JP5129109B2 - Polyacetal resin composition and molded product formed by molding the same - Google Patents
Polyacetal resin composition and molded product formed by molding the same Download PDFInfo
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- JP5129109B2 JP5129109B2 JP2008327215A JP2008327215A JP5129109B2 JP 5129109 B2 JP5129109 B2 JP 5129109B2 JP 2008327215 A JP2008327215 A JP 2008327215A JP 2008327215 A JP2008327215 A JP 2008327215A JP 5129109 B2 JP5129109 B2 JP 5129109B2
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- 229930182556 Polyacetal Natural products 0.000 title claims description 31
- 229920006324 polyoxymethylene Polymers 0.000 title claims description 31
- 239000011342 resin composition Substances 0.000 title claims description 28
- 238000000465 moulding Methods 0.000 title description 3
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 12
- 238000004898 kneading Methods 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 6
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- CZLMRJZAHXYRIX-UHFFFAOYSA-N 1,3-dioxepane Chemical compound C1CCOCOC1 CZLMRJZAHXYRIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリアセタール樹脂組成物及びそれからなる成形品に関する。本発明により提供されるポリアセタール樹脂組成物は、剛性及び耐熱性に優れており、表面外観に優れた成形品を与える。 The present invention relates to a polyacetal resin composition and a molded article comprising the same. The polyacetal resin composition provided by the present invention is excellent in rigidity and heat resistance, and gives a molded product excellent in surface appearance.
ポリアセタール樹脂は、バランスの取れた機械的性質と良好な自己潤滑特性及び電気特性を有しており、エンジニアリングプラスチックとして各種の機械部品や電気部品等に広く使用されている。また高度の剛性や耐熱性が要求される用途には、他の熱可塑性樹脂と同様に、ポリアセタール樹脂にガラス繊維や炭素繊維を配合した強化組成物が広く用いられている。
一方、近年、地球温暖化に関し、再生可能資源として植物由来のものが注目を集めている。熱可塑性樹脂の強化材としても、セルロース系物質を用いることが検討されている。
Polyacetal resins have well-balanced mechanical properties and good self-lubricating properties and electrical properties, and are widely used as engineering plastics for various mechanical and electrical components. For applications that require a high degree of rigidity and heat resistance, reinforced compositions in which glass fibers or carbon fibers are blended with polyacetal resins are widely used, as with other thermoplastic resins.
On the other hand, in recent years, those derived from plants have attracted attention as renewable resources in relation to global warming. The use of cellulosic materials has also been studied as a reinforcing material for thermoplastic resins.
例えば、特許文献１〜３には、ポリプロピレン樹脂等のポリオレフィン系樹脂とセルロース系物質からなる樹脂組成物が提案されている。
特許文献４〜５には、スチレン系樹脂とセルロース系物質からなる樹脂組成物が提案されている。
特許文献６〜７には、ポリアミド樹脂とセルロース系物質からなる樹脂組成物が提案されている。
For example, Patent Documents 1 to 3 propose a resin composition composed of a polyolefin resin such as a polypropylene resin and a cellulose material.
Patent Documents 4 to 5 propose resin compositions comprising a styrene resin and a cellulose material.
Patent Documents 6 to 7 propose resin compositions comprising a polyamide resin and a cellulosic material.
特許文献８には、メタクリル樹脂、ポリカーボネート樹脂、ゴム強化アクリロニトリル−スチレン系樹脂、飽和ポリエステル樹脂などとセルロース系物質からなる樹脂組成物が提案されている。
特許文献９〜１１には、ポリ乳酸等の脂肪族ポリエステル樹脂とセルロース系物質からなる樹脂組成物が提案されている。
Patent Document 8 proposes a resin composition comprising a cellulose material and a methacrylic resin, a polycarbonate resin, a rubber-reinforced acrylonitrile-styrene resin, a saturated polyester resin, and the like.
Patent Documents 9 to 11 propose a resin composition comprising an aliphatic polyester resin such as polylactic acid and a cellulosic material.
