KR100846764B1 - Method of preparing toner by suspension process with reverse-neutralization - Google Patents

Method of preparing toner by suspension process with reverse-neutralization Download PDF

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KR100846764B1
KR100846764B1 KR1020010079880A KR20010079880A KR100846764B1 KR 100846764 B1 KR100846764 B1 KR 100846764B1 KR 1020010079880 A KR1020010079880 A KR 1020010079880A KR 20010079880 A KR20010079880 A KR 20010079880A KR 100846764 B1 KR100846764 B1 KR 100846764B1
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toner
weight
acid
water
monomer
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KR1020010079880A
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KR20030049625A (en
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김도균
김효성
김충길
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김도균
삼성전자주식회사
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Priority to KR1020010079880A priority Critical patent/KR100846764B1/en
Priority to JP2003553343A priority patent/JP4095554B2/en
Priority to CNB028281578A priority patent/CN100414441C/en
Priority to PCT/KR2002/002358 priority patent/WO2003052520A1/en
Priority to AU2002366482A priority patent/AU2002366482A1/en
Priority to US10/498,919 priority patent/US7723006B2/en
Priority to DE60231837T priority patent/DE60231837D1/en
Priority to EP02791088A priority patent/EP1459136B1/en
Publication of KR20030049625A publication Critical patent/KR20030049625A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/0802Preparation methods
    • G03G9/0804Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/087Binders for toner particles
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/09Colouring agents for toner particles
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00Developers
    • G03G9/08Developers with toner particles
    • G03G9/097Plasticisers; Charge controlling agents

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  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

본 발명은 (1) 말단에 카르복실기를 갖는 선상 수지중합체를 제조하는 단계The present invention (1) preparing a linear resin polymer having a carboxyl group at the terminal

(2) 분산제 기능을 가지도록 단계(1)의 선상 수지중합체를 염기성 화합물과 반응시켜 중화하고 이 반응혼합물을 물에 용해시켜서 수분산 수지조성물을 얻는 단계; (3) 상기 수분산 수지조성물에 착색제, 전하제어제, 및 이형제를 넣고 분산시켜서 착색수지 분산물을 제조하는 단계; 및 (4) 산성화합물을 용해한 수중에 전단력을 가하면서 단계(3)의 착색수지 분산물을 적가하여 역(탈)중화를 동반한 현탁처리시켜 5∼15㎛ 입자경의 토너입자를 생성시키는 단계를 포함하는 토너 제조방법을 제공한다. 또한 본 발명의 토너는 염기성 화합물을 용해한 수용액에 재용해 가능함으로 이를 다시 역(탈)중화 현탁시키면 토너입자가 얻어짐으로 소비자가 사용한 후 발생되는 폐토너를 수거하여 재생할 수 있으므로 친환경적인 사회적 가치를 가지는 토너제조방법이다.(2) neutralizing the linear resin polymer of step (1) with a basic compound to have a dispersant function and dissolving the reaction mixture in water to obtain a water-dispersible resin composition; (3) preparing a colored resin dispersion by dispersing a colorant, a charge control agent, and a release agent in the aqueous dispersion resin composition; And (4) dropping the colored resin dispersion of step (3) dropwise while applying shear force to the water in which the acidic compound is dissolved to suspend the suspension with reverse (de) neutralization to produce toner particles having a particle diameter of 5 to 15 µm. It provides a toner manufacturing method comprising. In addition, the toner of the present invention can be re-dissolved in an aqueous solution in which the basic compound is dissolved. If the toner is de-neutralized again, the toner particles are obtained, so that the waste toner generated by the consumer can be collected and recycled. Is a toner manufacturing method.

Description

역(탈)중화 현탁법에 의한 토너 제조방법{Method of preparing toner by suspension process with reverse-neutralization}Method of preparing toner by suspension process with reverse-neutralization

본 발명은 전자사진용 중합토너에 관한 것으로, (1) 말단에 카르복실기를 갖는 선상 수지중합체를 제조하는 단계; (2) 분산제 기능을 가지도록 단계(1)의 선상 수지중합체를 염기성 화합물과 반응시켜 중화하고 이 반응혼합물을 물에 용해시켜서 수분산 수지조성물을 얻는 단계; (3) 상기 수분산 수지조성물에 착색제, 전하제어제, 및 이형제를 넣고 분산시켜서 착색수지 분산물을 제조하는 단계; 및 (4) 산성화합물을 용해한 수중에 전단력을 가하면서 단계(3)의 착색수지 분산물을 적가하여 역(탈)중화를 동반한 현탁처리시켜 5∼15㎛ 입자경의 토너입자를 생성시키는 단계를 포함하는 토너 제조방법에 관한 것이다.The present invention relates to an electrophotographic polymerized toner, comprising the steps of: (1) preparing a linear resin polymer having a carboxyl group at its terminal; (2) neutralizing the linear resin polymer of step (1) with a basic compound to have a dispersant function and dissolving the reaction mixture in water to obtain a water-dispersible resin composition; (3) preparing a colored resin dispersion by dispersing a colorant, a charge control agent, and a release agent in the aqueous dispersion resin composition; And (4) dropping the colored resin dispersion of step (3) dropwise while applying shear force to the water in which the acidic compound is dissolved to suspend the suspension with reverse (de) neutralization to produce toner particles having a particle diameter of 5 to 15 µm. It relates to a toner manufacturing method comprising.

