ＩＩ．ポリプロピレン系樹脂二層成形体の製造方法、ＩＩＩ．スキン層（Ｓ）に用いられるポリプロピレン樹脂組成物（Ａ）の構成成分と製造、ＩＶ．コア層（Ｃ）に用いられるポリプロピレン樹脂組成物（Ｂ）の構成成分と製造、Ｖ．ポリプロピレン系樹脂二層成形体の用途について、詳細に説明する。
The polypropylene-based resin bilayer molded body of the present invention is a polypropylene-based resin bilayer molded body composed of a skin layer (S) and a core layer (C), and the skin layer (S) includes (a) a polypropylene resin, (B) contains an ethylene / ethyl acrylate copolymer and (c) a fatty acid amide or a derivative thereof, and further contains (d) a thermoplastic elastomer, (e) an inorganic filler, and (f) a colorant as necessary. The polypropylene resin composition (A) and the core layer (C) contain (α) polypropylene resin and (β) inorganic filler, and (γ) thermoplastic elastomer and (δ) coloring as necessary. It consists of a polypropylene resin composition (B) containing an agent.
In the following, I.I. Structure of polypropylene resin two-layer molded article, II. A method for producing a polypropylene resin two-layer molded article, III. Component and production of polypropylene resin composition (A) used for skin layer (S), IV. Component and production of polypropylene resin composition (B) used for core layer (C), The use of the polypropylene resin two-layer molded body will be described in detail.
Ｉ．ポリプロピレン系樹脂二層成形体の構成
本発明のポリプロピレン系樹脂二層成形体の実施態様としては、耐汚染性を有する前記ポリプロピレン樹脂組成物（Ａ）を衣装面となるスキン層（Ｓ）に用い、内面となるコア層（Ｃ）には、寸法安定性に優れたポリプロピレン樹脂組成物（Ｂ）を用いて、スキン層（Ｓ）とコア層（Ｃ）を積層すれば、本発明の効果を発現することができる。
望ましいスキン層（Ｓ）とコア層（Ｃ）との積層体の厚みとしては、例えば、ポリプロピレン樹脂組成物（Ａ）からなるスキン層（Ｓ）の厚みが０．２〜２ｍｍであり、好ましくは、０．５〜１．５ｍｍであり、一方、ポリプロピレン樹脂組成物（Ｂ）からなるコア層（Ｃ）の厚みが１．５〜５ｍｍであり、好ましくは、２〜４ｍｍであり、また、積層体全体の厚みが１．５〜７ｍｍであり、好ましくは、２．５〜５ｍｍである。
耐汚染性については、各層の厚みによってその効果が変化するものでは無いものの、積層体としての諸性能は各層の厚みによって変化するので、積層体としての諸性能に適した層厚みにすれば良いが、例えば、本発明の効果の一つである寸法安定性（低線膨張性、低反り変形性）については、スキン層（Ｓ）厚みを薄くする方が良く、スキン層（Ｓ）／コア層（Ｃ）の比率を１以下、好ましくは０．５以下にするのが良い。また、スキン層（Ｓ）とコア層（Ｃ）の間に接着層を設けても、本発明の効果を発現することができる。
I. Configuration of Polypropylene Resin Two-Layer Molded Body As an embodiment of the polypropylene resin two-layer molded body of the present invention, the polypropylene resin composition (A) having stain resistance is used for a skin layer (S) serving as a clothing surface. If the skin layer (S) and the core layer (C) are laminated on the inner core layer (C) using the polypropylene resin composition (B) excellent in dimensional stability, the effects of the present invention can be obtained. Can be expressed.
As the thickness of the laminate of the desired skin layer (S) and core layer (C), for example, the thickness of the skin layer (S) made of the polypropylene resin composition (A) is 0.2 to 2 mm, preferably The thickness of the core layer (C) made of the polypropylene resin composition (B) is 1.5 to 5 mm, preferably 2 to 4 mm, and laminated. The whole body has a thickness of 1.5 to 7 mm, preferably 2.5 to 5 mm.
Contamination resistance does not change its effect depending on the thickness of each layer, but various performances as a laminate change depending on the thickness of each layer, so the layer thickness should be suitable for the performance as a laminate. However, for example, with regard to dimensional stability (low linear expansion property, low warpage deformability) which is one of the effects of the present invention, it is better to reduce the thickness of the skin layer (S), and the skin layer (S) / core. The ratio of the layer (C) is 1 or less, preferably 0.5 or less. Moreover, even if an adhesive layer is provided between the skin layer (S) and the core layer (C), the effect of the present invention can be exhibited.
ＩＩ．ポリプロピレン系樹脂二層成形体の製造方法
本発明のポリプロピレン系樹脂二層成形体である前記構成からなる積層体は、二層射出成形法、インサート射出成形法などの製造方法を用いることにより、作製が可能であり、スキン層（Ｓ）の厚みをより薄くする方法として、射出圧縮成形や、金型のＨｅａｔ ａｎｄ ｃｏｏｌ法、高速射出成形と、組あわせて成形することが好ましい。
II. Method for Producing Polypropylene Resin Two-Layer Molded Product A laminate having the above-described structure, which is a polypropylene resin two-layer molded product of the present invention, is produced by using a production method such as a two-layer injection molding method or an insert injection molding method. As a method for further reducing the thickness of the skin layer (S), it is preferable to form by a combination of injection compression molding, die heat and cool method, and high-speed injection molding.
例えば、上記二層射出成形法（図１参照。）においては、スキン層（Ｓ）となるポリプロピレン樹脂組成物（Ａ）を１次材として射出成形した後に、該成形体の表面上に、コア層（Ｃ）となるポリプロピレン樹脂組成物（Ｂ）を２次材として射出成形する方法（工法ａ）、又はコア層（Ｃ）となるポリプロピレン樹脂組成物（Ｂ）を１次材として射出成形した後に、該成形体の表面上に、スキン層（Ｓ）となるポリプロピレン樹脂組成物（Ａ）を２次材として射出成形する方法（工法ｂ）を用いることができるが、得られた積層体の反り・変形を少なくする観点から、前者（工法ａ）の射出成形法が好ましい。
これは、二層成形体の反り変形の発生メカニズム（図３参照。）として、２次材として成形された樹脂が収縮する際の収縮応力が１次材の剛性より強いことに起因するものであり、反り変形抑止のためには、２次材の収縮率を小さくすることが有効であり、そのメカニズムの考察結果から、本発明では、コア層（Ｃ）となるポリプロピレン樹脂組成物（Ｂ）は、低収縮材であるので、これを２次材として成形することにより、反り変形に優れた積層体を得ることができる。
For example, in the above-described two-layer injection molding method (see FIG. 1), after a polypropylene resin composition (A) to be the skin layer (S) is injection molded as a primary material, a core is formed on the surface of the molded body. A method of injection molding using the polypropylene resin composition (B) to be the layer (C) as a secondary material (construction method a), or an injection molding using the polypropylene resin composition (B) to be the core layer (C) as a primary material Later, on the surface of the molded body, a method (construction method b) of injection molding using the polypropylene resin composition (A) to be the skin layer (S) as a secondary material can be used. From the viewpoint of reducing warpage and deformation, the former (construction method a) injection molding method is preferred.
This is due to the fact that the shrinkage stress when the resin molded as the secondary material shrinks is stronger than the rigidity of the primary material as a mechanism of occurrence of warp deformation of the two-layer molded body (see FIG. 3). In order to suppress warpage deformation, it is effective to reduce the shrinkage rate of the secondary material. From the result of consideration of the mechanism, in the present invention, the polypropylene resin composition (B) to be the core layer (C) Since it is a low shrinkage material, a laminate having excellent warpage deformation can be obtained by forming this as a secondary material.
更には、１次材、２次材を成形する際に、射出圧縮成形法（図２参照。）を用いると、薄肉化が可能なだけではなく、キャビティ内に樹脂が流動した後の冷却固化の際に生じる残留応力が抑えられるので、更に、反り変形に優れた積層体を得ることができる。ここで、射出圧縮成形法とは、雌雄一対からなる金型のキャビティ内に樹脂を射出注入する際に、予め雌雄互いの金型を少し開いた状態（キャビティを拡大した状態）で、射出注入を開始し、射出注入過程もしくは射出注入完了後に、雌雄の金型を閉じて樹脂を圧縮して賦形させる工法であり、拡大されたキャビティ内に射出注入することにより、金型内の樹脂圧力を低減でき、比較的型締め力の小さい成形機で大型の成形品や薄肉の成形品が得られるといった利点がある。 Furthermore, when the primary material and the secondary material are molded, if an injection compression molding method (see FIG. 2) is used, not only the thickness can be reduced, but also cooling and solidification after the resin flows into the cavity. Since the residual stress generated at the time is suppressed, a laminate excellent in warp deformation can be obtained. Here, the injection compression molding method refers to injection injection in a state where the molds of both males and females are slightly opened in advance (when the cavity is enlarged) when injecting and injecting the resin into the cavity of the mold consisting of a pair of males and females. After the injection injection process or after injection injection is completed, the male and female molds are closed and the resin is compressed to form the resin. By injection injection into the enlarged cavity, the resin pressure in the mold There is an advantage that a large molded product or a thin molded product can be obtained with a molding machine having a relatively small clamping force.
