JP2007056176A - Fiber reinforced foamable resin composition and foamed molding therefrom - Google Patents
Fiber reinforced foamable resin composition and foamed molding therefrom Download PDFInfo
- Publication number
- JP2007056176A JP2007056176A JP2005245183A JP2005245183A JP2007056176A JP 2007056176 A JP2007056176 A JP 2007056176A JP 2005245183 A JP2005245183 A JP 2005245183A JP 2005245183 A JP2005245183 A JP 2005245183A JP 2007056176 A JP2007056176 A JP 2007056176A
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- Prior art keywords
- resin
- weight
- resin composition
- foam
- foamable
- Prior art date
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Abstract
Description
本発明は、外観、剛性、発泡性などに優れ、焼却処理による残渣が実質的に生じない発泡成形体と、この成形体を形成するのに有用な発泡性樹脂組成物（又は発泡性熱可塑性樹脂組成物）に関する。特に、水を通さず水分を透過可能な防水透湿性を有する発泡シートを調製するために有用な発泡性樹脂組成物に関する。 The present invention provides a foamed molded article that is excellent in appearance, rigidity, foamability, etc., and is substantially free from residues caused by incineration, and a foamable resin composition (or foamable thermoplasticity) useful for forming this molded article. Resin composition). In particular, the present invention relates to a foamable resin composition useful for preparing a waterproof and moisture-permeable foam sheet that allows water to pass therethrough.
自動車部品、オフィスオートメーション（ＯＡ）機器などを構成する成形体は、その強度及び剛性を向上させるため、ガラス繊維などの強化繊維で強化されている。例えば、特開平７−８０８３４号公報（特許文献１）には、熱可塑性樹脂と強化繊維とを含み、均一に分散した強化繊維の重量平均繊維長と数平均繊維長との割合、重量平均繊維長を特定することにより、成形性、機械的性質や表面平滑性に優れた繊維強化熱可塑性樹脂構造物が開示されている。このような技術は発泡体にも応用されており、例えば、特開平８−２０７０６８号公報（特許文献２）には、特定のプロピレン系樹脂とガラス繊維とを７５／２５〜９５／５（重量部）の割合で含む樹脂組成物に対して、ラジカル発生剤と架橋助剤と発泡剤とを所定の割合で含む発泡性シート形成用組成物が開示されている。この文献には、発泡性シート形成用組成物を、発泡剤が分解しない温度でシート成形し、バッキング材を裏打ちし、発泡性シートに電離性放射線を照射してプロピレン系樹脂を架橋させた後、加熱して発泡させ、発泡シートが冷却固化しないうちに表面材を載置してプレス成形加工する自動車用成形天井材の製造方法も記載されている。特開２００３−２４５９６７号公報（特許文献３）には、γ線を照射して架橋させた架橋ポリプロピレン系樹脂をさらに含む発泡性シート形成用組成物が開示されている。なお、特公平３−５２３４２号公報（特許文献４）には、繊維長１３ｍｍ以下の無機繊維が分散されたスチレン系樹脂ペースト又はエマルジョンを有機繊維不織布に含浸した樹脂強化シートと、この樹脂強化シートの両面に積層したスチレン系樹脂発泡シートとを備えた積層体が開示されている。 Molded bodies constituting automobile parts, office automation (OA) equipment, and the like are reinforced with reinforcing fibers such as glass fibers in order to improve the strength and rigidity thereof. For example, Japanese Patent Application Laid-Open No. 7-80834 (Patent Document 1) discloses a ratio of a weight average fiber length and a number average fiber length of a reinforced fiber including a thermoplastic resin and a reinforced fiber, and a weight average fiber. By specifying the length, a fiber reinforced thermoplastic resin structure excellent in moldability, mechanical properties and surface smoothness is disclosed. Such a technique is also applied to a foam. For example, in Japanese Patent Application Laid-Open No. Hei 8-207068 (Patent Document 2), a specific propylene-based resin and glass fiber are 75/25 to 95/5 (weight). Part)), a foamable sheet forming composition containing a radical generator, a crosslinking aid and a foaming agent in a predetermined ratio is disclosed. In this document, a foamable sheet-forming composition is formed at a temperature at which the foaming agent does not decompose, the backing material is lined, and the foamable sheet is irradiated with ionizing radiation to crosslink the propylene-based resin. Also described is a method for producing a molded ceiling material for automobiles in which foaming is performed by heating, and a surface material is placed and press-molded before the foamed sheet is cooled and solidified. Japanese Patent Application Laid-Open No. 2003-245967 (Patent Document 3) discloses a foamable sheet-forming composition further comprising a crosslinked polypropylene resin that has been crosslinked by irradiation with γ rays. In Japanese Patent Publication No. 3-52342 (Patent Document 4), a resin reinforced sheet in which an organic fiber nonwoven fabric is impregnated with a styrene resin paste or emulsion in which inorganic fibers having a fiber length of 13 mm or less are dispersed, and the resin reinforced sheet. The laminated body provided with the styrene-type resin foam sheet laminated | stacked on both surfaces is disclosed.
しかし、このような成形体は無機物を含有しており、使用済みの成形体を焼却すると、残渣が生じる。そのため、残渣の埋め立て処理などが必要となり、処理コストが増大するとともに、環境上も好ましくない。さらに、ガラス繊維などの無機繊維により押出機のスクリューの摩耗が激しくなるため、無機繊維の使用は工業的な発泡体の製造に対して障害となる。 However, such a molded body contains an inorganic substance, and when a used molded body is incinerated, a residue is generated. This necessitates a landfill process for the residue, which increases the processing cost and is not preferable in terms of the environment. Furthermore, the use of inorganic fibers is an obstacle to the production of industrial foams because inorganic fibers such as glass fibers cause severe wear on the screw of the extruder.
特開平７−３２９２３２号公報（特許文献５）には、熱可塑性樹脂発泡体の少なくとも一面に植物繊維補強熱可塑性樹脂シートからなる表面材が積層された発泡複合体が提案されている。この発泡複合体は、燃焼させても残渣が生じず、焼却により容易に廃棄処理が行えるという利点がある。しかし、基材である発泡体と植物繊維補強熱可塑性シートとの貼り合わせる必要があり、コストの点でも好ましくない。 Japanese Laid-Open Patent Publication No. 7-329232 (Patent Document 5) proposes a foam composite in which a surface material made of a plant fiber reinforced thermoplastic resin sheet is laminated on at least one surface of a thermoplastic resin foam. This foamed composite has the advantage that no residue is produced even when it is burned and can be easily disposed of by incineration. However, it is necessary to bond the foam as a base material and the vegetable fiber reinforced thermoplastic sheet, which is not preferable in terms of cost.
特開２００５−６０６８９号公報（特許文献６）には、植物資源由来の樹脂、天然由来の有機充填剤を配合した樹脂組成物からなる発泡体であって、発泡倍率が１．０２〜１５倍である発泡体が開示されている。この文献には、天然由来の有機充填材として、紙粉などの粉末状充填材、ケナフ繊維などのパルプやセルロース繊維などが例示され、有機充填材の大きさが、１０ｍｍ以下、０．１μｍ以上であること、有機充填材の使用量が、ポリ乳酸樹脂を１００重量部としたとき、１〜３５０重量部であること、発泡体密度が０．０３〜１．２５ｇ／ｃｍ3であること、気泡サイズが０．１〜１０００μｍであることも記載されている。しかし、植物資源由来の樹脂と天然由来の有機充填材とを組み合わせると、均一に発泡した発泡体を得ることが困難である。また、植物資源由来の樹脂に代えてポリプロピレンを用いると、発泡が著しく不均一となり、発泡倍率を向上できず、発泡成形体としての商品価値を大きく低下させる。さらに、防水性と透湿性とを有する発泡体については言及されていない。
従って、本発明の目的は、ポリプロピレン系樹脂などのポリオレフィン系樹脂を用いても均一な発泡が可能なセルロース繊維強化発泡性樹脂組成物及びその発泡体を提供することにある。 Accordingly, an object of the present invention is to provide a cellulose fiber reinforced foamable resin composition capable of uniform foaming even when a polyolefin resin such as a polypropylene resin is used, and a foamed product thereof.
本発明の他の目的は、発泡効率が高く、焼却処理しても残渣が実質的に生じない発泡性樹脂組成物及びその発泡体を提供することにある。 Another object of the present invention is to provide a foamable resin composition having a high foaming efficiency and substantially free of residue even when incinerated, and a foamed product thereof.
本発明のさらに他の目的は、発泡倍率が高く軽量であり、しかも剛性と強度に優れる発泡体と、この発泡体を製造するのに適した発泡性樹脂組成物を提供することにある。 Still another object of the present invention is to provide a foam having a high foaming ratio and a light weight and excellent in rigidity and strength, and a foamable resin composition suitable for producing the foam.
本発明の別の目的は、水に対して非透過性であり、かつ透湿性を有する発泡体（又は発泡シート）及びこの発泡体の調製に適した発泡性樹脂組成物を提供することにある。 Another object of the present invention is to provide a foam (or foam sheet) that is impermeable to water and has moisture permeability and a foamable resin composition suitable for the preparation of the foam. .
本発明者らは、前記課題を達成するため鋭意検討した結果、ポリオレフィン系樹脂を有機繊維（セルロース繊維など）で強化した発泡性樹脂組成物において、ポリオレフィン系樹脂（メタロセン触媒を用いたポリオレフィン系樹脂など）と有機繊維（セルロース繊維など）と必要により変性オレフィン系化合物とを組み合わせると、均一に効率よく発泡できることを見いだし、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a polyolefin resin (a polyolefin resin using a metallocene catalyst) in a foamable resin composition in which a polyolefin resin is reinforced with organic fibers (such as cellulose fibers). Etc.), organic fibers (cellulose fibers, etc.) and, if necessary, modified olefinic compounds were found to be able to foam uniformly and efficiently, and the present invention was completed.
すなわち、本発明の発泡性樹脂組成物は、少なくともポリオレフィン系樹脂（Ａ１）で構成された熱可塑性樹脂（Ａ）と、有機繊維（Ｂ）とで構成され、発泡剤により発泡可能である。ポリオレフィン系樹脂（Ａ１）はメタロセン触媒により重合されたポリオレフィン系樹脂であってもよい。前記ポリオレフィン系樹脂（Ａ１）は、例えば、ポリエチレン系樹脂及びポリプロピレン系樹脂から選択された少なくとも一種であってもよい。また、ポリオレフィン系樹脂（Ａ１）は、温度１９０℃、荷重２１．６Ｎ（２．１６ｋｇｆ）の条件下でのメルトフローレートが０．１〜１００ｇ／１０分のポリエチレン系樹脂、および２３０℃、荷重２１．６Ｎ（２．１６ｋｇｆ）の条件下でのメルトフローレートが０．１〜１００ｇ／１０分のポリプロピレン系樹脂から選択された少なくとも一種であってもよい。さらに、熱可塑性樹脂（Ａ）は少なくともポリオレフィン系樹脂（Ａ１）で構成すればよく、ポリオレフィン系樹脂（Ａ１）と他の熱可塑性樹脂（Ａ２）とで構成してもよい。他の熱可塑性樹脂（Ａ２）としては、例えば、（１）融点２３０℃以下の結晶性樹脂、および（２）温度２００℃、せん断速度１００ｓｅｃ-1、キャピラリーレオメーターで測定した溶融粘度が１０〜１０4Ｐａ・ｓ（１０2〜１０5ポイズ）の非晶性樹脂から選択された少なくとも一種が例示できる。他の熱可塑性樹脂（Ａ２）としては、例えば、オレフィン系樹脂及びスチレン系樹脂から選択された少なくとも一種が例示できる。熱可塑性樹脂（Ａ）を構成する樹脂成分の割合は、適当に選択でき、例えば、ポリオレフィン系樹脂（Ａ１）と、他の熱可塑性樹脂（Ａ２）とを前者／後者＝５０／５０〜１００／０（重量比）の割合で含んでいてもよい。 That is, the foamable resin composition of the present invention is composed of at least a thermoplastic resin (A) composed of a polyolefin resin (A1) and an organic fiber (B), and can be foamed with a foaming agent. The polyolefin resin (A1) may be a polyolefin resin polymerized with a metallocene catalyst. The polyolefin resin (A1) may be at least one selected from, for example, a polyethylene resin and a polypropylene resin. The polyolefin resin (A1) is a polyethylene resin having a melt flow rate of 0.1 to 100 g / 10 min under the conditions of a temperature of 190 ° C. and a load of 21.6 N (2.16 kgf), and a load of 230 ° C. and a load. The melt flow rate under the condition of 21.6 N (2.16 kgf) may be at least one selected from polypropylene resins of 0.1 to 100 g / 10 min. Furthermore, the thermoplastic resin (A) may be composed of at least the polyolefin resin (A1), and may be composed of the polyolefin resin (A1) and another thermoplastic resin (A2). Examples of the other thermoplastic resin (A2) include (1) a crystalline resin having a melting point of 230 ° C. or lower, and (2) a temperature of 200 ° C., a shear rate of 100 sec −1 , and a melt viscosity measured with a capillary rheometer of 10 to 10. Examples thereof include at least one selected from an amorphous resin of 10 4 Pa · s (10 2 to 10 5 poise). Examples of the other thermoplastic resin (A2) include at least one selected from olefin resins and styrene resins. The ratio of the resin component constituting the thermoplastic resin (A) can be appropriately selected. For example, the polyolefin resin (A1) and the other thermoplastic resin (A2) are divided into the former / the latter = 50/50 to 100 / It may be contained at a ratio of 0 (weight ratio).
