JPH06850B2 - Method for pulverizing thermoplastic resin containing carbon black - Google Patents
Method for pulverizing thermoplastic resin containing carbon blackInfo
- Publication number
- JPH06850B2 JPH06850B2 JP60154476A JP15447685A JPH06850B2 JP H06850 B2 JPH06850 B2 JP H06850B2 JP 60154476 A JP60154476 A JP 60154476A JP 15447685 A JP15447685 A JP 15447685A JP H06850 B2 JPH06850 B2 JP H06850B2
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- carbon black
- weight
- ethylene
- parts
- 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.)
- Expired - Fee Related
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 34
- 239000006229 carbon black Substances 0.000 title claims description 18
- 238000010298 pulverizing process Methods 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000004945 emulsification Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/081—Preparation methods by mixing the toner components in a liquefied state; melt kneading; reactive mixing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08759—Polyethers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Developing Agents For Electrophotography (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【発明の詳細な説明】 〔発明の目的〕 （産業上の利用分野） 本発明は、カーボンブラックを含有した熱可塑性樹脂の
真球状微粉末化方法に関するものであり、得られた微粉
末は、トナー材料として有効に利用できる。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a method for pulverizing a thermoplastic resin containing carbon black into a true spherical fine powder. It can be effectively used as a toner material.
（従来の技術） 電子印刷に使用するトナーは、熱可塑性樹脂７５〜９０
部、着色剤５〜２０部（カーボンブラックまたは顔
料），荷電制御部１〜５部，その他の添加物１〜５部を
混合した状態の組成物である。通常トナーは、上記組成
物を原料として混練分散→粉砕造粒→表面処理→分級の
工程を得て製造される。表面処理の工程で不定形の粉砕
部トナーは、一部球状化されるものの、全体としては不
定形であり、実質上１５ミクロン以下のものを作ること
は難しい。(Prior Art) Toner used for electronic printing is a thermoplastic resin 75-90.
Parts, 5 to 20 parts of colorant (carbon black or pigment), 1 to 5 parts of charge control part, and 1 to 5 parts of other additives. Usually, the toner is manufactured by the steps of kneading and dispersing, crushing and granulating, surface treatment, and classification using the above composition as a raw material. The pulverized part toner having an irregular shape in the surface treatment step is partly spheroidized, however, it has an irregular shape as a whole, and it is difficult to produce a toner having a particle size of 15 μm or less.
また、流動性も良好とはいえず、取扱い面と画像形成時
に不都合が生じる。流動性を改良するため、特開昭５０
−５００４２号公報−、特開昭５０−８７６５２号公
報−、特公５７−５１６７５号公報−などの方法が
提案されている。しかしながらの方法は、トナー粉末
を約５００〜６００℃に加熱された空気の流れに直角に
通過させ、冷却時重力によって沈降させて球状化する方
法である。しかしこの方法では、非常に容量の大きい冷
却室を必要とし、また高温熱気流の再利用ができないた
めエネルギー損失が大きい。In addition, the fluidity is not good, which causes inconveniences in handling and image formation. To improve fluidity, Japanese Patent Laid-Open No.
Methods such as JP-A-50042, JP-A-50-87652, and JP-B-57-51675 are proposed. However, the method is to pass the toner powder at right angles to the flow of air heated to about 500 to 600 ° C., and at the time of cooling, settle by gravity and spheroidize. However, this method requires a cooling chamber having a very large capacity, and the high temperature hot air stream cannot be reused, resulting in a large energy loss.
はスプレー乾燥による方法、回転羽根を備えた撹拌
容器で外部冷却しながら撹拌混合する方法であるが、使
用量の多少はあるものの，は、いずれも有機溶剤を
使用するため火災や爆発の危険性や、有機溶剤の回収な
どの処理が必要であるなど、まだ製造方法には問題が多
い。本発明者らは、これらの問題を解決し、効率よくか
つ安全に真球状のカーボンブラック含有熱可塑性樹脂微
粉末を得る方法を見出した。Is a method by spray drying, and is a method of stirring and mixing while externally cooling with a stirring vessel equipped with a rotating blade. However, although there is a small amount of use, both of them use organic solvents, so there is a risk of fire and explosion. In addition, there are still many problems in the manufacturing method, such as the need to recover the organic solvent. The present inventors have found a method for solving these problems and efficiently and safely obtaining a fine spherical carbon black-containing thermoplastic resin fine powder.