전자사진법이나 정전기록법 등은 대전, 노광공정에 의하여 감광체에 정전잠상을 형성하고 이를 현상제로 현상하여 가시화된 토너상을 미디어에 전사하고 정착공정을 거쳐서 용융가시화한다. 이 과정에서 선명하고 우수한 화상의 생성유무는 현상부 과정에서는 잠상에 부착되는 토너의 전기적 특성 및 입경의 크기가 미세하고 균일함의 정도, 토너입자단위에 각종 첨가제가 정교하게 분산된 정도에 따라 현상화 잔 상태가 결정되며 정착부과정에서는 정착되는 토너의 용융투성과 이 형성의 정도에 따라 화질이 결정된다. 그래서 종래부터 토너기능의 개선과 개발목적이 이런관점에 집중되었다. 토너제조방법에는 크게 분쇄법과 중합법이 있다. 분쇄법은 결착수지와 착색제, 전하제어제, 이형제를 혼련기에 넣어 가열에 의해서 용융혼합한 후에 분쇄하여 분급하여 토너를 만든다. 이 방법에 의하면 정교한 분산이 불가능하여 첨가제의 기능을 제대로 살릴 수가 없으며 입자분포가 넓은 관계로 분급에 의한 생산물이 소량으로 생산수율이 낮고 구형상태의 토너가 생산되지 않으므로 성능이 부족한 토너가 생산될 위험이 상존한다. 중합법에는 에말죠 응집법과 현탁중합법이 있는데 에말죤 응집법은 중합성 모노마를 유화 중합시킨후 라텍스를 만들고, 여기에 착색제, 전하제어제, 이형제 등을 혼합하여 가열을 수반한 교반을 계속하여 수시간 내지는 수십시간 소요하여 에말죠입자끼리 응집을 유도하여 단계적으로 응집크기를 양생하여 원하는 입자를 얻기 때문에 장시간 응집 과정에서 입자분포가 넓은 불안정한 제법으로 이 기술은 일본 특개소 63-282752, 동 63-282756, 일본 특개평 6-250439, 미국특허 5352521, 동 4996127, 동 4797339, 대한민국특허 1997-033856, 동 1998-073192, 동 특 2001-037273에 제한된 토너제법이 있지만 이들 모두가 장시간 가열하여 응집에 의해 생성됨으로 미세입자가 불가능한 불안정한 제조법이고 또한 분자량이 너무커서 용융점탄성이 높아 정착성에 문제가 되고 있다. Electrophotographic and electrostatic recording methods form electrostatic latent images on the photoconductor by charging and exposing, developing them with a developer, transferring the visualized toner image to the media, and melting and visualizing the same through a fixing process. In this process, whether or not a clear and excellent image is generated is developed according to the degree of fineness and uniformity of the electrical characteristics and particle size of the toner attached to the latent image in the developing part process and the degree of finely dispersed various additives in the toner particle unit. The remaining state is determined, and in the fixing unit process, the image quality is determined by the melt permeability of the toner to be fixed and the degree of formation thereof. Therefore, the purpose of improving and developing the toner function has been focused on this point. Toner production methods are classified into a pulverization method and a polymerization method. In the pulverization method, a binder resin, a colorant, a charge control agent, and a release agent are put into a kneader, melt mixed by heating, and then pulverized and classified to form a toner. According to this method, it is impossible to precisely disperse the additives, so that the function of the additives can not be properly used, and because of the large particle distribution, the product produced by classification is low in production yield and the spherical toner is not produced. This remains. There are two types of polymerization methods: emal coagulation and suspension polymerization. The emal coagulation method emulsion-polymerizes the polymerizable monoma, forms a latex, and mixes a colorant, a charge control agent, a release agent, and the like, and continues stirring with heating. It takes time or tens of hours to induce aggregation between emerald particles to cure the coagulation size step by step to obtain the desired particles.This technique is an unstable method with a wide particle distribution during a long time aggregating process. 282756, Japanese Patent Laid-Open No. 6-250439, U.S. Patent 5352521, 4996127, 4797339, Korea Patent 1997-033856, 1998-0773192, and Japanese Patent No. 2001-037273 have all the toner preparations limited. It is an unstable manufacturing method in which fine particles are impossible due to the production, and also has a high molecular weight and high melt viscoelasticity, which is a problem in fixability.                         

현탁중합법은 모노마에 착색제, 전하제어제, 이형제를 미리 혼합하고 고전단력으로 분산하여 원하는 입자경의 모노마 액적을 형성한 후 안정제를 첨가하고 중합하여 생성된 중합체가 입자화 되어 침전하면 이를 회수하여 토너를 제조하는 방법으로 함유된 첨가제가 중합반응을 방해하여 중합도 조절이 어렵고 안정성이 좋지않아 이상 반응에 의한 불량품이 생성될 가능성이 높을 뿐만 아니라 생성된 토너입자는 높은 연화점 때문에 정착성에 문제점이 발생한다. 이 기술은 일본 특개소 61-118758, 일본특개평 7-128908, 동 9-311503, 미국특허 5219697, 동 5288577, 대한민국특허공개 2000-057424, 동 특2001-037032, 대한민국특허등록 10-285183에 제안된 토너제조법이 있으나 이들 모두가 불안정한 반응에 의한 중합도 조절이 어렵고 정착성의 문제점이 노출되고 있다.The suspension polymerization method premixes the colorant, the charge control agent and the release agent to the monoma and disperses it with high shear force to form monoma droplets of the desired particle size, and then adds a stabilizer and polymerizes the polymer produced by granulation to precipitate and recover the toner. The additives contained in the method of inhibiting the polymerization reaction are difficult to control the degree of polymerization and the stability is not good, it is highly likely to produce defective products due to the abnormal reaction, and the resulting toner particles have a problem in fixability due to the high softening point. This technique is proposed in Japanese Patent Laid-Open No. 61-118758, Japanese Laid-Open Patent Publication No. 7-128908, East 9-311503, US Patent 5219697, East 5288577, Korea Patent Publication 2000-057424, Korea Patent 2001-037032, and Korea Patent Registration 10-285183 Although there is a toner manufacturing method, all of them are difficult to control the degree of polymerization due to unstable reaction and the problem of fixability is exposed.