しかしながら、これらの樹脂組成物における耐熱性の向上効果は未だ不十分である。また一般に、熱可塑性樹脂にセルロース系物質を配合した樹脂組成物を常法により成形すると、しばしば成形品に木目調と称されるような独特の模様が生ずることがあり、意匠性の点で成形品の用途が限られてしまうという問題がある。 However, the effect of improving heat resistance in these resin compositions is still insufficient. Also, in general, when a resin composition in which a cellulose-based material is blended with a thermoplastic resin is molded by a conventional method, a unique pattern often referred to as wood grain may be formed on the molded product, which is molded in terms of design. There is a problem that the use of the product is limited.
特許文献１２には、ポリアセタール樹脂とセルロース系物質からなる樹脂組成物が提案されているが、セルロース系物質として如何なるものを用いるべきかの記載も、セルロース系物質の特性により樹脂組成物の物性が如何様に変化するかの記載も無く、また耐熱性に関する記載も無い。 Patent Document 12 proposes a resin composition composed of a polyacetal resin and a cellulosic material, but the description of what should be used as the cellulosic material is also based on the properties of the cellulosic material. There is no description of how it changes, and there is no description of heat resistance.
本発明の目的は、再生可能資源である繊維状セルロース系物質を強化材とし、剛性及び耐熱性に優れ、且つ良好な表面外観を有する成形品を与えるポリアセタール樹脂組成物を提供しようとするものである。また本発明の他の目的は、この樹脂組成物を成形してなる剛性、耐熱性及び表面外観のいずれにも優れたポリアセタール樹脂成形品を提供することにある。 An object of the present invention is to provide a polyacetal resin composition that uses a fibrous cellulosic material, which is a renewable resource, as a reinforcing material, and gives a molded product having excellent rigidity and heat resistance and a good surface appearance. is there. Another object of the present invention is to provide a polyacetal resin molded article excellent in all of rigidity, heat resistance and surface appearance formed by molding this resin composition.
本発明者は、強化材として用いるセルロース系物質について検討した結果、セルロース系物質の嵩密度が、得られる樹脂組成物の特性に大きく影響することを知得し、本発明を完成させるに至った。 As a result of studying the cellulosic material used as the reinforcing material, the present inventor has learned that the bulk density of the cellulosic material greatly affects the properties of the resulting resin composition, and has completed the present invention. .
即ち本発明の要旨は、ポリアセタール樹脂１００重量部に、嵩密度０．１〜０．５ｇ／ｍｌの繊維状セルロース系物質を５〜１００重量部配合したことを特徴とするポリアセタール樹脂組成物に存する。また、本発明の他の要旨は、この樹脂組成物からなる成形品に存する。 That is, the gist of the present invention resides in a polyacetal resin composition comprising 5 to 100 parts by weight of a fibrous cellulosic material having a bulk density of 0.1 to 0.5 g / ml in 100 parts by weight of a polyacetal resin. . Moreover, the other summary of this invention exists in the molded article which consists of this resin composition.
本発明のポリアセタール樹脂組成物は、剛性及び耐熱性に優れており、かつこれらの特性に加えて表面外観にも優れた成形品を与える。従ってこの成形品は、自動車内装部品、家屋等の内装部品（熱水混合栓等）、衣料部品（ファスナー、ベルトバックル等）や建材用途（配管・ポンプ部品等）、電気部品（プリンター、複写機、ファクシミリなどの事務用機器や、時計部品などの精密機器等の樹脂部品、歯車等）に好適に使用することが出来る。 The polyacetal resin composition of the present invention is excellent in rigidity and heat resistance, and gives a molded product excellent in surface appearance in addition to these characteristics. Therefore, this molded product is used for automobile interior parts, interior parts for houses (hot water mixing taps, etc.), clothing parts (fasteners, belt buckles, etc.) and building materials (piping / pump parts, etc.), electrical parts (printers, copying machines, etc.) It can be suitably used for office equipment such as facsimiles, resin parts such as precision parts such as watch parts, and gears.