有機繊維（Ｂ）としては種々の繊維、例えば、セルロース繊維が使用できる。セルロース繊維は、純度が高い繊維であるのが好ましく、例えば、αセルロース含量が８０重量％以上の繊維であるのが好ましい。セルロース繊維などの有機繊維（Ｂ）としては、平均繊維径０．１〜１０００μｍ及び平均繊維長０．０１〜５ｍｍを有する繊維が使用できる。また、有機繊維（Ｂ）は、熱可塑性樹脂（Ａ）中に分散（例えば、均一に分散）していてもよい。有機繊維（Ｂ）の割合は、熱可塑性樹脂（Ａ）１００重量部に対して、１〜５００重量部程度であってもよい。 As the organic fiber (B), various fibers such as cellulose fiber can be used. The cellulose fiber is preferably a fiber having high purity. For example, the cellulose fiber is preferably a fiber having an α cellulose content of 80% by weight or more. As organic fibers (B) such as cellulose fibers, fibers having an average fiber diameter of 0.1 to 1000 μm and an average fiber length of 0.01 to 5 mm can be used. Moreover, the organic fiber (B) may be dispersed (for example, uniformly dispersed) in the thermoplastic resin (A). About 1-500 weight part may be sufficient as the ratio of an organic fiber (B) with respect to 100 weight part of thermoplastic resins (A).
発泡性樹脂組成物は、さらに、酸変性又はエポキシ変性オレフィン系化合物（Ｃ）を含んでいてもよい。変性オレフィン系化合物（Ｃ）は、カルボキシル基、酸無水物基及びエポキシ基から選択された少なくとも一種の変性基で変性されており、この変性基の割合は、単量体換算で、１〜３０重量％程度であってもよい。変性オレフィン系化合物（Ｃ）の重量平均分子量は１．５×１０4〜３０×１０4程度であってもよい。なお、変性オレフィン系化合物（Ｃ）の割合は、熱可塑性樹脂（Ａ）１００重量部に対して１〜３０重量部程度であってもよい。また、発泡剤（Ｄ）の割合は、熱可塑性樹脂（Ａ）１００重量部に対して０．１〜２０重量部程度であってもよい。 The foamable resin composition may further contain an acid-modified or epoxy-modified olefin compound (C). The modified olefin compound (C) is modified with at least one modified group selected from a carboxyl group, an acid anhydride group and an epoxy group, and the ratio of the modified group is 1 to 30 in terms of monomer. It may be about wt%. The weight average molecular weight of the modified olefin compound (C) may be about 1.5 × 10 4 to 30 × 10 4 . In addition, about 1-30 weight part may be sufficient as the ratio of a modified olefin type compound (C) with respect to 100 weight part of thermoplastic resins (A). The ratio of the foaming agent (D) may be about 0.1 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A).
樹脂組成物は、さらに種々の成分、例えば、収縮防止剤（Ｅ）及び／又はフッ素系樹脂（Ｆ）などを含有していてもよい。フッ素系樹脂（Ｆ）としては、ポリ（フルオロアルケン）重合体が例示できる。収縮防止剤（Ｅ）及び／又はフッ素系樹脂（Ｆ）の割合は、例えば、熱可塑性樹脂（Ａ）１００重量部に対して、収縮防止剤（Ｅ）０〜１０重量部、フッ素系樹脂（Ｆ）０〜１０重量部程度であってもよい。 The resin composition may further contain various components such as an anti-shrinkage agent (E) and / or a fluororesin (F). Examples of the fluororesin (F) include poly (fluoroalkene) polymers. The proportion of the anti-shrink agent (E) and / or the fluororesin (F) is, for example, from 0 to 10 parts by weight of the anti-shrink agent (E) to 100 parts by weight of the thermoplastic resin (A). F) About 0-10 weight part may be sufficient.
本発明は、前記樹脂組成物で構成された発泡体も包含する。この発泡体において、発泡倍率は１．５〜１５倍程度であってもよく、発泡構造は少なくとも連続気泡構造を有していてもよい。発泡体の形状も特に制限されず、例えば、発泡シートであってもよい。また、発泡シートは、 厚み０．０５〜５ｍｍのシートであり、４０℃及び９０％ＲＨで測定したとき、透湿度が１００〜１００００ｇ／（ｍ2・２４ｈ）程度であってもよい。 The present invention also includes a foam composed of the resin composition. In this foam, the foaming ratio may be about 1.5 to 15 times, and the foam structure may have at least an open cell structure. The shape of the foam is not particularly limited, and may be a foam sheet, for example. Further, the foam sheet is a sheet having a thickness of 0.05 to 5 mm, and the moisture permeability may be about 100 to 10,000 g / (m 2 · 24 h) when measured at 40 ° C. and 90% RH.
本発明では、ポリオレフィン系樹脂と有機繊維と必要により変性ポリオレフィン系樹脂とを組み合わせるため、ポリプロピレン系樹脂などのポリオレフィン系樹脂を用いても均一な発泡が可能であり発泡効率が高い。しかも、有機繊維で強化されているため、発泡体の機械的特性を向上できるとともに、焼却処理しても残渣が実質的に生じない。そのため、発泡倍率が高く軽量で、しかも剛性と強度に優れる発泡体を得ることができる。さらに、連続気泡構造を有する発泡体を得ることができ、水に対しては非透過性であり、かつ透湿性を有する発泡体を得ることもできる。 In the present invention, the polyolefin resin, the organic fiber, and the modified polyolefin resin, if necessary, are combined. Therefore, even if a polyolefin resin such as a polypropylene resin is used, uniform foaming is possible and the foaming efficiency is high. In addition, since it is reinforced with organic fibers, the mechanical properties of the foam can be improved, and a residue is not substantially produced even when incinerated. Therefore, it is possible to obtain a foam having a high foaming ratio and light weight and having excellent rigidity and strength. Furthermore, a foam having an open cell structure can be obtained, and a foam that is impermeable to water and has moisture permeability can also be obtained.
本発明の発泡性樹脂組成物（熱可塑性樹脂組成物）は、熱可塑性樹脂（Ａ）と、有機繊維（Ｂ）と、必要により変性ポリオレフィン系樹脂（Ｃ）とで構成されており、前記熱可塑性樹脂（Ａ）は少なくともポリオレフィン系樹脂（Ａ１）で構成されている。 The foamable resin composition (thermoplastic resin composition) of the present invention comprises a thermoplastic resin (A), an organic fiber (B), and, if necessary, a modified polyolefin resin (C). The plastic resin (A) is composed of at least a polyolefin resin (A1).
本発明では、ポリオレフィン系樹脂（Ａ１）として、チーグラー・ナッタ触媒、フィリップス触媒、メタロセン触媒などの触媒を用いて製造された種々のポリオレフィン系樹脂が使用できる。ポリオレフィン系樹脂は、架橋性基［熱架橋性基（ビニル基、（メタ）アクリロイル基などの重合性不飽和基）、光架橋性基、加水分解縮合性基［例えば、ケイ素原子に加水分解性基（例えば、メトキシ基、エトキシ基などのアルコキシ基）、ハロゲン原子（塩素原子など）など］が直接結合した基（例えば、アルコキシシリル基、ハロシリル基）などの架橋性基］を有する架橋性ポリオレフィン系樹脂であってもよいが、通常、架橋性基を有しない非架橋性ポリオレフィン系樹脂である場合が多い。このようなポリオレフィン系樹脂としては、オレフィンの単独重合体又は共重合体、オレフィンと共重合性単量体との共重合体などが挙げられる。 In the present invention, various polyolefin resins produced using a catalyst such as a Ziegler-Natta catalyst, a Phillips catalyst, or a metallocene catalyst can be used as the polyolefin resin (A1). Polyolefin resins include crosslinkable groups [thermally crosslinkable groups (polymerizable unsaturated groups such as vinyl groups, (meth) acryloyl groups), photocrosslinkable groups, hydrolytic condensable groups [for example, hydrolyzable to silicon atoms. Crosslinkable polyolefin having a group (for example, alkoxysilyl group, halosilyl group, etc.) directly bonded to a group (for example, alkoxy group such as methoxy group, ethoxy group, etc.), halogen atom (chlorine atom, etc.)] However, it is usually a non-crosslinkable polyolefin resin that does not have a crosslinkable group. Examples of such polyolefin resins include olefin homopolymers or copolymers, and copolymers of olefins and copolymerizable monomers.
オレフィン（又はポリオレフィン系樹脂の単量体）としては、例えば、エチレン、プロピレン、１−ブチレン、イソブチレン、１−ペンテン、３−メチル−１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン等のα−Ｃ2-20オレフィン（好ましくはα−Ｃ2-10オレフィン、さらに好ましくはα−Ｃ2-4オレフィン、特にα−Ｃ2-3オレフィン）などが挙げられる。これらのオレフィンは、単独で又は２種以上組み合わせて使用してもよい。 Examples of the olefin (or the monomer of the polyolefin resin) include ethylene, propylene, 1-butylene, isobutylene, 1-pentene, 3-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, Α-C 2-20 olefins such as 1-nonene, 1-decene, 1-undecene and 1-dodecene (preferably α-C 2-10 olefins, more preferably α-C 2-4 olefins, especially α-C 2-3 olefins). These olefins may be used alone or in combination of two or more.
