JPH0570601A - Thermoplastic elastomer powder composition for powder molding and powder molding method using the same composition and its molded body - Google Patents
Thermoplastic elastomer powder composition for powder molding and powder molding method using the same composition and its molded bodyInfo
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- JPH0570601A JPH0570601A JP4055105A JP5510592A JPH0570601A JP H0570601 A JPH0570601 A JP H0570601A JP 4055105 A JP4055105 A JP 4055105A JP 5510592 A JP5510592 A JP 5510592A JP H0570601 A JPH0570601 A JP H0570601A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、粉末成形用の熱可塑性
エラストマーパウダー組成物、それを用いる粉末成形法
及びその成形体に関する。TECHNICAL FIELD The present invention relates to a thermoplastic elastomer powder composition for powder molding, a powder molding method using the same, and a molded product thereof.
【０００２】[0002]
【従来の技術、発明が解決しようとする課題】自動車内
装材、例えばインストルメントパネル、コンソールボッ
クス、アームレスト、ヘッドレスト、ドアトリム等の表
皮材として、可塑剤を含む塩化ビニルパウダー組成物の
粉末成形体が使用されている。しかしながら、該成形体
は、軽量性に劣るのみならず廃車時の焼却処分により酸
性物質を発生し、大気汚染、酸性雨等を惹起しクリーン
性に劣るという塩化ビニル由来の欠点、更には自動車の
窓ガラス内面に曇りを生ぜしめる等の可塑剤由来の欠点
があり、満足し得るものではない。BACKGROUND OF THE INVENTION As a skin material for automobile interior materials such as instrument panels, console boxes, armrests, headrests, door trims, etc., a powder molded product of a vinyl chloride powder composition containing a plasticizer is available. It is used. However, the molded product is not only inferior in lightness but also generates an acidic substance by incineration at the time of disposal of a vehicle, and causes air pollution, acid rain, etc., and is inferior in cleanness, resulting in a defect derived from vinyl chloride. There is a drawback derived from a plasticizer, such as the formation of fog on the inner surface of the window glass, and it is not satisfactory.
【０００３】本発明者等は、かかる塩化ビニルパウダー
組成物の欠点を改善すべく検討を加え、既に、粉末成形
用のオレフィン系熱可塑性エラストマーパウダーを提案
している（特願平3-199579号、特願平3-199589号) 。そ
の後、検討を続けたところ、熱可塑性エラストマーパウ
ダーは粉砕直後には良好な粉体流動性を示すが、長時間
放置中にパウダー同士が凝集して粉末成形に必要な粉体
流動性を示さなくなるという問題が生じた。The present inventors have conducted studies to improve the drawbacks of such vinyl chloride powder composition, and have already proposed an olefinic thermoplastic elastomer powder for powder molding (Japanese Patent Application No. 3-199579). , Japanese Patent Application No. 3-199589). After that, when the investigation was continued, the thermoplastic elastomer powder showed good powder flowability immediately after pulverization, but the powders agglomerated during standing for a long time and the powder flowability required for powder molding was lost. The problem arises.
【０００４】さらに、パウダーを加熱した金型に触れさ
せることによりパウダー同士を熱融着させ、熱融着しな
かったパウダーは粉体供給ボックスに戻すという粉末ス
ラッシュ成形法を実施した場合は、熱融着しなかったパ
ウダーが繰り返し実施により、徐々に温められて粉体供
給ボックス内で蓄熱し、次第にパウダー同士が凝集して
粉体流動性が悪化する結果、長時間連続して実施するに
つれて、欠肉及びピンホールを有する成形体が生産され
るという問題が生じた。Further, when the powder slush molding method is carried out in which the powders are heat-sealed to each other by bringing the powders into contact with a heated mold, and the powders which have not been heat-sealed are returned to the powder supply box. By repeatedly performing the powder that has not been fused, the powder is gradually warmed and heat is stored in the powder supply box, and as a result of gradually aggregating the powders and deteriorating the powder fluidity, as a continuous operation for a long time, There was a problem in that a molded body having a deficiency and pinholes was produced.
【０００５】かかる状況下に、本発明者らは、熱可塑性
エラストマーパウダーを用いる粉末成形について種々検
討を重ねた結果、熱可塑性エラストマーパウダーと特定
量の微細粉体からなるパウダー組成物が長期間保存して
も良好な粉体流動性を示すことを見出すとともに、該パ
ウダー組成物を使用すれば、例えば粉末スラッシュ成形
法で長時間連続実施しても欠肉、ピンホール等のない成
形体が製造し得ることを見出し、さらに種々の検討を加
えて本発明を完成した。Under these circumstances, the present inventors have conducted various studies on powder molding using a thermoplastic elastomer powder, and as a result, a powder composition comprising the thermoplastic elastomer powder and a specific amount of fine powder can be stored for a long period of time. Even if it is found that the powder composition exhibits good powder fluidity, the use of the powder composition produces, for example, a molded product having no wall defects or pinholes even if it is continuously carried out for a long time by the powder slush molding method. The present invention has been completed by finding out that it can be done, and further conducting various studies.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明は、下
記（Ａ）の熱可塑性エラストマーパウダー 100重量部に
対して、平均粒子径30μｍ以下の微細粉体を0.05〜20重
量部含有することを特徴とする粉末成形用熱可塑性エラ
ストマーパウダー組成物、それを用いる粉末成形方法及
びその成形体を提供するものである。 （Ａ）エチレン・α−オレフィン系共重合体ゴムとポリ
オレフィン系樹脂との組成物からなる熱可塑性エラスト
マーのパウダーまたはエチレン・α−オレフィン系共重
合体ゴムとポリオレフィン系樹脂との部分架橋型組成物
からなる熱可塑性エラストマーのパウダーであって、25
0 ℃における周波数１ラジアン／秒での複素動的粘度η
* (1) が 1.5×105 ポイズ以下であり、かつ上記複素動
的粘度η* (1) と周波数100 ラジアン／秒での複素動的
粘度η* (100) とを用いて次式で算出されるニュートン
粘性指数ｎが0.67以下である熱可塑性エラストマーパウ
ダー。 ｎ＝｛ｌｏｇη* (1) −ｌｏｇη* (100) ｝／２That is, according to the present invention, 0.05 to 20 parts by weight of a fine powder having an average particle diameter of 30 μm or less is contained with respect to 100 parts by weight of the following (A) thermoplastic elastomer powder. A thermoplastic elastomer powder composition for powder molding, a powder molding method using the same, and a molded body thereof are provided. (A) Thermoplastic elastomer powder composed of a composition of ethylene / α-olefin copolymer rubber and polyolefin resin or a partially crosslinked composition of ethylene / α-olefin copolymer rubber and polyolefin resin A thermoplastic elastomer powder consisting of 25,
Complex dynamic viscosity η at a frequency of 1 rad / sec at 0 ° C
* (1) is less than or equal to 1.5 × 10 5 poise, and calculated using the above complex dynamic viscosity η * (1) and complex dynamic viscosity η * (100) at a frequency of 100 rad / sec by the following formula A thermoplastic elastomer powder having a Newton viscosity index n of 0.67 or less. n = {logη * (1) -logη * (100)} / 2
【０００７】また、本発明は上記粉末成形用熱可塑性エ
ラストマーパウダー組成物を用いる粉末成形方法、上記
粉末成形用熱可塑性エラストマーパウダー組成物を用い
て製造してなる成形体を提供するものである。The present invention also provides a powder molding method using the above thermoplastic elastomer powder composition for powder molding, and a molded article produced by using the above thermoplastic elastomer powder composition for powder molding.