以下、本発明について詳細に説明する。
周知のようにポリアセタール樹脂は、―（―Ｏ―ＣＲＨ―）ｎ―（但しＲは水素原子又は有機基を示す。）で表されるアセタールを構成単位とする高分子であり、種々のグレードのものが市場で入手し得る。ポリアセタール樹脂は通常はＲが水素原子であるオキシメチレン基（−ＣＨ２Ｏ−）を主たる構成単位とするが、本発明で用いるポリアセタール樹脂はこの構成単位のみからなるホモポリマー以外に、オキシメチレン基以外の繰り返し単位を含むコポリマー（ブロックコポリマー）やターポリマー等であってもよく、更には線状構造のみならず分岐や架橋構造を有するものであってもよい。
Hereinafter, the present invention will be described in detail.
As is well known, a polyacetal resin is a polymer having an acetal represented by — (— O—CRH—) n— (wherein R represents a hydrogen atom or an organic group) as a structural unit, and has various grades. Things are available on the market. The polyacetal resin usually has an oxymethylene group (—CH 2 O—) in which R is a hydrogen atom as a main structural unit. However, the polyacetal resin used in the present invention has an oxymethylene group other than a homopolymer consisting of only this structural unit. It may be a copolymer (block copolymer) or a terpolymer containing a repeating unit other than the above, and may have not only a linear structure but also a branched or crosslinked structure.
オキシメチレン基以外の繰り返し単位としては、例えば、オキシエチレン基（−ＣＨ２ＣＨ２Ｏ−）、オキシプロピレン基（−ＣＨ２ＣＨ２ＣＨ２Ｏ−）、オキシブチレン基（−ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ−）等の炭素数２〜１０のオキシアルキレン基が挙げられる。これらのオキシアルキレン基は直鎖でなく分岐鎖であってもよい。なかでも好ましいのは炭素数２〜４の分岐していてもよいオキシアルキレン基であり、最も好ましいのはオキシエチレン基である。またポリアセタール樹脂に占めるオキシメチレン基以外のオキシアルキレン基の含有量は、０．１重量％〜２０重量％が好ましい。ポリアセタール樹脂のメルトインデックスは、ＩＳＯ１１３３に準拠し、１９０℃、２．１６Ｋｇの条件で測定して通常１〜６０ｇ/１０分であるが、本発明では２〜３０ｇ/１０分、特に３〜２０ｇ/１０分のものを用いるのが好ましい。 Examples of the repeating unit other than the oxymethylene group include an oxyethylene group (—CH 2 CH 2 O—), an oxypropylene group (—CH 2 CH 2 CH 2 O—), and an oxybutylene group (—CH 2 CH 2 CH). And an oxyalkylene group having 2 to 10 carbon atoms such as 2 CH 2 O—). These oxyalkylene groups may be branched instead of linear. Of these, an oxyalkylene group having 2 to 4 carbon atoms which may be branched is preferable, and an oxyethylene group is most preferable. The content of oxyalkylene groups other than oxymethylene groups in the polyacetal resin is preferably 0.1% by weight to 20% by weight. The melt index of the polyacetal resin is usually 1 to 60 g / 10 minutes as measured under the conditions of 190 ° C. and 2.16 kg according to ISO 1133, but in the present invention, it is 2 to 30 g / 10 minutes, particularly 3 to 20 g / minute. It is preferred to use a 10 minute one.
ポリアセタール樹脂の製造方法はいくつも知られているが、本発明ではいずれの製造方法で得られたものも用いることができる。例えば、オキシメチレン基と、炭素数２〜４のオキシアルキレン基を構成単位とするポリアセタール樹脂であれば、ホルムアルデヒドの３量体（トリオキサン）や４量体（テトラオキサン）等のオキシメチレン基の環状オリゴマーと、エチレンオキサイド、１，３−ジオキソラン、１，３，６−トリオキソカン、１，３−ジオキセパン等の炭素数２〜４のオキシアルキレン基を含む環状オリゴマーとを共重合することによって製造されたものを用いることができる。本発明で用いるポリアセタール樹脂としては、トリオキサンやテトラオキサン等の環状オリゴマーと、エチレンオキサイド又は１，３−ジオキソランとの共重合体が好ましく、トリオキサンと１，３−ジオキソランとの共重合体が特に好ましい。 A number of methods for producing a polyacetal resin are known, but those obtained by any method can be used in the present invention. For example, if it is a polyacetal resin which has an oxymethylene group and a C2-C4 oxyalkylene group as a structural unit, cyclic oligomers of oxymethylene groups such as formaldehyde trimer (trioxane) and tetramer (tetraoxane) And a cyclic oligomer containing an oxyalkylene group having 2 to 4 carbon atoms such as ethylene oxide, 1,3-dioxolane, 1,3,6-trioxocane and 1,3-dioxepane. Can be used. The polyacetal resin used in the present invention is preferably a copolymer of a cyclic oligomer such as trioxane or tetraoxane and ethylene oxide or 1,3-dioxolane, and particularly preferably a copolymer of trioxane and 1,3-dioxolane.
