JPS6094459A - Powdery thermoplastic resin composition - Google Patents

Powdery thermoplastic resin composition

Info

Publication number
JPS6094459A
JPS6094459A JP20073783A JP20073783A JPS6094459A JP S6094459 A JPS6094459 A JP S6094459A JP 20073783 A JP20073783 A JP 20073783A JP 20073783 A JP20073783 A JP 20073783A JP S6094459 A JPS6094459 A JP S6094459A
Authority
JP
Japan
Prior art keywords
bulk density
particle size
powder
fatty acid
thermoplastic resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP20073783A
Other languages
Japanese (ja)
Other versions
JPH0454699B2 (en
Inventor
Yoshinori Akana
赤名 義徳
Masato Karaiwa
唐岩 正人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Petrochemical Industries Ltd
Original Assignee
Mitsui Petrochemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Petrochemical Industries Ltd filed Critical Mitsui Petrochemical Industries Ltd
Priority to JP20073783A priority Critical patent/JPS6094459A/en
Publication of JPS6094459A publication Critical patent/JPS6094459A/en
Publication of JPH0454699B2 publication Critical patent/JPH0454699B2/ja
Granted legal-status Critical Current

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Abstract

PURPOSE:A composition, obtained by incorporating a powdery metallic salt of a fatty acid having a bulk density and an average particle diameter within a specific range with a thermosetting resin, having improved release property in molding, capable of giving molded articles having remarkably smooth inner skin and improved mechanical strength without poor deforming, and suitable for rotary molding. CONSTITUTION:A powdery thermoplastic resin composition obtained by incorporating (A) 100pts.wt. powdery thermoplastic resin, preferably powdery polyethylene, obtained by suspension polymerization in the presence of a Ziegler catalyst, etc. and having 0.92-0.95g/cm<3> density, with (B) 0.02-1pts.wt., preferably 0.07-0.3pts.wt. powdery metallic salt of a fatty acid having 0.35-0.85g/cm<3>, preferably 0.4-0.7g/cm<3> bulk density and 5-500mu, preferably 10-500mu average particle diameter, passing through a 16-mesh screen, and having >=130 deg.C melting point as a lubricant, e.g. obtained by pulverizing mechanically calcium stearate, magnesium stearate, etc. produced by the melting method (dry method).

Description

【発明の詳細な説明】 本発明は粉末成形、とくに回転成形に好適な粉末状熱可
塑性樹脂組成物に関するものであり、成形時の離型性に
優れ、内面肌が著しく平滑で脱泡不良もなく、かつ機械
的強度にも優れた成形品を与える原料粉末組成物を提供
するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a powdered thermoplastic resin composition suitable for powder molding, particularly rotary molding, which has excellent mold release properties during molding, has an extremely smooth inner surface, and is free from defoaming. The object of the present invention is to provide a raw material powder composition that provides a molded article with excellent mechanical strength.

回転成形に代表される粉末成形においては、何らかの方
法で得られる粉末状熱可塑性樹脂を用いるが、用いる粉
末の粒径、粒度分布、粒子形状によっては成形性、とく
に細孔部充填性や平滑性に劣るという問題があった。ま
た、たとえば特開昭57−38839において述べられ
ている如く、懸濁重合法によって直接得られた粉末ポリ
エチレンでは、離型性が悪いという欠点がある。これら
の課題に対し、■特開昭56−41213においては、
特定の性状を有する粉末を使用することを提案し、■特
開昭57−38839においては、懸濁法で得られる粉
末ポリエチレンに特定の融点範囲を有する飽和脂肪酸等
の滑剤を混合分散した組成物を使用することを提案し、
■特開昭58−84719においては特定の球状粉末ポ
リエチレンに機械粉砕した粉砕ポリエチレンを混合して
使用することを提案している。これらの提案においては
、用いる粉体の製造法に制限があり、また■については
、使用する滑剤の融点に上限があり、使用できるものが
限られるという欠点がある。
In powder molding, typified by rotary molding, powdered thermoplastic resin obtained by some method is used, but moldability, especially pore filling and smoothness, depends on the particle size, particle size distribution, and particle shape of the powder used. There was a problem that it was inferior to Furthermore, as described in, for example, JP-A No. 57-38839, powdered polyethylene directly obtained by suspension polymerization has the disadvantage of poor mold release properties. In response to these issues, ■Japanese Patent Application Laid-Open No. 56-41213,
He proposed the use of powder with specific properties, and in JP-A-57-38839, he proposed a composition in which a lubricant such as a saturated fatty acid having a specific melting point range was mixed and dispersed in powdered polyethylene obtained by a suspension method. I suggest using
(1) Japanese Patent Laid-Open No. 58-84719 proposes the use of a mixture of mechanically pulverized pulverized polyethylene with a specific spherical powdered polyethylene. These proposals have the disadvantage that there are restrictions on the manufacturing method of the powder used, and as for (2), there is an upper limit on the melting point of the lubricant used, which limits what can be used.

本発明者らは、粉末成形、とくに回転成形において所定
の粉末性状を示す滑剤の所定量が混合分散された粉末状
!:ハ可塑性樹脂組成物を用いることにより、上記の如
き欠点もなく、¥1!、濁重合若しくは気相重合による
粉末樹脂のみならず、ペレット等を機械粉砕した粉体樹
脂のいずれにも適用でき、成形時の離型性に優れ、内面
肌が著しく平滑で脱泡不良もなく、機械的強度にも優れ
た成形品を与えることを見い出し、本発明を完成させる
ことができた。
The present inventors have developed a powder-form product in which a predetermined amount of a lubricant exhibiting predetermined powder properties is mixed and dispersed in powder molding, particularly rotary molding. : By using the plastic resin composition, there are no drawbacks as mentioned above, and it is only ¥1! It can be applied not only to powdered resins produced by turbid polymerization or gas phase polymerization, but also to powdered resins obtained by mechanically crushing pellets, etc. It has excellent mold release properties during molding, has an extremely smooth inner surface, and has no defoaming defects. It was discovered that a molded article having excellent mechanical strength can be obtained, and the present invention was completed.