共重合性単量体としては、例えば、（メタ）アクリル酸、（メタ）アクリル酸エステル[例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチルなどの（メタ）アクリル酸Ｃ1-6アルキルエステル]、ビニルエステル類（例えば、酢酸ビニル、プロピオン酸ビニルなど）、環状オレフィン類（ノルボルネン、エチリデンノルボルネン、シクロペンテン、シクロペンタジエン、シクロヘキセン等）、ジエン類（ブタジエン、イソプレン、１，４−ペンタジエンなど）などが例示できる。共重合性単量体は、単独で又は２種以上組み合わせて使用できる。オレフィンと共重合性単量体との割合（重量比）は、前者／後者＝１００／０〜５０／５０程度の範囲で選択でき、例えば、９５／５〜６０／４０程度、好ましくは９０／１０〜６５／３５程度、さらに好ましくは８５／１５〜７０／３０程度であってもよい。ポリオレフィン系共重合体（樹脂）は、ランダム共重合体又はブロック共重合体であってもよい。 Examples of the copolymerizable monomer include (meth) acrylic acid, (meth) acrylic acid ester [for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl (meth) acrylate etc. ) Acrylic acid C 1-6 alkyl ester], vinyl esters (for example, vinyl acetate, vinyl propionate, etc.), cyclic olefins (norbornene, ethylidene norbornene, cyclopentene, cyclopentadiene, cyclohexene, etc.), dienes (butadiene, isoprene) , 1,4-pentadiene, etc.). A copolymerizable monomer can be used individually or in combination of 2 or more types. The ratio (weight ratio) between the olefin and the copolymerizable monomer can be selected in the range of the former / the latter = 100/0 to 50/50, for example, about 95/5 to 60/40, preferably 90 / It may be about 10 to 65/35, more preferably about 85/15 to 70/30. The polyolefin copolymer (resin) may be a random copolymer or a block copolymer.
代表的なポリオレフィン系樹脂としては、例えば、ポリエチレン系樹脂［例えば、低、中又は高密度ポリエチレン樹脂、直鎖状低密度ポリエチレン樹脂などのエチレンホモポリマー；エチレン−プロピレン共重合体、エチレン−ブテン−１共重合体、エチレン−プロピレン−ブテン−１共重合体、エチレン−（４−メチルペンテン−１）共重合体など］、ポリプロピレン系樹脂（例えば、ポリプロピレン；プロピレン−エチレン共重合体、プロピレン−ブテン−１共重合体、プロピレン−エチレン−ブテン−１共重合体などのプロピレン含有８０モル％以上のプロピレン−α−オレフィン共重合体など）、ポリ（メチルペンテン−１）樹脂、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸共重合体又はその金属塩、エチレン−（メタ）アクリル酸Ｃ1-4アルキルエステル共重合体（エチレン−メタクリル酸メチル共重合体など）などが例示できる。これらのポリオレフィン系樹脂は、単独で又は二種以上組み合わせてもよい。 Typical polyolefin resins include, for example, polyethylene resins [for example, ethylene homopolymers such as low, medium or high density polyethylene resins, linear low density polyethylene resins; ethylene-propylene copolymers, ethylene-butene- 1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene- (4-methylpentene-1) copolymer, etc.], polypropylene resin (for example, polypropylene; propylene-ethylene copolymer, propylene-butene) -1 copolymer, propylene-containing propylene-α-olefin copolymer such as propylene-ethylene-butene-1 copolymer), poly (methylpentene-1) resin, ethylene-vinyl acetate copolymer Polymer, ethylene- (meth) acrylic acid copolymer or metal salt thereof, ethylene (Meth) acrylic acid C 1-4 alkyl ester copolymer (ethylene - methyl methacrylate copolymer, etc.), and others. These polyolefin resins may be used alone or in combination of two or more.
均一な発泡性、発泡体の組織の均一化などの点から、好ましいポリオレフィン系樹脂は、メタロセン触媒により重合されたポリオレフィン系樹脂を主たる成分として含む。メタロセン触媒とは、２個の平面環（シクロペンタジエンおよびその誘導体）の間に金属原子が挟まれた構造を有する金属錯体を総称し、フェロセン（η5−Ｃ5Ｈ5）2Ｆｅに代表されるビス（シクロペンタジエニル）金属錯体（η5−Ｃ5Ｈ5）2Ｍ（Ｍ：遷移金属を示し、以下、η5−Ｃ5Ｈ5はＣｐとする）が含まれる。なお、遷移金属としては、周期表第４、第５、第６周期の遷移金属が挙げられる。具体的には、第４周期遷移金属のメタロセンとして、Ｃｐ2Ｔｉ（チタノセン）、Ｃｐ2Ｖ（バナドセン）、Ｃｐ2Ｃｒ（クロモセン）、Ｃｐ2Ｍｎ（マンガノセン）、Ｃｐ2Ｆｅ（フェロセン）、Ｃｐ2Ｃｏ（コバルトセン）、Ｃｐ2Ｎｉ（ニッケロセン）およびその誘導体など、第５および第６周期遷移金属のメタロセンとして、Ｃｐ2Ｚｒ（ジルコノセン）、Ｃｐ2Ｒｕ（ルテノセン）、Ｃｐ2Ｏｓ（オスモセン）およびその誘導体などが挙げられる。これらメタロセン触媒は、単独で又は２種以上を組み合わせてもよい。これらのうち、ＦｅとＣｐとの結合がもっとも強く、このためフェロセンがもっとも安定である。メタロセン触媒を用いたポリオレフィン系樹脂（Ａ１）は分子量分布がシャープであり、結晶性も高い。そのため、他のポリオレフィン系樹脂と異なり、セルロース繊維などの有機繊維（Ｂ）で強化しても有効に発泡させることができるとともに、機械的特性（剛性、強度）を有効に向上できる。 From the viewpoints of uniform foaming properties and uniform foam structure, a preferred polyolefin resin contains a polyolefin resin polymerized by a metallocene catalyst as a main component. A metallocene catalyst is a generic term for metal complexes having a structure in which a metal atom is sandwiched between two planar rings (cyclopentadiene and its derivatives), and is represented by ferrocene (η 5 -C 5 H 5 ) 2 Fe. Bis (cyclopentadienyl) metal complex (η 5 -C 5 H 5 ) 2 M (M represents a transition metal, and η 5 -C 5 H 5 is hereinafter referred to as Cp). In addition, as a transition metal, the transition metal of the periodic table 4th, 5th, 6th period is mentioned. Specifically, as the metallocene of the fourth period transition metal, Cp 2 Ti (titanocene), Cp 2 V (vanadocene), Cp 2 Cr (chromocene), Cp 2 Mn (manganocene), Cp 2 Fe (ferrocene), Cp Cp 2 Zr (zirconocene), Cp 2 Ru (ruthenocene), Cp 2 Os (osmocene) as metallocenes of the fifth and sixth period transition metals such as 2 Co (cobaltene), Cp 2 Ni (nickelocene) and derivatives thereof And derivatives thereof. These metallocene catalysts may be used alone or in combination of two or more. Of these, the bond between Fe and Cp is the strongest, and therefore ferrocene is the most stable. The polyolefin resin (A1) using a metallocene catalyst has a sharp molecular weight distribution and high crystallinity. Therefore, unlike other polyolefin-based resins, foaming can be effectively performed even when reinforced with organic fibers (B) such as cellulose fibers, and mechanical properties (rigidity and strength) can be effectively improved.
メタロセン触媒により重合されたポリオレフィン系樹脂は、ポリエチレン系樹脂やポリプロピレン系樹脂であってもよく、これらの樹脂はホモポリマーであってもよくコポリマーであってもよい。 The polyolefin resin polymerized by the metallocene catalyst may be a polyethylene resin or a polypropylene resin, and these resins may be a homopolymer or a copolymer.
前記ポリエチレン系樹脂のメルトフローレートは、温度１９０℃、荷重２１．６Ｎ（２．１６ｋｇｆ）の条件下、例えば、０．１〜１００ｇ／１０分程度の範囲から選択でき、通常、０．１〜２０ｇ／１０分（例えば、０．１５〜１５ｇ／１０分）、好ましくは０．２〜１２ｇ／１０分（例えば、０．２〜１０ｇ／１０分）、さらに好ましくは０．２５〜８ｇ／１０分（例えば、０．３〜７ｇ／１０分）程度であってもよい。 The melt flow rate of the polyethylene resin can be selected from a range of, for example, about 0.1 to 100 g / 10 minutes under conditions of a temperature of 190 ° C. and a load of 21.6 N (2.16 kgf). 20 g / 10 min (for example, 0.15 to 15 g / 10 min), preferably 0.2 to 12 g / 10 min (for example, 0.2 to 10 g / 10 min), more preferably 0.25 to 8 g / 10 Minutes (for example, 0.3-7 g / 10 minutes) may be sufficient.
また、ポリプロピレン系樹脂のメルトフローレートは、温度２３０℃、荷重２１．６Ｎ（２．１６ｋｇｆ）の条件下、例えば、０．１〜１００ｇ／１０分程度であり、通常、０．１〜２０ｇ／１０分（例えば、０．１５〜１５ｇ／１０分）、好ましくは０．２〜１２ｇ／１０分（例えば、０．２〜１０ｇ／１０分）、さらに好ましくは０．２５〜８ｇ／１０分（例えば、０．３〜７ｇ／１０分）程度であってもよい。 The melt flow rate of the polypropylene resin is, for example, about 0.1 to 100 g / 10 minutes under the conditions of a temperature of 230 ° C. and a load of 21.6 N (2.16 kgf), and usually 0.1 to 20 g / 10 minutes (for example, 0.15 to 15 g / 10 minutes), preferably 0.2 to 12 g / 10 minutes (for example, 0.2 to 10 g / 10 minutes), more preferably 0.25 to 8 g / 10 minutes ( For example, it may be about 0.3 to 7 g / 10 minutes.
なお、ポリエチレン系樹脂の密度は、例えば、０．９０〜０．９７０ｇ／ｃｍ3、好ましくは０．９１〜０．９６ｇ／ｃｍ3、さらに好ましくは０．９１５〜０．９５ｇ／ｃｍ3程度であってもよい。また、ポリプロピレン系樹脂の密度は、０．９〜０．９８ｇ／ｃｍ3、好ましくは０．９１〜０．９７ｇ／ｃｍ3、さらに好ましくは０．９３〜０．９６ｇ／ｃｍ3程度であってもよい。 The density of the polyethylene resin, for example, 0.90~0.970g / cm 3, preferably 0.91~0.96g / cm 3, more preferably at about 0.915~0.95g / cm 3 There may be. The density of the polypropylene resin is 0.9 to 0.98 g / cm 3 , preferably 0.91 to 0.97 g / cm 3 , and more preferably about 0.93 to 0.96 g / cm 3. Also good.
前記ポリエチレン系樹脂の融点は、例えば、１５０℃以下（例えば、８０〜１４０℃程度）の範囲から選択でき、１３０℃以下（例えば、９０〜１２５℃程度）、好ましくは１２５℃以下（例えば、９５〜１２０℃程度）、さらに好ましくは１２０℃以下（例えば、１００〜１１５℃程度）であってもよい。また、ポリプロピレン系樹脂の融点は、例えば、１２０〜２００℃、好ましくは１３０〜１８０℃、さらに好ましくは１４０〜１６０℃程度であってもよい。 The melting point of the polyethylene resin can be selected, for example, from a range of 150 ° C. or lower (for example, about 80 to 140 ° C.), 130 ° C. or lower (for example, about 90 to 125 ° C.), preferably 125 ° C. or lower (for example, 95 ˜120 ° C.), more preferably 120 ° C. or less (eg, about 100-115 ° C.). Moreover, the melting point of the polypropylene resin may be, for example, about 120 to 200 ° C, preferably about 130 to 180 ° C, and more preferably about 140 to 160 ° C.
また、メタロセンポリオレフィン系樹脂の分子量分布は、例えば、１．０１〜３．０、好ましくは１．０２〜２．０（例えば、１．０５〜１．８）、さらに好ましくは１．１〜１．５（例えば、１．１５〜１．４）程度であってもよい。 The molecular weight distribution of the metallocene polyolefin resin is, for example, 1.01 to 3.0, preferably 1.02 to 2.0 (for example, 1.05 to 1.8), and more preferably 1.1 to 1. .5 (for example, 1.15 to 1.4).