本発明で用いる繊維状セルロース系物質とはセルロースを主体とする繊維状物質であり、典型的には所謂セルロースパルプ（以下、これをパルプと称することがある）である。パルプは木材を始め種々の植物から製造し得ることが知られているが、本発明ではいずれの植物を原料とするものも用いることができる。またパルプの製造法も種々知られており、製造法によりパルプの品位が異なるが、いずれの製造法によるものであってもよい。例えば、木材を種々の化学薬品で蒸解処理して共雑物であるリグニンなどを溶解除去し、さらに漂白剤で処理して精製したパルプを用いることができる。 The fibrous cellulosic material used in the present invention is a fibrous material mainly composed of cellulose, and is typically a so-called cellulose pulp (hereinafter sometimes referred to as pulp). It is known that pulp can be produced from various plants including wood, but in the present invention, any pulp made from any plant can be used. Various methods for producing pulp are also known, and the quality of the pulp differs depending on the production method, but any method may be used. For example, pulp obtained by digesting wood with various chemicals to dissolve and remove lignin, which is a contaminant, and then treating with a bleaching agent can be used.
本発明ではこれらのパルプのうち、嵩密度が０．１〜０．５ｇ/ｍｌのものを用いる。なかでも嵩密度が０．２〜０．４ｇ/ｍｌのものを用いるのが好ましい。木材を原料として大量に生産されている製紙用パルプの場合には、繊維は長いほうが強度の大きい紙が得られるとされており、例えば製紙用に好適な針葉樹を原料とするパルプの平均繊維長は４ｍｍ程度である。これに対し、本発明で用いる上記の嵩密度を有するパルプは、平均繊維長が数十〜数百μｍ程度であり、製紙用パルプに比して平均繊維長が著しく短いものであり、例えば常法により得られたパルプを更に粉砕して、微細化することにより得られたものである。 In the present invention, among these pulps, those having a bulk density of 0.1 to 0.5 g / ml are used. Of these, those having a bulk density of 0.2 to 0.4 g / ml are preferred. In the case of papermaking pulp that is produced in large quantities using wood as a raw material, it is said that the longer the fiber, the stronger the paper will be obtained.For example, the average fiber length of pulp made from softwood suitable for papermaking Is about 4 mm. On the other hand, the pulp having the above-described bulk density used in the present invention has an average fiber length of about several tens to several hundreds of μm, and the average fiber length is significantly shorter than that of paper pulp. It is obtained by further pulverizing and refining the pulp obtained by the method.