【０００８】以下、本発明を詳細に説明する。本発明で
用いるエチレン・α−オレフィン系共重合体ゴムとして
は、例えば、エチレン・プロピレン共重合体ゴム、エチ
レン・プロピレン・非共役ジエン共重合体ゴム等のオレ
フィンを主成分としたゴムが挙げられる。非共役ジエン
としては、例えば、ジシクロペンタジエン、エチリデン
ノルボルネン、１，４−ヘキサジエン、シクロオクタジ
エン、メチレンノルボルネン等が挙げられる。なかで
も、エチレン・プロピレン・エチリデンノルボルネンゴ
ム（以下ＥＰＤＭと称する）が好ましく、これを用いる
と、耐熱性、引張特性等に優れた成形体が得られる。The present invention will be described in detail below. Examples of the ethylene / α-olefin copolymer rubber used in the present invention include rubbers containing olefin as a main component such as ethylene / propylene copolymer rubber and ethylene / propylene / non-conjugated diene copolymer rubber. .. Examples of the non-conjugated diene include dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and the like. Among them, ethylene / propylene / ethylidene norbornene rubber (hereinafter referred to as EPDM) is preferable, and when it is used, a molded product excellent in heat resistance, tensile properties and the like can be obtained.
【０００９】エチレン・α−オレフィン系共重合体ゴム
のムーニー粘度（ASTM D-927-57Tに準じて100 ℃で測定
したムーニー粘度（ＭＬ1+4 100 ℃））は、通常130 以
上350 以下、好ましくは 200以上 300以下である。ま
た、エチレン・α−オレフィン系共重合体ゴムにパラフ
ィン系プロセスオイル等の鉱物油系軟化剤を添加した油
展オレフィン系共重合体ゴムを使用することも好まし
く、この場合には溶融流動性が向上するのみならず成形
体の柔軟性が向上する。鉱物油系軟化剤の含量は、エチ
レン・α−オレフィン系共重合体ゴム 100重量部あた
り、通常30〜 120重量部である。The Mooney viscosity of the ethylene / α-olefin copolymer rubber (the Mooney viscosity measured at 100 ° C. according to ASTM D-927-57T (ML 1 + 4 100 ° C.)) is usually 130 or more and 350 or less, It is preferably 200 or more and 300 or less. Further, it is also preferable to use an oil-extended olefin-based copolymer rubber obtained by adding a mineral oil-based softening agent such as a paraffin-based process oil to an ethylene / α-olefin-based copolymer rubber. Not only is it improved, but the flexibility of the molded product is also improved. The content of the mineral oil type softening agent is usually 30 to 120 parts by weight per 100 parts by weight of the ethylene / α-olefin type copolymer rubber.
【００１０】ポリオレフィン系樹脂としては、ポリプロ
ピレン、プロピレンとエチレンの共重合体、プロピレン
とプロピレン以外のα−オレフィンの共重合体が好まし
く用いられる。特に、プロピレンとブテンとの共重合体
樹脂を用いることにより、成形体の硬度を下げることも
可能である。ポリオレフィン系樹脂のメルトフローレー
ト（ＭＦＲ、JIS K-7210に準拠し、230 ℃、2.16kg荷重
で測定）が、20g ／10分未満の場合は、粉末成形時にパ
ウダー同士が溶融付着し難くなり成形体の強度が低下す
るので、通常20g ／10分以上のものが使用される。好ま
しくは50g ／10分以上である。As the polyolefin resin, polypropylene, a copolymer of propylene and ethylene, and a copolymer of propylene and an α-olefin other than propylene are preferably used. In particular, it is possible to reduce the hardness of the molded product by using a copolymer resin of propylene and butene. If the melt flow rate of polyolefin resin (MFR, measured according to JIS K-7210, 230 ° C, 2.16kg load) is less than 20g / 10 minutes, it becomes difficult to melt and adhere powders during powder molding. Since the strength of the body decreases, 20g / 10 min or more is usually used. It is preferably 50 g / 10 minutes or more.
【００１１】本発明における熱可塑性エラストマーは、
上記のようなエチレン・α−オレフィン系共重合体ゴム
とポリオレフィン系樹脂との組成物、または該組成物を
動的架橋した部分架橋型組成物であるが、エチレン・α
−オレフィン系共重合体ゴムとオレフィン系樹脂の比率
は、重量比で通常５：95〜80：20であることが好まし
い。動的架橋をせしめるに当たっては、架橋剤として有
機過酸化物が通常用いられる。有機過酸化物としては、
ジアルキルパーオキサイドが好ましく用いられる。ま
た、ビスマレイミド化合物などの架橋助剤の存在下、ご
く少量の有機過酸化物を用いて動的架橋することが好ま
しく、この場合エチレン・α−オレフィン系共重合体ゴ
ムを適度に架橋し耐熱性を持たせると同時に、高流動性
を実現し得る。架橋剤は、エチレン・α−オレフィン系
共重合体ゴムとポリオレフィン系樹脂との組成物100 重
量部あたり、1.5 重量部以下、好ましくは0.6 重量部以
下用いられ、有機過酸化物は、0.2 重量部以下、好まし
くは0.1 重量部以下、より好ましくは0.07重量部以下用
いられる。The thermoplastic elastomer in the present invention is
A composition of the ethylene / α-olefin copolymer rubber and a polyolefin resin as described above, or a partially crosslinked composition obtained by dynamically crosslinking the composition.
The ratio of the olefin copolymer rubber to the olefin resin is preferably 5:95 to 80:20 by weight. In carrying out dynamic crosslinking, an organic peroxide is usually used as a crosslinking agent. As the organic peroxide,
Dialkyl peroxide is preferably used. Further, in the presence of a crosslinking aid such as a bismaleimide compound, it is preferable to dynamically crosslink with a very small amount of organic peroxide. In this case, the ethylene / α-olefin copolymer rubber is appropriately crosslinked to obtain a heat resistance. It is possible to realize high liquidity at the same time as providing liquidity. The cross-linking agent is used in an amount of 1.5 parts by weight or less, preferably 0.6 parts by weight or less, per 100 parts by weight of the composition of the ethylene / α-olefin copolymer rubber and the polyolefin resin, and 0.2 parts by weight of the organic peroxide. The following is used, preferably 0.1 part by weight or less, more preferably 0.07 part by weight or less.