（問題点を解決するための手段）（作用） 本発明の要旨は、カーボンブラックを含有した熱可塑性
樹脂を微粉末化するにあたり、水を媒体とし、エチレン
オキシド−プロピレンオキシド共重合体、必要ならばエ
チレン−アクリル酸共重合体の存在下、加熱，加圧下に
溶解撹拌して乳化液を得、これを熱可塑性樹脂の軟化点
以下の温度に冷却することを特徴とするカーボンブラッ
ク含有熱可塑性樹脂の微粉末化方法である。(Means for Solving Problems) (Action) The gist of the present invention is to use an ethylene oxide-propylene oxide copolymer, if necessary, in water as a medium when pulverizing a thermoplastic resin containing carbon black. A carbon black-containing thermoplastic resin characterized by dissolving and stirring under heating and pressurization in the presence of an ethylene-acrylic acid copolymer to obtain an emulsion, and cooling the emulsion to a temperature below the softening point of the thermoplastic resin. This is a method for making fine powder.
ここで使用される熱可塑性樹脂とは、ポリエチレン，ポ
リプロピレン，エチレン−プロピレン共重合体，ポリス
チレン，スチレン−アクリル系共重合体等であり、スチ
レンと共重合するアクリル系モノマーとしては、アクリ
ル酸，アクリル酸メチル，アクリル酸エチル，アクリル
酸ブチル，アクリル酸ドデシル，アクリル酸オクチル，
アクリル酸フェニル，メタクリル酸，メタクリル酸メチ
ル，メタクリル酸エチル，メタクリル酸ブチル，メタク
リル酸オクチル，アクリロニトリル，メタクリロニトリ
ル，アクリルアミドなどがある。The thermoplastic resin used here is polyethylene, polypropylene, ethylene-propylene copolymer, polystyrene, styrene-acrylic copolymer, and the like. Acrylic monomers copolymerized with styrene include acrylic acid and acrylic. Methyl acid, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate,
Examples include phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, and acrylamide.
熱可塑性樹脂中に含有させるカーボンブラックには、チ
ャンネルブラック，ファーネスブラック，サーマルブラ
ック，アセチレンブラックなどの種類があり、その粒径
は１０〜４０ミリミクロンのものがほとんどであるが、
いずれも本発明に使用することができる。There are various types of carbon black contained in the thermoplastic resin, such as channel black, furnace black, thermal black, and acetylene black, and most of them have a particle size of 10 to 40 millimicrons.
Either can be used in the present invention.
カーボンブラックの使用量は、所望される物性により決
定されるので一概にはいえないが熱可塑性樹脂１００重
量部に対し、２０重量部以下が適当である。The amount of carbon black used is determined by the desired physical properties and cannot be generally stated, but is suitably 20 parts by weight or less relative to 100 parts by weight of the thermoplastic resin.
熱可塑性樹脂の粉末化方法は大別して、機械粉砕法，溶
解法，分散法の三つの方法がある。The powdering method of the thermoplastic resin is roughly classified into three methods, that is, a mechanical pulverizing method, a dissolving method and a dispersing method.
機械粉砕法は、高せん断微粉化装置を用い、不規則な形
をした粉末を作ることができるが、その平均粒子径は１
００〜３００ミクロンであり、トナーとして使用する場
合に適した５〜２０ミクロンのものは得られない。The mechanical pulverization method uses a high-shear pulverization device to produce an irregularly shaped powder, but the average particle size is 1
It is from 0 to 300 μm, and a product having a particle size of 5 to 20 μm suitable for use as a toner cannot be obtained.
溶解法は、熱可塑性樹脂を溶剤に溶解し、必要ならば貧
溶剤を加え、冷却により粉末を析出させたり、溶剤を蒸
発させたりして粉末を得る方法である。The dissolution method is a method in which a thermoplastic resin is dissolved in a solvent, a poor solvent is added if necessary, and the powder is precipitated by cooling or the solvent is evaporated to obtain the powder.
