JPS59215335A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To facilitate the production by a conventional single-screw extruder of a thermoplastic resin composition in which a high-viscosity liquid additive is uniformly distributed in a high concentration, by employing a mixture of the high-viscosity liquid additive and a fine powder of an anhydrous inorganic compound. CONSTITUTION:Use is made of a mixture of 10-90wt% high-viscosity liquid additive of a viscosity (at room temperature) >=5,000cSt (e.g., mineral or silicone oils having the above properties) and/or a solid additive of a m.p. >=40 deg.C (e.g., waxes or silicone greases having the above properties) and 90-10wt% fine powder (average particle diameter <=50nm) of an anhydrous inorganic compound (e.g., SiO2 or Al2O3). Namely, a thermoplastic resin (e.g., polybutadiene, rubber- modified styrene resin, or polyvinyl chloride) is mixed with the above mixture so that the content of the additive may be at least 0.5wt%, and the mixture is kneaded with a kneading machine such as a single-screw extruder.

Description

【発明の詳細な説明】 本発明は、高粘性液状添加剤及び／または低融点固体添
加剤を高濃度で含有する熱可塑性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermoplastic resin compositions containing high concentrations of high viscosity liquid additives and/or low melting point solid additives.

熱可塑性樹脂、特に耐衝撃性スチレン系樹脂、ＡＢＳ樹
脂等のゴム変性熱可塑性樹脂の機械的な物性の改良１表
面のすべり性の改良等の目的で従来鉱油、シリコンオイ
ル、ポリエチレンワックス等、液状または低融点の固体
添加剤が上記樹脂に配合されてｂた。Improving the mechanical properties of thermoplastic resins, especially rubber-modified thermoplastic resins such as impact-resistant styrene resins and ABS resins 1. Conventionally, liquid materials such as mineral oil, silicone oil, polyethylene wax, etc. Alternatively, a low melting point solid additive was blended with the resin.

しかしながら、高粘度、特に室温でｊθ００ｃｓｔ以上
の粘度の液状添加剤まだは、低融点固体添加剤を熱可塑
性樹脂にｏ３重倉％以上の高濃度に添加、混線すること
は単軸押出機で十分に均一に混ぜることが事実上不可能
であり、二軸押出機その他の特殊な混練装髄を用いる必
要があった。However, for liquid additives with high viscosity, especially those with a viscosity of more than jθ00cst at room temperature, a single-screw extruder is sufficient for adding low-melting point solid additives to thermoplastic resins at high concentrations of more than O3% and mixing. It is virtually impossible to mix uniformly, and it is necessary to use a twin-screw extruder or other special kneading equipment.

本発明者等は、熱可塑性樹脂の加工業界において普及し
ている単軸押出機を用いても容易に製造し得る、上記添
加剤を高濃度に含有する熱可塑性樹脂及びその製造方法
を開発することを目的として鋭意研究を車ねだ結果、本
発明に到達したものであって、本発明の上記の目的は、
室温における粘度がｊθ００　ｃｓｔ以上である高粘度
液状添加剤及び／または融点が７０℃以下である固体添
加剤７０〜７０重量％ならびに平均粒径が５００ｍ以下
である無水無機化合物粉末り０〜１０重量％からなる混
合物を上記添加剤がθ、夕重′ｆＵ−Ｎ以上含有される
ように熱可塑性樹脂と配合して得られる熱可塑性樹脂組
成物によシ達せられる。The present inventors have developed a thermoplastic resin containing a high concentration of the above-mentioned additives, which can be easily produced using a single-screw extruder that is popular in the thermoplastic resin processing industry, and a method for producing the same. The present invention was arrived at as a result of intensive research aimed at the above-mentioned purposes.
70 to 70% by weight of a high viscosity liquid additive whose viscosity at room temperature is jθ00 cst or more and/or a solid additive whose melting point is 70°C or less and 0 to 10% by weight of anhydrous inorganic compound powder whose average particle size is 500 m or less A thermoplastic resin composition is obtained by blending the above-mentioned additive with a thermoplastic resin in such a manner that the additive is contained in an amount of .theta.