【００１２】動的架橋に使用する装置としては、一軸混
練押出機あるいは二軸混練押出機等の連続混練押出機が
好適に用いられる。二軸混練押出機を用いる場合は、剪
断速度＜103sec-1で押出架橋を行なうとエチレン・α−
オレフィン系共重合体ゴムの分散粒子径が大きくなり本
発明の粘度条件を実現することが難しくなるので、剪断
速度≧103sec-1で連続押出架橋を行なうことが好まし
い。本発明における熱可塑性エラストマーは、250 ℃、
周波数１ラジアン／秒で測定した複素動的粘度η* (1)
が1.5 ×105 ポイズ以下、好ましくは1.0 ×105 ポイズ
以下である。1.5 ×105 ポイズを超えると該エラストマ
ーのパウダーは、金型面上で溶融流動しなくなり、加工
時の剪断速度が１sec -1以下の非常に低い粉末成形法で
は成形ができなくなる。As a device used for dynamic crosslinking, a continuous kneading extruder such as a single-screw kneading extruder or a twin-screw kneading extruder is preferably used. When a twin-screw kneading extruder is used, extrusion-crosslinking at a shear rate of <10 3 sec -1 results in ethylene / α-
Since the dispersed particle size of the olefin-based copolymer rubber becomes large and it becomes difficult to realize the viscosity conditions of the present invention, it is preferable to carry out continuous extrusion crosslinking at a shear rate ≧ 10 3 sec −1 . The thermoplastic elastomer in the present invention has a temperature of 250 ° C.,
Complex dynamic viscosity η * (1) measured at a frequency of 1 rad / sec
Is 1.5 × 10 5 poise or less, preferably 1.0 × 10 5 poise or less. When it exceeds 1.5 × 10 5 poise, the elastomer powder does not melt and flow on the mold surface, and cannot be molded by a very low powder molding method in which the shear rate during processing is 1 sec −1 or less.
【００１３】また、250 ℃、周波数１ラジアン／秒で測
定した複素動的粘度η* (1) と周波数100 ラジアン／秒
で測定した複素動的粘度η* (100) とを用いて次式で算
出されるニュートン粘性指数ｎが0.67以下、好ましくは
0.60以下である。 ｎ＝｛ｌｏｇη* (1) −ｌｏｇη* (100) ）｝／２ ニュートン粘性指数ｎが0.67を超えると、仮に周波数１
ラジアン／秒で測定した複素動的粘度η* (1) が1.5 ×
105ポイズ以下であっても、複素動的粘度の周波数依存
性が大きくなり、粉末成形のように成形時の賦形圧力が
１kg／cm2 以下と非常に小さい成形法では溶融したエラ
ストマーパウダー粒子同士の熱融着が不完全になり機械
的物性の低い成形体しか得られない。Further, using the complex dynamic viscosity η * (1) measured at 250 ° C. and a frequency of 1 radian / sec and the complex dynamic viscosity η * (100) measured at a frequency of 100 radian / sec, The calculated Newton viscosity index n is 0.67 or less, preferably
It is less than 0.60. n = the {logη * (1) -logη * (100))} / 2 Newtonian viscosity index n exceeds 0.67, if frequency 1
Complex dynamic viscosity η * (1) measured in radians / second is 1.5 ×
Even if the porosity is 10 5 poise or less, the frequency dependence of the complex dynamic viscosity becomes large, and the melted elastomer powder particles are produced by a very small molding method such as powder molding in which the shaping pressure at the time of molding is 1 kg / cm 2 or less. The heat fusion between them is incomplete, and only a molded product having low mechanical properties can be obtained.
【００１４】本発明に用いる熱可塑性エラストマー組成
物は、未架橋のエチレン−α−オレフィン共重合体ゴム
あるいはエチレン−α−オレフィン共重合体樹脂を、エ
ラストマー100 重量部に対し50重量部以下ブレンドして
使用し、成形体の柔軟性をより向上させることもでき
る。この場合のα−オレフィンは、プロピレン及びブテ
ン等が単独または併用して用いられる。特にエチレン含
有量が40〜90重量％、好ましくは70〜85重量％のエチレ
ン−プロピレン共重合体ゴムでＭＬ1+4 100 ℃が50以下
のものが好ましい。熱可塑性エラストマーパウダーは、
上記のような熱可塑性エラストマー組成物を、例えばガ
ラス転移温度以下の低温で粉砕することにより製造され
る。その平均粒子系は通常100 μｍ〜300 μｍである。The thermoplastic elastomer composition used in the present invention is a blend of uncrosslinked ethylene-α-olefin copolymer rubber or ethylene-α-olefin copolymer resin in an amount of 50 parts by weight or less per 100 parts by weight of the elastomer. It is also possible to further improve the flexibility of the molded product by using it. As the α-olefin in this case, propylene, butene and the like are used alone or in combination. Particularly, an ethylene-propylene copolymer rubber having an ethylene content of 40 to 90% by weight, preferably 70 to 85% by weight and having an ML 1 + 4 100 ° C. of 50 or less is preferable. The thermoplastic elastomer powder is
It is produced by crushing the above-mentioned thermoplastic elastomer composition at a low temperature of, for example, a glass transition temperature or lower. The average particle size is usually 100 μm to 300 μm.
【００１５】本発明の熱可塑性エラストマーパウダー組
成物は、上記のような熱可塑性エラストマーパウダーと
特定量の微細粉体からなる点に特徴を有するものである
が、微細粉体としては、その平均粒子径が30μｍ以下、
より好ましくは、0.1 〜10μｍのものが使用される。
ここで平均粒子径が30μｍを超えると長期保存において
良好な粉体流動性を維持し続けることができない。かか
る微細粉体としては、例えば、アゾ系、フタロシアン
系、スレン系、染色レーキ系等の有機顔料、酸化チタン
等の酸化物系、クロモ酸モリブデン酸系、硫化物セレン
化合物系、フェロシアン化物系、カーボンブラック等の
無機顔料、ペースト用塩化ビニル樹脂、酸化アルミニウ
ム、水酸化アルミニウム、炭酸カルシウム等の粉体が挙
げられる。中でも、顔料は少量でも良好な粉体流動性を
維持し続けると同時に成形体を着色するため、後の着色
工程を省略することもできるので好ましい。The thermoplastic elastomer powder composition of the present invention is characterized in that it comprises the above-mentioned thermoplastic elastomer powder and a specific amount of fine powder. Diameter less than 30μm,
It is more preferably 0.1 to 10 μm.
Here, if the average particle size exceeds 30 μm, good powder fluidity cannot be maintained during long-term storage. Examples of such fine powders include organic pigments such as azo, phthalocyanine, slene, and dye lake, oxides such as titanium oxide, molybdic acid chromoate, selenium sulfide compounds, and ferrocyanides. Inorganic pigments such as carbon black and carbon black, vinyl chloride resin for paste, powders of aluminum oxide, aluminum hydroxide, calcium carbonate and the like. Among them, the pigment is preferable because even if it is a small amount, the molded body is colored at the same time while maintaining good powder fluidity, and the subsequent coloring step can be omitted.