この場合、強力な撹拌を与えることにより細かい粉末を
得る方法がよく採用されるが、その場合でも平均粒子径
は、せいぜい２０〜５０ミクロン程度であり、形状も真
球状のものは得られない。In this case, a method of obtaining fine powder by giving strong stirring is often adopted, but even in that case, the average particle diameter is at most about 20 to 50 microns, and a spherical shape cannot be obtained.
分散法は、種々の分散剤の作用で熱可塑性樹脂の粉末を
得る方法であり、熱可塑性樹脂を溶剤に溶解し、分散液
と水とを混合することにより分散させる方法もあるが、
工業的には溶剤の回収が不必要な水媒体のみで分散させ
るのが最も好ましく有利である。Dispersion method is a method of obtaining a powder of a thermoplastic resin by the action of various dispersants, there is a method of dissolving the thermoplastic resin in a solvent, there is a method of dispersing by mixing the dispersion liquid and water,
It is most preferable and advantageous to disperse the solvent only in an aqueous medium which is industrially unnecessary to recover the solvent.
このような状況に鑑み、本発明者らは熱可塑性樹脂の微
粉末化方法について鋭意検討した結果、水を媒体とし、
エチレンオキシド−プロピレンオキシド共重合体、必要
ならばエチレン−アクリル酸共重合体の存在下、加熱，
加圧の条件で熱可塑性樹脂を溶融撹拌して乳化液を得、
これを熱可塑性樹脂の軟化温度以下に冷却し、常法によ
り濾過乾燥することにより、平均粒子径５〜２０ミクロ
ンのカーボンブラック含有の真球状熱可塑性樹脂微粉末
を得る方法を見出し本発明を完成するに至った。In view of such a situation, the inventors of the present invention have diligently studied a method of pulverizing a thermoplastic resin, and using water as a medium,
Heating in the presence of an ethylene oxide-propylene oxide copolymer and, if necessary, an ethylene-acrylic acid copolymer,
An emulsified liquid is obtained by melting and stirring the thermoplastic resin under pressure.
The present invention was completed by finding a method for obtaining a true spherical thermoplastic resin fine powder containing carbon black having an average particle size of 5 to 20 microns by cooling this to a temperature below the softening temperature of the thermoplastic resin and filtering and drying by a conventional method. Came to do.
本発明に用いる熱可塑性樹脂とは、前述のポリエチレ
ン，ポリプロピレン，エチレン−プロピレン共重合体，
ポリスチレン，スチレン−アクリル系共重合体等であ
り、乳化温度における原料熱可塑性樹脂の溶融指数が２
０以上、好ましくは５０以上のものを用いる。（ＪＩＳ
Ｋ7210記載の方法で測定、試験荷重2.16Kg/10分間） エチレンオキシド−プロピレンオキシド共重合体とは なる構造式を有し、Ｘ＝２〜１５０，Ｙ＝１０〜９０，
Ｚ＝２〜１５０の共重合体の総称であるが、例えば、旭
電化社製；商品名；プルロニックのごとく本発明で用い
られるエチレンオキシド−プロピレンオキシド共重合体
はそれらの内Ｘ＝６０〜１３０，Ｙ＝３０〜７０，Ｚ＝
６０〜１３０の範囲のものが適当である。The thermoplastic resin used in the present invention means the above-mentioned polyethylene, polypropylene, ethylene-propylene copolymer,
Polystyrene, styrene-acrylic copolymer, etc., and the melting index of the raw material thermoplastic resin at the emulsification temperature is 2
The one used is 0 or more, preferably 50 or more. (JIS
Measured by the method described in K7210, test load 2.16 Kg / 10 minutes) What is an ethylene oxide-propylene oxide copolymer? X = 2-150, Y = 10-90,
Z is a general term for copolymers of 2 to 150, for example, Asahi Denka Co., Ltd .; trade name; like Pluronic, the ethylene oxide-propylene oxide copolymer used in the present invention has X = 60 to 130 of them. Y = 30 to 70, Z =
Those in the range of 60 to 130 are suitable.