본 발명자는 상기의 문제점을 해결하기위해 입자경이 미세하고 입자분포가 좁은 토너로서 화상농도의 안정성 및 포그가 발생하지 않으며 내옵셋성이 우수하고 오래 사용해도 토너의 열화가 발생하지 않고 정착성, 박리성, 고화질의 화상을 얻을 수 있는 토너를 제조함에 있어서 결착수지가 분자내에 계면활성기능을 갖는 관능기에 도입하면 수분산수지 조성물이 가능하게 되어 이를 역(탈)중화를 동반한 현탁작용으로 물에 쉽게 또한 순간적으로 현탁시켜 입자화가 가능한 토너수지 조성물을 얻을 수 있다는 것을 알게되어 미세한 입자경과 좁은 분포도를 가지며 높은 수율로 토너입자를 제조하는 것이 특징인 정전하현상용 토너제조 방법을 제공하는 것이다.In order to solve the above problems, the present inventors have a fine particle size and a narrow particle distribution, which do not generate stability and fog of image density, have good offset resistance, and do not deteriorate toner even after long use. In the production of toner capable of obtaining high-quality and high-quality images, when the binder resin is introduced into a functional group having an interfacial function in the molecule, a water-dispersible resin composition becomes possible, and this is suspended in water by the suspension action accompanied with reverse (de) neutralization. The present invention provides a method for producing a toner for electrostatic charge, which is characterized by producing a toner particle having a fine particle size and a narrow distribution and having a high yield, by finding that the toner resin composition which can be easily and instantaneously suspended into particles can be obtained.

본 발명자등은 상기의 문제점을 해소하기 위하여 예의 연구한 결과 다음과 같은 구성이 그 문제를 해결할 수 있다는 결론에 도달하여 본 발명을 완성하였다.MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, the present inventors came to the conclusion that the following structure can solve the problem, and completed this invention.

본 발명은 (1) 말단에 카르복실기를 갖는 선상 수지중합체를 제조하는 단계;
(2) 분산제 기능을 가지도록 단계(1)의 선상 수지중합체를 염기성 화합물과 반응시켜 중화하고 이 반응혼합물을 물에 용해시켜서 수분산 수지조성물을 얻는 단계;
(3) 상기 수분산 수지조성물에 착색제, 전하제어제, 및 이형제를 넣고 분산시켜서 착색수지 분산물을 제조하는 단계; 및
(4) 산성화합물을 용해한 수중에 전단력을 가하면서 단계(3)의 착색수지 분산물을 적가하여 역(탈)중화를 동반한 현탁처리시켜 5∼15㎛ 입자경의 토너입자를 생성시키는 단계를 포함하는 토너 제조방법에 관한 것이다.
상기 (1)단계의 선상 수지 중합체는 분자내에 카르복실기를 갖는 수평균분자량 5,000∼50,000, 산가 40∼110mgKOH/g인 수지중합체로서 용액중합법으로 제조된다.
The present invention (1) preparing a linear resin polymer having a carboxyl group at the terminal;
(2) neutralizing the linear resin polymer of step (1) with a basic compound to have a dispersant function and dissolving the reaction mixture in water to obtain a water-dispersible resin composition;
(3) preparing a colored resin dispersion by dispersing a colorant, a charge control agent, and a release agent in the aqueous dispersion resin composition; And
(4) adding the colored resin dispersion of step (3) dropwise while applying shear force to the dissolved water of the acidic compound to suspend treatment with reverse (de) neutralization to produce toner particles having a particle diameter of 5 to 15 탆; It relates to a toner manufacturing method.
The linear resin polymer of step (1) is a resin polymer having a number average molecular weight of 5,000 to 50,000 and an acid value of 40 to 110 mgKOH / g having a carboxyl group in a molecule, and is prepared by solution polymerization.

상기 단계 (3)의 착색수지 분산물에 중량평균분자량이 100,000∼1,000,000이고, 겔함량이 5~50중량%인 유화중합 생성물인 가교된 고분자량 수분산 라텍스를 더 혼합분산시킬 수 있다.The crosslinked high molecular weight aqueous dispersion latex, which is an emulsion polymerization product having a weight average molecular weight of 100,000 to 1,000,000 and a gel content of 5 to 50% by weight, may be further mixed and dispersed in the colored resin dispersion of step (3).

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상기 단계 (4)의 현탁 처리시켜 입자화하고 가열하여 토너를 안정화시킬 수 있다.
상기 단계 (5) 이후에 토너입자를 여과하고 수세하는 과정을 2∼3번 반복하여 토너입자를 수득하고 45℃에서 진공건조시켜 착색토너입자 조성물을 제조할 수 있다.
The toner can be stabilized by suspending in step (4) to granulate and heat.
After the step (5), the process of filtration and washing with toner particles is repeated 2-3 times to obtain toner particles, followed by vacuum drying at 45 ° C. to prepare colored toner particle compositions.

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(7) 단계 (6)에서 얻어진 착색토너 입자조성물 100중량부에 대하여 소수성 실리카 1~5중량부를 가하여 헨셀믹서로 혼합하여 정전하상 현상용 토너를 얻을 수 있다.(7) 1 to 5 parts by weight of hydrophobic silica is added to 100 parts by weight of the colored toner particle composition obtained in step (6), followed by mixing in a Henschel mixer to obtain an electrostatic charge image developing toner.

본 발명을 더욱 상세히 설명하면 다음과 같다.The present invention is described in more detail as follows.