また、かかる組成物は、室温における粘度が−ｔ０θＯ
ｃｓｔ以上である高粘度液状添加剤及び／または融点が
７０℃以下である固体添加剤をＯ，Ｓ重量％以上含有す
る熱可塑性樹脂組成物を製造する方法において、上記液
状及び／または固体添加剤７０〜７０重量％を平均粒径
がｊθｎｍ以下である無水無機化合物粉末り０〜７０重
量％と予め混合したものを上記熱可塑性位（脂と単軸押
出機により混練する方法（τよシ製造することができる
。Further, such a composition has a viscosity of −t0θO at room temperature.
cst or more and/or a solid additive having a melting point of 70° C. or less in a method for producing a thermoplastic resin composition containing O, S weight % or more, the liquid and/or solid additive as described above. A method of kneading 70 to 70% by weight of anhydrous inorganic compound powder with an average particle size of jθnm or less with 0 to 70% by weight of anhydrous inorganic compound powder having an average particle size of jθnm or less using a single-screw extruder (τyoshi manufacturing method) can do.

本発明に用いられる熱可塑性樹脂としては、ポリブタジ
ェン、スチレン−ブタジェン共重合体、ポリアクリル酸
エステル、エチレン−プロピレン系ゴム（ＦＰＲ，ＦＰ
ＤＭ）その他のゴム弾性体にスチレン、α−メチルスチ
レン、ビニルトルエン類等の芳香族ビニル単量体及び必
要に応じてア′クリロニトリル、メタクリロニトリル、
アクリル酸エステル、メタクリル酸ニスチル等のビニル
単量体をグラフト重合式せて得らハるコム変性スチレン
系樹脂その他ポリスチレン、ポリ塩化ビニル等の熱可塑
性樹脂等が挙げられる。Thermoplastic resins used in the present invention include polybutadiene, styrene-butadiene copolymer, polyacrylic ester, ethylene-propylene rubber (FPR, FP
DM) Other rubber elastic bodies include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluenes, and if necessary, acrylonitrile, methacrylonitrile,
Examples include comb-modified styrenic resins obtained by graft polymerization of vinyl monomers such as acrylic acid esters and nistyl methacrylate, and thermoplastic resins such as polystyrene and polyvinyl chloride.

また、高粘性液状添加剤としては、鉱油、シリコ州ル（
ポリオルガノシロキサン）、α−オレフィン類の重合体
、ポリエステル系可塑剤等が挙げられる。これらの添加
剤の粘度け！０θθｃｓｔ以上、好ましくけ、／θθ０
０ｃＳｔ以上のものが用いられる。ｊθ００ｃｓｔ未溝
の添加剤であっても特に不都合はないが、これらは従来
の技術によっても特に問題なく混練できるので本発明の
効果は発揮されない。In addition, examples of high viscosity liquid additives include mineral oil, silicone oil (
(polyorganosiloxane), α-olefin polymers, polyester plasticizers, and the like. The viscosity of these additives! 0θθcst or more, preferably /θθ0
A material having a value of 0 cSt or more is used. Although there is no particular disadvantage in using additives without jθ00cst grooves, the effects of the present invention are not exerted because these can be kneaded without any particular problems using conventional techniques.

まだ、固体添加剤としては、ワックス類、ワセリン、グ
リース状の鉱油、シリコングリース等が挙げられる。こ
れの固体添加剤の融点が７０℃を超えても特に不都合で
はないが、高融点の固体添加剤の場合は、従来の技術に
よっても混練することができるので本発明の効果は発揮
されない。Still, examples of solid additives include waxes, petrolatum, mineral oil in the form of grease, silicone grease, and the like. It is not particularly disadvantageous if the melting point of the solid additive exceeds 70°C, but in the case of a solid additive with a high melting point, the effect of the present invention is not exhibited because it can be kneaded by conventional techniques.