すなわぢ本発明は、粉末状熱可塑性樹脂(A)100重
量部に、嵩密度が0.35ないし0.85g/cd、平
均粒径が5ないし500μでかつ16メツシユの篩を通
過する粉末状の脂肪酸金属塩(B) 0.02ないし1
.0重量部が混合分散されていることを特徴とする粉末
状熱可塑性樹脂組成物を要旨とするものである。
In other words, in the present invention, powder having a bulk density of 0.35 to 0.85 g/cd, an average particle size of 5 to 500 μm, and passing through a 16-mesh sieve is added to 100 parts by weight of the powdered thermoplastic resin (A). fatty acid metal salt (B) 0.02 to 1
.. The gist of the invention is a powdered thermoplastic resin composition characterized in that 0 parts by weight are mixed and dispersed.

以下、本発明の詳細な説明する 本発明の組成物を構成する粉末状熱可塑性樹脂(A)は
粉末成形に用いられる樹脂であれば、とくにポリオレフ
ィンに限られない。これらの樹脂として、例えば低密度
、中密度および高密度ポリエチレンをはじめ、ポリプロ
ピレン、プロピレン−エチレンブロック共重合体、ポリ
−1−ブテン、ポリ−4−メチル−1−ペンテンなど各
種ポリオレフィン樹脂のほか、ポリカーボネート、ポリ
フェニレンオキサイド(PPO)、アセタール樹脂、ポ
リスチレン、ABS樹脂、エチレン−酢酸ビニル共重合
体、ポリエステル樹脂、ポリアミド樹脂など種々の熱可
塑性を用いることができる。これらの中ではポリエチレ
ン、とくに低密度および中密度のポリエチレンに好んで
用いられる。これらのポリエチレンには、エチレン単独
重合物のほかにエチレンとα−オレフィン、例えばプロ
ピレン、■−ブテン、イソブチン、■−ペンテン、4−
メチル−1−ペンテン、1−ヘキセン、1−オクテン、
1−デセン等との共重合物も含まれる。このうち低密度
ポリエチレンの一つの例は、通常高圧ラジカル重合によ
って得られるもので、密度は約0.91ないし約0.9
3g/cotである。また低密度から中密度領域のポリ
エチレンは通常チーグラー型触媒を用いて溶液重合法、
懸濁重合法又は気相重合法によって得られ、密度は通雷
約0.91ないし約0.95g/cM程度のものである
。これらの中低密度ポリエチレンの中では、後述の理由
により懸濁重合や気相重合によって得られるものが好ま
しく、密度0.920ないし0.950のものがとくに
好ましい。
The powdered thermoplastic resin (A) constituting the composition of the present invention, which will be described in detail below, is not particularly limited to polyolefin, as long as it is a resin used for powder molding. These resins include various polyolefin resins such as low-density, medium-density, and high-density polyethylene, polypropylene, propylene-ethylene block copolymers, poly-1-butene, poly-4-methyl-1-pentene, etc. Various thermoplastics can be used, such as polycarbonate, polyphenylene oxide (PPO), acetal resin, polystyrene, ABS resin, ethylene-vinyl acetate copolymer, polyester resin, and polyamide resin. Among these, polyethylene is preferably used, especially low density and medium density polyethylene. In addition to ethylene homopolymers, these polyethylenes contain ethylene and α-olefins such as propylene, ■-butene, isobutyne, ■-pentene, and 4-
Methyl-1-pentene, 1-hexene, 1-octene,
Also included are copolymers with 1-decene and the like. One example of low-density polyethylene is usually obtained by high-pressure radical polymerization, and has a density of about 0.91 to about 0.9.
It is 3g/cot. Polyethylene in the low to medium density range is usually produced by solution polymerization using a Ziegler type catalyst.
It is obtained by a suspension polymerization method or a gas phase polymerization method, and has a density of about 0.91 to about 0.95 g/cM. Among these medium-low density polyethylenes, those obtained by suspension polymerization or gas phase polymerization are preferred for the reasons described below, and those with a density of 0.920 to 0.950 are particularly preferred.

上記の熱可塑性樹脂は、前述の如く何らかの方法で粉末
状にすればよく、各種重合法で得られた樹脂ベレットを
機械的に粉砕したもの、冷凍粉砕したもの更に懸濁重合
もしくは気相重合等によって直接製造したものを用いる
ことができる。しかし、機械的に粉砕した粉末状熱可塑
性樹脂は、一般に嵩密度は低く、安息角は高く、粒度分
布が広く、粒子形状も不ぞろいであることが多いので、
懸濁重合等によって直接製造した粉末状熱可塑性樹脂を
用いるのが好ましい。更にこれらの中でも該粉末の形状
が球状又は楕円体状あるいはこれらに近い形状であって
、糸状物やヒゲ状物を本質的に含んでいないことが回転
成形品の表面肌、とくに細部を平滑に仕上げる上で好ま
しい。また粉末成形、とくに回転成形に通した樹脂の性
状として、嵩密度が通常0.3ないし0.6g/ci、
好ましくは0.4ないし0.5g/cJ、平均粒子径(
50%粒子径)が通常150ないし400μであり、粒
子径が/15゜ないし400μの範囲にあるものが全体
の70重量%以上を占めるものが好ましい。また回転成
形において、粉体の流動性を増し、充分な細部成形性を
確保するためには、安息角は1ffi常25°ないし4
5°、好ましくは30°ないし40°である。また前述
の好ましい熱可塑性樹脂に掲げたポリエチレンにおいて
は、メルトフローレート(MFR: 190’c。
The above-mentioned thermoplastic resin may be made into powder form by any method as described above, such as mechanically pulverizing resin pellets obtained by various polymerization methods, freeze-pulverizing, suspension polymerization, gas phase polymerization, etc. It is possible to use one directly manufactured by. However, mechanically pulverized powdered thermoplastic resins generally have a low bulk density, a high angle of repose, a wide particle size distribution, and often have irregular particle shapes.
It is preferable to use a powdered thermoplastic resin directly produced by suspension polymerization or the like. Furthermore, among these, the powder has a spherical or ellipsoidal shape or a shape close to these, and essentially does not contain filaments or whiskers, which makes the surface of the rotary molded product smooth, especially the details. Good for finishing. In addition, the properties of the resin that has been subjected to powder molding, especially rotational molding, are such that the bulk density is usually 0.3 to 0.6 g/ci,
Preferably 0.4 to 0.5 g/cJ, average particle size (
The particle size (50% particle size) is usually 150 to 400μ, and preferably 70% by weight or more of the total particle size is in the range of /15° to 400μ. In addition, in rotational molding, in order to increase the fluidity of the powder and ensure sufficient detail moldability, the angle of repose must be 1ffi, usually 25° to 4°.
5°, preferably 30° to 40°. Furthermore, the polyethylene listed as the above-mentioned preferred thermoplastic resin has a melt flow rate (MFR: 190'c).