본발명에서 선상저분자량 중합체는 용액중합법에 의해 제조된다. 사용할 수 있는 단량체는 방향족비닐계단량체 및 아크릴레이트 단량체 및 상기 단량체와 공중합가능한 카르복실기를 갖는 단량체를 사용할 수 있다. 방향족비닐계 단량체는 스티렌, 메틸스티렌, 디메틸스틸렌, 할로겐화 스티렌 등이고, 단량체 혼합물 전체에 대하여 20∼45중량%의 양으로 사용됨이 바람직하다. 아크릴레이트계 단량체는 메틸 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 2-에틸헥실 아크릴레이트, 글리시딜 메타아크릴레이트등이다. 이들 중 하나 이상이 단량체 혼합물 전체에 대하여 5∼50중량%의 양으로 사용됨이 바람직하다. 상기 방향족 비닐계 단량체 및 상기 아크릴레이트계 단량체와 공중합가능한 카르복실기를 갖는 단량체는 아크릴산, 메타아크릴산, 무수마레인산, 마레인화 로진, 푸말산, 및 이타콘산으로 이루어진 군에서 선택된 적어도 하나이다. 이들 중 하나 이상이 단량체 혼합물 전체에 대하여 10∼50중량%의 양으로 사용됨이 바람직하다. 상기 단량체는 토너의 정착특성, 용융특성의 관점에서 연화점, 유리전이점을 조절하도록 조성비율을 설계하여햐 함이 바람직하다. 본 발명에서 용제는 알콜류, 케톤류, 셀솔브류, 테트라하이드로푸란, N-메틸피로리돈, 디메틸포름아미드, 디메틸아세트아미드 등을 단독 또는 혼합하여 단량체 혼합물 전체에 대하여 20∼100중량%의 양으로 사용함이 바람직하다. 이들 용제는 중합 반응이 완결되면 감압하여 완전하게 제거할 수도 있다.In the present invention, the linear low molecular weight polymer is prepared by a solution polymerization method. As the monomer that can be used, an aromatic vinyl monomer and an acrylate monomer and a monomer having a carboxyl group copolymerizable with the monomer can be used. The aromatic vinyl monomers are styrene, methyl styrene, dimethyl styrene, halogenated styrene and the like, and are preferably used in an amount of 20 to 45% by weight based on the entire monomer mixture. The acrylate monomers are methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate and the like. It is preferred that at least one of these is used in an amount of from 5 to 50% by weight, based on the total monomer mixture. The monomer having a carboxyl group copolymerizable with the aromatic vinyl monomer and the acrylate monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, marinated rosin, fumaric acid, and itaconic acid. It is preferred that at least one of these is used in an amount of from 10 to 50% by weight, based on the total monomer mixture. It is preferable that the monomer be designed in such a manner that the softening point and the glass transition point are controlled in view of the fixing property and the melting property of the toner. In the present invention, the solvent may be used alone or in combination with alcohols, ketones, cellsolves, tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like in an amount of 20 to 100% by weight based on the total monomer mixture. desirable. These solvents can also be removed by complete pressure reduction when the polymerization reaction is completed.

본 발명의 중합개시제는 벤조일퍼옥사이드, 2,2'-아조비스이소부티로니트릴, 디멜2.2아조비스(2-메틸프로피오네이트), 2,2'-아조비스(2.4-디메틸발레로니트릴), 디-t-부틸퍼록사이드, 디쿠밀퍼록사이드, 라우로일퍼록사이드, t-부탈퍼록시-2-에틸헥사노에이트등이 있다. 이 중합개시제 중에서 유용성의 라디칼 개시제가 바람직하다. 이들 사용량은 단량체 총량에 대하여 0.01∼3중량%이다.The polymerization initiator of the present invention is benzoyl peroxide, 2,2'-azobisisobutyronitrile, dimer 2.2 azobis (2-methylpropionate), 2,2'-azobis (2.4-dimethylvaleronitrile) , Di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, t-butalperoxy-2-ethylhexanoate and the like. Of these polymerization initiators, oil-soluble radical initiators are preferred. These usage amounts are 0.01 to 3 weight% with respect to the monomer total amount.

본 발명의 분자량 조정제는 t-도데실머캅탄, n-도데실머캅탄, n-옥틸머캅탄, 사염화탄소, 사브롬화탄소 등이고, 사용량은 단량체 총량에 대하여 0.01∼10중량%이다. 염기성 화합물은 수산화나트륨, 수산화칼륨, 암모니아수, 트리에틸아민, 사용량은 5∼30중량%이다.The molecular weight modifier of the present invention is t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, carbon tetrachloride, carbon tetrabromide and the like, and the amount of use thereof is 0.01 to 10% by weight based on the total amount of monomers. The basic compound is sodium hydroxide, potassium hydroxide, aqueous ammonia, triethylamine, and the amount used is 5 to 30% by weight.

본 발명의 가교된 고분자량수분산 라텍스는 유화중합법에 의하여 제조된다. 스티렌 20∼90중량%, 아크릴레이트계 단량체 5∼90중량%, 가교성단량체 5∼50중량%를 사용하며 음이온계면활성제는 소디움스테아레이트, 소디움라우릴설페이트,소디움도네실벤젠설포네이트등을 단독 또는 혼합하여 단량체 전체에 1∼20중량%사용함이 바람직하고 비이온계면활성제는 폴리옥시에틸렌노닐페닐에테르, 옥틸메투시폴리에틸옥시에타놀, 솔비탄라우릴에틸렌옥사이드부가물을 단독 또는 혼합하여 단량체 전체에 1∼30중량%사용하고 수용성 개시제로 과류산카리, 과류산암모늄, 중아류산소다. 중탄산소 등 레독스계의 산화 환원계 개시제를 단량체혼합물 전체에 대하여 0.01∼2중량%사용한다. 얻어진 가교된 고분자량 수분산 라텍스는 겔함량이 5∼50중량%, 중량평균 분자량이 100.000∼1,000,000이다.The crosslinked high molecular weight water dispersion latex of the present invention is prepared by emulsion polymerization method. 20 to 90% by weight of styrene, 5 to 90% by weight of acrylate monomer, and 5 to 50% by weight of crosslinking monomer are used. The anionic surfactants include sodium stearate, sodium lauryl sulfate, sodium donesylbenzenesulfonate, etc. Or 1 to 20% by weight of the total monomer is preferably used. The nonionic surfactant is polyoxyethylene nonyl phenyl ether, octyl methoxy polyethyloxy ethanol, sorbitan lauryl ethylene oxide adduct alone or mixed to the whole monomer. It is 1 to 30% by weight, and is a water-soluble initiator, such as carry peroxide, ammonium peroxide, and hypochlorous acid. Redox-based redox initiators such as bicarbonate are used in an amount of 0.01 to 2% by weight based on the entire monomer mixture. The resulting crosslinked high molecular weight aqueous dispersion latex has a gel content of 5 to 50% by weight and a weight average molecular weight of 100.000 to 1,000,000.