【００１６】また、微細粉体の含量は、熱可塑性エラス
トマーパウダー100 重量部に対して、0.05〜20重量部で
あり、好ましくは0.1 〜８重量部であり、更に好ましく
は0.1 〜４重量部である。含量が0.05重量部未満では、
長期保存において良好な粉体流動性を維持し続け難く、
20重量部を超えると粉体粒子間の熱融着強度の充分に大
きな成形体が得られない。The content of the fine powder is 0.05 to 20 parts by weight, preferably 0.1 to 8 parts by weight, and more preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the thermoplastic elastomer powder. is there. If the content is less than 0.05 parts by weight,
It is difficult to maintain good powder fluidity during long-term storage,
If it exceeds 20 parts by weight, a molded product having a sufficiently high heat fusion strength between powder particles cannot be obtained.
【００１７】熱可塑性エラストマーパウダーに微細粉体
を含有させる方法としては、微細粉体が均一に分散する
方法であれば特に限定されるものではなく、例えば、加
熱用ジャケットのついたブレンダーや高速回転型ミキサ
ー等を使用してブレンドする方法等が挙げられる。中で
も、スーパーミキサーのように剪断力を加えることによ
り粉体の互着を防止して均一に分散させる方法が好まし
い。また、粉体同士が熱融着しない範囲で加熱しながら
添加してもよい。The method of incorporating the fine powder into the thermoplastic elastomer powder is not particularly limited as long as the fine powder is uniformly dispersed. For example, a blender with a heating jacket or a high speed rotation is used. Examples include a method of blending using a mold mixer or the like. Above all, a method of preventing mutual adhesion of the powders and uniformly dispersing them by applying a shearing force like a super mixer is preferable. Alternatively, the powders may be added while being heated in a range where they do not heat-bond together.
【００１８】また本発明のエラストマーパウダー組成物
は、内部添加離型剤を含有することもできる。内部添加
離型剤としては、メチルポリシロキサン化合物が好まし
く、エラストマパウダー組成物100 重量部あたり２重量
部以下含有することが効果的である。この場合の添加時
期は粉末化前後のいずれでもよい。この場合のメチルポ
リシロキサン化合物としては、25℃における粘度が20セ
ンチストークス以上であれば良いが、好ましくは50〜50
00センチストークスである。粘度が大きくなりすぎる
と、離型剤としての効果が減少する。また、内部添加離
型剤が２重量部より多くなると、エラストマーパウダー
間の熱融着を阻害し、機械的物性に劣った成形体しか得
られず、しかも、金型表面に内部添加離型剤がブリード
し、金型が汚染され好ましくない。The elastomer powder composition of the present invention may also contain an internally added release agent. As the internally added release agent, a methylpolysiloxane compound is preferable, and it is effective to contain 2 parts by weight or less per 100 parts by weight of the elastomer powder composition. In this case, the timing of addition may be before or after pulverization. In this case, the methylpolysiloxane compound may have a viscosity at 25 ° C. of 20 centistokes or more, but preferably 50 to 50.
It is 00 centistokes. If the viscosity becomes too high, the effect as a release agent decreases. Further, when the amount of the internally added release agent is more than 2 parts by weight, the heat fusion between the elastomer powders is hindered and only a molded product having poor mechanical properties can be obtained, and moreover, the internally added release agent is formed on the surface of the mold. Bleeds and the mold is contaminated, which is not preferable.
【００１９】さらに本発明のエラストマーパウダー組成
物は、フェノール系、サルファイト系、フェニルアルカ
ン系、フォスファイト系、アミン系またはアミド系安定
剤のような公知の耐熱安定剤、老化防止剤、耐候安定
剤、帯電防止剤、金属石けん、ワックス等の滑剤、着色
用顔料等を必要量含有することができる。かかるエラス
トマーパウダー組成物は、粉体流動性に優れるのみなら
ず、低剪断速度かつ低圧力下、金型から供給される熱で
容易に溶融し得るので、粉末成形法、例えば流動浸漬、
静電塗装、粉末溶射、粉末回転成形、粉末スラッシュ成
形等の成形方法用の組成物として優れており、なかでも
粉末スラッシュ成形法（特開昭58-132507 号公報 )用の
組成物として優れている。粉末成形するに当たり、金型
の加熱方式は、特に制限されるものではなく、例えば、
ガス加熱炉方式、熱媒体油循環方式、熱媒体油または熱
流動砂内への浸漬方式あるいは高周波誘導加熱方式等が
挙げられる。Furthermore, the elastomer powder composition of the present invention comprises known heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine- or amide-based stabilizers, anti-aging agents, and weather-resistant stabilizers. Agents, antistatic agents, metallic soaps, lubricants such as waxes, coloring pigments and the like can be contained in required amounts. Such an elastomer powder composition is not only excellent in powder fluidity, but can be easily melted by heat supplied from a mold under a low shear rate and a low pressure, so that a powder molding method, for example, fluidized dipping,
It is excellent as a composition for molding methods such as electrostatic coating, powder spraying, powder rotational molding, powder slush molding, and among others, it is excellent as a composition for powder slush molding (JP-A-58-132507). There is. In powder molding, the heating method of the mold is not particularly limited, for example,
Examples thereof include a gas heating furnace method, a heat medium oil circulation method, a dipping method in heat medium oil or heat fluidized sand, or a high frequency induction heating method.
【００２０】[0020]
【発明の効果】本発明のエラストマーパウダー組成物
は、長期間保存しても優れた粉体流動性を示す。更に、
該パウダー組成物を使用すれば、長時間連続で粉末成形
しても均一な肉厚でしかもピンホール等のない成形体を
製造し得るのみならず、軽量性、クリーン性にも優れた
成形体を製造し得る。また、本発明の成形体は、例えば
家電用品、事務用品、いす、家具等の表皮材、特に自動
車のインストルメントパネル表皮、コンソールボック
ス、アームレスト、ドアトリム等のカバーリング材料と
して使用し得る。The elastomer powder composition of the present invention exhibits excellent powder fluidity even when stored for a long period of time. Furthermore,
When the powder composition is used, not only a molded product having a uniform thickness even when continuously powder-molded for a long time and having no pinhole, etc., but also excellent in lightness and cleanness can be obtained. Can be manufactured. Further, the molded product of the present invention can be used as a covering material for home electric appliances, office supplies, chairs, furniture and the like, particularly for automobile instrument panel skins, console boxes, armrests, door trims and the like.
【００２１】[0021]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれら実施例に限定されるものでは
ない。なお、実施例、比較例における熱可塑性エラスト
マーパウダー組成物及びパウダーの動的粘弾性、粉体性
状及び成形性は次の方法により行なった。EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The dynamic viscoelasticity, powder properties and moldability of the thermoplastic elastomer powder compositions and powders in Examples and Comparative Examples were measured by the following methods.