2.161tg荷重〕は通常lないし20g/10分、
好ましくは2ないし10g/分である。
2.161tg load] is usually 1 to 20g/10 minutes,
Preferably it is 2 to 10 g/min.

次に粉末状の脂肪酸金属塩(B)について説明する。本
発明に使用する脂肪酸金属塩としては、例えばステアリ
ン酸カルシウム、ステアリン酸マグネシウム、ステアリ
ン酸リチウム、ステアリン酸ストロンチウム、ステアリ
ン酸バリウム、ステアリン酸亜鉛、ステアリン酸アルミ
ニウム、ラウリン酸バリウム、ラウリン酸カルシウム、
ラウリン酸亜鉛、12−ヒドロキシステアリン酸カルシ
ウムなどを挙げることができる。これらの中では、後述
の理由によりステアリン酸カルシウム、ステアリン酸マ
グネシウム、ステアリン酸リチウム、ステアリン酸ナト
リウムを用いるのが好ましい。
Next, the powdered fatty acid metal salt (B) will be explained. Examples of fatty acid metal salts used in the present invention include calcium stearate, magnesium stearate, lithium stearate, strontium stearate, barium stearate, zinc stearate, aluminum stearate, barium laurate, calcium laurate,
Examples include zinc laurate and calcium 12-hydroxystearate. Among these, calcium stearate, magnesium stearate, lithium stearate, and sodium stearate are preferably used for the reasons described below.

なお上記脂肪酸金属塩は各単独で用いることもできるし
、二種以上を単に混合したもの、あるいは溶融混合した
ものを用いてもよい。更にこれらの脂肪酸金属塩には遊
離脂肪酸等を実質的に含まないことが好ましいが、本発
明の効果を害さない範囲内で微量程度含まれていてもよ
い。また脂肪酸金属塩としては融点(J I S KO
O64に準拠)が80℃以上のものが好ましく、とくに
は130’C以上のものが好ましい。これは80°C以
下の融点を有するものを用いると粉末成形品よりこれら
の化合物がブリーディングしやすくなるからである。
The fatty acid metal salts mentioned above can be used alone, or simply a mixture of two or more kinds, or a mixture of two or more kinds can be used. Furthermore, it is preferable that these fatty acid metal salts do not substantially contain free fatty acids, but they may contain a trace amount within a range that does not impair the effects of the present invention. In addition, as a fatty acid metal salt, the melting point (JIS KO
(according to O64) is preferably 80°C or higher, particularly preferably 130'C or higher. This is because if a material having a melting point of 80° C. or lower is used, these compounds will bleed more easily than in a powder molded product.

更に本発明で使用する粉末状の脂肪酸金属塩(B)は嵩
密度(J I S [6721に準拠して測定)が0.
30ないし0.85g/clであることがa・要であり
、好ましくは0.40ないし0.85g/cJ、更に好
ましくは0.40ないし0.70g/cJであり、また
平均粒径が5ないし500μの粉末状であることが必要
であり、好ましくは10ないし500μである。ここで
平均粒径とは(J I S Z8801)のふるいを使
用したふるい残分試験方法((J I S K0069
)による累積分布曲線からめた累積分布の50%の径、
すなわち50%粒径を指す。嵩密度が0.30g/cJ
より小さいと、回転成形中に粉末状熱可塑性樹脂組成物
中に空気がまきこまれてやすくなり、その結果成形中の
溶融内面層に多(の気泡を含み、脱泡しにくくなり、こ
れが原因となって樹脂粉末の溶融速度が遅くなり、成形
品の内面肌の平滑性を著しく損うこととなる。また嵩密
度の上限0.85g/caは後で述べる方法によって得
られる平均粒径が上述の必須範囲にある粉末状脂肪酸金
属塩(B)の上限値が0.85g/caであることに基
づく。更に平均粒径が500μよりも大きい場合は、該
脂肪酸金属塩等の粒子のため成形品の内面肌が平滑でな
くなるので、上記範囲は必須である。また平均粒径が5
μ未満のものは、嵩密度の下限を下廻るようになるとと
もに、一般に製造コストもかさむようになり、不利であ
る。
Furthermore, the powdered fatty acid metal salt (B) used in the present invention has a bulk density (measured according to JIS [6721) of 0.
It is essential that the particle size is 30 to 0.85 g/cl, preferably 0.40 to 0.85 g/cJ, more preferably 0.40 to 0.70 g/cJ, and the average particle size is 5 It is necessary to be in powder form with a thickness of 10 to 500μ, preferably 10 to 500μ. What is the average particle size here? The sieve residue test method using a sieve (JIS Z8801)
) is the 50% diameter of the cumulative distribution calculated from the cumulative distribution curve,
That is, it refers to the 50% particle size. Bulk density is 0.30g/cJ
If the size is smaller, air will easily be mixed into the powdered thermoplastic resin composition during rotary molding, and as a result, the molten inner layer will contain a large number of air bubbles during molding, making it difficult to defoam. This slows down the melting rate of the resin powder and significantly impairs the smoothness of the inner surface of the molded product.Also, the upper limit of the bulk density of 0.85 g/ca is determined by the average particle diameter obtained by the method described later. Based on the fact that the upper limit of the powdered fatty acid metal salt (B) in the essential range is 0.85 g/ca.Furthermore, if the average particle size is larger than 500μ, molding is required due to the particles of the fatty acid metal salt, etc. The above range is essential because the inner surface of the product will not be smooth.Also, if the average particle size is 5.
If it is less than μ, the bulk density will fall below the lower limit and the manufacturing cost will generally increase, which is disadvantageous.

また粉末の脂肪酸金属塩(B)は16メツシユの篩(T
yler標準篩)を通過するものであることが必要であ
り、とくに好ましくは32メツシユの篩を通過するもの
である。16メツシユの篩を通過しないものが含まれて
いると、たとえ嵩密度や平均粒径が前記の必須範囲に含
まれていても、成形品の内面肌の平滑性を損うようにな
る。なお以下において、使用する粉末状脂肪酸金属塩(
B)が全部通過する最も孔の細い篩のメツシュNoをF
粒度Jと呼ぶこととする。
In addition, the powdered fatty acid metal salt (B) was sieved through a 16-mesh sieve (T
yler standard sieve), particularly preferably a 32-mesh sieve. If particles that do not pass through a 16-mesh sieve are included, even if the bulk density and average particle size are within the above-mentioned essential ranges, the smoothness of the inner surface of the molded product will be impaired. In the following, the powdered fatty acid metal salt (
F is the mesh number of the sieve with the narrowest holes through which all B)
This will be referred to as particle size J.