본 발명의 산성화합물은 염산, 황산, 질산, 초산, 의산, 수산, p-톨루엔술폰산이고, 사용량은 착색분산물에 대하여 5∼30중량% 사용함이 바람직하다.The acidic compound of the present invention is hydrochloric acid, sulfuric acid, nitric acid, acetic acid, acid, oxalic acid, p-toluenesulfonic acid, and the amount of the acid compound is preferably 5 to 30% by weight based on the colored dispersion.

착색제는 카본블랙, 아세틸렌블랙, 마그네타이트 등 흑색안료. 산화철황한자옐로우, 퍼머넌트예로우 등 황생안료. 프탈로시아닌블루, 바이오렛 등 청색안료. 산화철적, 카민, 톨루이진레드, 퀴나크리돈레드 등 적색안료. 프탈로시아닌그린, 크롬그린등 녹색안료등이고 결착수지에 대해서 1∼50중량%의 양으로 사용됨이 바람직하다.Colorants are black pigments such as carbon black, acetylene black and magnetite. Yellow pigment, such as iron oxide yellow Chinese yellow and permanent yellow. Blue pigments such as phthalocyanine blue and biolet. Red pigments such as iron oxide, carmine, toluzin red and quinacridone red. Green pigments such as phthalocyanine green, chromium green, and the like are preferably used in an amount of 1 to 50% by weight based on the binder resin.

전하조절제는 니그로신, 제4급암모늄, 살리실산계 금속염, 금속-아조화합물 등이있고 상품명 오리엔트사의 BONTRON N-01, BONTRON N-07, BONTRON S-34, BONTRON E-84 등이 있고 결착수지에 대해 0.5∼15중량%로 사용함이 바람직하다. 이형제는 파라핀왁스, 폴리에틸렌 왁스, 폴리프로필렌 왁스, 카나바 왁스, 몬탄왁스, 에스텔 왁스, 사졸왁스 등이 있고 결착수지에 대해 1∼30중량%사용됨이 바람직하다.Charge control agents include nigrosine, quaternary ammonium, salicylic acid-based metal salts, metal-azo compounds, and the like. Orient's BONTRON N-01, BONTRON N-07, BONTRON S-34, BONTRON E-84, etc. It is preferable to use at 0.5 to 15% by weight relative to. Release agents include paraffin wax, polyethylene wax, polypropylene wax, canava wax, montan wax, ester wax, sol wax, and the like, and are preferably used in an amount of 1 to 30% by weight based on the binder resin.

본 발명은 아래와 같이 실시예에 의해 보다 상세히 설명하지만 이들에 의해 본 발명이 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

〈제조예 1〉<Production example 1>

교반기, 환류냉각기, 온도계, 질소주입구를 갖춘 반응기예 에틸셀솔브 150g, 스티렌 250g, 2-에틸헥실아크릴레이트 120g, 아크릴산 60g, 스티렌-이소프렌디블록공중합체 30g, n-도데실머캅탄 1.1g, AIBN 0.5g을 넣고 혼합하여 2/10를 먼저넣고 교반하면서 가열하여 125℃ 45분간 반응하여 시드중합체를 제조한후 나머지를 130℃에서 3시간동안 적가첨가하여 125℃에서 6시간 반응시킨후 에틸셀솔브를 150g넣어 희석시켜 산가 75mgKOH/g, 유리전이점 35℃, 중량평균 분자량 11,000인 중합체를 만들어 20% 수산화나트륨 수용액 100g을 첨가하여 85℃에서 30분동안 중화반응시킨후 증류수 300g넣고 희석시켜서 수분산수지 수용액을 제조하였다.Reactor example with stirrer, reflux cooler, thermometer, nitrogen inlet Example: ethyl cell solution 150g, styrene 250g, 2-ethylhexyl acrylate 120g, acrylic acid 60g, styrene-isoprendiblock copolymer 30g, n-dodecyl mercaptan 1.1g, AIBN 0.5g was added, mixed 2/10 first, heated with stirring to react for 45 minutes at 125 ° C. to prepare a seed polymer, and the remainder was added dropwise at 130 ° C. for 3 hours and reacted at 125 ° C. for 6 hours, followed by ethyl cell solution. 150g was added to dilute acid value 75mgKOH / g, glass transition point 35 ℃, and weight average molecular weight 11,000 to make a polymer. Add 100g of 20% sodium hydroxide aqueous solution, neutralize reaction at 85 ℃ for 30 minutes, add 300g of distilled water, and dilute water. An aqueous resin solution was prepared.