【００２２】熱可塑性エラストマー組成物の動的粘弾性 レオメトリックス社製ダイナミックアナライザーDRS-77
00型を用い、振動周波数１ラジアン／秒及び 100ラジア
ン／秒での動的粘弾性を測定し、複素動的粘度η* (1)
及びη* (100）を算出した。なお、測定は平行平板モー
ドで行ない、印加歪みは５％、サンプル温度は250℃で
測定した。また、η* (1) とη*(100）の結果をもとに
次式でニュートン粘性指数ｎを算出した。 ｎ＝｛ｌｏｇη* (1) −ｌｏｇη* (100）｝／２ Dynamic Viscoelasticity of Thermoplastic Elastomer Composition Dynamic Analyzer DRS-77 manufactured by Rheometrics
Using model 00, the dynamic viscoelasticity was measured at vibration frequencies of 1 rad / sec and 100 rad / sec, and the complex dynamic viscosity η * (1)
And η * (100) were calculated. The measurement was performed in the parallel plate mode, the applied strain was 5%, and the sample temperature was 250 ° C. Also, based on the results of η * (1) and η * (100), the Newtonian viscosity index n was calculated by the following equation. n = {logη * (1) -logη * (100)} / 2
【００２３】パウダーの粉体流動性 25℃雰囲気下でエラストマーパウダー組成物を１ケ月放
置した。そのエラストマーパウダー組成物100ml をJIS
K-6721のかさ比重測定装置の漏斗に入れ、ダンパーを引
き抜いてパウダーが落下し始めてから全パウダーが落下
し終わるまでの時間（秒数）を測定した。 時間の短い
ほど粉体流動性のよいことを示す。 Powder fluidity of powder The elastomer powder composition was allowed to stand for 1 month in an atmosphere of 25 ° C. JIS 100 ml of the elastomer powder composition
It was put in the funnel of the bulk density measuring device of K-6721, the damper was pulled out, and the time (seconds) from the start of the powder drop until the end of all the powder drop was measured. The shorter the time, the better the powder fluidity.
【００２４】ブロッキング性 25℃雰囲気下でエラストマーパウダー組成物に500 kg／
m2の圧力をかけて１ケ月間放置した。そのパウダー組成
物をタイラー標準篩の32メッシュ篩に静かに移して10秒
間篩を振とうさせて32メッシュの篩上に残ったパウダー
の重量％を算出した 。重量％が小さい程ブロッキング
の起こしにくいエラストマーパウダー組成物であること
を示す。 Blocking property 500 kg / in elastomer powder composition at 25 ° C.
A pressure of m 2 was applied and left for 1 month. The powder composition was gently transferred to a Tyler standard sieve, 32 mesh sieve, and shaken for 10 seconds to calculate the weight% of the powder remaining on the 32 mesh sieve. The smaller the weight% is, the more the elastomer powder composition is less likely to cause blocking.
【００２５】パウダーの成形性（粉末成形性） エラストマーパウダー組成物500 ｇを表面温度が 250℃
に加熱された大きさ30cm×30cm、厚さ３mmのニッケル電
鋳シボ板にふりかけ14秒間付着させた後、該エラストマ
ーパウダー組成物の未溶着粉末を排出させ、パウダー溶
着シボ板を雰囲気温度 280℃の加熱炉中で60秒間加熱溶
融させた。金型上でのパウダーの融合状態及び金型を70
℃に水冷後脱型して得られた成形シートの性状から次の
判定基準で粉末成形性の評価を行なった。 ◎：パウダー組成物が互いに十分融合し、得られた成形
シートの引張強度は十分強い。 ○：パウダー組成物が互いに十分融合し、得られた成形
シートの引張強度は強い。 △：パウダー組成物が互いに融合するが、得られた成形
シートの引張強度は低くもろい。 ×：パウダー組成物が互いに融合せず、パウダー組成物
のままで金型上に存在する。 ◎と○は最終製品まで加工できるが、△と×は最終製品
まで加工できない。 Powder moldability (powder moldability) 500 g of an elastomer powder composition having a surface temperature of 250 ° C.
After sprinkling on a nickel electroformed grain board of 30 cm x 30 cm and thickness of 3 mm heated for 14 seconds to adhere it, the unfused powder of the elastomer powder composition is discharged, and the powder-fused grain board is heated to an ambient temperature of 280 ° C. It was heated and melted for 60 seconds in the heating furnace. 70 states of powder fusion and mold on the mold
The powder formability was evaluated according to the following criteria based on the properties of the formed sheet obtained by demolding after cooling with water at ℃. ⊚: The powder compositions are sufficiently fused with each other, and the resulting molded sheet has sufficiently high tensile strength. ◯: The powder compositions are sufficiently fused with each other, and the resulting molded sheet has high tensile strength. Δ: The powder compositions fuse with each other, but the resulting molded sheet has low tensile strength and is fragile. X: The powder compositions do not fuse with each other, and remain on the mold as the powder composition. ◎ and ○ can process the final product, but △ and × cannot process the final product.
【００２６】参考例１ ＥＰＤＭ（ＭＬ1+4 100 ℃＝242 、プロピレン含量＝28
重量％、ヨウ素価＝12）100 重量部あたり鉱物油系軟化
剤（出光興産製、登録商標ダイアナプロセスＰＷ─380
）100 重量部を添加した油展ＥＰＤＭ（ＭＬ1+4 100
℃＝53）40重量部と、プロピレン─ブテンランダム共重
合体樹脂（ブテン含量＝24重量％、ＭＦＲ＝90ｇ／10
分）60重量部及び架橋助剤（住友化学製、登録商標スミ
ファインＢＭ─ビスマレイミド化合物）0.4 重量部をバ
ンバリーミキサーを用いて10分間混練した後、押出機を
用いてペレット状の架橋用のマスターバッチ（以下Ｍ．
Ｂ．と称する）とした。このＭ．Ｂ．100 重量部に対
し、有機過酸化物（三建化工製、登録商標サンペロック
スＡＰＯ、2,5-ジメチル−2,5-ジ（ｔ−ブチルペルオキ
シノ）ヘキサン）0.04重量部を添加し、２軸混練機（日
本製鋼所製、登録商標ＴＥＸ─44）を用いて 220℃で動
的架橋を行ない、エラストマー組成物ペレットを得た。
このペレットを液体窒素を用いて−100 ℃の温度に冷却
後、冷凍粉砕を行ない複素動的粘度η* (1) が７×103
ポイズ、ニュートン粘性指数ｎが 0.39 である熱可塑性
エラストマーパウダーを得た。Reference Example 1 EPDM (ML 1 + 4 100 ° C. = 242, propylene content = 28
% By weight, iodine value = 12) Per 100 parts by weight of mineral oil-based softener (Idemitsu Kosan, registered trademark Diana Process PW-380
) 100 parts by weight of oil-extended EPDM (ML 1 + 4 100
40 ° C by weight and propylene-butene random copolymer resin (butene content = 24% by weight, MFR = 90 g / 10
Min) 60 parts by weight and 0.4 parts by weight of a crosslinking aid (Sumifine BM-Bismaleimide compound manufactured by Sumitomo Chemical Co., Ltd.) were kneaded for 10 minutes using a Banbury mixer, and then pelletized for crosslinking using an extruder. Masterbatch (hereinafter referred to as M.
B. Called)). This M. B. To 100 parts by weight, 0.04 parts by weight of an organic peroxide (Sanken Chemical Co., Ltd., registered trademark Sampelox APO, 2,5-dimethyl-2,5-di (t-butylperoxyno) hexane) was added, and 2 Dynamic cross-linking was performed at 220 ° C. using a shaft kneader (manufactured by Japan Steel Works, registered trademark TEX-44) to obtain elastomer composition pellets.