粉末状脂肪酸金属塩(B)の 粉末状熱可塑性樹脂(A
)に対する配合割合は、(A)が100重部に対しくB
)が0.02ないし1.0重量部であり、好ましくは0
.05ないし0.5重量部、更に好ましくは0.07な
いし0.3重量部である。(B)の配合割合が0.02
重量部よりも少ないと、成形品が金型がら離型しないと
いう問題が生じ、また1、0重量部よりも多いと、成形
品内面肌の平滑さが失われたり、成形品強度を損ねるよ
うになるので、上記範囲にあることが必要である。なお
、本発明の組成物には、本発明の効果を損わない限り、
通當熱可塑性樹脂に配合される各種安定剤、抗酸化剤、
紫外線吸収剤、帯電防止剤、別種の滑剤、可塑剤、顔料
、充填剤、補強剤、!i燃剤、離型剤などの各種添加剤
を配合することができる。
Powdered thermoplastic resin (A) of powdered fatty acid metal salt (B)
) is the blending ratio of (A) to 100 parts of B.
) is 0.02 to 1.0 parts by weight, preferably 0
.. 0.05 to 0.5 parts by weight, more preferably 0.07 to 0.3 parts by weight. The blending ratio of (B) is 0.02
If it is less than 1 part by weight, there will be a problem that the molded product will not release from the mold, and if it is more than 1.0 part by weight, the smoothness of the inner surface of the molded product may be lost or the strength of the molded product may be impaired. Therefore, it must be within the above range. In addition, the composition of the present invention may contain, as long as it does not impair the effects of the present invention.
Various stabilizers, antioxidants, and
UV absorbers, antistatic agents, different types of lubricants, plasticizers, pigments, fillers, reinforcing agents,! Various additives such as refueling agents and mold release agents can be added.

粉末状熱可塑性樹脂(A)と粉末状脂肪酸金属塩(B)
を混合して本発明の組成物を製造するには、通常タンブ
ラ−やリボンブレンダーあるいはヘンシェルミキサー等
を用いる。混合時の組成物の温度は、樹脂又は滑剤が融
解しない温度で行ない、通常Oないし100’C,とく
に好ましくは10ないし70℃である。
Powdered thermoplastic resin (A) and powdered fatty acid metal salt (B)
A tumbler, ribbon blender, Henschel mixer, or the like is usually used to mix the ingredients to produce the composition of the present invention. The temperature of the composition during mixing is such that the resin or lubricant does not melt, usually from 0 to 100°C, particularly preferably from 10 to 70°C.

本発明の粉末状熱可塑性樹脂組成物は粉末成形、とくに
回転成形に好適である。粉末成形は一般に成形品に応じ
ためす型に樹脂粉末を入れて外観より加熱することによ
り、内部の樹脂粉末を金型面に沿って焼結して一体融合
物を作ったのち、金型外部より冷却して金型から成形品
を取出すものである。粉末成形には金型の動き方、加熱
方法等により、■エンゲル法(静置法)−1■ハヤシプ
ロセス、■ハイスラー法などの一軸回転法、■二軸回転
法、■ロックフロール法(回転動揺法)などがあり、こ
のほかに■加熱基体を回転させながら粉体を被覆するパ
ウダーコーティングも含まれる。
The powdered thermoplastic resin composition of the present invention is suitable for powder molding, particularly rotational molding. Powder molding generally involves placing resin powder in a sample mold according to the molded product and heating it from the outside.The resin powder inside is sintered along the mold surface to create an integral fusion product, and then the outside of the mold is heated. The molded product is removed from the mold after being cooled further. Powder compaction depends on the movement of the mold, heating method, etc. ■Engel method (static method) - 1 ■Hayashi process, ■One-axis rotation method such as Heisler method, ■Two-axis rotation method, ■Rockflor method (rotation method) Other methods include powder coating, in which powder is coated while rotating a heated substrate.

本発明の組成物は上記のいずれも成形法にも好適である
が、とくに■、■、■、■などの回転成形法に好適であ
る。
The composition of the present invention is suitable for any of the above-mentioned molding methods, but is particularly suitable for rotational molding methods such as (1), (2), (2), and (2).

ここで本発明の組成物に用いる粉末状脂肪酸金属塩(B
)の製造法について説明する。本発明に用いられる粉末
状脂肪酸金属塩(B)は前述の如く所定の平均粒径等を
有するとともに、0.30ないし0.85g/c+dの
如く比較的高い嵩密度を有するものでなければならない
。このような金属塩(B)は金属石けんの一つの製造法
である溶融法(乾式法あるいは直接法とも呼ばれる方法
)で製造される脂肪酸金属塩を機械的に粉砕したものが
一般的に該当する。この方法は、金属の酸化物や水酸化
物、あるいは炭酸塩と脂肪酸あるいは脂肪酸エステルを
直接加熱反応せしめて製造する方法であり、冷却固化し
た反応物の粉砕品は通禽本発明で使用することのできる
程度の嵩密度を有する。一方、他の金属石けんの製造方
法である複分解法(複分解沈澱法あるいは湿式法とも呼
ばれる方法)で製造される粉末状脂肪酸金属塩は、一般
に嵩密度が0.3以下であり、そのままでは本発明に使
用することができない。嵩密度の低い脂肪酸金属塩の粉
末からは、次のような方法で嵩密度の高い粉末をえるこ
とができる。
Here, the powdered fatty acid metal salt (B
) manufacturing method will be explained. The powdered fatty acid metal salt (B) used in the present invention must have a predetermined average particle size as described above, and a relatively high bulk density of 0.30 to 0.85 g/c+d. . Such metal salts (B) are generally those obtained by mechanically pulverizing fatty acid metal salts produced by the melting method (also called dry method or direct method), which is one of the manufacturing methods for metal soaps. . This method is a method of producing metal oxides, hydroxides, or carbonates by direct heating reaction with fatty acids or fatty acid esters, and the pulverized product of the cooled and solidified reaction product cannot be used in the present invention. It has a bulk density that allows for. On the other hand, powdered fatty acid metal salts produced by the double decomposition method (also called double decomposition precipitation method or wet method), which is another method for manufacturing metal soaps, generally have a bulk density of 0.3 or less, and cannot be used as is. cannot be used for Powder with high bulk density can be obtained from powder of fatty acid metal salt with low bulk density by the following method.