〈제조예 2〉 <Production example 2>                     

반응기에 부틸셀솔브 150g, 스티렌 250g, 부틸아크릴레이트 120g, 아크릴산 60g, n-도데실머캅탄 1.Ig, AIBN 0.5g을 넣고 〈제조예 1〉과 동일한 방법으로 실시하여 산가 81mgKOH/g, 유리전이점 59℃, 중량평균 분자량 9,000인 중합체를 만들어 수용화하여 수분산 수지 수용액을 제조하였다.150 g of butyl cellsolve, 250 g of styrene, 120 g of butyl acrylate, 60 g of acrylic acid, 1.Ig of n-dodecylmercaptan and 0.5 g of AIBN were added and the acid value was 81 mgKOH / g, glass field was prepared in the same manner as in <Preparation Example 1>. Advantages A polymer having a weight average molecular weight of 9,000 at 59 ° C. was prepared and hydrated to prepare an aqueous dispersion resin solution.

〈라텍스 제조예 A〉<Latex Production Example A>

교반기, 환류냉각기, 온도계, 질소주입구를 갖춘 반응기에 스티렌 100g, 메틸 메타크릴레이트 100g, 에틸 아크릴레이트 100g, 아크릴산 6g, 디비닐벤젠 10g을 혼합하여 음이온 유화제 9g, 비이온 유화제 16g, 증류수 190g을 혼합한 용액에 적가하여 프레에멀젼을 만든후 다른 반응기에 음이온 유화제 4g, 비이온유화제 8g, 과류산 카리 1.5g, 증류수 200g을 혼합한 용액을 80℃로 가열하여 3시간동안 적가하여 중합반응을 시키면서 90℃로 승온하여 중아류산소다 1.5g을 증류수 30g의 수용액을 적가하면서 5시간동안 계속반응시켜서 가교된 고분자량 에멀젼라텍스를 제조한다. 유리전이점 65℃, 중량평균분자량 300,000, 겔함량 45중량%이다.In a reactor equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen inlet, 100 g of styrene, 100 g of methyl methacrylate, 100 g of ethyl acrylate, 6 g of acrylic acid, and 10 g of divinylbenzene were mixed, and 9 g of anionic emulsifier, 16 g of nonionic emulsifier, and 190 g of distilled water were mixed. After adding dropwise to one solution to form a preemulsion, a solution containing 4 g of anionic emulsifier, 8 g of nonionic emulsifier, 1.5 g of peroxide carriage, and 200 g of distilled water was heated to 80 ° C. and added dropwise for 3 hours to conduct a polymerization reaction. The reaction mixture was heated to ℃, and 1.5 g of sodium hypochlorous acid was continuously added for 30 hours while dropwise adding an aqueous solution of 30 g of distilled water to prepare a crosslinked high molecular weight emulsion latex. Glass transition point 65 degreeC, weight average molecular weight 300,000, and gel content 45 weight%.

〈라텍스 제조예 B〉<Latex Production Example B>

스티렌 250g, 부틸아크릴레이트 120g,아크릴산 7g, 디비닐벤젠 15g, 음이온 유화제 10g, 비이온유화제 16g, 증류수 190g을 혼합하고 적가하여 프레에멀젼을 만든후 다른 반응기에 음이온 유화제 5g, 비이온유화제 8g 과류산카리 1.5g, 증류수 200g, 중아류산소다 1.5g을 증류수 30g 수용액을 〈라텍스 제조예 A〉와 동일한 방법으로 제조한다. 유리전이점 55℃,중량평균분자량 350,000, 겔함량 50중량%이다.250 g of styrene, 120 g of butyl acrylate, 7 g of acrylic acid, 15 g of divinylbenzene, 10 g of anionic emulsifier, 16 g of nonionic emulsifier, and 190 g of distilled water are mixed and added dropwise to form a preemulsion. 1.5 g of carry, 200 g of distilled water, and 1.5 g of sodium bisulfite were prepared in the same manner as in <Latex Production Example A> in a 30 g aqueous solution of distilled water. Glass transition point is 55 ℃, weight average molecular weight 350,000, gel content 50% by weight.

〈실시예 1〉 <Example 1>                     

카본블랙(PRINTEX 150T) 3g, 전하제어제(BONTRON S-34) 0.5g,증류수 30g을 혼합하여 〈제조예 1〉의 수지용액에 넣고 고속분산기로 분산시켜서 착색수지 분산액을 만들고 여기에 이형제를 혼합하여 또다시 분산시켜서 착색수지 분산액을 만든다. 다른용기에 염산 5g, 증류수 100g을 넣어 혼합한 수용액을 만들어 상기의 착색수지 분산액을 서서히 첨가하여 50℃에서 고속교반하면서 역(탈)중화를 동반한 현탁처리시켜 토너입자를 형성함으로써 입자경이 9㎛평균체적직경, 1.29 GSD를 갖는 포테이토 형상의 토너입자를 99%수율로 얻어 토너입자를 수세하고 여과하고 건조하여 건조된 토너입자 조성물 100중량부에 대하여 1중량부의 소수성실리카(데구사 R972)를 헨셀믹서로 혼합하여 정전하 현상토너를 제조하였다. 이 토너를 시판 삼성전자의 레이져프리터(ML6060)를 개조하여 만든 카트리지에 넣고 화상을 형성한 결과 선명한 고화질의 화상을 얻을 수 있었다.3 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 30 g of distilled water are mixed, dispersed in a resin solution of <Production Example 1>, dispersed with a high-speed disperser to form a colored resin dispersion, and a release agent is mixed there. To disperse again to form a colored resin dispersion. 5g of hydrochloric acid and 100g of distilled water were mixed in another container to make an aqueous solution, and the colored resin dispersion was added slowly, and then stirred at high temperature at 50 ° C with suspension (de) neutralization to form toner particles. Obtained toner particles having a mean volume diameter of 1.29 GSD in 99% yield, washed with toner particles, filtered and dried, and 1 part by weight of hydrophobic silica (Degussa R972) was applied to 100 parts by weight of the dried toner particle composition. Electrostatic developing toner was prepared by mixing with a mixer. The toner was placed in a cartridge made by remodeling a commercially available laser scanner (ML6060) of Samsung, and images were formed to obtain clear, high-quality images.