熱可塑性樹脂（Ａ）は、少なくともポリオレフィン系樹脂（Ａ１）で構成されていればよく、ポリオレフィン系樹脂（Ａ１）単独に限らず、ポリオレフィン系樹脂（Ａ１）と他の熱可塑性樹脂（Ａ２）とで構成してもよい。特に熱可塑性樹脂（Ａ）は、メタロセン触媒を用いたポリオレフィン系樹脂を少なくとも含む樹脂であるのが好ましい。他の熱可塑性樹脂（Ａ２）は、通常、（１）融点２３０℃以下（例えば、１２０〜２１０℃、好ましくは１３０〜２００℃）の結晶性樹脂、および（２）温度２００℃、せん断速度１００ｓｅｃ-1、キャピラリーレオメーターで測定した溶融粘度が１０〜１０4Ｐａ・ｓ（１０2〜１０5ポイズ）（好ましくは５０〜５×１０3Ｐａ・ｓ、さらに好ましくは１０2〜３×１０3Ｐａ・ｓ）の非晶性樹脂から選択された少なくとも一種である場合が多い。このような熱可塑性樹脂（Ａ２）のうち、結晶性樹脂としては、例えば、メタロセン触媒以外の触媒を用いたポリオレフィン系樹脂（ポリエチレン、ポリエチレン系共重合体などのポリエチレン系樹脂、ポリプロピレン、ポリプロピレン系共重合体などのポリプロピレン系樹脂）、ポリアミド系樹脂（ポリアミド６、１１、１２など）、芳香族ポリエステル系樹脂（ポリエチレンテレフタレート系樹脂、ポリブチレンテレフタレート系樹脂などのポリアルキレンアリレート系樹脂など）、ポリビニルアルコール系樹脂などが例示できる。また、非晶質樹脂としては、例えば、スチレン系樹脂（ポリスチレンＧＰＰＳ、ゴム強化スチレン系樹脂（中衝撃ポリスチレンＭＩＰＳ，高衝撃ポリスチレンＨＩＰＳ）、アクリロニトリル−スチレン系樹脂ＡＳ、アクリロニトリル−ブタジエン−スチレン系樹脂ＡＢＳなど）、アクリル系樹脂（ポリメタクリル酸メチルＰＭＭＡなど）、ポリエステル系樹脂（ポリアリレート系樹脂などの芳香族ポリエステル系樹脂、脂肪族ポリエステル系樹脂など）などが例示できる。これらの熱可塑性樹脂（Ａ２）は単独で又は二種以上組み合わせて使用できる。これらの熱可塑性樹脂（Ａ２）のうち、結晶性樹脂としてはポリオレフィン系樹脂（ポリエチレン系樹脂、ポリプロピレン系樹脂など）が好ましく、非晶質樹脂としてはスチレン系樹脂（ポリスチレンなど）が好ましい。 The thermoplastic resin (A) only needs to be composed of at least the polyolefin resin (A1), and is not limited to the polyolefin resin (A1) alone, but the polyolefin resin (A1) and other thermoplastic resins (A2) You may comprise. In particular, the thermoplastic resin (A) is preferably a resin containing at least a polyolefin resin using a metallocene catalyst. The other thermoplastic resin (A2) is usually (1) a crystalline resin having a melting point of 230 ° C. or lower (for example, 120 to 210 ° C., preferably 130 to 200 ° C.), and (2) a temperature of 200 ° C. and a shear rate of 100 sec. -1 , the melt viscosity measured with a capillary rheometer is 10 to 10 4 Pa · s (10 2 to 10 5 poise) (preferably 50 to 5 × 10 3 Pa · s, more preferably 10 2 to 3 × 10 3 In many cases, it is at least one selected from an amorphous resin of Pa · s). Among such thermoplastic resins (A2), as the crystalline resin, for example, polyolefin resins using a catalyst other than a metallocene catalyst (polyethylene resins such as polyethylene and polyethylene copolymers, polypropylene and polypropylene copolymers) can be used. Polypropylene resins such as polymers), polyamide resins (polyamide 6, 11, 12, etc.), aromatic polyester resins (polyalkylene arylate resins such as polyethylene terephthalate resin and polybutylene terephthalate resin), polyvinyl alcohol Examples of such resins are listed below. Examples of the amorphous resin include styrene resin (polystyrene GPPS, rubber-reinforced styrene resin (medium impact polystyrene MIPS, high impact polystyrene HIPS), acrylonitrile-styrene resin AS, acrylonitrile-butadiene-styrene resin ABS. Etc.), acrylic resins (polymethyl methacrylate PMMA, etc.), polyester resins (aromatic polyester resins such as polyarylate resins, aliphatic polyester resins, etc.). These thermoplastic resins (A2) can be used alone or in combination of two or more. Of these thermoplastic resins (A2), the crystalline resin is preferably a polyolefin resin (polyethylene resin, polypropylene resin, etc.), and the amorphous resin is preferably a styrene resin (polystyrene, etc.).
ポリオレフィン系樹脂（Ａ１）と、他の熱可塑性樹脂（Ａ２）との割合（重量比）は、前者／後者＝５０／５０〜１００／０、好ましくは５５／４５〜１００／０、さらに好ましくは６０／４０〜９５／５程度であってもよい。 The ratio (weight ratio) between the polyolefin resin (A1) and the other thermoplastic resin (A2) is the former / the latter = 50/50 to 100/0, preferably 55/45 to 100/0, more preferably It may be about 60/40 to 95/5.
本発明では補強剤として有機繊維（Ｂ）を用いる。そのため、焼却後に残渣が残るのを防止できるとともに、押出機のスクリューなどの部材の損耗を防止できる。有機繊維（Ｂ）としては、例えば、植物繊維（又はセルロース繊維）、動物繊維（羊毛、絹など）、合成繊維（例えば、ナイロン系繊維、ポリエステル系繊維、アクリル系繊維、ポリウレタン系繊維、ポリエチレン又はポリプロピレンなどのポリオレフィン系繊維、ポリビニルアルコール系繊維、ポリ塩化ビニル系繊維、フッ素樹脂系繊維など）、再生繊維（レーヨン繊維など）、半合成繊維（セルロースアセテートなどのセルロースエステル繊維）などであってもよい。これらの有機繊維は単独で又は二種以上組み合わせて使用できる。なお、セルロース繊維と合成繊維などの他の繊維（ポリエステル系繊維、ナイロン系繊維およびアクリル系繊維から選択された少なくとも一種の繊維など）とは組み合わせて使用してもよいが、セルロース繊維と合成繊維（ポリエステル系繊維、ナイロン系繊維およびアクリル系繊維から選択された少なくとも一種の繊維など）とは組み合わせて使用する必要はない。 In the present invention, organic fiber (B) is used as a reinforcing agent. Therefore, it is possible to prevent residues from remaining after incineration and to prevent wear of members such as screws of the extruder. Examples of organic fibers (B) include plant fibers (or cellulose fibers), animal fibers (wool, silk, etc.), synthetic fibers (for example, nylon fibers, polyester fibers, acrylic fibers, polyurethane fibers, polyethylene or Polyolefin fibers such as polypropylene, polyvinyl alcohol fibers, polyvinyl chloride fibers, fluororesin fibers, etc.), recycled fibers (rayon fibers, etc.), semi-synthetic fibers (cellulose ester fibers such as cellulose acetate), etc. Good. These organic fibers can be used alone or in combination of two or more. Cellulose fibers and synthetic fibers may be used in combination with other fibers such as cellulose fibers and synthetic fibers (at least one fiber selected from polyester fibers, nylon fibers and acrylic fibers). It is not necessary to use in combination with (at least one kind of fiber selected from polyester fiber, nylon fiber and acrylic fiber).
有機繊維（Ｂ）は少なくともセルロース繊維（又は植物繊維）で構成してもよい。セルロース繊維としては、麻繊維、竹繊維、綿繊維、木材繊維、ケナフ繊維、ヘンプ繊維、ジュート繊維、バナナ繊維、ココナツ繊維などの種々の植物繊維を使用してもよい。これらの繊維は単独で又は二種以上組み合わせて使用できる。好ましいセルロース繊維は、αセルロース含量が高く、αセルロース含量は、例えば、αセルロース含量８０重量％以上（例えば、８５〜１００重量％）、好ましくは８５重量％以上（例えば、９０〜９９重量％）、さらに好ましくは９５〜１００重量％程度である。αセルロース含量が低いセルロース繊維を用いると、熱安定性が乏しく、成形加工により著しく黄色に着色して外観を損ねたり、不快臭も発生しやすい。また、やけや着色、黒点異物も生成しやすい。これに対してαセルロース含量が高いセルロース繊維を用いると、熱安定性が高く、着色、やけや黒点などの生成を有効に防止できるとともに、成形体の製造に伴ってダイでの目やにが生じることが殆どなく、高品質の発泡体を得ることができる。好ましいセルロース繊維は、パルプ（針葉樹パルプ、広葉樹パルプなどの木材パルプ、リンターパルプなど）、特にαセルロース含量が高い溶解パルプである。 The organic fiber (B) may be composed of at least cellulose fiber (or plant fiber). As the cellulose fiber, various plant fibers such as hemp fiber, bamboo fiber, cotton fiber, wood fiber, kenaf fiber, hemp fiber, jute fiber, banana fiber and coconut fiber may be used. These fibers can be used alone or in combination of two or more. Preferred cellulose fibers have a high α cellulose content, and the α cellulose content is, for example, an α cellulose content of 80% by weight or more (eg, 85 to 100% by weight), preferably 85% by weight or more (eg, 90 to 99% by weight). More preferably, it is about 95 to 100% by weight. When cellulose fibers having a low α-cellulose content are used, the thermal stability is poor, and the color is markedly yellow by molding to deteriorate the appearance, and an unpleasant odor is likely to occur. In addition, burns, coloring, and black spot foreign matter are easily generated. On the other hand, when cellulose fibers having a high α cellulose content are used, heat stability is high, and it is possible to effectively prevent the generation of coloring, burns, black spots, etc. There is almost no and a high-quality foam can be obtained. Preferred cellulose fibers are pulps (wood pulps such as softwood pulps and hardwood pulps, linter pulps, etc.), particularly dissolving pulps having a high α cellulose content.
セルロース繊維などの有機繊維（Ｂ）の平均繊維径は、例えば、０．１〜１０００μｍ、好ましくは１〜５００μｍ（例えば、３〜３００μｍ）、さらに好ましくは５〜２００μｍ（例えば、１０〜１００μｍ）、特に１０〜５０μｍ（例えば、１５〜４５μｍ）程度である。セルロース繊維などの有機繊維（Ｂ）の平均繊維長は、０．０１〜１０ｍｍ程度の範囲から選択でき、例えば、０．０１〜５ｍｍ（例えば、０．０５〜３ｍｍ）、好ましくは０．１〜２ｍｍ（例えば、０．１５〜１．５ｍｍ）、さらに好ましくは０．２〜１．３ｍｍ（例えば、０．５〜１．２ｍｍ）程度である。 The average fiber diameter of the organic fiber (B) such as cellulose fiber is, for example, 0.1 to 1000 μm, preferably 1 to 500 μm (for example, 3 to 300 μm), more preferably 5 to 200 μm (for example, 10 to 100 μm), Particularly, it is about 10 to 50 μm (for example, 15 to 45 μm). The average fiber length of organic fibers (B) such as cellulose fibers can be selected from a range of about 0.01 to 10 mm, for example, 0.01 to 5 mm (for example, 0.05 to 3 mm), preferably 0.1 to 0.1 mm. It is about 2 mm (for example, 0.15 to 1.5 mm), more preferably about 0.2 to 1.3 mm (for example, 0.5 to 1.2 mm).
セルロース繊維などの有機繊維（Ｂ）の平均アスペクト比（長さ／径）は、例えば、２〜１０００、好ましくは３〜５００、さらに好ましくは５〜２００（例えば、１０〜１００）程度であってもよく、５〜７０（例えば、１０〜５０）程度であってもよい。 The average aspect ratio (length / diameter) of the organic fiber (B) such as cellulose fiber is, for example, about 2 to 1000, preferably about 3 to 500, and more preferably about 5 to 200 (for example, 10 to 100). Or about 5 to 70 (for example, 10 to 50).