無水無機化合物粉末としては、Ａｌ２Ｏ２，ＴｉＯ７好
ましくはＳｉＯ□等の粉末であって、結晶水、その他の
結合水を含まないものが好ましい。The anhydrous inorganic compound powder is preferably a powder of Al2O2, TiO7, preferably SiO□, and does not contain crystal water or other bound water.

含水物であると樹脂組成物の表面に水分が浸出するとと
デバあり好ましくない。If it is a water-containing material, it is not preferable that water leaches out onto the surface of the resin composition, which may cause problems.

これらＳｉｎ、、等の粉末は湿式法ではなく、気相法、
例えば、ＳｉＣ２，、５ｉＨＯＪ、３．５ｉＨ２０ＪＶ
、、、　。These powders such as Sin, etc. are not produced by a wet method, but by a gas phase method.
For example, SiC2, 5iHOJ, 3.5iH20JV
,,, .

５ｉＨ３０２，ＳｉＨ４，Ｔｉ０Ｊ１４．等を気相で酸
素の存在下に高温で分解したものが特に好ましい。かが
る方法によると、得られた化合物は、極めて微細な粉末
となり、かつ、無水物となる。5iH302, SiH4, Ti0J14. Particularly preferred are those decomposed in the gas phase at high temperatures in the presence of oxygen. According to the method, the obtained compound becomes an extremely fine powder and anhydrous.

本発明ＶＣ用すられる無水無機化合物の平均粒径けｓ　
ｏ　ｎｍ以下好ましくは／　Ｏｎｍ以下が適当である。Average particle size of the anhydrous inorganic compound used for the VC of the present invention
Onm or less, preferably /Onm or less, is suitable.

なお、「平均粒径」とり一次粒子の平均粒径である。−
ｆ　Ｏｎｍを超えると比表面積が低下し、添加剤の吸着
量が減少し、がっ、樹脂酸物の表面光沢の低下、機械的
物性の劣化等の問題が生じるので好ましくない。Note that the "average particle size" is the average particle size of primary particles. −
If it exceeds f Onm, the specific surface area decreases, the amount of adsorbed additives decreases, and problems such as gas, a decrease in the surface gloss of the resin acid, and deterioration of mechanical properties occur, which is not preferable.

平均粒径が！θｎｍ〜、２ｎｍの範囲であれは比表面積
よ０〜グθｏｒｒｚ７ｙ、見かけ比重！θ〜λθＯｔ　
／　を程度となる。Average particle size! In the range of θnm~, 2nm, the specific surface area is 0~gθorrz7y, apparent specific gravity! θ〜λθOt
/ is the degree.

添加剤と無機化合物粉末の混合比率は添加ＭａＪが１０
〜２０重量％好ましくけ、ＴＯ−♂θ重量％残部が上記
粉末となるように混合するのが適当である。The mixing ratio of additives and inorganic compound powder is such that the addition MaJ is 10
It is appropriate to mix the powder so that the powder is preferably 20% by weight and the rest is TO-♂θ and the rest is the above-mentioned powder.

７０重量％未満では、無機化合物粉末の使用量が多くな
り、また、り０重量％を超えると、添加剤が上記粉末に
十分吸着しなくなるので熱可塑性樹脂との混線が困難と
なる。If it is less than 70% by weight, the amount of inorganic compound powder used will be large, and if it exceeds 0% by weight, the additive will not be sufficiently adsorbed to the powder, making it difficult to mix with the thermoplastic resin.

添加剤と無機化合物粉末を混合する場合は所定量の添加
剤を上記粉末に一時に加えるか又はスプレー等により加
える。また、混合はヘンシエルミキザー、スーパーミキ
サー等通常の混合機により室温またはそれ以上の温度、
好ましくは６０〜と０℃の温度で３θ秒以上、好ましく
は／〜Δ゛分混合することによって行なわれる。When an additive and an inorganic compound powder are mixed, a predetermined amount of the additive is added to the powder at once or by spraying or the like. In addition, mixing can be done at room temperature or higher using a normal mixer such as a Henschel mixer or super mixer.
Preferably, mixing is carried out at a temperature of 60 to 0° C. for 3θ seconds or more, preferably ≈Δ° minutes.