第一の方法は、該脂肪酸金属塩粉末をその融点以下の温
度にて加圧圧縮したのち、必要に応じて機械的に粉砕す
るものである。融点以下の温度であれば、加圧圧縮によ
って脂肪酸金属塩粉末が融解しない限りできるだけ高温
の方が望ましい。また圧縮圧は温度にもよるが、同じく
脂肪酸金属塩粉末が融解しない限り高圧を用いることが
望ましい。圧縮は種々の方法が採用でき、具体的には、
■原料粉末を一定の型の中に入れて、プレスにて圧縮す
る方法、■二つの回転するロール間に原料粉末を導き圧
縮する方法あるいは■シリンダーの中に粉末を入れてピ
ストンで圧縮する方法などを挙げることができる。これ
らの中では■の方法によるが比較例容易にしかも大量に
嵩密度ムラの少ない粉末を得ることができるの点で好ま
しい。このようにして得られた圧縮物を必要に応して機
械的に粉砕し、本発明で使用するのに必要な平均粒径等
を有する粉末とする。機械的手段としては、フェザ−ミ
ル、ボールミル、クラッシャーさらに人為的手段として
は、乳鉢ですりつぶすなどがある。
The first method is to pressurize and compress the fatty acid metal salt powder at a temperature below its melting point, and then mechanically crush the powder, if necessary. As long as the temperature is below the melting point, the temperature is preferably as high as possible unless the fatty acid metal salt powder is melted by pressure compression. Although the compression pressure depends on the temperature, it is also desirable to use high pressure unless the fatty acid metal salt powder is melted. Various methods can be used for compression, specifically:
■Method of putting raw material powder in a certain mold and compressing it with a press, ■Method of introducing raw material powder between two rotating rolls and compressing it, or ■Method of putting powder in a cylinder and compressing it with a piston. etc. can be mentioned. Among these, method (2) is preferable in the comparative example since it is easy to obtain a large amount of powder with little unevenness in bulk density. The compressed product thus obtained is mechanically pulverized as required to obtain a powder having an average particle size etc. necessary for use in the present invention. Mechanical means include a feather mill, ball mill, crusher, and artificial means include grinding in a mortar.

第二の方法は、嵩密度の低い粉末状脂肪酸金属塩を好ま
しくは不活性ガス雰囲気のもとで、圧力下もしくは圧力
をかけないまま融点以上に加熱溶融し、次いで冷却固化
させたのち、塊状脂肪酸金属塩を上記第一の方法と同様
の機械的手段等によって粉末とするのである。
The second method involves heating and melting a powdered fatty acid metal salt with a low bulk density to a temperature above its melting point under pressure or without applying pressure, preferably under an inert gas atmosphere, then cooling and solidifying it, and then melting it into a lump. The fatty acid metal salt is powdered by mechanical means similar to the first method described above.

第三の方法は、該嵩密度の低い脂肪酸金属塩粉末にポリ
オレフィンワックス又は飽和脂肪酸のグリセライド(油
脂)を添加し、ポリオレフィンワックス又は飽和脂肪酸
のグリセライドの融点以上に加熱混合し、ペースト状混
合物を冷却固化する。
The third method is to add polyolefin wax or saturated fatty acid glyceride (oil) to the fatty acid metal salt powder with low bulk density, heat and mix to a temperature above the melting point of the polyolefin wax or saturated fatty acid glyceride, and cool the paste mixture. solidify.

添加量は溶融混合物がペースト状になるに充分な程度で
よい。こうして得られる塊状物を上記第一の方法と同様
の機械的手段等によって粉末とするものである。この方
法で使用するポリオレフィンワックスとしては、例えば
エチレン、プロピレン、1−ブテン、1−ヘキセン、4
−メチル−1−ペンテン、1−デセンなどのα−オレフ
ィンの単独重合体又は2種以上のα−オレフィンの共重
合体であって、極限粘度(デカリン溶媒中で135℃に
て測定したもの)が通常0.04〜0.5d1/gの範
囲にあるものである。また飽和脂肪酸グリセライドとし
ては、例えばステアリン酸やパルミチン酸のトリグリセ
リドを挙げることができる。また上記加熱諸条件は、上
記混合物がペースト状を示す程度になるように選べばよ
い。
The amount added may be sufficient to make the molten mixture paste-like. The thus obtained lumps are made into powder by the same mechanical means as in the first method described above. Examples of the polyolefin wax used in this method include ethylene, propylene, 1-butene, 1-hexene,
- A homopolymer of α-olefin such as methyl-1-pentene or 1-decene or a copolymer of two or more α-olefins, which has an intrinsic viscosity (measured at 135°C in a decalin solvent) is usually in the range of 0.04 to 0.5 d1/g. Examples of saturated fatty acid glycerides include triglycerides of stearic acid and palmitic acid. Further, the heating conditions may be selected so that the mixture exhibits a paste-like state.

本発明の粉末状熱可塑性樹脂組成物を用いることによっ
て、粉末成形、とくに回転成形において成形時の離形性
に優れ、内面肌が著しく事情で脱泡不良もなく、機械的
強度に優れた回転成形品が得られるようになった。
By using the powdered thermoplastic resin composition of the present invention, powder molding, especially rotary molding, has excellent mold release properties during molding, and there is no defective defoaming due to excessive inner skin, and rotary molding with excellent mechanical strength. Molded products can now be obtained.

以下、本発明を実施例によって具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.