〈실시예 2〉<Example 2>

카본블랙(PRINTEX 150T) 3g, 전하제어제(BONTRON S-34) 0.5g,증류수 30g을 혼합하여 〈제조예 2〉의 수지용액 50g에 넣고 고속분산기로 분산시켜서 착색수지분산액을 만들고 여기에 〈라텍스 제조예 A〉의 라텍스 50g을 넣고 혼합하여 재차 분산시켜서 착색수지 분산액을 만든다. 다른 용기에 염산 3.5g, 증류수 100g을 넣고 혼합한 수용액을 만들어 여기에 상기의 착색수지 분산액을 서서히 첨가하여 50℃에서 고속교반하면서 역(탈)중화를 동반한 현탁 처리시켜 토너입자를 형성함으로써 입자경이 7㎛, 평균체적직경 1.27 GSD를 갖는 포테이토 형상의 토너입자를 99%수율로 얻어 토너입자를 수세하고 여과하고 건조하여 건조된 토너입자 조성물 100 중량부에 대하여 1중량부의 소수성실리카(데구사 R972)를 헨셀믹서로 혼합하여 정전하 현상토너를 제조하였다. 이 토너를 시판 삼성전자의 레이져프리터(ML6060)를 개조하여 만든 카트리지에 넣고 화상을 형성한 결과 선명한 고화질의 화상을 얻을 수 있었다.3 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 30 g of distilled water are mixed and placed in 50 g of the resin solution of <Production Example 2> and dispersed with a high-speed disperser to form a colored resin dispersion. 50 g of latex of Preparation Example A> was added, mixed, and dispersed again to form a colored resin dispersion. 3.5 g of hydrochloric acid and 100 g of distilled water were added to another container to make an aqueous solution, and the colored resin dispersion was slowly added thereto, followed by suspension treatment with reverse (de) neutralization at 50 ° C. to form toner particles. Obtained toner particles having a shape of 7 µm and an average volume diameter of 1.27 GSD in 99% yield were washed with water, filtered and dried to obtain 1 part by weight of hydrophobic silica (Degussa R972) based on 100 parts by weight of the dried toner particle composition. ) Was mixed with a Henschel mixer to produce a static charge developing toner. The toner was placed in a cartridge made by remodeling a commercially available laser scanner (ML6060) of Samsung, and images were formed to obtain clear, high-quality images.

본 발명에 따른 토너입자형성 방법은 종래의 기술과 전혀다른 새로운 원천 기술인 역(탈)중화를 동반하는 현탁작용을 도입함으로써 수중에서 쉽게 순간적으로 입자조성물을 형성시키는 제조방법으로 생성되는 토너입자가 입자경이 5~15㎛로 미세하고 입자분포가 1.30 GSD이하의 좁은 분포라서 포그 현상이 없고 오래 사용하여도 열화되지 않는 정착성이 좋고 내옵셋성이 우수한 고화질의 화상을 얻을 수 있는 정전화상 현상용 토너제조방법을 제공하는 것이다. 또한 재생이 가능하므로 폐토너를 수거하여 재활용이 가능한 환경친화적인 정전화상 현상용 토너제조 방법이다.The toner particle forming method according to the present invention is a toner particle produced by the manufacturing method of forming a particle composition easily and instantly in water by introducing a suspension action with de-neutralization, which is a new source technology that is completely different from the conventional technology. This toner for electrostatic image development, which has a fine distribution of 5 to 15 μm and a small particle distribution of 1.30 GSD or less, has no fog and does not deteriorate even after long use, and has a high definition image with excellent offset resistance. It is to provide a manufacturing method. In addition, it is a recyclable, environmentally friendly electrostatic toner manufacturing method that can collect and recycle waste toner.

Claims (8)