二層射出成形を行うための成形機や金型について、特に限定は無いが、一般には射出シリンダーが２個あり１次材と２次材を個別に射出できるものを使用し、例えば、図１において、金型については１個のキャビティ型（１）に対して１次材形成用にキャビティ厚みが調整されたコア型（１）と２次材形成用にキャビティ厚みが調整されたコア型（２）の２個のコア型から成り、コア型（１）を用いて１次材を成形し、その後コア型（１）とコア型（２）を入れ替えてコア型（２）にて２次材を成形する方法を用いることができる。 There are no particular limitations on the molding machine or mold for performing the two-layer injection molding, but generally there are two injection cylinders that can inject the primary material and the secondary material individually. For example, FIG. In the mold, the core mold (1) whose cavity thickness is adjusted for forming the primary material and the core mold (for adjusting the cavity thickness for forming the secondary material) for one cavity mold (1). 2), the core material (1) is used to form the primary material, and then the core mold (1) and the core mold (2) are switched to obtain the secondary material by the core mold (2). A method of forming the material can be used.
さらに、上記の各成形法のうち、インサート射出成形法とは、予めコア層となるポリプロピレン系樹脂組成物（Ｂ）を射出成形し、賦形された成形品を金型内にインサートした後、該成形品と金型との間の空隙に、スキン層（Ｓ）となるポリプロピレン樹脂組成物（Ａ）を射出成形する成形方法である。 Furthermore, among the above molding methods, the insert injection molding method is a method in which a polypropylene resin composition (B) that becomes a core layer is injection molded in advance, and the molded product is inserted into a mold, This is a molding method in which a polypropylene resin composition (A) to be a skin layer (S) is injection molded into a gap between the molded product and a mold.
成形条件については、ポリプロピレン樹脂の一般的な成形条件範囲であれば良く、例えば、成形温度は１９０℃〜２５０℃、金型温度は２０℃〜６０℃の範囲であることが好ましく、所望する成形品の形状に合わせて、適宜変更可能である。 The molding conditions may be in the range of general molding conditions for polypropylene resin. For example, the molding temperature is preferably 190 ° C to 250 ° C, and the mold temperature is preferably in the range of 20 ° C to 60 ° C. It can be changed appropriately according to the shape of the product.
ＩＩＩ．スキン層（Ｓ）用ポリプロピレン樹脂組成物（Ａ）の構成成分と製造
（１）ポリプロピレン樹脂（ａＡ）
本発明に係るポリプロピレン樹脂組成物（Ａ）に用いるポリプロピレン樹脂（ａ）は、（ｉ）耐汚染性に優れるプロピレン単独重合体や、（ｉｉ）プロピレンと炭素数２〜１０のプロピレン以外のα−オレフィンとの共重合体、例えば、プロピレン・α−オレフィンランダム共重合体、プロピレン・α−オレフィンブロック共重合体などから選ばれる樹脂である。共重合体に用いるα−オレフィンとしては、例えば、エチレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテンなどから選ばれ、中でも、エチレン、１−ブテン、１−ヘキセンが好ましく、特にエチレンが好ましい。
III. Components and production of polypropylene resin composition (A) for skin layer (S) (1) Polypropylene resin (a A )
The polypropylene resin (a) used in the polypropylene resin composition (A) according to the present invention includes (i) a propylene homopolymer excellent in stain resistance, and (ii) α- other than propylene and propylene having 2 to 10 carbon atoms. It is a resin selected from copolymers with olefins, for example, propylene / α-olefin random copolymers, propylene / α-olefin block copolymers, and the like. The α-olefin used in the copolymer is, for example, selected from ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and the like. Among them, ethylene, 1-butene, 1-hexene Is preferable, and ethylene is particularly preferable.
ポリプロピレン樹脂（ａ）のメルトフローレート（ＭＦＲ）は、１０〜２００ｇ／１０分が好ましく、３０〜１５０ｇ／１０分がより好ましく、５０〜１２０ｇ／１０分がさらに好ましい。ＭＦＲが１０ｇ／１０分未満では、成形性が劣り、スキン層の薄肉化が困難となる。一方、ＭＦＲが２００ｇ／１０分を超えると、衝撃強度、引張り伸びが低下するので、積層体（二層成形体）としての機械的特性が低下する。
ここで、ＭＦＲは、ＪＩＳ Ｋ７２１０の「プラスチック―熱可塑性プラスチックのメルトマスフローレイト（ＭＦＲ）及びメルトボリュームフローレイト（ＭＶＲ）の試験方法」に準拠し、試験条件：２３０℃、２．１６ｋｇ荷重で測定する値である。
The melt flow rate (MFR) of the polypropylene resin (a) is preferably 10 to 200 g / 10 minutes, more preferably 30 to 150 g / 10 minutes, and further preferably 50 to 120 g / 10 minutes. When the MFR is less than 10 g / 10 min, the moldability is inferior and it is difficult to reduce the thickness of the skin layer. On the other hand, when the MFR exceeds 200 g / 10 min, the impact strength and the tensile elongation are lowered, so that the mechanical properties as a laminate (two-layer molded product) are lowered.
Here, MFR is measured in accordance with JIS K7210 “Plastics—Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics” at 230 ° C. and 2.16 kg load. Is the value to be
ポリプロピレン樹脂（ａ）が、プロピレンとα−オレフィンランダム共重合体である場合、共重合体中のα−オレフィン含量は、０．１〜２０重量％が好ましく、０．５〜１２重量％がより好ましく、１〜８重量％がさらに好ましい。 When the polypropylene resin (a) is propylene and an α-olefin random copolymer, the α-olefin content in the copolymer is preferably 0.1 to 20% by weight, more preferably 0.5 to 12% by weight. Preferably, 1 to 8% by weight is more preferable.
また、ポリプロピレン樹脂（ａ）が、プロピレン単独重合体部分である結晶性ポリプロピレン部分とプロピレン・α−オレフィン共重合体部分からなるプロピレン・α−オレフィンブロック共重合体である場合、ブロック共重合体全体のα−オレフィン含量は、２〜３５重量％が好ましく、プロピレン・α−オレフィン共重合体部分のα−オレフィン含有量は、７０重量％以下が好ましく、３０〜６０重量％がより好ましい。また、結晶性ポリプロピレン部分のＭＦＲは、３０〜４００ｇ／１０分が好ましく、５０〜３００ｇ／１０分がより好ましく、１００〜２００ｇ／１０分がさらに好ましい。結晶性ポリプロピレン部分のＭＦＲとブロック共重合体全体のＭＦＲの組合せが上記範囲を逸脱した場合、流動性や耐衝撃性、引張伸び性が不良となる。 When the polypropylene resin (a) is a propylene / α-olefin block copolymer comprising a crystalline polypropylene portion which is a propylene homopolymer portion and a propylene / α-olefin copolymer portion, the entire block copolymer The α-olefin content is preferably 2 to 35% by weight, and the α-olefin content of the propylene / α-olefin copolymer portion is preferably 70% by weight or less, more preferably 30 to 60% by weight. The MFR of the crystalline polypropylene portion is preferably 30 to 400 g / 10 minutes, more preferably 50 to 300 g / 10 minutes, and further preferably 100 to 200 g / 10 minutes. When the combination of the MFR of the crystalline polypropylene portion and the MFR of the entire block copolymer deviates from the above range, fluidity, impact resistance, and tensile elongation become poor.
ポリプロピレン樹脂（ａ）は、高立体規則性触媒を用いてスラリー重合、バルク重合、気相重合により製造することが好ましい。高立体規則性触媒としては、塩化マグネシウムに四塩化チタン、有機ハイドライド、及び有機シラン化合物を接触させて形成した固体成分に有機アルミニウム化合物を組み合わせた触媒が挙げられる。重合方式としては、バッチ重合、連続重合のどちらの方式でも採用される。 The polypropylene resin (a) is preferably produced by slurry polymerization, bulk polymerization, or gas phase polymerization using a highly stereoregular catalyst. Examples of the highly stereoregular catalyst include a catalyst in which an organic aluminum compound is combined with a solid component formed by bringing magnesium chloride into contact with titanium tetrachloride, an organic hydride, and an organic silane compound. As the polymerization method, either batch polymerization or continuous polymerization can be employed.
（２）エチレン・エチルアクリレート共重合体（ｂ）
本発明に係るポリプロピレン樹脂組成物（Ａ）において、必須成分として用いるエチレン・エチルアクリレート共重合体（ｂ）は、エチルアクリレート重合単位の比率が５〜５０重量％であり、７〜３０重量％が好ましく、１０〜２０重量％が特に好ましい。エチルアクリレート重合単位の比率が５重量％未満であると、耐汚染性が劣り、一方、５０重量％を超えると、耐熱性、剛性が低下したり、層状剥離等の成形品の外観不良が発生したりするので好ましくない。
(2) Ethylene / ethyl acrylate copolymer (b)
In the polypropylene resin composition (A) according to the present invention, the ethylene / ethyl acrylate copolymer (b) used as an essential component has a ratio of ethyl acrylate polymerization units of 5 to 50% by weight, and 7 to 30% by weight. Preferably, 10 to 20% by weight is particularly preferable. When the ratio of the ethyl acrylate polymer units is less than 5% by weight, the stain resistance is inferior. On the other hand, when it exceeds 50% by weight, the heat resistance and rigidity are deteriorated, and appearance defects of the molded product such as delamination occur. This is not preferable.