得られた混合物は、湿潤な粉末状となる。The resulting mixture becomes a wet powder.

上記混合物は単軸押出機等通常用いられる混練装置を用
いて熱可塑性樹脂と混練される。混合比率は添加剤の濃
度が０．夕重量％以上／θ重量％以下が好ましい。ｏ３
重量％未満であると他の手段によっても混線できる。ま
た、７０重量％を超えても不都合はないが、実用上、上
記範囲が用いられる。The above mixture is kneaded with a thermoplastic resin using a commonly used kneading device such as a single screw extruder. The mixing ratio is such that the additive concentration is 0. It is preferable that the ratio is more than or equal to 0% by weight/less than or equal to θ% by weight. o3
If it is less than % by weight, crosstalk can also occur by other means. Further, although there is no problem even if the content exceeds 70% by weight, the above range is used practically.

本発明に係る製造方法によるとシリコンオイルその他の
高粘度の液状添加物、低融点の固体添加物を準軸押出磯
等を用いて容易かつ多Ｎ如熱可塑性樹脂と混練すること
かできる。また、本発明に係る組成物は耐衝撃性、引張
り強さ等のイ賎械的強度も改善され、用いた粉末が微粒
子であるので上記組成物を用すだ成形物の表面のすべり
性（滑性）、表面光沢等も良好である。According to the production method of the present invention, silicone oil and other high viscosity liquid additives and low melting point solid additives can be easily kneaded with the high-N thermoplastic resin using a quasi-axial extrusion mill or the like. In addition, the composition of the present invention has improved mechanical strength such as impact resistance and tensile strength, and since the powder used is fine particles, the surface slippage of the molded product using the composition is improved. lubricity), surface gloss, etc. are also good.

続いて、実施例及び比較例に基づいて本発明をさらに具
体的に曲間する。Next, the present invention will be explained in more detail based on Examples and Comparative Examples.

なお、実施例及び比較例中に示した物性シボ下記の測定
法によって測定した。The physical properties of grain shown in the Examples and Comparative Examples were measured by the following measuring method.

引張り強度（単位ｋｇ／ｃｒ／Ｌ）及び伸び（単位光）
Ｊ工ＳＫ−、ｇ了２／ 曲げ強度（単位に９　／　ａｌ　） ＡＳＴＭＤ−７２０ アイゾツト衝撃強度（単位１ｃｇ・ｃｍ／　ｃｍ　）Ａ
ＳＴＭＤ−２５６ ヤ Ｖ工ＯＡＴ軟化点（℃） Ｊ工ＳＫ−乙ど７０ メルトフローインデックス（単位７／７０分）ＡＳＴＭ
　Ｄ　／２３！、Ｂ法 成形品外観 目視判定 静摩擦係数 被測定試料と同一の拐料で作った斜面に２３”朋×／２
６ｍｍの試験片を置き、５グ３２の荷重をかけて、斜面
の傾きを変化させて、試験片が動き始める傾き角（斜面
と水平面のなす角）θを測定、その正接の値（ｔａｎθ
）を静摩擦係数とした。Tensile strength (unit: kg/cr/L) and elongation (unit: light)
J Engineering SK-, g-2/Bending strength (unit: 9/al) ASTM D-720 Izod impact strength (unit: 1cg/cm/cm) A
STMD-256 YaV-OAT Softening Point (℃) J-Tech SK-Otto 70 Melt Flow Index (Unit: 7/70 minutes) ASTM
D/23! , Visual judgment of external appearance of B method molded product Coefficient of static friction
Place a 6mm test piece, apply a load of 5g32, change the inclination of the slope, measure the inclination angle (the angle between the slope and the horizontal plane) θ at which the test piece begins to move, and calculate its tangent value (tanθ
) was taken as the static friction coefficient.