使用量は原料熱可塑性樹脂に対して３〜６０重量％が適
当であり、更に好ましくは８〜５０重量％である。それ
以下では充分な乳化を行なうことが難かしい、それ以上
用いることは製品の微粉末中への混入が多くなり、好ま
しくない場合が多い。The amount used is suitably 3 to 60% by weight, more preferably 8 to 50% by weight, based on the raw material thermoplastic resin. If it is less than that, it is difficult to carry out sufficient emulsification, and if it is used more than that, the product is often mixed into the fine powder, which is not preferable in many cases.
更に必要により、エチレン−アクリル酸共重合体を使用
するが、特開昭60-212430号公報参照）この場合使用と
するエチレン−アクリル酸共重合体とは、エチレンとア
クリル酸とを例えば高圧下重合させて得られた重合体
で、 の構造を有し、エチレンにアクリル酸が不規則に結合し
たものであり、アクリル酸を３〜２０重量％含むもので
ある。（ダウケミカル社製：商品名ＥＡＡ） 本発明に用いるエチレン−アクリル酸共重合体は苛性ソ
ーダー、苛性カリ，アンモニアなどを用い部分的に中和
したものも使用できる。中和度は０〜２０％まで可能で
あるが好ましくは０〜１５％の範囲である。中和度がそ
れ以上になるとエチレン−アクリル酸共重合体が水に溶
解し、乳化剤としての機能を失なうので好ましくない。
中和のため苛性ソーダー，苛性カリ，アンモニアなどの
添加はあらかじめ別の容器で行なうこともできるし、エ
チレン−アクリル酸共重合体を仕込んだ耐圧オートクレ
ープ内で、必要量だけ苛性ソーダー，苛性カリ，アンモ
ニアなどを添加することにより使用することもできる。
工業的には後者の方が簡便であり、有利である場合が多
い。乳化時に使用するエチレン−アクリル酸共重合体量
は、原料熱可塑性樹脂に対し１〜２０重量％の範囲であ
る。Further, if necessary, an ethylene-acrylic acid copolymer is used, but refer to JP-A-60-212430). In this case, the ethylene-acrylic acid copolymer used is ethylene and acrylic acid under high pressure, for example. A polymer obtained by polymerization, It has a structure of, and irregularly bonds with acrylic acid to ethylene, and contains 3 to 20% by weight of acrylic acid. (Product name: EAA, manufactured by Dow Chemical Co.) The ethylene-acrylic acid copolymer used in the present invention may be partially neutralized with caustic soda, caustic potash, ammonia or the like. The degree of neutralization can be from 0 to 20%, but is preferably from 0 to 15%. When the degree of neutralization is higher than that, the ethylene-acrylic acid copolymer is dissolved in water and loses its function as an emulsifier, which is not preferable.
For neutralization, caustic soda, caustic potash, ammonia, etc. can be added in advance in a separate container, or only the required amount of caustic soda, caustic potash, ammonia can be placed in a pressure-resistant autoclave charged with an ethylene-acrylic acid copolymer. It can also be used by adding such as.
The latter is industrially simpler and often advantageous. The amount of ethylene-acrylic acid copolymer used during emulsification is in the range of 1 to 20% by weight based on the raw material thermoplastic resin.
乳化時媒体として使用する水は原料熱可塑性樹脂１００
重量部に対して５０〜３０００重量部の範囲、好ましく
は１００〜２０００重量部の範囲である。Water used as a medium during emulsification is 100% of the raw material thermoplastic resin.
It is in the range of 50 to 3000 parts by weight, preferably in the range of 100 to 2000 parts by weight, based on parts by weight.