なお、有機繊維（Ｂ）は、表面処理剤、例えば、カップリング剤（アミノ基、置換アミノ基、エポキシ基やグリシジル基などの官能基を有するシランカップリング剤など）で表面処理してもよい。 The organic fiber (B) may be surface-treated with a surface treatment agent, for example, a coupling agent (such as a silane coupling agent having a functional group such as an amino group, a substituted amino group, an epoxy group or a glycidyl group). .
セルロース繊維などの有機繊維（Ｂ）の使用量は、熱可塑性樹脂（Ａ）１００重量部に対して、例えば、１〜５００重量部、好ましくは３〜３００重量部、さらに好ましくは５〜１００重量部、特に１０〜７５重量部（例えば、１５〜５０重量部）程度である。 The amount of the organic fiber (B) such as cellulose fiber used is, for example, 1 to 500 parts by weight, preferably 3 to 300 parts by weight, and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). Parts, especially 10 to 75 parts by weight (for example, 15 to 50 parts by weight).
なお、外観がよく、発泡倍率の高い成形体（シート）を得るためには、熱可塑性樹脂中への有機繊維（Ｂ）の分散性が重要となる。この有機繊維（Ｂ）の分散性が十分でないと、成形体表面に、いわゆる「ホワイトスポット」と称される大きめの有機繊維（Ｂ）塊が点在して外観を損ねるとともに、発泡が不安定となり発泡倍率が低くなる。従来、一般的な２軸押出機ではセルロース繊維などの有機繊維（Ｂ）の分散性が十分でないため前記「ホワイトスポット」の生成を抑制することが困難であった。 In order to obtain a molded body (sheet) having a good appearance and a high expansion ratio, the dispersibility of the organic fiber (B) in the thermoplastic resin is important. If the dispersibility of the organic fiber (B) is not sufficient, the surface of the molded product is scattered with large organic fiber (B) clusters called “white spots” and the appearance is impaired, and foaming is unstable. And the expansion ratio becomes low. Conventionally, in a general twin screw extruder, the dispersibility of organic fibers (B) such as cellulose fibers is insufficient, and thus it has been difficult to suppress the generation of the “white spot”.
このような「ホワイトスポット」の発生を抑制するため、熱可塑性樹脂とセルロース繊維などの有機繊維（Ｂ）との混合において、セルロース繊維などの有機繊維（Ｂ）を解繊し、熱可塑性樹脂に分散させた後、成形する方法を適用するのが有利である。なお、有機繊維（Ｂ）を解繊し、分散させる場合、有機繊維（Ｂ）を解繊した後、熱可塑性樹脂に分散させる方法と、有機繊維（Ｂ）の解繊と分散とを並行して行う方法が含まれる。以下に、セルロース繊維などの有機繊維（Ｂ）の解繊及び分散方法の好ましい実施形態を説明する。 In order to suppress the occurrence of such “white spots”, in mixing the thermoplastic resin and organic fibers (B) such as cellulose fibers, the organic fibers (B) such as cellulose fibers are defibrated to form a thermoplastic resin. It is advantageous to apply a method of forming after dispersing. When the organic fiber (B) is defibrated and dispersed, the method of defibrating the organic fiber (B) and then dispersing the organic fiber (B) in the thermoplastic resin and the defibrating and dispersing of the organic fiber (B) are performed in parallel. And how to do it. Below, preferable embodiment of the defibration and dispersion | distribution method of organic fibers (B), such as a cellulose fiber, is described.
［方法１］
熱可塑性樹脂及び有機繊維（Ｂ）を前記割合で用い、好ましくは予め予備混合し、これらの成分を、加温装置を備えた混合機（例えば、ヘンシェルミキサー、三井鉱山（株）製、ＦＭ２０、ヒーター付き）に投入し、攪拌しながら加温する。例えば、混合機の混合槽（例えば、容量２０Ｌの混合槽）に、所定量の熱可塑性樹脂及び有機繊維（Ｂ）（例えば、１０００〜３０００ｇ）を入れ、熱可塑性樹脂の溶融温度近傍にて、所定の周速（例えば、周速１０〜５０ｍ／ｓｅｃ）で、所定時間（例えば、１０〜３０分間）混練することにより、セルロース繊維などの有機繊維（Ｂ）を均一に分散できる。
[Method 1]
The thermoplastic resin and the organic fiber (B) are used in the above ratios, preferably premixed in advance, and these components are mixed with a mixer equipped with a heating device (for example, Henschel mixer, manufactured by Mitsui Mining Co., Ltd., FM20, Heated with stirring. For example, a predetermined amount of thermoplastic resin and organic fiber (B) (for example, 1000 to 3000 g) are put into a mixing tank of a mixer (for example, a mixing tank having a capacity of 20 L), and near the melting temperature of the thermoplastic resin, By kneading at a predetermined peripheral speed (for example, a peripheral speed of 10 to 50 m / sec) for a predetermined time (for example, 10 to 30 minutes), the organic fibers (B) such as cellulose fibers can be uniformly dispersed.
［方法２］
熱可塑性樹脂及び有機繊維（Ｂ）の予備混合物を、２軸混練型押出機に投入し、樹脂の溶融温度近傍にて、スクリューを回転させながら溶融混練する。例えば、所定量の熱可塑性樹脂及び有機繊維（Ｂ）の予備混合物（例えば、５０ｋｇの予備混合物）を、２軸混練型押出機［例えば、シーティーイー社製，ＨＴＭ６５,スクリュー径６５ｍｍ、ホットカット（水中）カット付き］に投入し、樹脂の溶融温度近傍にて、スクリュー回転数２００〜８００ｒ／ｍで溶融混練紙、セルロース繊維などの有機繊維（Ｂ）を分散させる。
[Method 2]
The premixed mixture of the thermoplastic resin and the organic fiber (B) is put into a twin-screw kneading type extruder, and melt kneaded while rotating the screw in the vicinity of the melting temperature of the resin. For example, a premix of a predetermined amount of thermoplastic resin and organic fiber (B) (for example, 50 kg of premix) is mixed with a twin-screw kneading extruder [for example, HTM65, manufactured by CTE Co., Ltd., screw diameter 65 mm, hot cut (In water) with cut] and organic fibers (B) such as melt-kneaded paper and cellulose fibers are dispersed at a screw rotation speed of 200 to 800 r / m in the vicinity of the melting temperature of the resin.
このような解繊及び分散方法を適用すると、外観が美しく、「ホワイトスポット」のない均質な発泡体が得られる。なお、「ホワイトスポット」の評価は、発泡性樹脂組成物を射出成形、シート押出成形、又はプレス成形し、厚み１〜３ｍｍ程度のシート状成形体を調製し、シート状成形体の表面に存在するホワイトスポットの数をカウントすることにより行うことができる。ホワイトスポットの数について、成形体表面の５０ｃｍ２当たり、最大径が１ｍｍ以上の未解繊の有機繊維（Ｂ）の塊の数が１０個以下、好ましく５個以下にするのが好ましい。最大径とは、球の場合には直径を意味し、楕円の場合には長径を意味し、不定形の場合には最大長さを意味する。 When such a defibrating and dispersing method is applied, a homogeneous foam having a beautiful appearance and no “white spot” can be obtained. In addition, the evaluation of “white spot” is performed by injection molding, sheet extrusion molding, or press molding of the foamable resin composition to prepare a sheet-shaped molded body having a thickness of about 1 to 3 mm, and is present on the surface of the sheet-shaped molded body. This can be done by counting the number of white spots. Regarding the number of white spots, the number of undefibrated organic fibers (B) having a maximum diameter of 1 mm or more per 50 cm 2 on the surface of the molded body is preferably 10 or less, preferably 5 or less. The maximum diameter means the diameter in the case of a sphere, the long diameter in the case of an ellipse, and the maximum length in the case of an indefinite shape.
変性オレフィン系化合物（Ｃ）は、少なくともポリオレフィン系樹脂（Ａ１）を含む熱可塑性樹脂（Ａ）とセルロース繊維などの有機繊維（Ｂ）との親和性を改善する。このような変形オレフィン系化合物（Ｃ）としては、酸変性又はエポキシ変性オレフィン系化合物、例えば、カルボキシル基、酸無水物基及びエポキシ基から選択された少なくとも一種の変性基を有する変性オレフィン系化合物が使用できる。なお、エポキシ基はグリシジル基も包含する。 The modified olefin compound (C) improves the affinity between the thermoplastic resin (A) containing at least the polyolefin resin (A1) and the organic fiber (B) such as cellulose fiber. Examples of such modified olefinic compounds (C) include acid-modified or epoxy-modified olefinic compounds, for example, modified olefinic compounds having at least one modified group selected from a carboxyl group, an acid anhydride group, and an epoxy group. Can be used. In addition, an epoxy group also includes a glycidyl group.
変性オレフィン系化合物としては、酸変性又はエポキシ変性オレフィン系ワックス［例えば、ポリエチレンワックス、ポリプロピレンワックスなどのポリオレフィン系ワックスを、不飽和ポリカルボン酸又はその酸無水物（マレイン酸、無水マレイン酸など）、グリシジル（メタ）アクリレートなどのエポキシ基含有単量体などで処理した変性オレフィンワックス；前記ポリオレフィン系ワックスの構成モノマー（エチレン、プロピレンなどのα−オレフィンなど）と、共重合成分としての不飽和カルボン酸又は酸無水物（（メタ）アクリル酸、マレイン酸、無水マレイン酸など）、グリシジル（メタ）アクリレートなどとの共重合により形成される変性オレフィンワックスなど］の他、変性オレフィン系樹脂などが使用できる。これらの変性オレフィン系化合物は、単独で又は二種以上組み合わせて使用できる。また、前記変性オレフィン系ワックスと、変性オレフィン系樹脂とを併用してもよい。これらの変性オレフィン化合物のうち、熱可塑性樹脂組成物を効率よく改質でき、成形品に高い表面特性（表面平滑性）及び耐熱性を付与できるとともに、強度（耐衝撃性、ウェルド強度など）を向上できる点から、少なくとも変性オレフィン系樹脂を用いるのが好ましい。 Examples of the modified olefin compound include acid-modified or epoxy-modified olefin wax [for example, polyolefin wax such as polyethylene wax and polypropylene wax, unsaturated polycarboxylic acid or acid anhydride thereof (maleic acid, maleic anhydride, etc.), Modified olefin wax treated with an epoxy group-containing monomer such as glycidyl (meth) acrylate; constituent monomer of the polyolefin wax (α-olefin such as ethylene and propylene) and unsaturated carboxylic acid as a copolymerization component In addition to acid anhydrides (modified olefin waxes formed by copolymerization with (meth) acrylic acid, maleic acid, maleic anhydride, etc.), glycidyl (meth) acrylate, etc.], modified olefin resins can be used. . These modified olefinic compounds can be used alone or in combination of two or more. The modified olefin wax and the modified olefin resin may be used in combination. Among these modified olefin compounds, the thermoplastic resin composition can be efficiently modified, and high surface properties (surface smoothness) and heat resistance can be imparted to the molded product, and strength (impact resistance, weld strength, etc.) can be imparted. From the viewpoint of improvement, it is preferable to use at least a modified olefin resin.