実施例1 チーブ1?−触媒を用いて懸濁重合で製造された粉末ポ
リエチレン(A)(密度0 、943g / cta、
メルトインデックス4.5g/10分)の100重量部
に対し、ステアリン酸カルシウム(三共有機合成@製、
嵩密度0 、22g / cc、粒度200メツシユ、
複分解法)を円型落し差金型(直径20cm)に入れプ
レス成形機を用いて室温で加圧(150kg/CA)圧
縮させて固めた後、ボールミルを用いて粉砕して得られ
た嵩密度0.46g/ccの粉末ステアリン酸カルシウ
ム(粒度100mesh、平均粒径50μ) 0.15
重量部を滑剤として添加し、ヘンシェルミキサーを用い
て室温で3分間混合した。得られた粉末ポリエチレン組
成物の4に+rを鋼板製金型(タテ30cmxヨコ30
cm×深さ40cm)内に仕込み二軸回転成形機にセッ
トしてプロパンガスバーナーで金型外部から10分間加
熱し、次いで5分間の自然放冷、2分間の水冷を行った
後、成形を終了した。得られた成型品の離型性、脱泡状
態および内面肌の状態を観察した。
Example 1 Chive 1? - Powdered polyethylene (A) produced by suspension polymerization with a catalyst (density 0, 943 g/cta,
To 100 parts by weight of melt index 4.5 g/10 minutes), calcium stearate (manufactured by Sanshaki Synthesis @,
Bulk density 0, 22g/cc, particle size 200 mesh,
Metathesis method) was placed in a circular drop mold (diameter 20 cm) and compressed under pressure (150 kg/CA) at room temperature using a press molding machine to solidify it, and then crushed using a ball mill to obtain a bulk density of 0. .46g/cc powdered calcium stearate (particle size 100mesh, average particle size 50μ) 0.15
Parts by weight were added as a lubricant and mixed for 3 minutes at room temperature using a Henschel mixer. Add r to 4 of the obtained powder polyethylene composition in a steel plate mold (vertical 30cm x horizontal 30cm).
cm x depth of 40 cm), set it in a two-shaft rotary molding machine, heated it from the outside of the mold with a propane gas burner for 10 minutes, then left it to cool naturally for 5 minutes, cooled it in water for 2 minutes, and then molded it. finished. The releasability, defoaming state, and inner skin state of the obtained molded product were observed.

また観察しにくい成型品内部の小さな泡の製品物性に及
ぼす悪影響をみるため成型品から試験片をASTM4号
ダンヘルで打抜き引張試験を行って破断までの伸びを調
べた。
In addition, in order to examine the adverse effect of small bubbles inside the molded product, which are difficult to observe, on the physical properties of the product, a test piece from the molded product was punched out using an ASTM No. 4 Danher and a tensile test was conducted to examine the elongation until breakage.

結果を表1に示した(以下の実施例、比較例も同じ)。The results are shown in Table 1 (the same applies to the following Examples and Comparative Examples).

実施例2 実施例1において、チーグラー触媒を用いて懸濁重合で
製造された粉末ポリエチレン(B)(密度0.935g
/cJ、イルトインデックス4.0g/10分)を用い
る以外は、全〈実施例1と同じ条件で回転成形を行った
Example 2 In Example 1, powder polyethylene (B) produced by suspension polymerization using a Ziegler catalyst (density 0.935 g
Rotational molding was carried out under the same conditions as in Example 1, except that the molding was performed using the following methods:

比較例1 実施例1において、滑剤として、ステアリン酸カルシウ
ム(三共有機合成@製、嵩密度0.22g/cc、粒度
200メツシユ、複分解法)を円型落し差金型(直径2
0cm)に入れプレス成形機を用いて室温で加圧(30
kg/cut)圧縮させて固めた後、粉砕して得られた
嵩比重0.34g/ccの粉末(粒度200mesh 
、平均粒径10μ)を用いる以外は全く、実施例1と同
じ条件下で回転成形をおこなった。
Comparative Example 1 In Example 1, calcium stearate (manufactured by Sankyoki Synthesis@, bulk density 0.22 g/cc, particle size 200 mesh, double decomposition method) was used as a lubricant in a circular drop mold (diameter 2
0 cm) and pressurized (30 cm) at room temperature using a press molding machine.
kg/cut) was compressed and solidified, and then crushed to obtain a powder with a bulk specific gravity of 0.34 g/cc (particle size: 200 mesh).
Rotational molding was carried out under the same conditions as in Example 1, except that particles with an average particle diameter of 10 μm were used.

実施例3 実施例1において、滑剤として、ステアリン酸カルシウ
ム(三共有機合成側製、嵩密度0.22g/cc、粒度
200メツシユ、複分解法)を円型落し差金型(直径2
0cm)に入れてプレス成形機を用いて温度100℃で
加圧(150kg / csl= )圧縮させて固めた
後、粉砕して得られた嵩密度0.50g/ccの粉末(
粒度80mesh、平均粒径80μ)を用いる以外は実
施例1と同じ条件下で回転成形をおこなった。
Example 3 In Example 1, calcium stearate (manufactured by Sankyoki Synthesis, bulk density 0.22 g/cc, particle size 200 mesh, double decomposition method) was used as a lubricant in a circular drop mold (diameter 2
0 cm) and compressed using a press molding machine at a temperature of 100°C under pressure (150 kg/csl =
Rotational molding was carried out under the same conditions as in Example 1, except that a particle size of 80 mesh and an average particle size of 80 μm were used.

実施例4 実施例1において、滑剤として、ステアリン酸カルシウ
ム(三共有機合成(掬製、嵩密度0.22g/cc、複
分解法)を円型落し差金型(直径4cm)に入れてプレ
ス成形機を用いて温度100℃で加圧(150kg/c
n+) 、圧縮させて固めた後、粉砕して得られた嵩密
度0.63g/ccの粉末(粒度80mesh、平均粒
径100μ)を用いる以外は実施例1と同じ条件下で回
転成形をおこなった。
Example 4 In Example 1, as a lubricant, calcium stearate (Sankyo-synthesized (manufactured by Kiki, bulk density 0.22 g/cc, double decomposition method) was placed in a circular drop mold (diameter 4 cm) and the press molding machine was turned on. pressure (150 kg/c) at a temperature of 100°C using
Rotational molding was carried out under the same conditions as in Example 1, except that a powder with a bulk density of 0.63 g/cc (particle size 80 mesh, average particle size 100 μ) obtained by compressing and solidifying and crushing was used. Ta.

実施例5 実施例1において、滑剤として、ステアリン酸カルシウ
ム(三共有機合成(4勾製、嵩密度0.22g/cc、
複分解法)を200℃以上で一度溶融させた後、冷却固
化させて出来た塊状物をボールミルを用いて粉砕して得
られた嵩密度0.57g/ccの粉末(粒度100me
sh、平均粒径50μ)を用いる以外は実施例1と同じ
条件下で回転成形をおこなった。
Example 5 In Example 1, as a lubricant, calcium stearate (trivalent synthesis (4 grade, bulk density 0.22 g/cc,
A powder with a bulk density of 0.57 g/cc (particle size of 100 me
Rotational molding was carried out under the same conditions as in Example 1 except that sh, average particle size: 50 μm) was used.

