JPS63108031A - Production of thermoplastic resin microparticle - Google Patents
Production of thermoplastic resin microparticleInfo
- Publication number
- JPS63108031A JPS63108031A JP25307486A JP25307486A JPS63108031A JP S63108031 A JPS63108031 A JP S63108031A JP 25307486 A JP25307486 A JP 25307486A JP 25307486 A JP25307486 A JP 25307486A JP S63108031 A JPS63108031 A JP S63108031A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- medium
- resin
- fine particles
- melting point
- 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.)
- Pending
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000011859 microparticle Substances 0.000 title abstract 3
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 4
- 229920005990 polystyrene resin Polymers 0.000 claims abstract 2
- 239000010419 fine particle Substances 0.000 claims description 24
- 229930182556 Polyacetal Natural products 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 229920002545 silicone oil Polymers 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は球状熱可塑性樹脂微粒子の製造法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing spherical thermoplastic resin particles.
製造された球状微粒子は塗料、化粧品基剤、吸着剤等工
業的に大きな価値を有している。The produced spherical fine particles have great industrial value as paints, cosmetic bases, adsorbents, etc.
熱可塑性樹脂を微粒子にする方法としてはペレットなど
の塊状物を機械的に粉砕する方法あるいは適当な溶媒を
用いて温度による溶解度差を利用するか、または貴溶媒
を加えて沈殿を析出させる方法などがあるが、形状が不
均一な不定形であったり多孔質状であったり均質な球状
微粒子が得られない欠点がある。一方従来からポリアミ
ド樹脂の球状微粒子の製造方法としてポリエチレングリ
コールを媒体とする方法が知られている。（例えば特開
昭６０−４０１３４号）
〔発明が解決しようとする問題点〕
しかしながらポリエチレングリコールを媒体とする方法
は媒体が常温で固体であり微粒子化したポリアミド樹脂
と媒体の分Ｍ操作に支障をきたす欠点を有する。また媒
体自身の耐熱性が１７０℃なので製造中に変質する欠点
を有している。Methods of making thermoplastic resin into fine particles include mechanically crushing agglomerates such as pellets, using an appropriate solvent to utilize the difference in solubility due to temperature, or adding a noble solvent to precipitate. However, they have the disadvantage that they are nonuniform, amorphous, porous, and cannot produce homogeneous spherical particles. On the other hand, a method using polyethylene glycol as a medium has been known as a method for producing spherical fine particles of polyamide resin. (For example, JP-A No. 60-40134) [Problems to be solved by the invention] However, in the method using polyethylene glycol as a medium, the medium is solid at room temperature, which hinders the operation of separating the finely divided polyamide resin and the medium. It has disadvantages. In addition, since the heat resistance of the medium itself is 170° C., it has the disadvantage of deterioration during production.
本発明者らは熱可塑性樹脂微粒子の製造法について鋭意
研究を重ねた結果、媒体中に熱可塑性樹脂を加熱分散す
る方法において、媒体として一般式
（式中、ｍは２０〜５００の数、Ｒ，、Ｒ２は炭素数１
〜１０のアルキル基、ｎは１〜１００の数、Ｐは１〜５
０の数、ｑは０〜５０の数である）
で表わされるポリエーテル変性シリコーンオイルを用い
た場合、均質な球状微粒子が得られ、しかも媒体からの
分離操作も極めて容易であることを見出した。As a result of extensive research into the method for producing thermoplastic resin fine particles, the present inventors found that in a method of heating and dispersing a thermoplastic resin in a medium, the medium is a general formula (where m is a number from 20 to 500, R ,,R2 has 1 carbon number
~10 alkyl groups, n is a number from 1 to 100, P is 1 to 5
It was discovered that when using a polyether-modified silicone oil represented by .