また、エチレン・エチルアクリレート共重合体（ｂ）は、メルトフローレート（ＭＦＲ）（試験条件：１９０℃、２．１６ｋｇ荷重）の値が、１〜１２０ｇ／１０分が好ましく、１０〜１００ｇ／１０分がより好ましく、２０〜８０ｇ／１０分がさらに好ましい。メルトフローレート（ＭＦＲ）がこの範囲にあると、耐汚染性がより向上するので好ましい。
ここで、メルトフローレート（ＭＦＲ）は、ＪＩＳ Ｋ７２１０の「プラスチック―熱可塑性プラスチックのメルトマスフローレイト（ＭＦＲ）及びメルトボリュームフローレイト（ＭＶＲ）の試験方法」に準拠し、試験条件：１９０℃、２．１６ｋｇ荷重で測定する値である。
The ethylene / ethyl acrylate copolymer (b) preferably has a melt flow rate (MFR) (test condition: 190 ° C., 2.16 kg load) of 1 to 120 g / 10 min, preferably 10 to 100 g / 10. Minute is more preferable, and 20 to 80 g / 10 minutes is further preferable. When the melt flow rate (MFR) is within this range, the stain resistance is further improved, which is preferable.
Here, the melt flow rate (MFR) is in accordance with JIS K7210 “Plastics—Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics”, test conditions: 190 ° C., 2 It is a value measured with a 16 kg load.
（３）脂肪酸アミド又はその誘導体（ｃ）
本発明に係るポリプロピレン樹脂組成物（Ａ）において、必須成分として用いる脂肪酸アミド又はその誘導体（ｃ）としては、ステアリン酸アミド、オレイン酸アミド、ベヘニン酸アミド、エルカ酸アミド、エチレンビスステアリン酸アミド、ヘキサメチレンビスステアリン酸アミド、ラウリン酸アミド、１２−ヒドロキシステアリル酸アミド等が挙げられ、これらの中から選ばれる一種又は二種以上を併用して使用することができ、中でも、オレイン酸アミドが好ましい。
(3) Fatty acid amide or its derivative (c)
In the polypropylene resin composition (A) according to the present invention, the fatty acid amide or derivative (c) used as an essential component includes stearic acid amide, oleic acid amide, behenic acid amide, erucic acid amide, ethylene bis-stearic acid amide, Hexamethylene bis stearic acid amide, lauric acid amide, 12-hydroxy stearic acid amide and the like can be mentioned, and one or two or more kinds selected from these can be used in combination, and among them, oleic acid amide is preferable. .
（４）熱可塑性エラストマー（ｄ）
本発明に係るポリプロピレン樹脂組成物（Ａ）において、任意成分として用いる熱可塑性エラストマー（ｄ）は、耐衝撃性、成形性の向上、収縮特性の調整等を目的に、用いられる。熱可塑性エラストマー（ｄ）としては、具体的には、エチレン−プロピレンエラストマー、エチレン−ブテン−１エラストマー、エチレン−オクテン−１エラストマー、エチレン−プロピレン−ジエンエラストマー、ポリブタジエン、スチレン−ジエン共重合体、アクリロニトリル−ブタジエン共重合体、ポリイソプレン等のジエン系ゴム、スチレン−ブタジエンブロック共重合体、水素化スチレン−ブタジエンブロック共重合体、エチレン系アイオノマー樹脂、水素化スチレン−イソプレンブロック共重合体等が挙げられる。これらの熱可塑性エラストマーは、１種又は２種以上を混合して使用することができる。
(4) Thermoplastic elastomer (d)
In the polypropylene resin composition (A) according to the present invention, the thermoplastic elastomer (d) used as an optional component is used for the purpose of improving impact resistance, moldability, adjusting shrinkage characteristics, and the like. Specific examples of the thermoplastic elastomer (d) include ethylene-propylene elastomer, ethylene-butene-1 elastomer, ethylene-octene-1 elastomer, ethylene-propylene-diene elastomer, polybutadiene, styrene-diene copolymer, acrylonitrile. -Diene rubber such as butadiene copolymer, polyisoprene, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene ionomer resin, hydrogenated styrene-isoprene block copolymer, etc. . These thermoplastic elastomers can be used alone or in combination of two or more.
（５）無機フィラー（ｅ）
本発明に係るポリプロピレン樹脂組成物（Ａ）において、任意成分として用いる無機フィラー（ｅ）は、積層体としての剛性の向上、寸法の調整等を目的に用いられる。無機フィラーとしては、タルク、ワラストナイト、炭酸カルシウム、硫酸バリウム、マイカ、ガラス繊維、炭素繊維などが挙げられるが、これらフィラーの添加は、光沢の低下や、表面粗れがおき、塗装並みの外観品質が得られなくなるので、添加する場合は量を少なくしたほうが良い。
(5) Inorganic filler (e)
In the polypropylene resin composition (A) according to the present invention, the inorganic filler (e) used as an optional component is used for the purpose of improving rigidity as a laminate, adjusting dimensions, and the like. Examples of inorganic fillers include talc, wollastonite, calcium carbonate, barium sulfate, mica, glass fiber, and carbon fiber. Since appearance quality cannot be obtained, it is better to reduce the amount when added.
（６）着色剤（ｆ）
本発明に係るポリプロピレン樹脂組成物（Ａ）には、目的とする色彩に応じて着色剤（ｆ）を配合することができる。着色剤（ｆ）としては、白色系の酸化チタン、亜鉛華、リトボン、鉛白、赤色系の弁柄、鉛炭、モリブデンレッド、カドミウムレッド、レーキレッドＣ、レーキレッドＤ、ブリリアントカーミン６Ｂ、リソールレッド、パーマネントレッド４Ｒ、ウォッチングレッド、チオインジゴレッド、アリザリンレッド、キナクリドンレッド、ローダミンレーキ、オレンジレーキ、ベンズイミダゾロンレッド、ピラゾロンレッド、縮合アゾレッド、ペリレンレッド、パーマネントカーミンＦＢ、キナクリドンマゼンダ、黄色系の黄鉛、カドミウムイエロー、チタンイエロー、鉄黄、イソインドリノンイエロー、ベンジジンイエロー、ファーストイエロー、フラボンスロンイエロー、ナフトールイエロー、キノリンイエロー、ベンズイミダゾロンイエロー、ＨＲイエロー、縮合アゾイエロー、橙色系のクロムオレンジ、カドミウムオレンジ、ベンズイミダゾロンオレンジ、ペリノンオレンジ、緑色系のクロムグリーン、酸化クロム、ギネグリーン、スピネルグリーン、フタロシアニングリーン、ピグメントグリーンＢ、ナフトールグリーン、アシッドグリーンレーキ、マラカイトグリーンレーキ、茶系の亜鉛フェライト、青色系の紺青、群青、コバルトブルー、フタロシアニンブルー、インダンスレンブルーＲＳ、ファーストスカイブルーレーキ、アルカリブルーレーキ、ビクトリアブルーレーキ、紫色系のマンガン紫、コバルト紫、紫弁柄、ファーストバイオレットＢ、メチルバイオレットレーキ、ジオキサジンバイオレット、黒色系のカーボンブラック、鉄黒等を挙げることができる。
(6) Colorant (f)
In the polypropylene resin composition (A) according to the present invention, a colorant (f) can be blended according to the target color. As the colorant (f), white titanium oxide, zinc white, lithobon, lead white, red petal, lead charcoal, molybdenum red, cadmium red, lake red C, lake red D, brilliant carmine 6B, resol Red, Permanent Red 4R, Watching Red, Thioindigo Red, Alizarin Red, Quinacridone Red, Rhodamine Lake, Orange Lake, Benzimidazolone Red, Pyrazolone Red, Condensed Azo Red, Perylene Red, Permanent Carmine FB, Quinacridone Magenta, Yellow Yellow Lead, cadmium yellow, titanium yellow, iron yellow, isoindolinone yellow, benzidine yellow, first yellow, flavonthrone yellow, naphthol yellow, quinoline yellow, benzimidazolone yellow HR yellow, condensed azo yellow, orange chrome orange, cadmium orange, benzimidazolone orange, perinone orange, green chrome green, chromium oxide, guinea green, spinel green, phthalocyanine green, pigment green B, naphthol green, Acid Green Lake, Malachite Green Lake, Brown Zinc Ferrite, Blue Bitumen, Ultramarine Blue, Cobalt Blue, Phthalocyanine Blue, Indanthrene Blue RS, First Sky Blue Lake, Alkaline Blue Lake, Victoria Blue Lake, Purple Manganese Purple, cobalt purple, purple petals, first violet B, methyl violet lake, dioxazine violet, black carbon black, iron black and the like can be mentioned.