After cooling this pellet to a temperature of -100 ° C using liquid nitrogen, it was frozen and pulverized to obtain a complex dynamic viscosity η * (1) of 7 × 10 3
A thermoplastic elastomer powder having a Poise and Newton viscosity index n of 0.39 was obtained.
【００２７】実施例１ 参考例１で得られた熱可塑性エラストマーパウダー100
重量部に黒色顔料（住化カラー製ＰＶ─817 、平均粒子
径0.02μｍ）0.1重量部をスーパーミキサーを用いて25
℃、500 ｒｐｍで10分間混練して粉末成形用の熱可塑性
エラストマーパウダー組成物を得た。この組成物を用い
て、粉体性状及び成形性の評価を行なった。評価結果を
表１に示した。Example 1 Thermoplastic elastomer powder 100 obtained in Reference Example 1
25 parts by weight of a black pigment (PV-817 manufactured by Sumika Color Co., Ltd., average particle size 0.02 μm) was added to 25 parts by weight using a super mixer.
The mixture was kneaded at 500 ° C. for 10 minutes to obtain a thermoplastic elastomer powder composition for powder molding. Using this composition, powder properties and moldability were evaluated. The evaluation results are shown in Table 1.
【００２８】実施例２ 実施例１において、黒色顔料の添加量を1.5 重量部に代
えた以外は、実施例１と同様に実施して粉末成形用の熱
可塑性エラストマーパウダー組成物を得た。評価結果を
表１に示した。Example 2 A thermoplastic elastomer powder composition for powder molding was obtained in the same manner as in Example 1 except that the addition amount of the black pigment was changed to 1.5 parts by weight. The evaluation results are shown in Table 1.
【００２９】実施例３ 実施例１において、黒色顔料の添加量を10重量部に代え
た以外は、実施例１と同様に実施して粉末成形用の熱可
塑性エラストマーパウダー組成物を得た。評価結果を表
１に示した。Example 3 A thermoplastic elastomer powder composition for powder molding was obtained in the same manner as in Example 1 except that the addition amount of the black pigment was changed to 10 parts by weight. The evaluation results are shown in Table 1.
【００３０】実施例４ 実施例２において、黒色顔料を赤色顔料（住化カラー製
ＰＶ─110 、平均粒子径0.18μｍ）に代えた以外は、実
施例２と同様に実施して粉末成形用の熱可塑性エラスト
マーパウダー組成物を得た。評価結果を表１に示した。Example 4 The procedure of Example 2 was repeated except that the black pigment was replaced with a red pigment (PV-110 manufactured by Sumika Color Co., Ltd., average particle size 0.18 μm). A thermoplastic elastomer powder composition was obtained. The evaluation results are shown in Table 1.
【００３１】実施例５ 実施例２において、黒色顔料を黄色顔料（住化カラー製
ＰＶ─354 、平均粒子径0.13μｍ）に代えた以外は、実
施例２と同様に実施して粉末成形用の熱可塑性エラスト
マーパウダー組成物を得た。 評価結果を表１に示し
た。Example 5 The procedure of Example 2 was repeated except that the black pigment was replaced with a yellow pigment (PV-354 manufactured by Sumika Color Co., Ltd., average particle size 0.13 μm), and powder molding was carried out. A thermoplastic elastomer powder composition was obtained. The evaluation results are shown in Table 1.
【００３２】実施例６ 実施例２において、黒色顔料を白色顔料（住化カラー製
ＰＶ─742 、平均粒子径0.2 μｍ）に代えた以外は、実
施例２と同様に実施して粉末成形用の熱可塑性エラスト
マーパウダー組成物を得た。 評価結果を表１に示し
た。Example 6 The procedure of Example 2 was repeated except that the black pigment was replaced with a white pigment (PV-742 manufactured by Sumika Color Co., Ltd., average particle size 0.2 μm), and powder molding was carried out. A thermoplastic elastomer powder composition was obtained. The evaluation results are shown in Table 1.
【００３３】実施例７ 実施例２において、黒色顔料を酸化アルミニウム（住友
化学製ＡＭ−21、平均粒子径５μｍ）に代えた以外は、
実施例２と同様に実施して粉末成形用の熱可塑性エラス
トマーパウダー組成物を得た。評価結果を表１に示し
た。Example 7 Example 3 was repeated except that the black pigment was changed to aluminum oxide (Sumitomo Chemical Co., AM-21, average particle size 5 μm).
The same procedure as in Example 2 was carried out to obtain a thermoplastic elastomer powder composition for powder molding. The evaluation results are shown in Table 1.
【００３４】実施例８ 実施例２において、黒色顔料を酸化アルミニウム（住友
化学製ＡＥＳ−12、平均粒子径0.4 μｍ）に代えた以外
は、実施例２と同様に実施して粉末成形用の熱可塑性エ
ラストマーパウダー組成物を得た。評価結果を表１に示
した。Example 8 The same procedure as in Example 2 was repeated except that aluminum oxide (AES-12 manufactured by Sumitomo Chemical Co., Ltd., average particle size 0.4 μm) was used in place of the black pigment in Example 2, and heat for powder molding was used. A plastic elastomer powder composition was obtained. The evaluation results are shown in Table 1.
【００３５】実施例９ 実施例２において、黒色顔料をペースト用塩化ビニル
（住友化学製ＰｘＱＬＴ、平均粒子径1.2 μｍ）に代え
た以外は、実施例２と同様に実施して粉末成形用の熱可
塑性エラストマーパウダー組成物を得た。評価結果を表
１に示した。Example 9 The same procedure as in Example 2 was repeated except that the black pigment was changed to vinyl chloride for paste (PxQLT manufactured by Sumitomo Chemical Co., Ltd., average particle size 1.2 μm) in Example 2, and heat treatment for powder molding was performed. A plastic elastomer powder composition was obtained. The evaluation results are shown in Table 1.
【００３６】実施例１０ 実施例２において、黒色顔料をペースト用塩化ビニル
（住友化学製、平均粒子径0.08μｍ）に代えた以外は、
実施例２と同様に実施して粉末成形用の熱可塑性エラス
トマーパウダー組成物を得た。 評価結果を表１に示し
た。Example 10 The procedure of Example 2 was repeated except that the black pigment was changed to vinyl chloride for paste (Sumitomo Chemical Co., Ltd., average particle size 0.08 μm).
The same procedure as in Example 2 was carried out to obtain a thermoplastic elastomer powder composition for powder molding. The evaluation results are shown in Table 1.
【００３７】比較例１ 実施例１において、黒色顔料を用いない以外は、実施例
１と同様に実施して熱可塑性エラストマーパウダー組成
物を得た。 評価結果を表１に示した。Comparative Example 1 A thermoplastic elastomer powder composition was obtained in the same manner as in Example 1, except that the black pigment was not used. The evaluation results are shown in Table 1.
