JPH03158864A - Toner and production thereof - Google Patents
Toner and production thereofInfo
- Publication number
- JPH03158864A JPH03158864A JP1300068A JP30006889A JPH03158864A JP H03158864 A JPH03158864 A JP H03158864A JP 1300068 A JP1300068 A JP 1300068A JP 30006889 A JP30006889 A JP 30006889A JP H03158864 A JPH03158864 A JP H03158864A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- toner
- polymer
- island
- spherical
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000002245 particle Substances 0.000 claims abstract description 87
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000003086 colorant Substances 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010558 suspension polymerization method Methods 0.000 claims description 7
- 238000004040 coloring Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000003466 welding Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 8
- 230000004927 fusion Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000012736 aqueous medium Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000003094 microcapsule Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene, ethylene-vinyl acetate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、電子写真、静電記録等で使用する静電荷像現
像用トナー及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a toner for developing electrostatic images used in electrophotography, electrostatic recording, etc., and a method for producing the same.
〈従来の技術〉
近年、電子写真法あるいは静電記録法等にて転写対象画
像の静電荷像を形成し、これを現像用トナーにより顕像
化して転写紙等に転写した後、定着を行って可視画像と
する方法が広く採用されている。<Prior art> In recent years, an electrostatic charge image of an image to be transferred is formed using an electrophotographic method or an electrostatic recording method, and this is visualized with a developing toner and transferred to a transfer paper, etc., and then fixed. A method of converting images into visible images is widely adopted.
静電荷像の現像に供される上記のトナーには鉄粉あるい
はガラスピーズ等のキャリアと混合される二成分トナー
、およびキャリアの不要な一成分トナーがある。これら
いずれのトナーも、通常バインダーとしての熱可塑性樹
脂に、カーボンブラック、染、顔料等の着色剤、および
帯電制御剤を加え、また磁性トナーの場合にはさらに磁
性体等を加えて混合し、溶融、混練した後粉砕、分級す
ることによって製造されている。The above toners used for developing electrostatic images include two-component toners that are mixed with a carrier such as iron powder or glass beads, and one-component toners that do not require a carrier. All of these toners are usually made by adding a thermoplastic resin as a binder, a coloring agent such as carbon black, a dye, a pigment, and a charge control agent, and in the case of a magnetic toner, further adding a magnetic material, etc., and mixing. It is manufactured by melting, kneading, pulverizing, and classifying.
このように粉砕工程を経て製造されたトナーは不定形で
あるため流動性に乏しく、保存性の点で好ましくない結
果を与える。このため外添剤としてシリカ等の微粉末を
トナー表面に添加する方法がとられている。しかしなが
ら、上記の外添剤のｆＡ加工程は別工程となるため、コ
ストアップを招来すると共に、これによって得られるト
ナーの流動性も充分ではない。したがって最近では、上
記の粉砕工程および外添剤の添加下８を要しない、懸濁
重合法等の溶液系での製造法により、球状のトナーを製
造する方法が研究され、保存性、その他諸特性の改善、
コストダウンが企てられている。The toner produced through such a pulverization process has an amorphous shape and thus has poor fluidity, resulting in undesirable results in terms of storage stability. For this reason, a method has been adopted in which a fine powder such as silica is added to the toner surface as an external additive. However, since the above fA processing of the external additive is a separate process, it increases the cost and the resulting toner does not have sufficient fluidity. Therefore, recently, research has been conducted on methods of producing spherical toner using solution-based production methods such as suspension polymerization, which do not require the above-mentioned pulverization process or the addition of external additives. improvement of characteristics,
Efforts are being made to reduce costs.
また定着方式としては熱ローラーによるトナーの溶融定
着が一般的となっているが、加熱方式による定着は、熱
源を必要とするために消費電力が大きいことや、ウオー
ムアツプが必要である等の欠点を有している。このよう
な欠点に対して、定着温度の低いトナーによる省エネル
ギー化や圧力定着方式の採用による省エネルギー化、ウ
オームアツプ時間ゼロを目積した研究が盛んに行われて
いる。これらはいずれも低分子量ポリマー、ワックスを
使用したものであり、低温または圧力で塑性変形を起こ
すトナーである。このようなトナーを粉砕法によって製
造すると、粉砕時にバインダーの熱による融着が発生し
やすく、安定した製造は非常に困難である。このため、
これらのトナーの製造にも懸濁重合法等のごとき溶液法
が検討されている。この場合には、トナーに用いられる
材質上保存性に問題が生じるため、さらにトナーの外殻
を硬質物質等で覆いマイクロカプセルトナーとする方法
が多く用いられている。Furthermore, the most common fixing method is to use a heated roller to melt and fix the toner, but fixing using a heating method has drawbacks such as high power consumption due to the need for a heat source and the need for warm-up. have. In order to address these drawbacks, much research is being conducted to save energy by using toner with a low fixing temperature, to save energy by adopting a pressure fixing method, and to eliminate the warm-up time. All of these toners use low molecular weight polymers and waxes, and undergo plastic deformation at low temperatures or pressure. If such a toner is produced by a pulverization method, the binder tends to be fused due to heat during pulverization, making stable production very difficult. For this reason,
Solution methods such as suspension polymerization are also being considered for the production of these toners. In this case, a problem arises in storage stability due to the material used for the toner, so a method is often used in which the outer shell of the toner is further covered with a hard substance or the like to form a microcapsule toner.