（７）その他の配合成分（任意成分）
本発明に係るポリプロピレン樹脂組成物（Ａ）においては、本発明の効果を損なわない範囲で、或いは、更に性能の向上をはかるために、上記成分以外に、以下に示す任意成分を、適宜配合することができる。具体的には、酸化防止剤、帯電防止剤、光安定剤、紫外線吸収剤、核剤、難燃剤、分散剤、顔料、発泡剤などを挙げることができる。
(7) Other ingredients (arbitrary ingredients)
In the polypropylene resin composition (A) according to the present invention, in addition to the above components, the following optional components are appropriately blended within a range not impairing the effects of the present invention, or in order to further improve performance. be able to. Specific examples include an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a nucleating agent, a flame retardant, a dispersant, a pigment, and a foaming agent.
（８）成分の配合割合
本発明に係るポリプロピレン樹脂組成物（Ａ）に配合される前記各成分の割合は、（ａ）ポリプロピレン樹脂１００重量部に対して、（ｂ）エチレン・エチルアクリレート共重合体０．５〜１５重量部、（ｃ）脂肪酸アミド又はその誘導体０．０５〜２．５重量部、（ｄ）熱可塑性エラストマー０〜３５重量部、（ｅ）無機フィラー０〜３５重量部、（ｆ）着色剤０〜５０重量部であり、好ましくは、ポリプロピレン樹脂１００重量部に対して、エチレン・エチルアクリレート共重合体１〜１１重量部、脂肪酸アミド又はその誘導体０．１〜１．５重量部、熱可塑性エラストマー０〜２５重量部、無機フィラー０〜２５重量部であり、さらに好ましくは、ポリプロピレン樹脂１００重量部に対して、エチレン・エチルアクリレート共重合体３〜８重量部、脂肪酸アミド又はその誘導体０．２〜１重量部、熱可塑性エラストマー０〜１５重量部、無機フィラー０〜１５重量部である。
(8) Component blending ratio The proportion of each component blended in the polypropylene resin composition (A) according to the present invention is as follows: (a) 100 parts by weight of the polypropylene resin; 0.5 to 15 parts by weight of the coalescence, (c) 0.05 to 2.5 parts by weight of a fatty acid amide or derivative thereof, (d) 0 to 35 parts by weight of a thermoplastic elastomer, (e) 0 to 35 parts by weight of an inorganic filler, (F) 0 to 50 parts by weight of a colorant, and preferably 1 to 11 parts by weight of an ethylene / ethyl acrylate copolymer, 0.1 to 1.5 parts of a fatty acid amide or a derivative thereof based on 100 parts by weight of a polypropylene resin. Parts by weight, thermoplastic elastomer 0 to 25 parts by weight, inorganic filler 0 to 25 parts by weight, more preferably 100 parts by weight of polypropylene resin, 3 to 8 parts by weight of a acrylate copolymer, 0.2 to 1 part by weight of a fatty acid amide or a derivative thereof, 0 to 15 parts by weight of a thermoplastic elastomer, and 0 to 15 parts by weight of an inorganic filler.
エチレン・エチルアクリレート共重合体（ｂ）の配合割合が０．５重量部未満であると、耐汚染性が悪化し、一方、１５重量部を超えると、表面硬度が低下し耐傷つき性が悪化する。また、脂肪酸アミド又はその誘導体（ｃ）の配合割合が０．０５重量部未満であると、耐汚染性が悪化し、一方、２．５重量部を超えると、表面へのブリード物発生などによるベタツキが発生する。
また、着色剤（ｆ）を用いる場合は、用いる着色剤により一概には決められないが、ポリプロピレン樹脂１００重量部に対して、０．１〜５０重量部が好ましい。
When the blending ratio of the ethylene / ethyl acrylate copolymer (b) is less than 0.5 parts by weight, the stain resistance is deteriorated. On the other hand, when it exceeds 15 parts by weight, the surface hardness is lowered and the scratch resistance is deteriorated. To do. Further, when the blending ratio of the fatty acid amide or the derivative thereof (c) is less than 0.05 parts by weight, the stain resistance is deteriorated. On the other hand, when it exceeds 2.5 parts by weight, bleeding occurs on the surface. Stickiness occurs.
Moreover, when using a coloring agent (f), although it cannot unconditionally be decided by the coloring agent to be used, 0.1-50 weight part is preferable with respect to 100 weight part of polypropylene resins.
（９）ポリプロピレン樹脂組成物（Ａ）の製造
本発明で用いるポリプロピレン樹脂組成物（Ａ）は、上記成分（ａ）〜（ｆ）を、従来公知の方法で、各配合成分を上記配合割合で配合・混合し、溶融混練することにより製造できる。
溶融混練は、一軸押出機、二軸押出機、バンバリーミキサー、ロールミキサー、ブラベンダープラストグラフ、ニーダー等の通常の混練機を用いて混練・造粒することによって、本発明に係るポリプロピレン樹脂組成物（Ａ）が得られる。
この場合、各成分の分散を良好にすることができる混練・造粒方法を選択することが好ましく、通常は二軸押出機を用いて行われる。この混練・造粒の際には、上記各成分の配合物を同時に混練してもよく、また性能向上をはかるべく各成分を分割して混練する、すなわち、例えば、先ずポリプロピレン樹脂の一部又は全部と熱可塑性エラストマーとを混練し、その後に残りの成分を混練・造粒するといった方法を採用することもできる。
(9) Production of Polypropylene Resin Composition (A) The polypropylene resin composition (A) used in the present invention comprises the above components (a) to (f) in a conventionally known method, and each compounding component at the above compounding ratio. It can be produced by blending, mixing and melt-kneading.
The melt kneading is performed by kneading and granulating using a normal kneader such as a single screw extruder, twin screw extruder, Banbury mixer, roll mixer, Brabender plastograph, kneader, etc., so that the polypropylene resin composition according to the present invention is used. (A) is obtained.
In this case, it is preferable to select a kneading and granulating method capable of improving the dispersion of each component, and it is usually performed using a twin-screw extruder. In this kneading and granulation, the above-mentioned components may be kneaded at the same time, and each component may be divided and kneaded in order to improve performance, that is, for example, first part of the polypropylene resin or It is also possible to employ a method in which all the thermoplastic elastomer is kneaded and then the remaining components are kneaded and granulated.
ＩＶ．コア層（Ｃ）用ポリプロピレン樹脂組成物（Ｂ）の構成成分と製造
（１）ポリプロピレン樹脂（α）
本発明に係るポリプロピレン樹脂組成物（Ｂ）に用いるポリプロピレン樹脂（α）は、（ｉ）プロピレン単独重合体や、（ｉｉ）プロピレンと炭素数２〜１０のプロピレン以外のα−オレフィンとの共重合体、例えば、プロピレン・α−オレフィンランダム共重合体、プロピレン・α−オレフィンブロック共重合体などから選ばれる樹脂である。共重合体に用いるα−オレフィンとしては、例えば、エチレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテンなどから選ばれ、中でも、エチレン、１−ブテン、１−ヘキセンが好ましく、特にエチレンが好ましい。
IV. Components and production of the polypropylene resin composition (B) for the core layer (C) (1) Polypropylene resin (α)
The polypropylene resin (α) used in the polypropylene resin composition (B) according to the present invention is composed of (i) propylene homopolymer, and (ii) co-polymerization of propylene and an α-olefin other than propylene having 2 to 10 carbon atoms. For example, a resin selected from a propylene / α-olefin random copolymer, a propylene / α-olefin block copolymer, and the like. The α-olefin used in the copolymer is, for example, selected from ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and the like. Among them, ethylene, 1-butene, 1-hexene Is preferable, and ethylene is particularly preferable.
ポリプロピレン樹脂（α）のメルトフローレート（ＭＦＲ）は、１０〜２００ｇ／１０分が好ましく、３０〜１５０ｇ／１０分がより好ましく、５０〜１２０ｇ／１０分がさらに好ましい。ＭＦＲが１０ｇ／１０分未満では、成形性が劣り、一方、ＭＦＲが２００ｇ／１０分を超えると、衝撃強度、引張り伸びが低下するので、積層体（二層成形体）としての機械的特性が低下する。
ここで、ＭＦＲは、ＪＩＳ Ｋ７２１０の「プラスチック―熱可塑性プラスチックのメルトマスフローレイト（ＭＦＲ）及びメルトボリュームフローレイト（ＭＶＲ）の試験方法」に準拠し、試験条件：２３０℃、２．１６ｋｇ荷重で測定する値である。
The melt flow rate (MFR) of the polypropylene resin (α) is preferably 10 to 200 g / 10 minutes, more preferably 30 to 150 g / 10 minutes, and further preferably 50 to 120 g / 10 minutes. If the MFR is less than 10 g / 10 minutes, the moldability is inferior. On the other hand, if the MFR exceeds 200 g / 10 minutes, the impact strength and the tensile elongation decrease, so that the mechanical properties as a laminate (two-layer molded product) are obtained. descend.
Here, MFR is measured in accordance with JIS K7210 “Plastics—Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics” at 230 ° C. and 2.16 kg load. Is the value to be
ポリプロピレン樹脂（α）が、プロピレンとα−オレフィンランダム共重合体である場合、共重合体中のα−オレフィン含量は、０．１〜２０重量％が好ましく、０．５〜１２重量％がより好ましく、１〜８重量％がさらに好ましい。 When the polypropylene resin (α) is a propylene and α-olefin random copolymer, the α-olefin content in the copolymer is preferably 0.1 to 20% by weight, more preferably 0.5 to 12% by weight. Preferably, 1 to 8% by weight is more preferable.