動摩擦係数 被測定試料と同一の材質で作った水平面に２！闘Ｘ　／
　２　Ｊ’　ｍｌの試験片を置き、これに３￥、３ｉｉ
＋の荷重（Ｗ）をかけ、コ０朋／かの速度で移動させた
場合の引張力（Ｐ）を測定し、Ｐ／Ｗの値を動摩擦係数
としだ。2 on a horizontal surface made of the same material as the sample to be measured for dynamic friction coefficient. Fighting X /
Place a 2 J' ml test piece and add 3 yen and 3ii to it.
The tensile force (P) when a + load (W) is applied and the object is moved at a speed of 0/k is measured, and the value of P/W is taken as the coefficient of dynamic friction.

実施例／ シリコンオイル（信越シリコン社Ｋ　Ｆ−２乙。Example/ Silicone oil (Shin-Etsu Silicon Co. K F-2 Otsu.

＋２！℃における粘度３×／θやｃｓｔ　）を重量比で
半量のＳｉＯ２粉末（日本アエロジル［有］う分間混合
した。+2! The SiO2 powder (viscosity 3x/θ or cst at ℃) was mixed with a half weight ratio of SiO2 powder (Nippon Aerosil Co., Ltd.).

その結果、湿潤な粉末が得られた。これを、ゴム変性ポ
リスチレン（Ｈｌ：ＰＳ　）　樹脂＜ゴム含量２重量％
）と単軸押出様により混練した。配合比、物性等は第１
表に示す。As a result, a wet powder was obtained. This was mixed into rubber-modified polystyrene (Hl:PS) resin <rubber content 2% by weight.
) and kneaded by single-screw extrusion. The blending ratio, physical properties, etc. are the first
Shown in the table.

比較例／ ５１０２粉末を使用しなかったこと以外は実施例／と同
様にして熱可塑性樹脂を製造した。十分に混線できなか
ったのでアイゾツト衝撃強度、外観等が劣化した。Comparative Example A thermoplastic resin was produced in the same manner as in Example except that 5102 powder was not used. Because the wires could not be cross-wired sufficiently, the Izotsu impact strength, appearance, etc. deteriorated.

結果を第１表に示す。The results are shown in Table 1.

比較例λ 無様化合物粉末として湿式法で製造したｓ１’０２ｎＨ
，、Ｏ（塩野義製薬■カープレックス）を用いたこと以
外は実施例／と同様にして熱可塑性１酎脂組成物を製造
した。Comparative example λ s1'02nH produced by wet method as amorphous compound powder
,, O (Shionogi & Co., Ltd. Carplex) was used. A thermoplastic lard composition was produced in the same manner as in Example.

結果を第１表に示す。The results are shown in Table 1.

実施例認 実施例／において使用しだ熱可塑性樹脂をＡＢＳ樹脂と
し、他の条件は全べて実施例／と同じとした。The thermoplastic resin used in Example 1 was ABS resin, and all other conditions were the same as in Example 1.

比較例３ 比較例／において使用しだ熱可塑性樹脂をＡＢＳ樹脂と
し、他の条件はすべて比較例／と同じとした。Comparative Example 3 The thermoplastic resin used in Comparative Example was ABS resin, and all other conditions were the same as in Comparative Example.

実施例コ及び比較例３の結果を第２表に示す。The results of Example 3 and Comparative Example 3 are shown in Table 2.

実施例３ 実施例／に於て無水５ＩＯ２／シリコンオイルの重量比
をそれぞれ％およびイとし、その他は全べて実施例／と
同じ方法でペレットを作成した。Example 3 Pellets were prepared in the same manner as in Example 3 except that the weight ratios of anhydrous 5IO2/silicone oil were % and A, respectively.

結果を第３表に示す。The results are shown in Table 3.