(1) 말단에 카르복실기를 갖는 선상 수지중합체를 제조하는 단계;(1) preparing a linear resin polymer having a carboxyl group at its terminal; (2) 분산제 기능을 가지도록 단계(1)의 선상 수지중합체를 염기성 화합물과 반응시켜 중화하고 이 반응혼합물을 물에 용해시켜서 수분산 수지조성물을 얻는 단계;(2) neutralizing the linear resin polymer of step (1) with a basic compound to have a dispersant function and dissolving the reaction mixture in water to obtain a water-dispersible resin composition; (3) 상기 수분산 수지조성물에 착색제, 전하제어제, 및 이형제를 넣고 분산시켜서 착색수지 분산물을 제조하는 단계; 및(3) preparing a colored resin dispersion by dispersing a colorant, a charge control agent, and a release agent in the aqueous dispersion resin composition; And (4) 산성화합물을 용해한 수중에 전단력을 가하면서 단계(3)의 착색수지 분산물을 적가하여 역(탈)중화를 동반한 현탁처리시켜 5∼15㎛ 입자경의 토너입자를 생성시키는 단계를 포함하는 토너 제조방법.(4) adding the colored resin dispersion of step (3) dropwise while applying shear force to the water in which the acidic compound was dissolved to suspend the suspension with reverse (de) neutralization to produce toner particles having a particle diameter of 5 to 15 탆. Toner manufacturing method. 제1항에 있어서, 상기 선상 수지중합체는 단량체 총중량을 기준으로 방향족 비닐계 단량체 20∼45중량%, 아크릴레이트계 단량체 5∼50중량%, 및 상기 방향족 비닐계 단량체 및 상기 아크릴레이트계 단량체와 공중합가능한 카르복실기를 갖는 단량체 10~50중량%가 공중합되어 형성된 것을 특징으로 하는 토너 제조방법.The linear resin according to claim 1, wherein the linear resin polymer is copolymerized with 20 to 45 wt% of aromatic vinyl monomer, 5 to 50 wt% of acrylate monomer, and the aromatic vinyl monomer and the acrylate monomer based on the total weight of monomers. 10 to 50% by weight of a monomer having a carboxyl group capable of copolymerization is formed. 제2항에 있어서, 상기 방향족 비닐계 단량체 및 상기 아크릴레이트계 단량체와 공중합가능한 카르복실기를 갖는 단량체는 아크릴산, 메타아크릴산, 무수마레인산, 마레인화 로진, 푸말산, 및 이타콘산으로 이루어진 군에서 선택된 적어도 하나인 것을 특징으로 하는 토너 제조방법.The monomer of claim 2, wherein the monomer having a carboxyl group copolymerizable with the aromatic vinyl monomer and the acrylate monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, maleinized rosin, fumaric acid, and itaconic acid. Toner manufacturing method, characterized in that one. 제1항에 있어서, 상기 염기성화합물은 수산화나트륨, 수산화칼륨, 수산화암모늄, 및 아민류로 이루어진 군에서 선택된 적어도 하나이고, 단계(1)의 선상 수지중합체에 대하여 5∼30중량%의 양으로 사용되는 것을 특징으로 하는 토너 제조방법.The method according to claim 1, wherein the basic compound is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, and amines, and is used in an amount of 5 to 30% by weight based on the linear resin polymer of step (1). Toner manufacturing method, characterized in that. 제1항에 있어서, 상기 단계 (3)의 착색수지 분산물에 중량평균분자량이 100,000∼1,000,000이고, 겔함량이 5~50중량%인 유화중합 생성물인 가교된 고분자량 수분산 라텍스를 더 혼합분산시키는 것을 특징으로 하는 토너 제조방법.The mixed-dispersion of the crosslinked high molecular weight aqueous dispersion latex according to claim 1, wherein the colored resin dispersion of step (3) is an emulsion polymerization product having a weight average molecular weight of 100,000 to 1,000,000 and a gel content of 5 to 50% by weight. Toner manufacturing method characterized in that. 제1항에 있어서, 상기 산성화합물은 염산, 황산, 질산, 초산, 의산, 수산, 및 p-톨루엔술폰산으로 이루어진 군에서 선택된 적어도 어느 하나이고, 단계(3)의 착색수지 분산물에 대하여 5∼30중량%의 양으로 사용되는 것을 특징으로 하는 토너 제조방법.The acidic compound according to claim 1, wherein the acidic compound is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, uric acid, oxalic acid, and p-toluenesulfonic acid, and is 5 to 5 with respect to the colored resin dispersion of step (3). A toner manufacturing method, characterized in that it is used in an amount of 30% by weight. 제1항에 있어서, 단계 (4)의 토너입자가 제조공정의 하자로 불량품이 생성되었을 경우에는 이를 여과하여 얻은 입자를 수거하여 다시 단계(2)로 투입하여 재생하는 것을 특징으로 하는 토너 제조방법.2. The toner manufacturing method according to claim 1, wherein when the toner particles of step (4) are defective due to defects in the manufacturing process, the particles obtained by filtration thereof are collected and recycled by input into step (2). . 제1항에 있어서, 단계(4)의 토너입자를 수세하고 여과하여 건조시켜서 생성된 토너입자 조성물 100중량부에 대하여 외첨제 1∼5중량부를 첨가하여 정전하 현상용 토너를 얻는 것을 특징으로 하는 토너 제조 방법.The toner for electrostatic development according to claim 1, wherein 1 to 5 parts by weight of an external additive is added to 100 parts by weight of the toner particle composition produced by washing with water, filtering and drying the toner particles in step (4). Toner manufacturing method.
KR1020010079880A 2001-12-15 2001-12-15 Method of preparing toner by suspension process with reverse-neutralization KR100846764B1 (en)

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JP2003553343A JP4095554B2 (en) 2001-12-15 2002-12-14 Toner for electrostatic charge development and method for producing toner for electrostatic charge development by suspension treatment with reverse neutralization
CNB028281578A CN100414441C (en) 2001-12-15 2002-12-14 A toner for electrostatic development and its fabrication method by treatment of suspension with reverse-neutralization
PCT/KR2002/002358 WO2003052520A1 (en) 2001-12-15 2002-12-14 A toner for electrostatic development and its fabrication method by treatment of suspension with reverse-neutralization
AU2002366482A AU2002366482A1 (en) 2001-12-15 2002-12-14 A toner for electrostatic development and its fabrication method by treatment of suspension with reverse-neutralization
US10/498,919 US7723006B2 (en) 2001-12-15 2002-12-14 Toner for electrostatic development and its fabrication method by treatment of suspension with reverse-neutralization
DE60231837T DE60231837D1 (en) 2001-12-15 2002-12-14 METHOD FOR THE PRODUCTION OF A TONER FOR ELECTROSTATIC DEVELOPMENT BY TREATMENT OF A SUSPENSION WITH REVERSAL NEUTRALIZATION
EP02791088A EP1459136B1 (en) 2001-12-15 2002-12-14 Fabrication method for toner for electrostatic development by treatment of suspension with reverse-neutralization

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08211655A (en) * 1994-12-09 1996-08-20 Dainippon Ink & Chem Inc Toner for developing electrostatic latent image and its production
KR0185630B1 (en) * 1995-05-22 1999-04-15 미따라이 후지오 Toner for developing electrostatic image
JP2000010343A (en) * 1998-04-23 2000-01-14 Canon Inc Manufacture of electrostatic charge image developing toner

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08211655A (en) * 1994-12-09 1996-08-20 Dainippon Ink & Chem Inc Toner for developing electrostatic latent image and its production
KR0185630B1 (en) * 1995-05-22 1999-04-15 미따라이 후지오 Toner for developing electrostatic image
JP2000010343A (en) * 1998-04-23 2000-01-14 Canon Inc Manufacture of electrostatic charge image developing toner

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