また、ポリプロピレン樹脂（α）が、プロピレン単独重合体部分である結晶性ポリプロピレン部分とプロピレン・α−オレフィン共重合体部分からなるプロピレン・α−オレフィンブロック共重合体である場合、ブロック共重合体全体のα−オレフィン含量は、２〜３５重量％が好ましく、プロピレン・α−オレフィン共重合体部分のα−オレフィン含有量は、７０重量％以下が好ましく、３０〜６０重量％がより好ましい。また、結晶性ポリプロピレン部分のＭＦＲは、３０〜４００ｇ／１０分が好ましく、５０〜３００ｇ／１０分がより好ましく、１００〜２００ｇ／１０分がさらに好ましい。結晶性ポリプロピレン部分のＭＦＲとブロック共重合体全体のＭＦＲの組合せが上記範囲を逸脱した場合、流動性や耐衝撃性、引張伸び性が不良となる。 When the polypropylene resin (α) is a propylene / α-olefin block copolymer comprising a crystalline polypropylene portion which is a propylene homopolymer portion and a propylene / α-olefin copolymer portion, the entire block copolymer The α-olefin content is preferably 2 to 35% by weight, and the α-olefin content of the propylene / α-olefin copolymer portion is preferably 70% by weight or less, more preferably 30 to 60% by weight. The MFR of the crystalline polypropylene portion is preferably 30 to 400 g / 10 minutes, more preferably 50 to 300 g / 10 minutes, and further preferably 100 to 200 g / 10 minutes. When the combination of the MFR of the crystalline polypropylene portion and the MFR of the entire block copolymer deviates from the above range, fluidity, impact resistance, and tensile elongation become poor.
ポリプロピレン樹脂（α）は、高立体規則性触媒を用いてスラリー重合、バルク重合、気相重合により製造することが好ましい。高立体規則性触媒としては、塩化マグネシウムに四塩化チタン、有機ハイドライド、及び有機シラン化合物を接触させて形成した固体成分に有機アルミニウム化合物を組み合わせた触媒が挙げられる。重合方式としては、バッチ重合、連続重合のどちらの方式でも採用される。 The polypropylene resin (α) is preferably produced by slurry polymerization, bulk polymerization, or gas phase polymerization using a highly stereoregular catalyst. Examples of the highly stereoregular catalyst include a catalyst in which an organic aluminum compound is combined with a solid component formed by bringing magnesium chloride into contact with titanium tetrachloride, an organic hydride, and an organic silane compound. As the polymerization method, either batch polymerization or continuous polymerization can be employed.
（２）無機フィラー（β）
本発明に係るポリプロピレン樹脂組成物（Ｂ）において、必須成分として用いる無機フィラー（β）は、積層体の寸法安定性（低線膨張性と低反り変形性）を目的に用いられる。
無機フィラー（β）としては、タルク、ワラストナイト、炭酸カルシウム、硫酸バリウム、マイカ、ガラス繊維、炭素繊維などが挙げられ、タルク、マイカ、ガラス繊維、炭素繊維などが好ましいが、無機フィラー（β）として炭素繊維を選定した場合には、少量の添加で効果があり、積層体の軽量化が可能となるので好ましい。
これらの無機フィラーは、１種または２種以上を混合して使用することができ、混合する場合は、炭素繊維とタルクの組み合わせが低線膨張性に優れるので、好ましい。
(2) Inorganic filler (β)
In the polypropylene resin composition (B) according to the present invention, the inorganic filler (β) used as an essential component is used for the purpose of dimensional stability (low linear expansion and low warpage deformability) of the laminate.
Examples of the inorganic filler (β) include talc, wollastonite, calcium carbonate, barium sulfate, mica, glass fiber, and carbon fiber. Talc, mica, glass fiber, carbon fiber, and the like are preferable, but the inorganic filler (β When carbon fiber is selected as (), the addition of a small amount is effective, and the weight of the laminate can be reduced, which is preferable.
These inorganic fillers can be used alone or in combination of two or more. When they are mixed, the combination of carbon fiber and talc is excellent in low linear expansion, which is preferable.
本発明で用いる炭素繊維としては、繊維径が１〜１５（μｍ）で、繊維長が１〜２０（ｍｍ）である。繊維径が１μｍ未満の場合は、溶融混練時の折損により、最終繊維長が０．３ｍｍを下回り、アスペクト比が低下し、一方、繊維径が１５μｍを超えると、繊維自体のアスペクト比が低下することに伴う補強効率の低下が起きてしまい、何れも、低線膨張性が得られなくなるので、好ましくない。また、繊維長が１ｍｍ未満の場合も、溶融混練時の折損により、最終繊維長が０．３ｍｍを下回るので、前記同様の補強効果が劣り、低線膨張性が得られなくなるので、好ましくない。一方、繊維長が２０ｍｍを超えると、成形体とした時の成形体表面の外観が著しく低下してしまうため、好ましくない。炭素繊維としては、タールピッチを主原料とするピッチ系炭素繊維と、アクリロニトリルを主原料とするＰＡＮ系炭素繊維のどちらかを用いるか、あるいは併用しても良いが、純度・均一性等の観点から、ＰＡＮ系炭素繊維がより好適に用いられる。 The carbon fiber used in the present invention has a fiber diameter of 1 to 15 (μm) and a fiber length of 1 to 20 (mm). When the fiber diameter is less than 1 μm, the final fiber length is less than 0.3 mm due to breakage during melt-kneading, and the aspect ratio decreases. On the other hand, when the fiber diameter exceeds 15 μm, the aspect ratio of the fiber itself decreases. As a result, the reinforcing efficiency is lowered, and low linear expansion cannot be obtained. Also, when the fiber length is less than 1 mm, the final fiber length is less than 0.3 mm due to breakage at the time of melt-kneading, so that the same reinforcing effect is inferior and low linear expansion cannot be obtained, which is not preferable. On the other hand, if the fiber length exceeds 20 mm, the appearance of the surface of the molded body when formed into a molded body is remarkably deteriorated. As the carbon fiber, either pitch-based carbon fiber mainly composed of tar pitch or PAN-based carbon fiber mainly composed of acrylonitrile may be used or may be used together. Therefore, PAN-based carbon fibers are more preferably used.
これらの炭素繊維は、繊維原糸を所望の長さに裁断した、所謂チョップドカーボンファイバーとして用いることができ、また、必要に応じて、各種サイジング剤を用いて、収束処理されたものであっても良い。この繊維収束に用いるサイジング剤は、ポリプロピレン樹脂（ＰＰ）との溶融混練において、融解する必要があるため、２００℃以下で溶融するものであることが好ましい。
また、このチョップドカーボンファイバーの形状は、直線状のものだけでなく、繊維が湾曲したカール状のカーボンファイバーであっても良い。
このようなチョップドカーボンファイバーの具体例としては、ＰＡＮ系炭素繊維では、東レ（株）社製商品名「トレカチョップ」、三菱レーヨン（株）社製商品名「パイロフィル（チョップ）」、東邦テナックス（株）社製商品名「ベスファイト（チョップ）」等を挙げることができ、ピッチ系炭素繊維では、三菱化学産資（株）社製商品名「ダイアリード」、大阪ガスケミカル（株）社製商品名「ドナカーボ（チョップ）」、呉羽化学（株）社製商品名「クレカチョップ」等を挙げることができる。
These carbon fibers can be used as so-called chopped carbon fibers obtained by cutting a fiber yarn into a desired length, and if necessary, are subjected to a convergence treatment using various sizing agents. Also good. Since the sizing agent used for fiber convergence needs to be melted in the melt-kneading with the polypropylene resin (PP), it is preferably melted at 200 ° C. or less.
The shape of the chopped carbon fiber is not limited to a straight one, and may be a curled carbon fiber having a curved fiber.
As specific examples of such chopped carbon fibers, PAN-based carbon fibers are trade names “Torayca Chop” manufactured by Toray Industries, Inc., “Pyrofil (chop)” manufactured by Mitsubishi Rayon Co., Ltd., Toho Tenax ( The product name “Besfite (chop)” manufactured by the company, etc. can be mentioned. For pitch-based carbon fiber, the product name “Dialead” manufactured by Mitsubishi Chemical Industries, Ltd., Osaka Gas Chemical Co., Ltd. Product names such as “Donna Carbo (chop)” and Kureha Chemical Co., Ltd. product name “Kureka chop” can be exemplified.
これらの炭素繊維は、上記ポリプロピレン樹脂（α）などと共に溶融混練されてポリプロピレン樹脂組成物（Ｂ）となるが、この溶融混練の際には、本発明に係るポリプロピレン樹脂組成物（Ｂ）の好ましい態様である、樹脂組成物ペレット中に存在する炭素繊維の平均長さが０．３ｍｍ以上となるような複合化方法を選択するのが好ましい。例えば、２軸押出機による溶融混練では、ポリプロピレン樹脂（α）などを十分に溶融混練した後、無機フィラー（β）成分である炭素繊維をサイドフィード法等によりフィードし、繊維の折損を最小限に押さえながら、収束繊維を分散させる等の工夫が必要である。 These carbon fibers are melt-kneaded together with the polypropylene resin (α) and the like to form a polypropylene resin composition (B). In this melt-kneading, the polypropylene resin composition (B) according to the present invention is preferable. It is preferable to select a compositing method that is an aspect in which the average length of the carbon fibers present in the resin composition pellets is 0.3 mm or more. For example, in melt kneading with a twin screw extruder, after sufficiently melting and kneading polypropylene resin (α), etc., carbon fiber as an inorganic filler (β) component is fed by a side feed method or the like to minimize fiber breakage. It is necessary to devise such as dispersing the converging fibers while holding down.