変性オレフィン系樹脂を構成するオレフィン系樹脂としては、エチレン、プロピレン、ブテン、メチルペンテン−１などのα−オレフィンの単独又は共重合体が利用できる。このようなオレフィン系樹脂としては、例えば、エチレン系樹脂（ポリエチレン、エチレン−プロピレン共重合体、エチレン−ブテン共重合体など）、プロピレン系樹脂（ポリプロピレン、プロピレン−エチレンランダム共重合体、プロピレン−エチレンブロック共重合体、プロピレン−ブテン共重合体など）などが例示できる。オレフィン系樹脂としては、少なくともプロピレンを含むプロピレン系樹脂であるのが好ましい。 As the olefin resin constituting the modified olefin resin, homo- or copolymers of α-olefins such as ethylene, propylene, butene and methylpentene-1 can be used. Examples of such olefin resins include ethylene resins (polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, etc.), propylene resins (polypropylene, propylene-ethylene random copolymer, propylene-ethylene). Examples thereof include block copolymers and propylene-butene copolymers. The olefin resin is preferably a propylene resin containing at least propylene.
変性オレフィン系樹脂は、前記α−オレフィンと変性剤との共重合、オレフィン系樹脂に対する変性剤のグラフトなどにより得ることができる。変性剤としては、カルボキシル基又は酸無水物基を有する単量体［例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、無水マレイン酸、フマル酸など］、グリシジル基又はエポキシ基を有する単量体［グリシジル（メタ）アクリレートなど］、エステル結合を有する単量体［（メタ）アクリル酸アルキルエステルなど］が例示できる。これらの単量体も単独で又は二種以上組み合わせて使用できる。変性剤としては、（メタ）アクリル酸、無水マレイン酸を用いる場合が多い。 The modified olefin resin can be obtained by copolymerization of the α-olefin and a modifier, grafting of the modifier to the olefin resin, or the like. As the modifier, a monomer having a carboxyl group or an acid anhydride group [for example, (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, etc.], a monomer having a glycidyl group or an epoxy group Examples thereof include isomers [glycidyl (meth) acrylate and the like] and monomers having an ester bond [(meth) acrylic acid alkyl ester and the like]. These monomers can also be used alone or in combination of two or more. As the modifier, (meth) acrylic acid or maleic anhydride is often used.
変性オレフィン系樹脂の具体例としては、例えば、（メタ）アクリル酸共重合オレフィン系樹脂、無水マレイン酸グラフトオレフィン系樹脂、グリシジル（メタ）アクリレート共重合オレフィン系樹脂などの共重合体；（メタ）アクリル酸グラフトオレフィン系樹脂、無水マレイン酸グラフトオレフィン系樹脂（ポリプロピレン系樹脂など）、グリシジル（メタ）アクリレートグラフトオレフィン系樹脂などのグラフト共重合体などが例示できる。これらの変性オレフィン系樹脂は、変性ポリエチレン系樹脂、変性ポリプロピレン系樹脂である場合が多い。 Specific examples of the modified olefinic resin include, for example, copolymers such as (meth) acrylic acid copolymerized olefinic resin, maleic anhydride grafted olefinic resin, glycidyl (meth) acrylate copolymerized olefinic resin; Examples thereof include graft copolymers such as acrylic acid graft olefin resin, maleic anhydride graft olefin resin (polypropylene resin, etc.), glycidyl (meth) acrylate graft olefin resin, and the like. These modified olefin resins are often modified polyethylene resins and modified polypropylene resins.
変性オレフィン系樹脂の重量平均分子量（ゲルパーミエーションクロマトグラフィー、ポリスチレン換算）は、例えば、１．５×１０4〜３０×１０4（例えば、２×１０4〜２５×１０4）、好ましくは２．５×１０4〜２３×１０4（例えば、２．５×１０4〜２０×１０4）、さらに好ましくは２．７×１０4〜２０×１０4（例えば、３×１０4〜１７×１０4）程度であり、通常、５×１０4〜１６×１０4程度であってもよい。なお、変性オレフィン系樹脂の数平均分子量は、例えば、０．５×１０4〜１０×１０4（例えば、０．７５×１０4〜１０×１０4）、好ましくは０．８×１０4〜７．５×１０4（例えば、０．８×１０4〜５×１０4）程度であってもよい。 The weight average molecular weight (gel permeation chromatography, in terms of polystyrene) of the modified olefin resin is, for example, 1.5 × 10 4 to 30 × 10 4 (for example, 2 × 10 4 to 25 × 10 4 ), preferably 2 5 × 10 4 to 23 × 10 4 (for example, 2.5 × 10 4 to 20 × 10 4 ), more preferably 2.7 × 10 4 to 20 × 10 4 (for example, 3 × 10 4 to 17 ×). About 10 4 ), and usually about 5 × 10 4 to 16 × 10 4 . The number-average molecular weight of the modified olefin resin is, for example, 0.5 × 10 4 to 10 × 10 4 (for example, 0.75 × 10 4 to 10 × 10 4 ), preferably 0.8 × 10 4 to It may be about 7.5 × 10 4 (for example, 0.8 × 10 4 to 5 × 10 4 ).
変性オレフィン系樹脂の融点は高く、例えば、１００〜１７０℃程度の範囲から選択でき、通常、１２０〜１７０℃（例えば、１２５〜１６５℃）、好ましくは１３０〜１６５℃（例えば、１３５〜１６５℃）程度であり、１４０〜１６５℃程度であってもよい。 The melting point of the modified olefin-based resin is high, and can be selected, for example, from a range of about 100 to 170 ° C., and is usually 120 to 170 ° C. (for example, 125 to 165 ° C.), preferably 130 to 165 ° C. About 140 to 165 ° C.
変性オレフィン化合物（変性オレフィン系樹脂など）において、酸性基やエポキシ基の導入量（変性量）は、変性基に対応する単量体換算で、例えば、０．１〜３０重量％（０．５〜２８重量％）、好ましくは１〜２５重量％、さらに好ましくは３〜２０重量％（例えば、５〜１５重量％）程度であってもよく、通常、１〜３０重量％程度である。さらに、変性オレフィン系樹脂のケン化価又は酸価（ＫＯＨｍｇ／ｇ）は、例えば、１０〜８０、好ましくは１０〜７０（例えば、２０〜７０）、さらに好ましくは１０〜６０（例えば、２０〜６０）程度である。 In the modified olefin compound (modified olefin resin, etc.), the introduction amount (modification amount) of the acidic group or epoxy group is, for example, 0.1 to 30% by weight (0.5%) in terms of the monomer corresponding to the modification group. -28 wt%), preferably 1-25 wt%, more preferably about 3-20 wt% (e.g., 5-15 wt%), and usually about 1-30 wt%. Furthermore, the saponification value or acid value (KOHmg / g) of the modified olefin resin is, for example, 10 to 80, preferably 10 to 70 (for example, 20 to 70), more preferably 10 to 60 (for example, 20 to 20). 60) or so.
変性オレフィン系化合物（Ｃ）の使用量は、熱可塑性樹脂（Ａ）１００重量部に対して０．１〜３０重量部（例えば、０．５〜２５重量部）、好ましくは０．７〜２０重量部（例えば、１〜１０重量部）、さらに好ましくは１〜７重量部（例えば、１〜５重量部）程度であってもよい。 The amount of the modified olefin compound (C) used is 0.1 to 30 parts by weight (for example, 0.5 to 25 parts by weight), preferably 0.7 to 20 parts per 100 parts by weight of the thermoplastic resin (A). It may be about 1 part by weight (for example, 1 to 10 parts by weight), more preferably about 1 to 7 parts by weight (for example, 1 to 5 parts by weight).
本発明の樹脂組成物は発泡剤（Ｄ）により発泡可能であればよく、発泡剤（Ｄ）は、揮発型発泡剤（物理発泡剤）であってもよく分解型発泡剤（化学発泡剤）であってもよい。発泡剤（Ｄ）のうち揮発型発泡剤としては、揮発性ガス及び／又は揮発性ガスを発生する発泡剤（例えば、プロパン、ブタン、ペンタン、ヘキサンなどの炭化水素類、ＨＣＦＣ２２,ＨＦＣ−１４２ｂ、ＨＦＣ−１３４ａなどのハロゲン化炭化水素、塩化メチレンや塩化メチルなどの塩素化炭化水素などの有機ガス、空気、炭酸ガス、窒素ガスなどの無機ガス）、水などが例示できる。分解型発泡剤としては、クエン酸、アゾ化合物（アゾジカルボン酸アミドなど）、ヒドラジド化合物（ｐ−トルエンスルホニルヒドラジドなど）、アジド化合物、炭酸塩（重炭酸ナトリウムなど）などが例示できる。これらの発泡剤は単独で又は二種以上組み合わせて使用できる。これらの発泡剤の使用量は特に限定されず、発泡剤の種類、所望の発泡倍率に応じて適宜選択できる。例えば、揮発型発泡剤の使用量（発泡剤の圧入量）は発泡倍率などに応じて適当に選択できる。発泡剤の使用量は、発泡倍率などに応じて、例えば、樹脂（Ａ）１００重量部に対して０．１〜２０重量部（例えば、１〜１０重量部）、好ましくは５〜１０重量部程度である。なお、発泡剤は、樹脂と混合して用いてもよく、樹脂に含浸させて用いてもよい。また、発泡剤は、樹脂（Ａ）の溶融温度であって発泡剤の分解温度未満の温度で樹脂（Ａ）と必要により有機繊維（Ｂ）と溶融混練したマスターバッチとして使用してもよい。さらに、発泡剤（揮発型発泡剤など）は溶融混練された樹脂に添加又は圧入してもよい。また、発泡剤には水を使用でき、押出機に直接ポンプなどを用いて水を与えてもよいが、樹脂に配合する有機繊維に予め含浸させてもよい。セルロース繊維などの有機繊維に水を含浸させる場合、有機繊維の総重量に対して、０．１〜２０重量％、好ましくは０．５〜１０重量％程度の割合で水を含浸させてもよい。 The resin composition of the present invention only needs to be foamable by the foaming agent (D), and the foaming agent (D) may be a volatile foaming agent (physical foaming agent) or a decomposable foaming agent (chemical foaming agent). It may be. Among the foaming agents (D), the volatile foaming agents include volatile gas and / or foaming agents that generate volatile gases (for example, hydrocarbons such as propane, butane, pentane, hexane, HCFC22, HFC-142b, Examples thereof include halogenated hydrocarbons such as HFC-134a, organic gases such as chlorinated hydrocarbons such as methylene chloride and methyl chloride, inorganic gases such as air, carbon dioxide, and nitrogen gas), water, and the like. Examples of the decomposable foaming agent include citric acid, azo compounds (such as azodicarboxylic amide), hydrazide compounds (such as p-toluenesulfonyl hydrazide), azide compounds, carbonates (such as sodium bicarbonate), and the like. These foaming agents can be used alone or in combination of two or more. The usage-amount of these foaming agents is not specifically limited, According to the kind of foaming agent and desired expansion ratio, it can select suitably. For example, the amount of the volatile foaming agent used (the amount of press-in of the foaming agent) can be appropriately selected according to the expansion ratio. The amount of the foaming agent used is, for example, 0.1 to 20 parts by weight (for example, 1 to 10 parts by weight), preferably 5 to 10 parts by weight with respect to 100 parts by weight of the resin (A), depending on the expansion ratio. Degree. The foaming agent may be used by mixing with a resin, or may be used by impregnating the resin. Further, the foaming agent may be used as a master batch obtained by melting and kneading the resin (A) and, if necessary, the organic fiber (B) at a temperature lower than the melting temperature of the resin (A) and lower than the decomposition temperature of the foaming agent. Further, a foaming agent (such as a volatile foaming agent) may be added or pressed into the melt-kneaded resin. Further, water can be used as the foaming agent, and water may be given directly to the extruder using a pump or the like, but it may be impregnated in advance with organic fibers blended in the resin. When water is impregnated into organic fibers such as cellulose fibers, water may be impregnated at a ratio of 0.1 to 20% by weight, preferably about 0.5 to 10% by weight, based on the total weight of the organic fibers. .