水の使用料がそれ以下では、カーボンブラックを含有す
る所望の粒子径の熱可塑性樹脂を安定に得ることが難し
く、粗大粒子径の熱可塑性樹脂が生成する場合もあり好
ましくなく、水の使用量がそれ以上になると反応器容積
に対する微粉末の取得の効率が悪くなり、工業的に不利
である。乳化方法は必要ならばＮ２など不活性ガスによ
り置換した耐圧オートクレープにまず水，あるいは蒸気
を入れ、次いであらかじめロール，ニーダーなどによ
り、カーボンブラツクを充分均一に混合した原料熱可塑
性樹脂，エチレンオキシド−プロピレンオキシド共重合
体，必要ならばエチレン−アクリル酸共重合体を入れ、
系内を密閉し、所定の温度まで昇温する。If the amount of water used is less than that, it is difficult to stably obtain a thermoplastic resin having a desired particle size containing carbon black, and a thermoplastic resin having a coarse particle size may be generated, which is not preferable. Is more than that, the efficiency of obtaining the fine powder with respect to the reactor volume becomes poor, which is industrially disadvantageous. Emulsification method such as N 2, if necessary first water in a pressure autoclave was replaced by an inert gas or put steam, and then advance the roll, by a kneader or the like, thoroughly mixed uniformly the carbon black raw material thermoplastic resin, ethylene - Propylene oxide copolymer, ethylene-acrylic acid copolymer if necessary,
The system is closed and the temperature is raised to a predetermined temperature.
通常はジャケットへ油，スチームなどを送入することに
より加熱し、必要ならば撹拌を行なって溶融を促進す
る。Normally, oil, steam, etc. are fed into the jacket for heating, and if necessary, stirring is performed to promote melting.
別法として水および蒸気を所定の温度まで昇温した耐圧
オートクレープ中に圧送などの方法でカーボンブラック
を含有する原料熱可塑性樹脂，エチレンオキシド−プロ
ピレンオキシド共重合体，必要ならばエチレン−アクリ
ル酸共重合体を添加する方法も採用できる。Alternatively, a raw material thermoplastic resin containing carbon black, ethylene oxide-propylene oxide copolymer, and ethylene-acrylic acid copolymer if necessary, may be prepared by pressure-feeding in a pressure-resistant autoclave in which water and steam are heated to a predetermined temperature. A method of adding a polymer can also be adopted.
温度，圧力条件は使用する熱可塑性樹脂の種類により異
なるが、一般的にはより高温，高圧の方が目的に合致し
た微粉末が得られる場合が多いが、ポリオレフィンの分
解や分散剤の分解などを考慮して条件を選定すればよ
い。加熱は原料熱可塑性樹脂のその乳化温度における溶
融指数が２０以上になる温度にまで行なう。例えば、熱
可塑性樹脂がポリエチレンの場合は、約２００℃程度ま
で、ポリスチレンの場合は、約１５０℃程度まで加熱す
る。そのときの系内圧力はおおむねその温度に対応する
水の蒸気圧を示す。昇温後の内容物の撹拌はオートクレ
ープの大きさ，仕込量などによって異なるが，通常２分
〜２時間撹拌翼先端速度は１〜５ｍ／秒で充分であり、
特に強力な撹拌は必要としない。以下実施例により本発
明を説明する。かくして得られた内容物は乳化液状態で
あり、これを常法により濾過乾燥して本発明のカーボン
ブラック含有真球状熱可塑性樹脂微粉末を得ることがで
きる。The temperature and pressure conditions vary depending on the type of thermoplastic resin used, but in general, higher temperatures and higher pressures often produce fine powders that match the purpose, but decomposition of polyolefin, decomposition of dispersants, etc. The condition may be selected in consideration of the above. The heating is performed until the melting index of the raw material thermoplastic resin at the emulsification temperature becomes 20 or more. For example, when the thermoplastic resin is polyethylene, it is heated to about 200 ° C, and when it is polystyrene, it is heated to about 150 ° C. The pressure in the system at that time generally indicates the vapor pressure of water corresponding to the temperature. The stirring of the contents after the temperature rise depends on the size of the autoclave, the charging amount, etc., but usually the stirring blade tip speed of 1 to 5 m / sec is sufficient for 2 minutes to 2 hours.
No particularly strong agitation is required. The present invention will be described below with reference to examples. The content thus obtained is in an emulsion state, and the carbon black-containing true spherical thermoplastic resin fine powder of the present invention can be obtained by filtering and drying this in a conventional manner.