また、無機フィラー（β）として用いられるタルクは、低線膨張性や衝撃強度の点で、好ましくは平均粒径が１．５〜１５μｍ、特に好ましくは２〜８μｍのものである。該タルクは、例えば、先ずタルク原石を衝撃式粉砕機やミクロンミル型粉砕機で粉砕して製造したり、更にジェットミルなどで粉砕した後、サイクロンやミクロンセパレータ等で分級調整する等の方法で製造する。タルクの平均粒径は、レーザ回折散乱方式粒度分布計（例えば、堀場製作所ＬＡ−９２０型）を用いて測定することができる。
また、見かけ比容を２．５０ｍｌ／ｇ以下にしたいわゆる圧縮タルクを用いても良い。
In addition, talc used as the inorganic filler (β) preferably has an average particle size of 1.5 to 15 μm, particularly preferably 2 to 8 μm, from the viewpoint of low linear expansion and impact strength. The talc is produced, for example, by first pulverizing raw talc with an impact pulverizer or micron mill type pulverizer, or further pulverizing with a jet mill or the like and then adjusting the classification with a cyclone or micron separator. To manufacture. The average particle diameter of talc can be measured using a laser diffraction / scattering particle size distribution analyzer (for example, Horiba LA-920 type).
Further, so-called compression talc having an apparent specific volume of 2.50 ml / g or less may be used.
さらに、無機フィラー（β）は、金属石鹸、パラフィンワックス、ポリエチレンワックスまたはそれらの変性物、有機シラン、有機ボラン、有機チタネ−ト等を使用して表面処理されたものであってもよい。 Further, the inorganic filler (β) may be surface-treated using metal soap, paraffin wax, polyethylene wax or a modified product thereof, organic silane, organic borane, organic titanate and the like.
（３）熱可塑性エラストマー（γ）
本発明に係るポリプロピレン樹脂組成物（Ｂ）において、任意成分として用いる熱可塑性エラストマー（γ）は、耐衝撃性、成形性の向上、線膨張係数、収縮率などの調整等を目的に用いられる。熱可塑性エラストマー（γ）としては、ポリプロピレン樹脂組成物（Ａ）に用いるものと、同様のものが使用できる。
(3) Thermoplastic elastomer (γ)
In the polypropylene resin composition (B) according to the present invention, the thermoplastic elastomer (γ) used as an optional component is used for the purpose of adjusting impact resistance, improvement of moldability, linear expansion coefficient, shrinkage rate, and the like. As the thermoplastic elastomer (γ), those used for the polypropylene resin composition (A) can be used.
（４）着色剤（δ）
本発明に係るポリプロピレン樹脂組成物（Ｂ）には、目的とする色彩に応じて着色剤（δ）を配合することができる。着色剤（δ）としては、ポリプロピレン樹脂組成物（Ａ）に用いるものと、同様のものが使用できる。
(4) Colorant (δ)
In the polypropylene resin composition (B) according to the present invention, a colorant (δ) can be blended according to the target color. As the colorant (δ), those similar to those used for the polypropylene resin composition (A) can be used.
（５）その他の配合成分（任意成分）
本発明に係るポリプロピレン樹脂組成物（Ｂ）においては、本発明の効果を損なわない範囲で、或いは、更に性能の向上をはかるために、上記成分以外に、以下に示す任意成分を、適宜配合することができる。具体的には、酸化防止剤、帯電防止剤、光安定剤、紫外線吸収剤、核剤、難燃剤、分散剤、顔料、発泡剤などを挙げることができる。
(5) Other ingredients (arbitrary ingredients)
In the polypropylene resin composition (B) according to the present invention, in addition to the above components, the following optional components are appropriately blended within a range not impairing the effects of the present invention, or in order to further improve the performance. be able to. Specific examples include an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a nucleating agent, a flame retardant, a dispersant, a pigment, and a foaming agent.
（６）成分の配合割合
本発明に係るポリプロピレン樹脂組成物（Ｂ）に配合される前記各成分の割合は、（α）ポリプロピレン樹脂１０〜９９重量％、（β）無機フィラー１〜３５重量％、（γ）熱可塑性エラストマー０〜５０重量％、（δ）着色剤０〜５重量％であり、好ましくは、ポリプロピレン樹脂２５〜９４重量％、無機フィラー１〜３０重量％、熱可塑性エラストマー５〜４０重量％、着色剤０〜５重量％、さらに好ましくは、ポリプロピレン樹脂３０〜８９重量％、無機フィラー１〜３０重量％、熱可塑性エラストマー１０〜３５重量％、着色剤０〜５重量％である。
必須成分である無機フィラーの配合割合が１重量％未満であると、線膨張係数が大きくなるので、積層体の寸法安定性、反り変形性が悪化し、一方、３５重量％を超えると、衝撃性や成形性が低下する。
(6) Component blending ratio The proportion of each component blended in the polypropylene resin composition (B) according to the present invention is (α) 10 to 99% by weight of the polypropylene resin, (β) 1 to 35% by weight of the inorganic filler. (Γ) 0 to 50% by weight of thermoplastic elastomer, (δ) 0 to 5% by weight of colorant, preferably 25 to 94% by weight of polypropylene resin, 1 to 30% by weight of inorganic filler, 5 to 5% of thermoplastic elastomer 40 wt%, colorant 0 to 5 wt%, more preferably polypropylene resin 30 to 89 wt%, inorganic filler 1 to 30 wt%, thermoplastic elastomer 10 to 35 wt%, and colorant 0 to 5 wt%. .
If the blending ratio of the inorganic filler, which is an essential component, is less than 1% by weight, the coefficient of linear expansion increases, so that the dimensional stability and warp deformability of the laminate deteriorate. On the other hand, if it exceeds 35% by weight, impact Properties and moldability are reduced.
また、本発明に係るポリプロピレン樹脂組成物（Ｂ）は、コア層に用いられるため、本発明の二層成形体、すなわち積層体の寸法安定性のために、２３℃から８０℃までにおける線膨張係数が６×１０−５ｃｍ／（ｃｍ・℃）以下であることが好ましい（尚、線膨張係数の単位：ｃｍ／（ｃｍ・℃）を、／℃または℃−１と記載することもある。）。線膨張係数をこの上限値以下にするため、コア層に用いられる無機フィラーの配合割合や種類を変えることにより、適宜行うことができる。さらに、寸法安定性のために、本発明の二層成形体の２３℃から８０℃までにおける線膨張係数が１０×１０−５ｃｍ／（ｃｍ・℃）以下であることが、好ましい。本発明の二層成形体の線膨張係数をこの上限値以下にするためには、二層成形体のスキン層（Ｓ）とコア層（Ｃ）の厚み比率を変えることなどにより、適宜なし得ることができる。こうして、本発明の二層成形体は、低線膨張性を有することとなり、その結果、寸法安定性（低線膨張性、低反り変形性）が優れたものになる。 Moreover, since the polypropylene resin composition (B) according to the present invention is used for the core layer, the linear expansion at 23 ° C. to 80 ° C. is required for the dimensional stability of the two-layer molded product of the present invention, that is, the laminate. The coefficient is preferably 6 × 10 −5 cm / (cm · ° C.) or less (in addition, the unit of linear expansion coefficient: cm / (cm · ° C.) may be described as / ° C. or ° C. −1. .) In order to make a linear expansion coefficient below this upper limit, it can carry out suitably by changing the compounding ratio and kind of the inorganic filler used for a core layer. Furthermore, it is preferable that the linear expansion coefficient in 23 to 80 degreeC of the two-layer molded object of this invention is 10 * 10 < -5 > cm / (cm * degreeC) or less for dimensional stability. In order to make the linear expansion coefficient of the two-layer molded article of the present invention below this upper limit value, it can be appropriately performed by changing the thickness ratio of the skin layer (S) and the core layer (C) of the two-layer molded article. be able to. Thus, the two-layer molded article of the present invention has low linear expansion, and as a result, has excellent dimensional stability (low linear expansion and low warpage deformability).
（７）ポリプロピレン樹脂組成物（Ｂ）の製造
本発明で用いるポリプロピレン樹脂組成物（Ｂ）は、上記成分（α）〜（δ）を、従来公知の方法で、各配合成分を上記配合割合で配合・混合し、溶融混練することにより製造できる。溶融混練などは、ポリプロピレン樹脂組成物（Ａ）に用いる方法と、同様の方法が使用できる。
(7) Production of Polypropylene Resin Composition (B) The polypropylene resin composition (B) used in the present invention comprises the above components (α) to (δ) in a conventionally known method, and the respective blending components at the above blending ratios. It can be produced by blending, mixing and melt-kneading. For melt kneading, the same method as that used for the polypropylene resin composition (A) can be used.