【００３８】比較例２ 実施例１において、黒色顔料を25重量部用いた以外は、
実施例１と同様に実施して熱可塑性エラストマーパウダ
ー組成物を得た。評価結果を表１に示した。Comparative Example 2 The procedure of Example 1 was repeated except that 25 parts by weight of the black pigment was used.
The same procedure as in Example 1 was carried out to obtain a thermoplastic elastomer powder composition. The evaluation results are shown in Table 1.
【００３９】比較例３ 実施例２において、黒色顔料を酸化アルミニウム（住友
化学製Ａ−21、平均粒子径50μｍ）に代えた以外は、実
施例２と同様に実施して熱可塑性エラストマーパウダー
組成物を得た。評価結果を表１に示した。Comparative Example 3 A thermoplastic elastomer powder composition was prepared in the same manner as in Example 2 except that aluminum oxide (A-21 manufactured by Sumitomo Chemical Co., Ltd., average particle size 50 μm) was used in place of the black pigment. Got The evaluation results are shown in Table 1.
【００４０】実施例11〜16 実施例１において、黒色顔料を表２に示す重量部用いた
以外は、実施例１と同様に実施して粉末成形用の熱可塑
性エラストマーパウダー組成物を得た。 評価結果を表
２に示した。Examples 11 to 16 A thermoplastic elastomer powder composition for powder molding was obtained in the same manner as in Example 1 except that the weight parts shown in Table 2 were used for the black pigment. The evaluation results are shown in Table 2.
【００４１】比較例４ 参考例１において、油展ＥＰＤＭを70重量部用い、プロ
ピレン─ブテンランダム共重合体樹脂をプロピレン─エ
チレンランダム共重合体樹脂（エチレン含量＝３重量
％、ＭＦＲ＝1.2 ｇ／10分）30重量部に代える以外は参
考例１と同様に実施して熱可塑性エラストマーパウダー
を得た。このものは、η* (1) が1.9 ×105 ポイズ、ニ
ュートン粘性指数ｎが 0.69 であった。次いで、これを
用いて、実施例１と同様に実施して熱可塑性エラストマ
ーパウダー組成物を得た。 結果を表２に示した。Comparative Example 4 In Reference Example 1, 70 parts by weight of oil-extended EPDM was used, and propylene-butene random copolymer resin was replaced with propylene-ethylene random copolymer resin (ethylene content = 3% by weight, MFR = 1.2 g / (10 minutes) A thermoplastic elastomer powder was obtained in the same manner as in Reference Example 1 except that 30 parts by weight was used. This product had η * (1) of 1.9 × 10 5 poise and Newtonian viscosity index n of 0.69. Subsequently, using this, it carried out like Example 1 and obtained the thermoplastic elastomer powder composition. The results are shown in Table 2.
【００４２】実施例１７ 実施例１において、微細粉体として黒色顔料0.22重量
部、赤色顔料(住化カラー製PV-110)0.53 重量部、黄色
顔料( 住化カラー製PV-354)1.15 重量部、白色顔料( 住
化カラー製PV-742)0.05 重量部用いる以外は、実施例１
と同様に実施して粉末成形用の熱可塑性エラストマーパ
ウダー組成物を得た。 結果を表３に示した。Example 17 In Example 1, 0.22 parts by weight of a black pigment as a fine powder, 0.53 parts by weight of a red pigment (PV-110 manufactured by Sumika Color Co., Ltd.), 1.15 parts by weight of a yellow pigment (PV-354 manufactured by Sumika Color Co., Ltd.) Example 1 except that 0.05 parts by weight of white pigment (PV-742 manufactured by Sumika Color Co., Ltd.) was used.
A thermoplastic elastomer powder composition for powder molding was obtained in the same manner as in. The results are shown in Table 3.
【００４３】実施例１８〜１９ 実施例１７と同様にして製造した熱可塑性エラストマー
パウダー組成物を40℃、60℃のギア式オーブン中にそれ
ぞれ８時間放置した後、粉末流動性、粉末成形性の評価
を実施し、結果を表３に示した。Examples 18 to 19 The thermoplastic elastomer powder compositions produced in the same manner as in Example 17 were left in a gear type oven at 40 ° C. and 60 ° C. for 8 hours, respectively, and then powder flowability and powder moldability were evaluated. Evaluation was carried out and the results are shown in Table 3.
【００４４】実施例２０ 実施例２で得られた熱可塑性エラストマーパウダー組成
物を、図１〜図３に示すステンレス製の角型容器（粉末
供給ボックス）に４kg投入した。この角型容器は 600mm
×220mm の長方形の開口部１を有し、深さが 210mmであ
り、一軸回転装置３に取り付けたものである。一方、図
１に示す粉末供給ボックスの開口部１と、同じ大きさの
開口部４を有する、図４〜図６に示すニッケル電鋳金型
を 300℃のガス炉中で予備加熱した。この金型は、厚さ
３mmであり、内面がなわ目模様５及び皮しぼ模様６の施
された複雑形状を有するものである。金型の表面温度が
２５０℃になった時点で、直ちに加熱された金型をその
開口部４（600mm ×220mm）が下向きになるように上記
粉末供給ボックスの開口部１に合わせて置き、双方の開
口部のまわりに取り付けられている外枠を密着させ、ク
リップ２で固定し一体化した。すぐに毎分30回転の速度
で、時計方向に２回転及び毎分30回転の速度で逆時計方
向に２回転した。その後、時計方向及び逆時計方向に１
回づつ約12０度の角度まで揺動し複雑形状部に付着した
過剰の粉を払い落とした。Example 20 4 kg of the thermoplastic elastomer powder composition obtained in Example 2 was placed in a square container (powder supply box) made of stainless steel shown in FIGS. This square container is 600mm
It has a rectangular opening 1 of × 220 mm, a depth of 210 mm, and is attached to a uniaxial rotating device 3. On the other hand, the nickel electroforming dies shown in FIGS. 4 to 6 having the opening 1 of the powder supply box shown in FIG. 1 and the opening 4 of the same size were preheated in a gas furnace at 300 ° C. This metal mold has a thickness of 3 mm and has a complicated shape in which the inner surface is provided with a grain pattern 5 and a leather grain pattern 6. When the surface temperature of the mold reaches 250 ° C., immediately place the heated mold in the opening 1 of the powder supply box so that the opening 4 (600 mm × 220 mm) faces downward. The outer frame attached around the opening of was closely contacted and fixed with the clip 2 to be integrated. Immediately, at a speed of 30 rpm, 2 clockwise rotations and at a speed of 30 rpm 2 counterclockwise rotations. Then 1 clockwise and counterclockwise
The powder was swung each time to an angle of about 120 degrees, and the excess powder adhering to the complicated shape part was brushed off.
【００４５】金型の開口部４が下向きの状態で回転及び
揺動操作を止め、粉末供給ボックスから金型を取り外し
280 ℃の加熱炉中で１分間後加熱したのち、水冷し、成
形皮膜を脱型した。成形皮膜は、重量150 ｇ、厚み0.9
〜1.1mm の欠肉のない、なわ目模様、皮しぼ模様が忠実
に再現され、複雑形状の金型の細部まで十分に再現され
た肉厚の均一性に優れたピンホールのない製品が得られ
た。Stop the rotation and rocking operation with the opening 4 of the mold facing downward, and remove the mold from the powder supply box.