実施例１ 直径５２mmのプロペラ型 撹拌羽根を備えた内径９３m
m，高さ２４０mmの内容積１の耐圧オートクレーブに
純水３４０ｇと、あらかじめニーダーを用いカーボンブ
ラック（三菱化成社製，商品名；カーボンブラック＃５
０）３ｇと溶融混合したポリエチレン（三洋化成社製，
商品名；サンワックス165−Ｐ）６０ｇ，エチレンオキ
シド−プロピレンオキシド共重合体 Ｘ＝126，Ｙ＝54，Ｚ＝126（旭電化社製；商品名，ブル
ロニックＦ−108）３０ｇとエチレン−アクリル酸共重
合体（ダウケミカル社製：商品名 ＥＡＡ XO-2375-3
3）６ｇ、苛性ソーダー0.07gを仕込み密閉する。次いで
オートクレーブ外部より加熱を行ない、オートクレーブ
内部の温度を２００℃まで昇温した。圧力はゲージ圧で
１７Kg/cm2を示した。撹拌機を始動させ、毎分1000回転
で１５分間撹拌した。撹拌翼先端速度は、2.7m/秒であ
る。次いで冷却を行ない、内温が９０℃になったところ
で内容物をオートクレーブより取出した。内容物は、乳
化液状態であり、これを分析したところ平均粒子径は5.
3ミクロンであった。Example 1 Propeller type having a diameter of 52 mm, inner diameter 93 m equipped with a stirring blade
Carbon black (manufactured by Mitsubishi Kasei Co., Ltd., trade name; carbon black # 5) with 340 g of pure water in a pressure-resistant autoclave with an internal volume of 1 and a height of 240 mm and a volume of 1
0) Polyethylene melt-mixed with 3 g (manufactured by Sanyo Kasei Co.,
Product name: Sun wax 165-P) 60 g, ethylene oxide-propylene oxide copolymer 30 g of X = 126, Y = 54, Z = 126 (manufactured by Asahi Denka Co., Ltd .; trade name, Bluronic F-108) and ethylene-acrylic acid copolymer (manufactured by Dow Chemical Co .: trade name EAA XO-2375-3)
3) Charge 6g and caustic soda 0.07g and seal. Next, heating was performed from the outside of the autoclave to raise the temperature inside the autoclave to 200 ° C. The pressure was a gauge pressure of 17 kg / cm 2 . The stirrer was started and stirred at 1000 rpm for 15 minutes. The stirring blade tip speed is 2.7 m / sec. Then, cooling was performed, and when the internal temperature reached 90 ° C., the contents were taken out from the autoclave. The content was in an emulsion state, and the analysis showed that the average particle size was 5.
It was 3 microns.
実施例２ ポリエチレンの代わりにポリスチレン（三洋化成社製：
商品名ハイマーＳＴ−９５）を用い、オートクレーブ内
の温度を１５０℃まで昇温する以外は、実施例１と同様
に乳化を行ない、冷却後内容物を取出した。内容物は乳
化液状態であり、これを分析したところ、平均粒子径は
15.2ミクロンであった。Example 2 Instead of polyethylene, polystyrene (manufactured by Sanyo Kasei Co., Ltd .:
Emulsification was performed in the same manner as in Example 1 except that the temperature inside the autoclave was raised to 150 ° C. using a trade name Heimer ST-95), and the contents were taken out after cooling. The contents were in an emulsion state, and when analyzed, the average particle size was
It was 15.2 microns.
実施例３ ポリスチレンの代わりにスチレン−アクリル系共重合体
（三洋化成社製，商品名；ハイマーSBM-100）を用いた
以外は実施例２と同様に乳化を行ない、冷却後内容物を
取出した。内容物は乳化液状態であり、これを分析した
ところ、平均粒子径は13.7ミクロンであった。Example 3 Emulsification was performed in the same manner as in Example 2 except that a styrene-acrylic copolymer (manufactured by Sanyo Kasei Co., trade name; Hymer SBM-100) was used instead of polystyrene, and the contents were taken out after cooling. . The content was in an emulsion state and was analyzed to find that the average particle size was 13.7 microns.