Ｖ．ポリプロピレン系樹脂二層成形体の用途
本発明のポリプロピレン系樹脂二層成形体は、耐汚染性や耐傷付き性に優れ、且つ寸法安定性（低線膨張性、低反り変形性）に優れていることから、各種家電製品、各種工業部品分野、特に大型化された自動車の外装製品、例えば、バンパー、サイドロッカーカバー、サイドモール、オーバーフェンダー、バックドア、ガーニッシュなどに使用可能な性能を有している。そのため、上記用途に好適に用いることができる。
V. Uses of Polypropylene Resin Two-Layer Molded Article The polypropylene resin two-layer molded article of the present invention is excellent in stain resistance and scratch resistance, and is excellent in dimensional stability (low linear expansion property and low warpage deformation property). Therefore, it has the performance that can be used for various home appliances, various industrial parts fields, especially automobile exterior products that have been enlarged, such as bumpers, side rocker covers, side moldings, over fenders, back doors, garnishes, etc. Yes. Therefore, it can be suitably used for the above applications.
以下、本発明のポリプロピレン系樹脂二層成形体の実施例及び比較例を示して、具体的に説明するが、本発明は、これらの実施例および比較例に限定されるものではない。 Hereinafter, although the Example and comparative example of a polypropylene resin two-layer molded object of this invention are shown and demonstrated concretely, this invention is not limited to these Examples and a comparative example.
［実施例１〜１４、比較例１〜９）
先ず、二層射出成形体の製造方法として、多数の材料評価を効率的に行う目的でインサート成形法を用い、以下の手順で試験片を作製した。
[Examples 1 to 14, Comparative Examples 1 to 9)
First, as a method for producing a two-layer injection molded body, an insert molding method was used for the purpose of efficiently evaluating a large number of materials, and test pieces were produced according to the following procedure.
手順１：１２０×１２０×１ｍｍｔのキャビティを有した金型を用いて、スキン層材を射出成形し、同形状のシートを得る。
手順２：１２０×１２０×３．５ｍｍｔのキャビティを有した金型に手順１で得たスキン層材の平板シートをインサートする。
手順３：手順２でインサートされたスキン層材の表面にコア層材を射出成形し、スキン層厚みが１ｍｍでコア層厚みが２．５ｍｍの二層成形体を得た。
尚、コア層となるポリプロピレン樹脂組成物（Ｂ）の線膨張係数測定用には、スキン層材をインサートしない状態で、コア層材のみを成形した１２０×１２０×３．５ｍｍｔの平板を用いた。
Procedure 1: Using a mold having a cavity of 120 × 120 × 1 mmt, the skin layer material is injection-molded to obtain a sheet having the same shape.
Procedure 2: Insert the flat sheet of the skin layer material obtained in Procedure 1 into a mold having a cavity of 120 × 120 × 3.5 mmt.
Procedure 3: The core layer material was injection-molded on the surface of the skin layer material inserted in Procedure 2, and a two-layer molded product having a skin layer thickness of 1 mm and a core layer thickness of 2.5 mm was obtained.
In addition, for measuring the linear expansion coefficient of the polypropylene resin composition (B) to be the core layer, a 120 × 120 × 3.5 mmt flat plate in which only the core layer material was molded without using the skin layer material was used. .
＜成形条件＞
成形条件は、以下のとおりである。
成形機：東芝機械社製 ＩＳ１７０ＦＩＩ
金 型：平板金型（１２０×１２０ｍｍのキャビティ入れ子が交換可能）
スキン層材成形温度：２４０℃
コア層材成形温度：２２０℃
金型温度：４０℃
<Molding conditions>
The molding conditions are as follows.
Molding machine: IS170FII manufactured by Toshiba Machine Co., Ltd.
Mold: Flat plate mold (120 x 120 mm cavity insert can be replaced)
Skin layer material molding temperature: 240 ° C
Core layer material molding temperature: 220 ° C
Mold temperature: 40 ℃
前記より得た二層射出成形体について、次の性能評価を実施した。その評価結果を表１、表２に示す。 The following performance evaluation was performed on the two-layer injection-molded product obtained as described above. The evaluation results are shown in Tables 1 and 2.
＜耐汚染性＞
ＪＩＳ Ｂ７７５３の「サンシャインカーボンアーク灯式耐光性及び耐候性試験機」に準拠したサンシャインカーボンアーク灯式耐候性試験機に取り付け、ＪＩＳ−Ｋ７３５０−４の「プラスチック−実験室光源による暴露試験方法−第４部：オープンフレームカーボンアークランプ」に準拠したブラックパネル６３℃、降雨時間１２分／６０分、の条件で１０００時間放置後、シートを流水下にて市販のスポンジにて洗浄し、汚れ度合いを目視にて、次の４段階の評価基準で評価した。
◎：汚れが目立たない
○：若干汚れが目立つ
△：やや汚れが目立つ
×：汚れが目立つ
<Contamination resistance>
JIS B7753 “Sunshine carbon arc lamp type light and weather resistance tester” is attached to a sunshine carbon arc lamp type weather resistance tester in accordance with JIS-K7350-4 “Plastics-Exposure test method with laboratory light source-No. After leaving for 1000 hours under conditions of black panel 63 ° C, rain time 12 minutes / 60 minutes in accordance with “Part 4: Open Frame Carbon Arc Lamp”, the sheet is washed with a commercially available sponge under running water to determine the degree of contamination. Visually, the evaluation was performed according to the following four evaluation criteria.
◎: Dirt is not noticeable ○: Dirt is slightly noticeable △: Dirt is slightly noticeable X: Dirt is noticeable
＜線膨張係数＞
ＪＩＳ Ｋ７１９７の「プラスチックの熱機械分析による線膨脹率試験方法」に準拠した熱機械分析装置（ＴＭＡ装置）を用い、成形体の中央部を長さ１０ｍｍ×幅１０ｍｍの短冊状に切削したものを試験片として、２３℃から８０℃までの平均線膨張率（℃−１）即ち（／℃）を測定した。
<Linear expansion coefficient>
Using a thermomechanical analyzer (TMA apparatus) compliant with JIS K7197 "Plastic thermal mechanical analysis test method for plastics", the center part of the molded product was cut into a strip of 10mm length x 10mm width. As a test piece, an average linear expansion coefficient (° C. −1 ), that is, (/ ° C.) from 23 ° C. to 80 ° C. was measured.
＜反り変形性＞
積層体の１端を固定した時の他端の浮き上がり量を計測し（図４参照。）、次の３段階の評価基準でランク付けした。
○：浮き上がり量が０ｍｍ〜１０ｍｍである。
△：浮き上がり量が１０ｍｍ〜２０ｍｍである。
×：浮き上がり量が２０ｍｍ以上である。
<War deformability>
The amount of lifting at the other end when one end of the laminate was fixed was measured (see FIG. 4), and ranked according to the following three evaluation criteria.
○: Lifting amount is 0 mm to 10 mm.
Δ: Lifting amount is 10 mm to 20 mm.
X: The amount of lifting is 20 mm or more.
本評価に用いたスキン層材は、下記（ａ）〜（ｄ）、（ｆ）であり、これらの成分を表１、表２に示す割合で、スーパーミキサーにてドライブレンドした後、押出し温度２００℃、吐出量３５ｋｇ／ｈの条件で２軸押出し機（神戸製鋼社製、ＫＴＸ４４）を用いて溶融混練した。
なお、溶融混練時の熱安定剤として、チバ・スペシャルティ・ケミカル（株）製の酸化防止剤「イルガノックス１０１０」を、組成物１００重量部に対して、０．１重量部添加し、評価材料とした。
The skin layer materials used in this evaluation are the following (a) to (d) and (f), and these components are dry blended at a ratio shown in Tables 1 and 2 with a super mixer, and then the extrusion temperature. The mixture was melt-kneaded using a twin screw extruder (manufactured by Kobe Steel, KTX44) at 200 ° C. and a discharge rate of 35 kg / h.
In addition, 0.1 parts by weight of an antioxidant “Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd. was added as a heat stabilizer during melt kneading to 100 parts by weight of the composition. It was.
（ａ）ポリプロピレン樹脂：
ａ−１：プロピレン単独重合体（日本ポリプロ（株） ノバテックＰＰ ＭＡ０６）
ａ−２：プロピレン・エチレンブロック共重合体（日本ポリプロ（株） ノバテックＰＰ ＢＣ０３Ｂ）
（ｂ）エチレン／エチルアクリレート共重合体（ＥＥＡ）：
エチルアクリレートの重合単位比率が２０ｗｔ％のＥＥＡを用いた。
（ｃ）肪酸アミド又はその誘導体：
市販のオレイン酸アミドを用いた。
（ｄ）熱可塑性エラストマー：
ｄ−１：エチレン−ブテン−１エラストマー
ｄ−２：エチレン−オクテン−１エラストマー
（ｆ）着色剤：
酸化チタン（石原産業製タイベークＣＲ−９０）
(A) Polypropylene resin:
a-1: Propylene homopolymer (Nippon Polypro Co., Ltd. Novatec PP MA06)
a-2: Propylene / ethylene block copolymer (Nippon Polypro Co., Ltd. Novatec PP BC03B)
(B) Ethylene / ethyl acrylate copolymer (EEA):
EEA having a polymerization unit ratio of ethyl acrylate of 20 wt% was used.