２７１− これらの結果より、無水ＳｉＯ２／シリコンオイルの混
合比を増していっても、実施例／と同様の効果が得られ
ることが明らかである。271- From these results, it is clear that even if the mixing ratio of anhydrous SiO 2 /silicon oil is increased, the same effects as in Example / can be obtained.

特許出願人　　　三菱モンサント化成株式会社代　理　
人　　弁理士　長谷用　　− （ほか７名） 手続補正書（自発） ■　事件の表示　昭和！ｇ年特　許　願第１１７２′号
２　発　明　の名称　　熱可塑性樹脂組成物およびその
製造方法３　補正をする者 事件との関係　特許出願人 名　称　（ｔｏｔ、ｔ）　　三菱モンサント化成株式会
社４代理人〒１００ ５　補正の対象　明細書の発明の詳細な説明の欄６　補
正の内容 明細書第７頁第１２〜／ｇ行目を「全比率はい。ＯＪ重
量係未満であると他の手段によっても混線できる。また
、７０重」と訂正する。Patent applicant Mitsubishi Monsanto Chemical Co., Ltd. Representative
Person Patent attorney Hase - (7 others) Procedural amendment (voluntary) ■ Display of case Showa! Patent Application No. 1172', Year G 2 Name of the invention Thermoplastic resin composition and its manufacturing method 3 Relationship with the case of the person making the amendment Name of patent applicant (tot, t) Mitsubishi Monsanto Chemical Co., Ltd. 4 Agents〒 100 5 Target of amendment Detailed explanation of the invention in the specification column 6 Contents of the amendment Page 7 of the specification, line 12 to /g: ``Total ratio yes. I can do it. Also, I am corrected, 70 times.”

以　　　上that's all

Claims (4)

【特許請求の範囲】[Claims] （１）室温における粘度が！θθＯｃｓｔ以上である高
粘度液状添加剤及び／または融点がり０℃以下である固
体添加剤／θ〜り０重量％ならびに平均粒径がまθｎｍ
以下である無水無機化合物粉末２０〜／θ重量九からな
る混合物を上記添加剤が０．！重高上含有されるように
熱可塑性樹脂と配合して得られる熱可塑性樹脂組成物。(1) Viscosity at room temperature! High viscosity liquid additive with a melting point of θθOcst or more and/or solid additive with a melting point of 0°C or less/θ~0% by weight and average particle diameter θnm
A mixture consisting of the following anhydrous inorganic compound powder 20~/θ weight 9 is mixed with the above additive at 0. ! A thermoplastic resin composition obtained by blending with a thermoplastic resin in such a manner that the composition contains a thermoplastic resin. （２）高粘度液状添加剤がシリコンオイルであることを
特徴とする特許請求の範囲第１項記載の組成物。(2) The composition according to claim 1, wherein the high viscosity liquid additive is silicone oil. （３）無水無機化合物粉末が５１ｏ２粉末である特許請
求の範囲第１項記載の組成物。(3) The composition according to claim 1, wherein the anhydrous inorganic compound powder is 51o2 powder. （４）室温における粘度が！θ０θｃｓｔ以上である高
粘度液状添加剤及び／まだは融点がり０℃以下である固
体添加剤をＯ，Ｓ重量％以上含有する熱可塑性樹脂組成
物を製造する方法において、上記液状添加剤及び／また
は固体添加剤１０〜り０重量％を平均粒径が６０　ｎｍ
以下である無水無様化合物粉末２０〜７０重量％と予め
混合したものを上記熱可塑性樹脂と単軸押出機によシ混
練することを特徴とする方法。(4) Viscosity at room temperature! In a method for producing a thermoplastic resin composition containing O,S weight% or more of a high viscosity liquid additive having a viscosity of θ0θcst or more and/or a solid additive having a melting point of 0°C or less, the liquid additive and/or 10 to 0% by weight of solid additives with an average particle size of 60 nm
A method characterized in that a mixture of 20 to 70% by weight of the following anhydrous amorphous compound powder is mixed in advance with the thermoplastic resin in a single-screw extruder.