嵩密度が０．１ｇ/ｍｌに満たないものを用いたのでは、所望の剛性及び耐熱性を有する樹脂組成物を得るのが困難である。これは繊維長が短かすぎるため、補強効果が小さいためと考えられる。またポリアセタール樹脂との溶融混練に際して凝集しやすく、その結果、樹脂組成物から得られる成形品の表面外観が劣ったものとなりやすい。逆に嵩密度が０．５ｇ/ｍｌを超えるものを用いても、所望の剛性及び耐熱性を有する樹脂組成物を得るのが困難である。その原因はパルプが十分に分散しないためと考えられる。すなわちパルプは単繊維が凝集して集合体を形成しているが、これをポリアセタール樹脂と溶融混練すると、集合体がせん断力により単繊維ないしは小さな集合体に解離して樹脂中に分散する。ところで嵩密度の大きいものは集合体が大きいので、単繊維ないしは小さな集合体への解離が十分に進行せず、従ってパルプがポリアセタール樹脂中に均一に分散し難いと考えられる。また嵩密度の大きいものは繊維が長いので絡まりを起こし易いことも、均一分散を妨げる要因と考えられる。 If a material having a bulk density of less than 0.1 g / ml is used, it is difficult to obtain a resin composition having desired rigidity and heat resistance. This is probably because the fiber length is too short and the reinforcing effect is small. Moreover, it is easy to aggregate at the time of melt-kneading with a polyacetal resin, As a result, the surface appearance of the molded product obtained from a resin composition tends to be inferior. On the other hand, it is difficult to obtain a resin composition having desired rigidity and heat resistance even if a bulk density exceeding 0.5 g / ml is used. The reason is considered to be that the pulp is not sufficiently dispersed. That is, in the pulp, single fibers aggregate to form an aggregate, but when this is melt kneaded with a polyacetal resin, the aggregate is dissociated into single fibers or small aggregates by shearing force and dispersed in the resin. By the way, since a large bulk density has a large aggregate, dissociation into single fibers or small aggregates does not proceed sufficiently, and therefore, it is considered that the pulp is difficult to uniformly disperse in the polyacetal resin. In addition, it is considered that the high bulk density is likely to cause entanglement because the fiber is long, which is also a factor hindering uniform dispersion.
本発明で用いる繊維状セルロース系物質は、製紙用パルプを粉砕して調製することもできるが、市場で入手することもできる。例えば食品用などとして販売されているレッテンマイヤー社の「ＡＲＢＯＣＥＬ」、［ＬＩＧＮＯＣＥＬ］、日本製紙社の［ＫＣフロック］、旭化成社の「アビセルＲＣ」などを用いることができる。なお嵩密度の測定は、ＪＩＳ Ｒ３１０５に準じ、１００ｍｌのメスシリンダーに軽くタッピングしながら、試料を入れ、重量を測定することにより行う。測定は５回行い、最大値及び最小値を除いた３回の測定値の平均値を以って嵩密度とする。 The fibrous cellulosic material used in the present invention can be prepared by pulverizing paper pulp, but can also be obtained on the market. For example, “ARBOCEL” and [LIGNOCEL] of Rettenmeier, which are sold for foods, etc., [KC Flock] of Nippon Paper Industries Co., Ltd., “Avicel RC” of Asahi Kasei Corporation and the like can be used. The bulk density is measured according to JIS R3105 by placing a sample and measuring the weight while tapping lightly on a 100 ml measuring cylinder. The measurement is performed 5 times, and the average value of the 3 measured values excluding the maximum value and the minimum value is taken as the bulk density.
繊維状セルロース系物質の配合量は、ポリアセタール樹脂１００重量部に対し、５〜１００重量部である。配合量が５重量部未満では、樹脂組成物に所望の剛性、耐熱性を発現させるのが困難である。また配合量が１００重量部を超えると、溶融混練によりポリアセタール樹脂中に均一に分散させるのが困難であり、その結果、得られる樹脂組成物を成形した成形品は、機械物性や表面外観の劣ったものとなる。ポリアセタール樹脂１００重量部に対する繊維状セルロース物質の配合量は１０〜８０重量部、特に１０〜５０重量部が好ましい。 The blending amount of the fibrous cellulosic material is 5 to 100 parts by weight with respect to 100 parts by weight of the polyacetal resin. If the blending amount is less than 5 parts by weight, it is difficult for the resin composition to exhibit desired rigidity and heat resistance. If the blending amount exceeds 100 parts by weight, it is difficult to uniformly disperse it in the polyacetal resin by melt kneading. As a result, the molded product obtained by molding the resulting resin composition has poor mechanical properties and surface appearance. It will be. The blending amount of the fibrous cellulose substance with respect to 100 parts by weight of the polyacetal resin is preferably 10 to 80 parts by weight, particularly preferably 10 to 50 parts by weight.