実施例6 実施例1において、滑剤として、直接法で製造されたス
テアリン酸カルシウム(日本油脂@製、嵩密度0.60
g/cc、粒度16mesh、平均粒径500 p )
をそのまま用いる以外は実施例1と同じ条件下で回転成
形を行った。
Example 6 In Example 1, calcium stearate produced by a direct method (manufactured by NOF@, bulk density 0.60) was used as a lubricant.
g/cc, particle size 16 mesh, average particle size 500 p)
Rotational molding was carried out under the same conditions as in Example 1, except that the sample was used as it was.

実施例7 実施例1において、滑剤として、直接法で製造されたス
テアリン酸カルシウム(日本油脂@製、嵩密度0.42
g/cc、粒度200mesh、平均粒径10μ)をそ
のまま用いる以外は実施例1と同じ条件下で回転成形を
行った。
Example 7 In Example 1, calcium stearate produced by a direct method (manufactured by NOF@, bulk density 0.42) was used as a lubricant.
Rotational molding was carried out under the same conditions as in Example 1, except that the particles (g/cc, particle size: 200 mesh, average particle size: 10 μm) were used as they were.

実施例8 実施例1において、ン骨剤として、ステアリン酸カルシ
ウム(三共有機合成■製、嵩密度0.22g/cc、複
分解法)に少量のステアリン酸トリグリセライドをバイ
ンダーとして添加し嵩密度0.40g/ccの粉末(粒
度32mesh、平均粒径100μ)を得、これを用い
る以外は、実施例1と同じ条件下で回転成形をおこなっ
た。
Example 8 In Example 1, a small amount of triglyceride stearate was added as a binder to calcium stearate (manufactured by Sankyoki Gosei, bulk density 0.22 g/cc, double decomposition method) as an aggregation agent to obtain a bulk density of 0.40 g. /cc powder (particle size: 32 mesh, average particle size: 100 μm) was obtained, and rotational molding was performed under the same conditions as in Example 1, except that this powder was used.

比較例2 実施例1において、滑剤として、複分解法ステアリン酸
カルシウム(三共有機合成側製、嵩密度0.22g/c
c、粒度200メツシユ)をそのまま粉末ポリエチレン
に添加し片を用いて混合する以外は実施例1と同じ条件
下で回転成型をおこなった。
Comparative Example 2 In Example 1, metathesis method calcium stearate (manufactured by Sankyoki Synthesis, bulk density 0.22 g/c) was used as a lubricant.
Rotation molding was carried out under the same conditions as in Example 1, except that the powder (particle size 200 mesh) was added as it was to powdered polyethylene and mixed using a piece.

比較例3 1例1において、ステアリン酸カルシウム(三共有機合
成@製、嵩密度0.22g/cc)を円型落し蓋(直径
20cm)に入れてプレス成形機を用いて100℃で加
圧(150kg/c艷)、圧縮させて固めた後、粉砕し
て得られた嵩密度0.75g/ccの粉末で平均粒径が
800μ(粒度14mesh)のものを角剤として用い
る以外は実施例1と同じ条件下で回転成形をおこなった
Comparative Example 3 1 In Example 1, calcium stearate (manufactured by Sankyoki Gosei@, bulk density 0.22 g/cc) was placed in a circular drop lid (diameter 20 cm) and pressurized at 100°C using a press molding machine (150 kg). Example 1 except that a powder with a bulk density of 0.75 g/cc and an average particle size of 800 μ (particle size 14 mesh) obtained by compressing, hardening, and pulverizing was used as the exfoliant. Rotational molding was carried out under the same conditions.

比較例4 実施例1において、滑剤を何ら添加しないで、粉末ポリ
エチレンをそのまま回転成形する以外は実施例1と同じ
条件で回転成形をおこなった。
Comparative Example 4 Rotational molding was carried out under the same conditions as in Example 1, except that the powdered polyethylene was rotomolded as it was without adding any lubricant.

実施例9 実施例1において、ステアリン酸ナトリウム(日本油脂
■製、嵩密度0.34g/cc)を融解後、冷却固化し
た塊状物を粉砕してiMられた嵩密度0.47g/cc
の粉末(粒度100mesh、平均粒径50.c+)を
滑剤として用いる以外は実施例1と同じ条件下で回転成
形をおこなった。
Example 9 In Example 1, sodium stearate (manufactured by NOF ■, bulk density 0.34 g/cc) was melted and then cooled and solidified, and the lump was crushed to iM with a bulk density of 0.47 g/cc.
Rotational molding was carried out under the same conditions as in Example 1, except that powder (particle size: 100 mesh, average particle size: 50.c+) was used as a lubricant.

比較例5 実施例1において、滑剤として、ステアリン酸ナトリウ
ム(日本油脂■製、嵩密度0.32g/cc)をそのま
ま用いる以外は実施例1と同し条件下で回転成形をおこ
なった。
Comparative Example 5 Rotational molding was carried out under the same conditions as in Example 1, except that sodium stearate (manufactured by NOF ■, bulk density 0.32 g/cc) was used as a lubricant.

実施例10 実施例2において、ステアリン酸リチウム(日本油脂@
製、嵩密度0.21g/cc、複分解法)を融解させた
後、冷却固化した塊状物を粉砕してf4Jられた嵩密度
0.51g/ccの粉末(粒度8Qmesl+、平均粒
度80μ)を滑剤として用いる以外は実施例2と同じ条
件下で回転成形をおこなった。
Example 10 In Example 2, lithium stearate (NOF@
A powder with a bulk density of 0.51 g/cc (particle size 8Q mesl+, average particle size 80 μ) obtained by crushing the solidified lump by cooling and crushing it (f4j) was used as a lubricant. Rotational molding was carried out under the same conditions as in Example 2, except that the sample was used as a sample.

比較例6 実施例2において、滑剤として、複分解法ステアリン酸
リチウム(日本油脂@製、嵩密度0,21g/cc)を
そのまま用いる以外は実施例2と同じ条件下で回転成形
をおこなった。
Comparative Example 6 In Example 2, rotational molding was carried out under the same conditions as in Example 2, except that metathesis method lithium stearate (manufactured by NOF@, bulk density 0.21 g/cc) was used as a lubricant.