本発明の発泡性樹脂組成物は、前記成分に加えて、必要により、収縮防止剤（Ｅ）、フッ素系樹脂（Ｆ）、発泡助剤（又は発泡核剤）（Ｇ）を含んでいてもよい。これらの成分は単独で又は二種以上組み合わせて使用できる。 The foamable resin composition of the present invention may contain an anti-shrinkage agent (E), a fluororesin (F), and a foaming auxiliary agent (or foaming nucleating agent) (G), if necessary, in addition to the above components. Good. These components can be used alone or in combination of two or more.
収縮防止剤（Ｅ）としては、界面活性剤、例えば、ノ二オン性界面活性剤（ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンショ糖脂肪酸エステル、グリセリン脂肪酸エステルなど）などが例示できる。収縮防止剤（Ｅ）の割合は、樹脂（Ａ）１００重量部に対して、例えば、０〜１０重量部、好ましくは０．１〜１０重量部（例えば、１〜５重量部）程度であってもよい。 Anti-shrinkage agents (E) include surfactants such as nonionic surfactants (polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sucrose fatty acid ester, glycerin fatty acid ester, etc.) Etc. can be exemplified. The proportion of the shrinkage inhibitor (E) is, for example, about 0 to 10 parts by weight, preferably about 0.1 to 10 parts by weight (for example, 1 to 5 parts by weight) with respect to 100 parts by weight of the resin (A). May be.
フッ素系樹脂（Ｆ）としては、ポリ（フルオロアルケン）重合体、例えば、ポリテトラフルオロエチレン、テトラフルオロエチレン−エチレン共重合体、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体などのフッ素含有単量体の単独又は共重合体が例示できる。これらのフッ素樹脂は単独で又は二種以上組み合わせて使用できる。フッ素系樹脂（Ｆ）の使用量は、例えば、熱可塑性樹脂（Ａ）１００重量部に対して０〜１０重量部程度の範囲から選択でき、例えば、０．５〜８重量部、好ましくは１〜５重量部程度であってもよい。 Examples of the fluororesin (F) include poly (fluoroalkene) polymers such as polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and tetrafluoroethylene-hexafluoro. Examples thereof include a homopolymer or a copolymer of fluorine-containing monomers such as a propylene copolymer and a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. These fluororesins can be used alone or in combination of two or more. The amount of the fluororesin (F) used can be selected, for example, from a range of about 0 to 10 parts by weight, for example, 0.5 to 8 parts by weight, preferably 1 with respect to 100 parts by weight of the thermoplastic resin (A). About 5 parts by weight may be used.
発泡助剤（Ｇ）としては、例えば、タルク、シリカ、カオリンなどの珪酸塩、炭酸カルシウムなどの金属炭酸塩、酸化亜鉛、酸化アルミニウムなどの金属酸化物、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、モンタン酸カルシウムなどの高級脂肪酸塩などが例示できる。発泡助剤（又は発泡核剤）の割合は、樹脂（Ａ）１００重量部に対して、例えば、０．１〜５重量部（例えば、０．５〜４重量部）、好ましくは１〜３重量部程度であってもよい。 Examples of the foaming aid (G) include silicates such as talc, silica and kaolin, metal carbonates such as calcium carbonate, metal oxides such as zinc oxide and aluminum oxide, calcium stearate, magnesium stearate, and aluminum stearate. And higher fatty acid salts such as calcium montanate. The ratio of the foaming aid (or foaming nucleating agent) is, for example, 0.1 to 5 parts by weight (for example, 0.5 to 4 parts by weight), preferably 1 to 3 parts per 100 parts by weight of the resin (A). It may be about parts by weight.
前記樹脂組成物は、種々の添加剤、例えば、安定剤［酸化防止剤（ヒンダードフェノール系酸化防止剤など）、紫外線吸収剤、耐熱安定剤、耐候安定剤など］、無機充填剤、滑剤、離型剤、潤滑剤、衝撃改良剤、着色剤（染料や顔料など）、可塑剤、結晶化促進剤、結晶核剤、帯電防止剤、難燃剤、抗菌剤、防腐剤などを含有していてもよい。添加剤は単独で又は２種以上組み合わせてもよい。 The resin composition includes various additives such as stabilizers [antioxidants (hindered phenol-based antioxidants, etc.), ultraviolet absorbers, heat stabilizers, weathering stabilizers, etc.], inorganic fillers, lubricants, Contains release agents, lubricants, impact modifiers, colorants (dyes and pigments, etc.), plasticizers, crystallization accelerators, crystal nucleating agents, antistatic agents, flame retardants, antibacterial agents, preservatives, etc. Also good. The additives may be used alone or in combination of two or more.
本発明の発泡性樹脂組成物は、各成分の混合物であってもよくペレット状などの形態であってもよい。発泡性樹脂組成物において、セルロース繊維などの有機繊維（Ｂ）は熱可塑性樹脂（Ａ）中に分散（特に均一に分散）しており、発泡体を有効に補強している。 The foamable resin composition of the present invention may be a mixture of components or may be in the form of pellets. In the foamable resin composition, the organic fibers (B) such as cellulose fibers are dispersed (particularly uniformly dispersed) in the thermoplastic resin (A), and the foam is effectively reinforced.
本発明の発泡体は、前記発泡性樹脂組成物で構成されている。発泡体の気泡構造は特に制限されず、独立気泡構造であっても連続気泡構造であってもよく、双方の気泡構造が混在していてもよい。好ましい気泡構造は、少なくとも連続気泡構造を有している。このような構造の発泡体は透湿性を改善できる。発泡体の透湿度（ｇ／（ｍ2・２４ｈ））は、４０℃及び９０％ＲＨで測定したとき、例えば、１００〜１００００、好ましくは２００〜７５００（例えば、２５０〜６０００）、さらに好ましくは３００〜５０００（例えば、５００〜３５００）程度である。なお、透湿度は、円筒状容器に所定量の塩化カルシウムを入れ、前記容器の開口部を所定の厚みの発泡シート（例えば、厚み２ｍｍの発泡シート）で緊密にカバーし、４０℃及び９０％ＲＨで１日間放置したとき、塩化カルシウムが吸収した水分量を測定することにより評価できる。 The foam of the present invention is composed of the foamable resin composition. The cell structure of the foam is not particularly limited, and may be a closed cell structure, an open cell structure, or a mixture of both cell structures. A preferred cell structure has at least an open cell structure. The foam having such a structure can improve moisture permeability. The moisture permeability (g / (m 2 · 24h)) of the foam is, for example, 100 to 10,000, preferably 200 to 7500 (eg, 250 to 6000), more preferably when measured at 40 ° C. and 90% RH. It is about 300-5000 (for example, 500-3500). The moisture permeability is determined by placing a predetermined amount of calcium chloride in a cylindrical container, and tightly covering the opening of the container with a foam sheet having a predetermined thickness (for example, a foam sheet having a thickness of 2 mm). It can be evaluated by measuring the amount of water absorbed by calcium chloride when left for 1 day in RH.
発泡体の発泡倍率は、用途に応じて選択できるが、通常、１．５倍以上（１．５〜１５倍程度）であり、２〜１２倍、好ましくは２．２〜１０倍、さらに好ましくは２．５〜８倍程度である。発泡倍率が小さいと、軽量化を実現できない。 The expansion ratio of the foam can be selected according to the use, but is usually 1.5 times or more (about 1.5 to 15 times), 2 to 12 times, preferably 2.2 to 10 times, and more preferably Is about 2.5 to 8 times. If the expansion ratio is small, weight reduction cannot be realized.
発泡体の平均気泡径は、それぞれ、例えば、０．３〜１．５ｍｍ、好ましくは０．４〜１．５ｍｍ、さらに好ましくは０．５〜１．３ｍｍ(例えば、０．６〜１．２ｍｍ)程度であり、０．７〜１．１ｍｍ程度であってもよい。なお、気泡の断面形状は円形状に限らず楕円形状などであってもよく、不定形状であってもよい。 The average cell diameter of the foam is, for example, 0.3 to 1.5 mm, preferably 0.4 to 1.5 mm, more preferably 0.5 to 1.3 mm (for example, 0.6 to 1.2 mm). About 0.7 to 1.1 mm. The cross-sectional shape of the bubbles is not limited to a circular shape, and may be an elliptical shape or an indefinite shape.
連続気泡構造を有する発泡体において、連続気泡率は、例えば、５０〜１００％程度の範囲から選択でき、通常、８０〜１００％（例えば、８５〜９８％）、好ましくは９０〜１００％（例えば、９３〜９８％）、さらに好ましくは９５〜１００％程度であってもよい。 In the foam having an open cell structure, the open cell ratio can be selected from the range of, for example, about 50 to 100%, and is usually 80 to 100% (for example, 85 to 98%), preferably 90 to 100% (for example, 93 to 98%), and more preferably about 95 to 100%.
発泡体の形状は特に制限されず、用途に応じて適当に選択でき、立体的な三次元的形状（ブロック状、ボックス状など）、二次元的形状（ボード状又は板状、シート状、フィルム状、網状など）であってもよく、一次元的形状（線状又は棒状など）であってもよい。透湿性などの利点を生かす用途では、発泡体は、シート状（または板状）の形態である場合が多い。発泡シートの厚みは、例えば、０．０５〜５ｍｍ、好ましくは０．１〜４ｍｍ（例えば、０．５〜３．５ｍｍ）、さらに好ましくは１〜３ｍｍ（例えば、１．５〜２．５ｍｍ）程度であってもよい。このようなシート状発泡体であっても、前記と同様の透湿度を有している。 The shape of the foam is not particularly limited and can be appropriately selected according to the application. A three-dimensional shape (block shape, box shape, etc.), a two-dimensional shape (board shape or plate shape, sheet shape, film) Shape, mesh shape, etc.) or a one-dimensional shape (line shape, rod shape, etc.). In applications that make use of advantages such as moisture permeability, the foam is often in the form of a sheet (or plate). The thickness of the foam sheet is, for example, 0.05 to 5 mm, preferably 0.1 to 4 mm (for example, 0.5 to 3.5 mm), and more preferably 1 to 3 mm (for example, 1.5 to 2.5 mm). It may be a degree. Even such a sheet-like foam has the same moisture permeability as described above.
なお、発泡体は慣用の発泡成形法で製造できる。例えば、発泡性樹脂組成物を加圧下で溶融混練し、大気圧下で、成形型に射出したり、ダイから押し出して発泡させることにより発泡体を得ることができる。発泡成形において、発泡剤は予め樹脂組成物に含有させていてもよく、押出機内の溶融混練系に注入又は添加してもよい。 The foam can be produced by a conventional foam molding method. For example, a foam can be obtained by melt-kneading a foamable resin composition under pressure and injecting the foamed resin composition into a mold under atmospheric pressure, or by extruding and foaming from a die. In foam molding, the foaming agent may be preliminarily contained in the resin composition, or may be injected or added to the melt-kneading system in the extruder.
本発明は、セルロース繊維などの有機繊維で補強しつつ、発泡倍率が高く、軽量でありながら機械的強度に優れる発泡体を得ることができる。そのため、本発明の発泡性樹脂組成物及び発泡体は種々の用途に利用できる。例えば、電気・電子部品の梱包用資材、建築資材（壁材など）、土木資材、農業資材、自動車部品（自動車天井材などの内装材、外装材など）、包装資材（容器、緩衝材など）、生活資材（日用品など）などに利用できる。 INDUSTRIAL APPLICABILITY The present invention can provide a foam that is reinforced with organic fibers such as cellulose fibers, has a high expansion ratio, is lightweight, and has excellent mechanical strength. Therefore, the foamable resin composition and foam of the present invention can be used for various applications. For example, packaging materials for electrical and electronic parts, building materials (wall materials, etc.), civil engineering materials, agricultural materials, automobile parts (interior materials such as automotive ceiling materials, exterior materials), packaging materials (containers, cushioning materials, etc.) , Can be used for daily life (such as daily necessities).