本発明のポリアセタール樹脂組成物には、本発明の効果を損なわない範囲内で、さらに公知の各種熱可塑性樹脂、添加剤などを配合してもよい。添加剤としては、例えば熱安定剤、滑剤、離型剤、帯電防止剤、紫外線吸収剤、光安定剤、摺動性改良剤、流動改質剤、ホルムアルデヒド捕捉剤等が挙げられる。更に顔料、染料を加えて所望の色目に仕上げてもよい。 The polyacetal resin composition of the present invention may further contain various known thermoplastic resins, additives and the like within a range not impairing the effects of the present invention. Examples of the additive include a heat stabilizer, a lubricant, a mold release agent, an antistatic agent, an ultraviolet absorber, a light stabilizer, a sliding property improver, a flow modifier, and a formaldehyde scavenger. Further, pigments and dyes may be added to achieve a desired color.
本発明のポリアセタール樹脂組成物は、ポリアセタールに所定量の繊維状セルロース系物質を加え、溶融混練することにより製造することができる。溶融混練は、単軸又は多軸押出機など常用の混練装置を用いて、１８０〜２５０℃で行えばよい。混練に要する時間は混練条件により異なるが通常は１〜５分である。繊維状セルロース系物質は柔軟なので、ガラス繊維などと異なり、通常の混練条件では破断することはない。 The polyacetal resin composition of the present invention can be produced by adding a predetermined amount of fibrous cellulosic material to polyacetal and melt-kneading. The melt-kneading may be performed at 180 to 250 ° C. using a conventional kneading apparatus such as a single-screw or multi-screw extruder. The time required for kneading varies depending on the kneading conditions, but is usually 1 to 5 minutes. Since the fibrous cellulosic material is flexible, it does not break under normal kneading conditions unlike glass fibers.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はその要旨を超えない限り、これらの実施例に限定されるものではない。尚、「部」は「重量部」を示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples, unless the summary is exceeded. “Part” means “part by weight”.
＜樹脂組成物の製造＞
表１に記した各成分を、表２および表３に記した割合（重量比）で配合し、タンブラーにて２０分間混合した。得られた混合物を４０ｍｍΦ単軸押出機（田辺プラスチックス社製、型式：ＶＳ−４０）を用いて、シリンダー温度１９０℃、吐出速度２０ｋｇ／ｈｒで溶融混練して、ポリアセタール樹脂組成物のペレットを製造した。
<Manufacture of resin composition>
Each component described in Table 1 was blended at the ratio (weight ratio) described in Table 2 and Table 3, and mixed for 20 minutes with a tumbler. The obtained mixture was melt-kneaded at a cylinder temperature of 190 ° C. and a discharge rate of 20 kg / hr using a 40 mmφ single screw extruder (manufactured by Tanabe Plastics Co., Ltd., model: VS-40) to produce polyacetal resin composition pellets. Manufactured.
＜試験片の製造＞
得られたペレットを用い、シリンダー温度１９０℃、金型温度８０℃の条件で、射出成形して、厚み３ｍｍのＩＳＯダンベル試験片を成形した。
<Manufacture of test pieces>
Using the obtained pellets, an ISO dumbbell specimen having a thickness of 3 mm was molded by injection molding under the conditions of a cylinder temperature of 190 ° C. and a mold temperature of 80 ° C.
＜表面外観＞
上記で得られた、ＩＳＯダンベル試験片の表面外観を目視にて観察し、繊維状セルロース系物質の凝集物（ダマ、かたまり）がほとんど認められなかったものを「○」、部位によりわずかに認められたものを「△」、成形品全体にわたり明らかに認められたものを「×」と評価した。
<Surface appearance>
The surface appearance of the ISO dumbbell test piece obtained above was visually observed, and “○” indicates that almost no agglomerates (lumps or clumps) of fibrous cellulosic material were observed. What was obtained was evaluated as “Δ”, and what was clearly recognized over the entire molded product was evaluated as “x”.
＜弾性率＞
ＩＳＯ１７８に準拠して曲げ弾性率を測定した。単位は、ＧＰａである。
<Elastic modulus>
The flexural modulus was measured according to ISO178. The unit is GPa.
＜荷重撓み温度＞
ＩＳＯ７５−１，２に従い、荷重１．８０ＭＰａにおける荷重撓み温度を測定した。単位は、℃である。
<Load deflection temperature>
The load deflection temperature at a load of 1.80 MPa was measured in accordance with ISO75-1,2. The unit is ° C.
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