すなわち本発明は、媒体とこれに溶解しない熱可塑性樹
脂とを熱可塑性樹脂の軟化点又は融点以上の温度で混合
分散せしめ、しかる後熱可塑性樹脂の軟化点又は融点よ
り低い温度に冷却し、固化した熱可塑性樹脂を媒体から
分離する熱可塑性樹脂微粒子の製造方法であって、前記
媒体が一般式
（式中、ｍは２０〜５００の数、Ｒ１、Ｒ２は炭素数１
〜１０のアルキル基、ｎは１〜１００の数、Ｐは１〜５
０の数、ｑはＯ〜５０の数である）
で表わされるポリエーテル変性シリコーンオイルである
ことを特徴とする熱可塑性樹脂微粒子の製造方法である
。That is, the present invention involves mixing and dispersing a medium and a thermoplastic resin that does not dissolve therein at a temperature higher than the softening point or melting point of the thermoplastic resin, and then cooling it to a temperature lower than the softening point or melting point of the thermoplastic resin to solidify it. A method for producing thermoplastic resin fine particles in which a thermoplastic resin is separated from a medium, the medium having a general formula (where m is a number from 20 to 500, R1 and R2 are carbon atoms of 1
~10 alkyl groups, n is a number from 1 to 100, P is 1 to 5
q is a number from 0 to 50.
以下本発明を具体的に説明する。The present invention will be specifically explained below.
本発明においては、熱可塑性樹脂は通常不活性ガス雰囲
気下で熱可塑性樹脂の軟化点又は融点以上の温度で媒体
と充分に混合する。In the present invention, the thermoplastic resin is sufficiently mixed with the medium at a temperature higher than the softening point or melting point of the thermoplastic resin, usually under an inert gas atmosphere.
これにより媒体中に熱可塑性樹脂の微小液滴が分散した
系を形成する。This forms a system in which minute droplets of thermoplastic resin are dispersed in the medium.
しかる後撹拌下に分散系全体を、そのまま又は熱可塑性
樹脂を溶解せずに媒体を溶解する溶剤例えばエタノール
、ＭＥＫ、トルエン、゛メタノール、ＩＰＡ、セロソル
ブ等の中に投入してから、熱可塑性樹脂の軟化点又は融
点好ましくはガラス転移点より低い温度に冷却すること
により前記微小液滴を固化し熱可塑性樹脂微粒子を、形
成する。Thereafter, the entire dispersion system is poured into a solvent such as ethanol, MEK, toluene, methanol, IPA, cellosolve, etc., which dissolves the medium without dissolving the thermoplastic resin, either as it is or with stirring, and then the thermoplastic resin is added. The fine droplets are solidified by cooling to a temperature lower than the softening point or melting point, preferably the glass transition point, to form thermoplastic resin fine particles.
その後濾過等の分離操作を行ない媒体がち熱可塑性樹脂
微粒子を単離する。Thereafter, a separation operation such as filtration is performed to isolate the medium-free thermoplastic resin fine particles.
このとき必要に応じ単離した前記微粒子を前記の如き媒
体を溶解する溶剤にて洗浄することにより前記微粒子よ
り媒体を完全に除去することができる。At this time, the medium can be completely removed from the fine particles by washing the isolated fine particles with a solvent that dissolves the medium as described above, if necessary.
熱可塑性樹脂と媒体の混合割合は熱可塑性樹脂が４０重
量％以下となる割合が好ましい。The mixing ratio of the thermoplastic resin and the medium is preferably such that the thermoplastic resin is 40% by weight or less.
熱可塑性樹脂の割合が４０重量％より大きくなった場合
には熱可塑性樹脂の媒体中への十分な均一分散ができず
球状微粒子の生成が困難となることがある。If the proportion of the thermoplastic resin exceeds 40% by weight, the thermoplastic resin may not be sufficiently uniformly dispersed in the medium, making it difficult to produce spherical fine particles.
本発明に従って得られる熱可塑性樹脂微粒子の粒径及び
粒度分布は媒体との混合割合や撹拌力、温度などの因子
によって影響され例えば撹拌を強くしたり、熱可塑性樹
脂の割合を小さくすれば球径は小さくなる。これら製造
条件を適当に選定し組み合わせることにより粒径及び粒
度分布を任意に調整することができる。The particle size and particle size distribution of the thermoplastic resin fine particles obtained according to the present invention are influenced by factors such as the mixing ratio with the medium, stirring force, and temperature. becomes smaller. By appropriately selecting and combining these manufacturing conditions, the particle size and particle size distribution can be adjusted as desired.