(C) Fatty acid amide or derivative thereof:
Commercially available oleic amide was used.
(D) Thermoplastic elastomer:
d-1: ethylene-butene-1 elastomer d-2: ethylene-octene-1 elastomer (f) Colorant:
Titanium oxide (Ishihara Sangyo Thai Bake CR-90)
本評価に用いたコア層材は、下記（α）〜（γ）であり、これらの成分を表１、表２に示す割合で、スーパーミキサーにてドライブレンドした後、押出し温度２００℃、吐出量３５ｋｇ／ｈの条件で２軸押出し機（神戸製鋼社製、ＫＴＸ４４）を用いて溶融混練した。
なお、溶融混練時の熱安定剤として、チバ・スペシャルティ・ケミカル（株）製の酸化防止剤「イルガノックス１０１０」を、組成物１００重量部に対して、０．１重量部添加し、評価材料を得た。
The core layer materials used in this evaluation are the following (α) to (γ), and after dry blending these components at the ratios shown in Tables 1 and 2, the extrusion temperature is 200 ° C. and the discharge is performed. It melt-kneaded using the twin-screw extruder (the Kobe Steel make, KTX44) on the conditions of 35 kg / h of quantity.
In addition, 0.1 parts by weight of an antioxidant “Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd. was added as a heat stabilizer during melt kneading to 100 parts by weight of the composition. Got.
（α）ポリプロピレン樹脂：
プロピレン・エチレンブロック共重合体（日本ポリプロ（株） ノバテックＰＰ ＢＣ０３Ｂ）
（β）無機フィラー：
β−１：炭素繊維（ＣＦ）；東レ社製 ＰＡＮ系炭素繊維 ＴＷ１２（繊維径７μｍ、繊維長６ｍｍ）
β−２：タルク；林化成社製 ミクロンホワイト５０００Ａ（粒径：７．８μｍ）
（γ）熱可塑性エラストマー：
γ−１：エチレン−ブテン−１エラストマー
γ−２：エチレン−オクテン−１エラストマー
(Α) Polypropylene resin:
Propylene / ethylene block copolymer (Nippon Polypro Co., Ltd. Novatec PP BC03B)
(Β) Inorganic filler:
β-1: Carbon fiber (CF); PAN-based carbon fiber TW12 (fiber diameter 7 μm, fiber length 6 mm) manufactured by Toray Industries, Inc.
β-2: Talc; Hayashi Kasei Co., Ltd. Micron White 5000A (particle size: 7.8 μm)
(Γ) Thermoplastic elastomer:
γ-1: ethylene-butene-1 elastomer γ-2: ethylene-octene-1 elastomer
表１、表２の実施例、比較例の評価結果に示す通り、本発明の実施例１〜１４は、従来材料としての比較例１〜９に比べて、スキン層材となるポリプロピレン樹脂（ａ）に、エチレン・エチルアクリレート共重合体（ＥＥＡ）（ｂ）及び脂肪酸アミド類（ｃ）を組み合わせることにより、二層射出成形体としての耐汚染性が向上し、且つコア層となるポリプロピレン樹脂（α）に、必須成分として無機フィラー（β）を適量添加することにより、低線膨張性で低反り変形性の二層射出成形体が得られる結果であった。すなわち、比較例１、２は、スキン層材に必須成分のＥＥＡ（ｂ）と脂肪酸アミド（ｃ）の両成分が無添加のため、耐汚染性が低下し、比較例３、４は、スキン層材に必須成分のＥＥＡと脂肪酸アミドの一成分が無添加のため、耐汚染性が低下し、比較例５、６は、スキン層材に必須成分のＥＥＡ（ｂ）と脂肪酸アミド（ｃ）の両成分を添加しているものの、その添加量が本発明で規定した範囲外であるため、耐汚染性が低下している。また、比較例７、８は、コア層材に必須成分の無機フィラー（β）が無添加のため、寸法安定性（線膨張性と反り変形性）が低下し、比較例９は、コア層材に必須成分の無機フィラー（β）を添加しているが、その添加量が本発明で規定した範囲外であるため、寸法安定性が良好であるものの、衝撃性が低下している。さらに、実施例１３、１４は、コア層材に必須成分の無機フィラー（β）を添加し、その添加量も本発明で規定した範囲内であるものの、コア層材の線膨張係数が高いため、二層成形体の寸法安定性が他の実施例に比べて、実用レベルであるものの比較的悪くなっている。 As shown in the evaluation results of Examples and Comparative Examples in Tables 1 and 2, Examples 1 to 14 of the present invention are polypropylene resins (a ) And ethylene / ethyl acrylate copolymer (EEA) (b) and fatty acid amides (c) are combined to improve the contamination resistance as a two-layer injection-molded product and to form a polypropylene resin (core layer) By adding an appropriate amount of the inorganic filler (β) as an essential component to α), it was a result that a two-layer injection molded article having low linear expansion and low warpage deformation was obtained. That is, in Comparative Examples 1 and 2, since both the essential components EEA (b) and fatty acid amide (c) are not added to the skin layer material, the stain resistance is lowered. Since one component of EEA and fatty acid amide, which are essential components, is not added to the layer material, the stain resistance is lowered, and Comparative Examples 5 and 6 are EEA (b) and fatty acid amide (c) as essential components for the skin layer material. However, since the addition amount is outside the range defined in the present invention, the stain resistance is reduced. In Comparative Examples 7 and 8, since the inorganic filler (β) as an essential component is not added to the core layer material, the dimensional stability (linear expansion and warp deformability) is lowered. Although the inorganic filler (β), which is an essential component, is added to the material, the amount of addition is outside the range defined in the present invention, so the dimensional stability is good, but the impact property is reduced. Furthermore, in Examples 13 and 14, an essential component inorganic filler (β) was added to the core layer material, and the amount added was also within the range defined by the present invention, but the core layer material has a high linear expansion coefficient. The dimensional stability of the two-layer molded body is relatively poor although it is a practical level as compared with other examples.
本発明の二層成形体は、耐汚染性や耐傷付き性に優れ、且つ寸法安定性（低線膨張性、低反り変形性）に優れていることから、各種家電製品、各種工業部品分野、特に大型化された自動車の外装製品、例えば、バンパー、サイドロッカーカバー、サイドモール、オーバーフェンダー、バックドア、ガーニッシュなどに使用可能な性能を有し、工業的に用いることができる。 The two-layer molded product of the present invention is excellent in stain resistance and scratch resistance, and is excellent in dimensional stability (low linear expansion property, low warpage deformability). In particular, it has performance that can be used for automobile exterior products that have been enlarged, such as bumpers, side rocker covers, side moldings, over fenders, back doors, garnishes, and the like, and can be used industrially.
Claims (8)
スキン層（Ｓ）は、下記ポリプロピレン樹脂組成物（Ａ）からなり、及び
コア層（Ｃ）は、下記ポリプロピレン樹脂組成物（Ｂ）からなることを特徴とするポリプロピレン系樹脂二層成形体。
ポリプロピレン樹脂組成物（Ａ）：
（ａ）ポリプロピレン樹脂：１００重量部
（ｂ）エチルアクリレート重合単位の比率が５〜５０重量％であるエチレン・エチルアクリレート共重合体：０．５〜１５重量部
（ｃ）脂肪酸アミドまたはその誘導体：０．０５〜２．５重量部
（ｄ）熱可塑性エラストマー：０〜３５重量部
（ｅ）無機フィラー：０〜３５重量部
（ｆ）着色剤：０〜５０重量部
ポリプロピレン樹脂組成物（Ｂ）：
（α）ポリプロピレン樹脂：１０〜９９重量％
（β）無機フィラー：１〜３５重量％
（γ）熱可塑性エラストマー：０〜５０重量％
（δ）着色剤：０〜５重量％ A polypropylene-based resin bilayer molded body comprising a skin layer (S) and a core layer (C),
The skin layer (S) is composed of the following polypropylene resin composition (A), and the core layer (C) is composed of the following polypropylene resin composition (B).
Polypropylene resin composition (A):
(A) Polypropylene resin: 100 parts by weight (b) Ethylene / ethyl acrylate copolymer having a ratio of ethyl acrylate polymer units of 5 to 50% by weight: 0.5 to 15 parts by weight (c) Fatty acid amide or derivative thereof: 0.05 to 2.5 parts by weight (d) Thermoplastic elastomer: 0 to 35 parts by weight (e) Inorganic filler: 0 to 35 parts by weight (f) Colorant: 0 to 50 parts by weight Polypropylene resin composition (B) :
(Α) Polypropylene resin: 10 to 99% by weight
(Β) Inorganic filler: 1 to 35% by weight
(Γ) Thermoplastic elastomer: 0 to 50% by weight
(Δ) Colorant: 0 to 5% by weight
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| CN112166021A (en) * | 2018-05-22 | 2021-01-01 | 旭化成株式会社 | Two-color injection molded body |
| US11034819B2 (en) | 2016-02-24 | 2021-06-15 | Exxonmobil Chemical Patents Inc. | Self-assembled propylene-based compositions and methods of production thereof |
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| JP4711907B2 (en) | 2011-06-29 |
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