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。実施例及び比較例では以下の材料を使用した。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, the following materials were used.
［熱可塑性樹脂（Ａ）］
ＰＰ−Ａ１：メタロセン触媒により重合したポリプロピレン（三井化学（株）製「ポリプロピレンＷＦＸ−６」、メルトマスフローレート２ｇ／分）
ＰＥ−Ａ１：メタロセン触媒により重合したポリエチレン（宇部興産（株）製「１５２０Ｆ」メルトマスフローレート２ｇ/分）
ＰＰ−１：ポリプロピレン樹脂（ブロックコポリマー，サンアロマ一（株）製「ＰＭＢ−６０Ａ」，融点１６８℃）
ＰＰ−２：ポリプロピレン樹脂（ホモポリマー，サンアロマー（株）製「ＰＭ９００」，融点１６８℃）
ＰＥ−１：ポリエチレン樹脂（低密度ポリエチレン樹脂，日本ポリエチレン（株）製、「ＪＦ４１４Ａ」，融点１２５℃）
ＰＳ−１：ポリスチレン（東洋スチレン（株）製「ＨＲＭ１４」，キャピラリーレオメーターで測定した溶融粘度１３００Ｐａ・ｓ（２００℃、せん断速度１００ｓｅｃ-1））
［セルロース繊維（Ｂ）］
パルプ［溶解パルプ（レヨニヤ社，「サルファテートＨＪ」，αセルロース含量９７重量％）のシートを幅３ｍｍ、長さ８ｍｍにシュレッダーで短冊状にシュレッドしたものを使用した（平均繊維径２０μｍ、平均繊維長０．８ｍｍ）。
[Thermoplastic resin (A)]
PP-A1: Polypropylene polymerized by a metallocene catalyst (“Polypropylene WFX-6” manufactured by Mitsui Chemicals, Inc., melt mass flow rate 2 g / min)
PE-A1: Polyethylene polymerized by metallocene catalyst (“1520F” melt mass flow rate 2 g / min, manufactured by Ube Industries, Ltd.)
PP-1: Polypropylene resin (block copolymer, “PMB-60A” manufactured by Sun Aroma Co., Ltd., melting point 168 ° C.)
PP-2: Polypropylene resin (Homopolymer, “PM900” manufactured by Sun Allomer Co., Ltd., melting point 168 ° C.)
PE-1: Polyethylene resin (low density polyethylene resin, manufactured by Nippon Polyethylene Co., Ltd., “JF414A”, melting point 125 ° C.)
PS-1: Polystyrene (“HRM14” manufactured by Toyo Styrene Co., Ltd., melt viscosity 1300 Pa · s (200 ° C., shear rate 100 sec −1 ) measured with a capillary rheometer)
[Cellulose fiber (B)]
Pulp [dissolved pulp (Rayonya, “sulfate HJ”, α cellulose content 97 wt%) sheet shredded into a strip shape with a shredder of 3 mm width and 8 mm length (average fiber diameter 20 μm, average fiber) 0.8mm long).
［変性オレフィン系樹脂（Ｃ）］
Ｍ−ＰＰ：変性ポリプロピレン（三洋化成工業（株）製「ユーメックス１０１０」，重量平均分子量３×１０4、無水マレイン酸変性量１０重量％）
発泡剤（Ｄ）（大日精化工業(株)製、重曹／クエン酸系発泡剤「ダイブロー」）
収縮防止剤（Ｅ）（ClariantMasterbatchGmbH & Co OHG社製、品名ハイドロセロール３２５（グリセリンモノステアリレート・ポリエチレンベース））
フッ素系樹脂（Ｆ）（三菱レイヨン（株）製，「メタブレンＡ３０００」）。
[Modified olefin resin (C)]
M-PP: Modified polypropylene (“Yumex 1010” manufactured by Sanyo Chemical Industries, Ltd., weight average molecular weight 3 × 10 4 , maleic anhydride modified amount 10% by weight)
Foaming agent (D) (manufactured by Dainichi Seika Kogyo Co., Ltd., baking soda / citric acid foaming agent “Die Blow”)
Antishrink agent (E) (ClariantMasterbatch GmbH & Co OHG, product name Hydrocerol 325 (glycerin monostearate / polyethylene base))
Fluorine resin (F) (Mitsubrene A3000 manufactured by Mitsubishi Rayon Co., Ltd.).
実施例１〜１１及び比較例１〜４
表に示す成分（Ａ）〜（Ｄ）（熱可塑性樹脂，パルプ，変性オレフィン系樹脂）をブレンダーで予備混合し、混合物５０ｋｇを、特殊押出機ＨＴＭ６５（シーティーイ一社製,スクリュー径６５ｍｍ、ホットカット（水中）カット付き）に投入し、２００℃で、スクリュー回転数２００〜８００ｒｐｍで溶融混練し、ペレットを得た。得られたペレットと発泡剤と収縮防止剤とフッ素樹脂とをブレンダーで混合し、タンデム型発泡押出機でブタンガスを注入して押出し、発泡シートを得た。
Examples 1-11 and Comparative Examples 1-4
Components (A) to (D) (thermoplastic resin, pulp, modified olefin resin) shown in the table are premixed in a blender, and 50 kg of the mixture is mixed with a special extruder HTM65 (CTI Co., Ltd., screw diameter 65 mm, hot cut) (Underwater) with cut) and melt-kneaded at 200 ° C. with a screw rotation speed of 200 to 800 rpm to obtain pellets. The obtained pellets, foaming agent, shrinkage inhibitor and fluororesin were mixed with a blender, butane gas was injected with a tandem foaming extruder and extruded to obtain a foamed sheet.
［透湿度］
吸湿により塩化カルシウムの重量変化を調べる方法に準じて、円筒状容器（６０ｍｍφ）に塩化カルシウム１５ｇを入れ、容器の開口部を７０ｍｍφのサイズにカットした試料（厚み２ｍｍ）で緊密に覆い、４０℃で９０％ＲＨの条件下に１日放置し、試料を介して塩化カルシウムが吸収した水分量を測定した（単位ｇ／（ｍ2・２４ｈ））
［発泡倍率］
発泡倍率は、次のようにして測定した。発泡成形前のペレットを射出成形してプレート（５ｃｍ×９ｃｍ、厚み３ｍｍ）を作製し、プレートの密度Ｄ１を求める。また、得られた発泡シートの密度Ｄ２を求め、Ｄ１をＤ２で除して発泡倍率とした。
[Moisture permeability]
According to the method of examining the weight change of calcium chloride by moisture absorption, 15 g of calcium chloride was put into a cylindrical container (60 mmφ), and the opening of the container was tightly covered with a sample (thickness 2 mm) cut to a size of 70 mmφ, and 40 ° C. At 90% RH for 1 day, and the amount of water absorbed by calcium chloride through the sample was measured (unit: g / (m 2 · 24 h)).
[Foaming ratio]
The expansion ratio was measured as follows. The pellets before foam molding are injection molded to produce a plate (5 cm × 9 cm, thickness 3 mm), and the density D1 of the plate is determined. Moreover, the density D2 of the obtained foam sheet was calculated | required, D1 was remove | divided by D2 and it was set as the expansion ratio.
［灰分］
得られたシートを短冊状に切断し、約１０ｇを精秤（Ｗ１）し、るつぼに入れた。これを８５０℃に設定された電気炉に入れ、１時間焼却処理をした。その後るつぼを取り出し、自然に室温まで冷却し、その残渣量（Ｗ２）を測定した。Ｗ２／Ｗ１×１００（％）を燃焼残渣量とした。なお、目視で残渣が確認されない時は測定せずに、残渣はなしと記録した。
[ash]
The obtained sheet was cut into strips, and about 10 g was precisely weighed (W1) and placed in a crucible. This was put into an electric furnace set at 850 ° C. and incinerated for 1 hour. Thereafter, the crucible was taken out and naturally cooled to room temperature, and the amount of residue (W2) was measured. W2 / W1 × 100 (%) was defined as the combustion residue amount. When no residue was visually confirmed, no measurement was made and no residue was recorded.
［発泡の形態］
発泡シートの断面の気泡構造を目視で観察した。
[Foam form]
The cell structure of the cross section of the foam sheet was visually observed.
［連続気泡率］
実施例及び比較例で得られた発泡体の重量ｗ1を予め測定し、水中に静置した後、−４０ｍｍＨｇの減圧下に１分間放置して、連続気泡構造の中に水を浸透させた。減圧状態から大気圧力に戻し、発泡体の表面に付着した水を除去して重量ｗ2を測定し、下記式（１）により連続気泡率を算出した。
[Open cell ratio]
The weight w 1 of the foams obtained in the examples and comparative examples was measured in advance and allowed to stand in water, then left under a reduced pressure of −40 mmHg for 1 minute to allow water to penetrate into the open cell structure. . The pressure was returned to atmospheric pressure from the reduced pressure state, the water adhering to the surface of the foam was removed, the weight w 2 was measured, and the open cell ratio was calculated by the following formula (1).
連続気泡発泡率（％）＝｛（ｗ2−ｗ1）／ｄ3｝／（ｗ1／ｄ1−ｗ1／ｄ2） （１）
（ｗ2は吸水後の発泡体の重量、ｗ1は吸水前の発泡体の重量、ｄ1は発泡体の見掛密度、ｄ2は発泡体に使用されている樹脂組成物の見掛密度、ｄ3は測定時の水の密度を示す）
［発泡セルの大きさ］
発泡シートの厚み方向の断面をミクロトームでスライスし、薄膜を得た。光学委顕微鏡を用いて観察し、発泡セルの直径を求めた。形状が楕円形だったので、発泡セルの直径、短径のそれぞれの大きさを測定した。
Open-cell foaming rate (%) = {(w 2 −w 1 ) / d 3 } / (w 1 / d 1 −w 1 / d 2 ) (1)
(W 2 is the weight of the foam after water absorption, w 1 is the weight of the foam before water absorption, d 1 is the apparent density of the foam, and d 2 is the apparent density of the resin composition used in the foam. D 3 indicates the density of water at the time of measurement)
[Size of foam cell]
A cross section in the thickness direction of the foam sheet was sliced with a microtome to obtain a thin film. Observation was performed using an optical microscope and the diameter of the foam cell was determined. Since the shape was elliptical, the diameters of the foamed cell and the minor axis were measured.
［剛性］
厚み２ｍｍの発泡シートを作製し、手でおり曲げた時の剛性感を下記の基準で評価した。
[rigidity]
A foam sheet having a thickness of 2 mm was prepared, and the rigidity when bent by hand was evaluated according to the following criteria.
５：コシが非常に強い
４：コシが強い
３：コシがある
２：コシが弱い
１：コシがかなり弱い。
5: Strong stiffness 4: Strong stiffness 3: Strong stiffness 2: Low stiffness 1: Strong stiffness
結果を表１に示す。 The results are shown in Table 1.
表１から明らかなように、比較例に比べ、実施例では高い発泡倍率及び剛性が得られるとともに連続気泡構造により透湿性が高い。なお、比較例１では、押出機のスクリューの鋼材がガラス繊維により激しく摩耗したため、押出できず、発泡体の評価もできなかった（ＮＡ）。また、比較例２及び３の発泡シートは剛性が小さく主に独立気泡構造であった。 As is clear from Table 1, compared to the comparative example, in the example, high foaming ratio and rigidity are obtained, and moisture permeability is high due to the open cell structure. In Comparative Example 1, since the steel material of the screw of the extruder was severely worn by the glass fiber, it could not be extruded and the foam could not be evaluated (NA). In addition, the foamed sheets of Comparative Examples 2 and 3 were small in rigidity and mainly had a closed cell structure.
Claims (18)
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011231237A (en) * | 2010-04-28 | 2011-11-17 | Daicel Polymer Ltd | Polypropylene composition and method for producing the same |
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