本発明において媒体として用いられるシリコーンオイル
は前記の如き一般式からなるものであり、例えばＴＳＦ
−４４４６、ＴＳＦ−４４５２（東芝シリコーン社製商
品名）、５Ｆ８４１０．５Ｈ−３７４９（東しシリコー
ン社製商品名）等が使用できるが、その粘度が１００ｃ
ｓｔ／２５℃以上のものが好ましく ５００ｃｓｔ／
２５℃以上のものが特に好ましい。The silicone oil used as a medium in the present invention has the general formula as described above, for example, TSF.
-4446, TSF-4452 (trade name manufactured by Toshiba Silicone Co., Ltd.), 5F8410.5H-3749 (trade name manufactured by Toshiba Silicone Co., Ltd.) etc. can be used, but their viscosity is 100c.
st/preferably 25°C or higher 500cst/
Particularly preferred is a temperature of 25°C or higher.
粘度が］００ｃｓｔ／２５℃未満の場合は熱可塑性樹脂
が均一に分散できないため球状の微粒子ができにくくな
る。If the viscosity is less than 00 cst/25°C, the thermoplastic resin cannot be uniformly dispersed, making it difficult to form spherical fine particles.
本発明に用いられる熱可塑性樹脂としては前記媒体に溶
解しないものであれば特に制限はされなく、例えばポリ
エチレン、ポリプロピレン、アクリル樹脂、ポリアセタ
ール、ポリアミド、ポリカーボネート、ポリエチレンテ
レフタレート、ポリブチレンテレフタレート、ポリフェ
ニレンサルファイド、フッ素樹脂、ポリフェニレンオキ
サイド、ポリメチルペンテンなどの熱可塑性樹脂が使用
できる。The thermoplastic resin used in the present invention is not particularly limited as long as it does not dissolve in the medium, and examples thereof include polyethylene, polypropylene, acrylic resin, polyacetal, polyamide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and fluorine. Thermoplastic resins such as resin, polyphenylene oxide, and polymethylpentene can be used.
以下実施例をあげて説明する。This will be explained below by giving examples.
実施例１
ナイロン−１２６０ｇとポリエーテル変性シリコーンオ
イル（１，０ＯＯｃｓｔ／２５℃）ＴＳＦ４４５２（東
芝シリコーン社製商品名）２４０ｇを窒素雰囲気で２３
０℃に加熱し１時間撹拌した後６０℃丈で冷却し加圧濾
過にて分離したナイロン−１２の微粒子を更にメタノー
ルにて洗浄した。Example 1 1260 g of nylon and 240 g of polyether-modified silicone oil (1,000cst/25°C) TSF4452 (trade name manufactured by Toshiba Silicone Co., Ltd.) were heated for 23 hours in a nitrogen atmosphere.
After heating to 0°C and stirring for 1 hour, the mixture was cooled to 60°C, and the fine particles of nylon-12 separated by pressure filtration were further washed with methanol.
得られたナイロン−１２の微粒子は粒径４０〜４００μ
の球状微粒子であった。The obtained fine particles of nylon-12 have a particle size of 40 to 400μ.
It was a spherical fine particle.
実施例２
ナイロン−１２のかわりにポリスチレン６０ｇを用いた
以外は実施１と同様に行い粒径２０〜２５０μのポリス
チレンの球状微粒子が得られた。Example 2 The same procedure as in Example 1 was carried out except that 60 g of polystyrene was used instead of nylon-12, and spherical fine particles of polystyrene with a particle size of 20 to 250 μm were obtained.