After post-heating in a heating furnace at 280 ° C. for 1 minute, it was cooled with water and the molded film was demolded. Molded film weighs 150 g and has a thickness of 0.9
It is possible to obtain a pinhole-free product with excellent wall thickness uniformity, which faithfully reproduces the grain pattern and skin grain pattern of ~ 1.1 mm without deficiency, and fully reproduces the details of the complex-shaped mold. Was given.
【００４６】容器には、3.8kg の異物の混入のないエラ
ストマーパウダー組成物が回収された。この回収エラス
トマーパウダー組成物に未使用のエラストマーパウダー
組成物を追加して４kgとし、同様の操作で成形を実施し
たところ、外観及び肉厚均一性に優れた製品が同様に得
られた。In the container, 3.8 kg of an elastomer powder composition free of foreign matter was collected. An unused elastomer powder composition was added to the recovered elastomer powder composition to obtain 4 kg, and molding was carried out by the same operation. As a result, a product excellent in appearance and thickness uniformity was similarly obtained.
【００４７】 [0047]
【００４８】 [0048]
【００４９】 [0049]
【図１】粉末供給ボックスの平面図である。FIG. 1 is a plan view of a powder supply box.
【図２】粉末供給ボックスの立面図である。FIG. 2 is an elevation view of a powder supply box.
【図３】粉末供給ボックスの側面図である。FIG. 3 is a side view of a powder supply box.
【図４】金型の平面図である。FIG. 4 is a plan view of a mold.
【図５】金型の立面図である。FIG. 5 is an elevational view of a mold.
【図６】金型の側面図である。FIG. 6 is a side view of a mold.
１・・・開口部 ２・・・クリ
ップ ３・・・一軸回転装置（ハンドル） ４・・・開口
部 ５・・・金型内なわ目模様部 ６・・・金型
内皮しぼ模様部DESCRIPTION OF SYMBOLS 1 ... Opening part 2 ... Clip 3 ... Uniaxial rotating device (handle) 4 ... Opening part 5 ... Rough pattern part in mold 6 ...
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 23/26 ＬＤＡ 7107−4Ｊ // Ｃ０８Ｌ 23:04 (72)発明者 日笠 忠 千葉県市原市姉崎海岸５の１ 住友化学工 業株式会社内 (72)発明者 妻鳥 浩昭 千葉県市原市姉崎海岸５の１ 住友化学工 業株式会社内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical display location C08L 23/26 LDA 7107-4J // C08L 23:04 (72) Inventor Tadashi Hikasa Ichihara City, Chiba Prefecture 5-1 Anesaki Kaigan Sumitomo Chemical Co., Ltd. (72) Inventor Hiroaki Tsumadori 1-5 Anesaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd.
Claims (4)
ー 100重量部に対して、平均粒子径30μｍ以下の微細粉
体を0.05〜20重量部含有することを特徴とする粉末成形
用熱可塑性エラストマーパウダー組成物。 （Ａ）エチレン・α−オレフィン系共重合体ゴムとポリ
オレフィン系樹脂との組成物からなる熱可塑性エラスト
マーのパウダーまたはエチレン・α−オレフィン系共重
合体ゴムとポリオレフィン系樹脂との部分架橋型組成物
からなる熱可塑性エラストマーのパウダーであって、25
0 ℃における周波数１ラジアン／秒での複素動的粘度η
* (1) が 1.5×105 ポイズ以下であり、かつ上記複素動
的粘度η* (1) と周波数100 ラジアン／秒での複素動的
粘度η* (100) とを用いて次式で算出されるニュートン
粘性指数ｎが0.67以下である熱可塑性エラストマーパウ
ダー。 ｎ＝｛ｌｏｇη* (1) −ｌｏｇη* (100) ｝／２1. A thermoplastic elastomer powder for powder molding, comprising 0.05 to 20 parts by weight of fine powder having an average particle diameter of 30 μm or less based on 100 parts by weight of the following (A) thermoplastic elastomer powder. Composition. (A) Thermoplastic elastomer powder composed of a composition of ethylene / α-olefin copolymer rubber and polyolefin resin or a partially crosslinked composition of ethylene / α-olefin copolymer rubber and polyolefin resin A thermoplastic elastomer powder consisting of 25,
Complex dynamic viscosity η at a frequency of 1 rad / sec at 0 ° C
* (1) is less than or equal to 1.5 × 10 5 poise, and calculated using the above complex dynamic viscosity η * (1) and complex dynamic viscosity η * (100) at a frequency of 100 rad / sec by the following formula A thermoplastic elastomer powder having a Newton viscosity index n of 0.67 or less. n = {logη * (1) -logη * (100)} / 2
ミニウム、水酸化アルミニウムまたは炭酸カルシウムか
ら選ばれる少なくとも１種の微細粉体である請求項１記
載の組成物。2. The composition according to claim 1, wherein the fine powder is at least one fine powder selected from pigments, vinyl chloride resin aluminum oxide, aluminum hydroxide and calcium carbonate.
トマーパウダー組成物を用いることを特徴とする粉末成
形法。3. A powder molding method comprising using the thermoplastic elastomer powder composition for powder molding according to claim 1.
トマーパウダー組成物を用いて製造してなる成形体。4. A molded product produced by using the thermoplastic elastomer powder composition for powder molding according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5510592A JP3136740B2 (en) | 1991-04-11 | 1992-03-13 | Thermoplastic elastomer powder composition for powder molding, powder molding method using the same, and molded article thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-78975 | 1991-04-11 | ||
| JP7897591 | 1991-04-11 | ||
| JP5510592A JP3136740B2 (en) | 1991-04-11 | 1992-03-13 | Thermoplastic elastomer powder composition for powder molding, powder molding method using the same, and molded article thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570601A true JPH0570601A (en) | 1993-03-23 |
| JP3136740B2 JP3136740B2 (en) | 2001-02-19 |
Family
ID=26395961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5510592A Expired - Fee Related JP3136740B2 (en) | 1991-04-11 | 1992-03-13 | Thermoplastic elastomer powder composition for powder molding, powder molding method using the same, and molded article thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3136740B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840229A (en) * | 1994-11-16 | 1998-11-24 | Sumitomo Chemical Company, Limited | Method for producing molded article by powder slush molding a thermoplastic elastomer powder |
| US10287424B2 (en) | 2016-02-29 | 2019-05-14 | Sumitomo Chemical Company, Limited | Thermoplastic elastomer composition |
-
1992
- 1992-03-13 JP JP5510592A patent/JP3136740B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840229A (en) * | 1994-11-16 | 1998-11-24 | Sumitomo Chemical Company, Limited | Method for producing molded article by powder slush molding a thermoplastic elastomer powder |
| US10287424B2 (en) | 2016-02-29 | 2019-05-14 | Sumitomo Chemical Company, Limited | Thermoplastic elastomer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3136740B2 (en) | 2001-02-19 |
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