実施例11 実施例2において、ステアリン酸マグネシウム(日本油
脂@製、嵩密度0.17g/cc、複分解法)を融解後
、冷却固化した塊状物を粉砕して得られた嵩密度0.5
4g/ccの粉末(粒度100mesh、平均粒径50
μ)を滑剤として用いる以外は実施例2と同し条件で回
転成形をおこなった。
Example 11 In Example 2, bulk density 0.5 was obtained by melting magnesium stearate (manufactured by NOF@, bulk density 0.17 g/cc, double decomposition method) and then crushing the solidified lump by cooling.
4g/cc powder (particle size 100mesh, average particle size 50
Rotational molding was carried out under the same conditions as in Example 2 except that μ) was used as a lubricant.

実施例12 実施例2において、滑剤として、直接法で製造されたス
テアリン酸亜鉛(日本油脂@製、嵩密度0.48g/c
c、粒度80mesh、平均粒径80μ)をそのまま用
いる以外は実施例1と同じ条件下で回転成形を行った。
Example 12 In Example 2, zinc stearate produced by a direct method (manufactured by NOF@, bulk density 0.48 g/c) was used as a lubricant.
Rotation molding was carried out under the same conditions as in Example 1, except that the sample (c, particle size: 80 mesh, average particle size: 80 μm) was used as it was.

比較例7 実施例2において、滑剤として、複分解法ステアリン酸
マグネシウム(日本油脂■製、嵩密度0.17g/cc
)をそのまま用いる以外は実施例2と同じ条件下で回転
成形を行った。
Comparative Example 7 In Example 2, metathesis method magnesium stearate (manufactured by NOF ■, bulk density 0.17 g/cc) was used as a lubricant.
) was used as it was, but rotational molding was performed under the same conditions as in Example 2.

比較例8 実施例2において、滑剤を何ら添加しないで、粉末ポリ
エチレンをそのまま回転成形する以外は実施例2と同じ
条件で回転成形をおこなった。
Comparative Example 8 In Example 2, rotational molding was carried out under the same conditions as in Example 2, except that the powdered polyethylene was rotomolded as it was without adding any lubricant.

Claims (1)

【特許請求の範囲】 (])粉末状熱可塑性樹脂(A) 100重量部に、嵩
密度が0.35ないし0.85g/cJ、平均粒径が5
ないし500μでかつ16メツシユの篩を通過する粉末
状の脂肪酸金属塩(B)0.02ないし1.0重量部が
混合分散されていることを特徴とする粉末状熱可塑性樹
脂組成物。 (2)脂肪酸金属塩(B)の融点が130℃を越えるも
のである特許請求の範囲第(1)項記載の粉末状熱可塑
性樹脂組成物。
[Scope of Claims] (]) 100 parts by weight of powdered thermoplastic resin (A) has a bulk density of 0.35 to 0.85 g/cJ and an average particle size of 5
1. A powdery thermoplastic resin composition comprising 0.02 to 1.0 parts by weight of a powdered fatty acid metal salt (B) having a particle size of 500 μm to 500 μm and passing through a 16-mesh sieve. (2) The powdered thermoplastic resin composition according to claim (1), wherein the fatty acid metal salt (B) has a melting point of over 130°C.
JP20073783A 1983-10-28 1983-10-28 Powdery thermoplastic resin composition Granted JPS6094459A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP20073783A JPS6094459A (en) 1983-10-28 1983-10-28 Powdery thermoplastic resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP20073783A JPS6094459A (en) 1983-10-28 1983-10-28 Powdery thermoplastic resin composition

Publications (2)

Publication Number Publication Date
JPS6094459A true JPS6094459A (en) 1985-05-27
JPH0454699B2 JPH0454699B2 (en) 1992-09-01

Family

ID=16429333

Family Applications (1)

Application Number Title Priority Date Filing Date
JP20073783A Granted JPS6094459A (en) 1983-10-28 1983-10-28 Powdery thermoplastic resin composition

Country Status (1)

Country Link
JP (1) JPS6094459A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001131407A (en) * 1999-11-05 2001-05-15 Asahi Kasei Corp Reinforced polyamide resin composition having excellent moldability
JP2002294068A (en) * 2001-03-30 2002-10-09 Asahi Kasei Corp Polyamide resin composition
JP2004277555A (en) * 2003-03-14 2004-10-07 Riken Technos Corp Solvent composition for sol-like resin composition and sol-like thermoplastic resin composition
JP2007314810A (en) * 1994-12-28 2007-12-06 Ciba Specialty Chem Holding Inc Low-dust granule of plastic additive
JP2020094153A (en) * 2018-12-14 2020-06-18 旭化成株式会社 Resin composition mainly comprising ethylenic polymer powder, and molded article comprising the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101179522B1 (en) 2003-09-29 2012-09-07 후지필름 가부시키가이샤 Inkjet recording material, producing method for inkjet recording material and inkjet recording method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5738839A (en) * 1980-08-20 1982-03-03 Asahi Chem Ind Co Ltd Powdered polyethylene composition
JPS5765752A (en) * 1980-10-08 1982-04-21 Continental Oil Co Manufacture of thermoplastic blend extrusion formation additive composition
JPS58152028A (en) * 1982-03-05 1983-09-09 Toagosei Chem Ind Co Ltd Powdery polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5738839A (en) * 1980-08-20 1982-03-03 Asahi Chem Ind Co Ltd Powdered polyethylene composition
JPS5765752A (en) * 1980-10-08 1982-04-21 Continental Oil Co Manufacture of thermoplastic blend extrusion formation additive composition
JPS58152028A (en) * 1982-03-05 1983-09-09 Toagosei Chem Ind Co Ltd Powdery polymer

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007314810A (en) * 1994-12-28 2007-12-06 Ciba Specialty Chem Holding Inc Low-dust granule of plastic additive
JP2001131407A (en) * 1999-11-05 2001-05-15 Asahi Kasei Corp Reinforced polyamide resin composition having excellent moldability
JP4488563B2 (en) * 1999-11-05 2010-06-23 旭化成ケミカルズ株式会社 Reinforced polyamide resin composition with excellent moldability
JP2002294068A (en) * 2001-03-30 2002-10-09 Asahi Kasei Corp Polyamide resin composition
JP2004277555A (en) * 2003-03-14 2004-10-07 Riken Technos Corp Solvent composition for sol-like resin composition and sol-like thermoplastic resin composition
JP2020094153A (en) * 2018-12-14 2020-06-18 旭化成株式会社 Resin composition mainly comprising ethylenic polymer powder, and molded article comprising the same

Also Published As

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