実施例３
ポリアセタール５０ｇとポリエーテル変性ジメチルシリ
コーンオイル（１，５００ｃｓｔ／ ２５℃）ＴＳＦ−
４４４６（東芝シリコーン社製商品名）２５０ｇを窒素
雰囲気で２４０℃に加熱し１時間撹拌した後６０℃まで
冷却し加圧濾過にて分離したポリアセクールの微粒子を
更にメタノールにて洗浄した。Example 3 50 g of polyacetal and polyether modified dimethyl silicone oil (1,500 cst/25°C) TSF-
250 g of 4446 (trade name manufactured by Toshiba Silicone Co., Ltd.) was heated to 240° C. in a nitrogen atmosphere, stirred for 1 hour, cooled to 60° C., and the polyacecool fine particles separated by pressure filtration were further washed with methanol.
得られたポリアセタールの微粒子は粒径５〜２０μの球
状微粒子であった。The obtained polyacetal fine particles were spherical fine particles with a particle size of 5 to 20 μm.
本発明の方法に従うと容易に均質な球状微粒子が得られ
るので、塗料、化粧品、吸着剤等の工業分野で巾広く利
用できる。Since homogeneous spherical fine particles can be easily obtained according to the method of the present invention, they can be widely used in industrial fields such as paints, cosmetics, and adsorbents.
Claims (1)
性樹脂の軟化点又は融点以上の温度で混合分散せしめ、
しかる後熱可塑性樹脂の軟化点又は融点より低い温度に
冷却し、固化した熱可塑性樹脂を媒体から分離する熱可
塑性樹脂微粒子の製造方法であって、前記媒体が一般式
▲数式、化学式、表等があります▼ （式中、ｍは２０〜５００の数、Ｒ＿１、Ｒ＿２は炭素
数１〜１０のアルキル基、ｎは１〜１００の数、Ｐは１
〜５０の数、ｑは０〜５０の数である） で表わされるポリエーテル変性シリコーンオイルである
ことを特徴とする熱可塑性樹脂微粒子の製造方法。 ２、熱可塑性樹脂がポリアミド樹脂である特許請求の範
囲第１項記載の熱可塑性樹脂微粒子の製造方法。 ３、熱可塑性樹脂がポリスチレン樹脂である特許請求の
範囲第１項記載の熱可塑性樹脂微粒子の製造方法。 ４、熱可塑性樹脂がポリアセタール樹脂である特許請求
の範囲第１項記載の熱可塑性樹脂微粒子の製造方法。[Claims] 1. A medium and a thermoplastic resin that does not dissolve in the medium are mixed and dispersed at a temperature higher than the softening point or melting point of the thermoplastic resin,
A method for producing thermoplastic resin fine particles, wherein the thermoplastic resin is then cooled to a temperature lower than the softening point or melting point of the thermoplastic resin, and the solidified thermoplastic resin is separated from a medium, the medium having a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, m is a number from 20 to 500, R_1 and R_2 are alkyl groups having 1 to 10 carbon atoms, n is a number from 1 to 100, and P is 1
50, q is a number from 0 to 50). 2. The method for producing thermoplastic resin fine particles according to claim 1, wherein the thermoplastic resin is a polyamide resin. 3. The method for producing thermoplastic resin fine particles according to claim 1, wherein the thermoplastic resin is a polystyrene resin. 4. The method for producing thermoplastic resin fine particles according to claim 1, wherein the thermoplastic resin is a polyacetal resin.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25307486A JPS63108031A (en) | 1986-10-23 | 1986-10-23 | Production of thermoplastic resin microparticle |
| US07/109,797 US4863646A (en) | 1986-10-23 | 1987-10-14 | Method of producing fine particles of thermoplastic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25307486A JPS63108031A (en) | 1986-10-23 | 1986-10-23 | Production of thermoplastic resin microparticle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63108031A true JPS63108031A (en) | 1988-05-12 |
Family
ID=17246128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25307486A Pending JPS63108031A (en) | 1986-10-23 | 1986-10-23 | Production of thermoplastic resin microparticle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63108031A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0705643A1 (en) * | 1994-10-05 | 1996-04-10 | Sanyo Chemical Industries, Ltd. | Improved water-absorbent resin particles and the production thereof |
-
1986
- 1986-10-23 JP JP25307486A patent/JPS63108031A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0705643A1 (en) * | 1994-10-05 | 1996-04-10 | Sanyo Chemical Industries, Ltd. | Improved water-absorbent resin particles and the production thereof |
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