実施例４ 実施例１においてエチレン−アクリル酸共重合体を添加
しなかったこと以外は実施例１と同様に操作して、乳化
液状物を得た。これを分析したところ、平均粒子径は1
0.2ミクロンであった。Example 4 An emulsion liquid was obtained in the same manner as in Example 1 except that the ethylene-acrylic acid copolymer was not added. When this was analyzed, the average particle size was 1
It was 0.2 micron.
本発明の方法によれば、流動性のすぐれたカーボンブラ
ック含有真球状微粉末が得られる。According to the method of the present invention, carbon black-containing true spherical fine powder having excellent fluidity can be obtained.
また製造の危険性についても全く問題はないので工業上
有利な方法を提供することができる。Further, since there is no problem in manufacturing risk, an industrially advantageous method can be provided.
───────────────────────────────────────────────────── 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 101/00 Ｃ０９Ｃ 1/56 ＰＢＪ 6904−4Ｊ // Ｇ０３Ｇ 9/087 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display area C08L 101/00 C09C 1/56 PBJ 6904-4J // G03G 9/087
Claims (7)
を微粉末化するにあたり、水を媒体とし、エチレンオキ
シド−プロピレンオキシド共重合体の存在下、加熱加圧
下に溶融撹拌して乳化液を得、これを熱可塑性樹脂の軟
化点以下の温度に冷却することを特徴とする熱可塑性樹
脂の微粉末化方法。1. When pulverizing a thermoplastic resin containing carbon black into fine powder, water is used as a medium in the presence of an ethylene oxide-propylene oxide copolymer, and the mixture is stirred under heat and pressure to obtain an emulsion. Is cooled to a temperature equal to or lower than the softening point of the thermoplastic resin.
１００重量部に対し、２０重量部以下である特許請求の
範囲(1)記載の方法。2. The method according to claim 1, wherein the content of carbon black is 20 parts by weight or less based on 100 parts by weight of the thermoplastic resin.
求の範囲(1)記載の方法。3. The method according to claim 1, wherein the thermoplastic resin is polyethylene.
求の範囲(1)記載の方法。4. The method according to claim 1, wherein the thermoplastic resin is polystyrene.
体である特許請求の範囲(1)記載の方法。5. The method according to claim 1, wherein the thermoplastic resin is a styrene-acrylic polymer.
し、１００〜２０００重量部である特許請求の範囲(1)
記載の方法。6. A method according to claim 1, wherein the amount of water is 100 to 2000 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
The method described.
重合体の量が、熱可塑性樹脂に対し、３〜６０重量％で
ある特許請求の範囲(1)記載の方法。7. The method according to claim 1, wherein the amount of the ethylene oxide-propylene oxide copolymer is 3 to 60% by weight based on the thermoplastic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60154476A JPH06850B2 (en) | 1985-07-12 | 1985-07-12 | Method for pulverizing thermoplastic resin containing carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60154476A JPH06850B2 (en) | 1985-07-12 | 1985-07-12 | Method for pulverizing thermoplastic resin containing carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6214936A JPS6214936A (en) | 1987-01-23 |
| JPH06850B2 true JPH06850B2 (en) | 1994-01-05 |
Family
ID=15585084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60154476A Expired - Fee Related JPH06850B2 (en) | 1985-07-12 | 1985-07-12 | Method for pulverizing thermoplastic resin containing carbon black |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06850B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6272727A (en) * | 1985-09-26 | 1987-04-03 | Konishiroku Photo Ind Co Ltd | Production of fine resin particle |
| IL116552A (en) * | 1995-01-10 | 2001-09-13 | Cabot Corp | Carbon black compositions, polymer compositions including the carbon black compositions and articles of manufacture including the polymer compositions |
| US5688624A (en) * | 1997-01-06 | 1997-11-18 | Xerox Corporation | Liquid developer compositions with copolymers |
| JP4620831B2 (en) * | 2000-04-26 | 2011-01-26 | 住友精化株式会社 | Method for producing aqueous polyester resin dispersion |
-
1985
- 1985-07-12 JP JP60154476A patent/JPH06850B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6214936A (en) | 1987-01-23 |
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