〈発明が解決しようとする課題〉
懸濁重合法は、水と相溶性を有しない重合性単量体と熱
により分解しラジカルを発生する開始剤およびトナーに
必要な添加剤を混合し、水中で油滴状に分散し、熱によ
り重合を行い球状の重合体を得る手法である。この方法
では度広途中に単量体および開始剤が一部水相へ移動す
る事により、微小な透明の粒子が生成する。これはトナ
ーとしての着色度の低下、帯電性不良、感光体への汚染
を引き起こすため、この微小透明粒子の発生防止が課題
となっている。<Problem to be solved by the invention> The suspension polymerization method involves mixing a polymerizable monomer that is incompatible with water, an initiator that decomposes with heat to generate radicals, and additives necessary for toner. This is a method in which the polymer is dispersed in the form of oil droplets and polymerized using heat to obtain a spherical polymer. In this method, a portion of the monomer and initiator migrate to the aqueous phase during expansion, resulting in the production of fine transparent particles. This causes a decrease in the degree of coloring of the toner, poor charging properties, and contamination of the photoreceptor, so preventing the generation of these fine transparent particles has become an issue.
さらに、懸濁重合法等の溶液法により製造される球状ト
ナーは、現在のところ完全に保存性が改善されるには到
っていない。Furthermore, spherical toner produced by a solution method such as a suspension polymerization method has not yet been completely improved in storage stability.
また、少エネルギーにより定着可能なトナーの場合、マ
イクロカプセル化するのにコアセルベーシコン法、界面
重合法、ｉｎ −ｓ ｉ ｍｕ重合法、スプレードライ
法、液中乾燥法等が適用されているが、トナー本来の製
造工程とは別工程を要し複雑であるため生産性が低いと
いう問題がある。In addition, in the case of toners that can be fixed with low energy, the core cell basic method, interfacial polymerization method, in-s imu polymerization method, spray drying method, submerged drying method, etc. are applied to microcapsule them. However, since it requires a process separate from the original toner manufacturing process and is complicated, there is a problem that productivity is low.
以上を鑑み、本発明は懸濁重合法で副生ずる透明粒子に
より生じる種々の問題、トナーの保存性、及び少エネル
ギーにより定着可能なトナーの生産性を改善するための
トナーの構造及びその製造方法を提供しようとするもの
である。In view of the above, the present invention provides a toner structure and a manufacturing method thereof for improving various problems caused by transparent particles produced as a by-product in suspension polymerization, toner storage stability, and productivity of a toner that can be fixed with less energy. This is what we are trying to provide.
く課題を解決するための手段〉
上記目的を達成するために本発明は、
着色剤を含んだ球状ポリマー粒子と、該球状ポリマー粒
子表面に存在する島状ポリマーとから成り、該島状ポリ
マーは上記球状ポリマー粒子を形成するポリマーよりも
ガラス転移温度が高い同種のポリマーよりなり、かつ帯
電制御剤を担持していることを特徴とするトナーを提供
する。Means for Solving the Problems> In order to achieve the above object, the present invention comprises spherical polymer particles containing a colorant and island-like polymers present on the surface of the spherical polymer particles, and the island-like polymers are The present invention provides a toner comprising a polymer of the same type having a higher glass transition temperature than the polymer forming the spherical polymer particles, and supporting a charge control agent.
また、本発明は懸濁重合法によフ、同種のポリマーより
なる着色剤を含有する第１Ｌ７）球状ポリマー粒子と該
第１の粒子より小さくガラス転移温度の高い第２の球状
ポリマー粒子を混合物として同時に合成する工程と、該
混合物に力学的エネルギーを加えて上記第１の粒子に上
記第２の粒子を島状に融合させる工程とを含むことを特
徴とする前記トナーの製造方法を提供する。Further, the present invention uses a suspension polymerization method to produce a mixture of first L7) spherical polymer particles containing a colorant made of the same type of polymer and second spherical polymer particles that are smaller than the first particles and have a higher glass transition temperature. and a step of applying mechanical energy to the mixture to fuse the second particles to the first particles in an island shape. .
本トナーを構成する着色剤を含んだ球状ポリマー粒子は
、熱可塑性樹脂８０〜９０重量の、着色剤５〜１５重量
％の組成を有しているものが好１しく、上記熱可塑性樹
脂としては、ポリスチレン、スチレン−メタクリル酸エ
ステル共重合体、スチレン−メタクリル酸共重合体、ス
チレン−アクリル酸エステル共重合体、スチレン−アク
リル酸共重合体等のスチレン系共重合体、ポリ塩化ビニ
ル、ポリ酢酸ビニル、ポリメタクリル酸エステル、ポリ
エチレン、エチレン−酢酸ビニル共重合体、石油系樹脂
、パラフィンワックス等の樹脂全単独または混合して用
いる。また着色剤としては、カーボンブラック、フタロ
シアニン系顔料等の染、顔料を単独、または混合して用
いる。本トナーを構成する島状ポリマーは上記球状ポリ
マー粒子表面のすべてを被覆している必要はなく、該表
面に島状に融合、分布していれば良い。また島状ポリマ
ーに担持さｎる帯電制御剤としては、正原性トナーの場
合ニグロシン系の電子供与性の染料、第四級アンモニウ
ム塩等を、負極性トナーの場合モノアゾ染料、電子受容
性の有機錯体または脂肪酸金属塩を用いる。″また、帯
電制御剤は少なくとも島状ポリマーに担持されておれば
良く、より好ましくは大部分またはすべての帯電制御剤
が島状ポリマーに担持されているのが良い。The spherical polymer particles containing the colorant constituting the present toner preferably have a composition of 80 to 90% by weight of thermoplastic resin and 5 to 15% by weight of colorant; , polystyrene, styrene copolymers such as styrene-methacrylic acid ester copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid ester copolymer, styrene-acrylic acid copolymer, polyvinyl chloride, polyacetic acid Resins such as vinyl, polymethacrylic acid ester, polyethylene, ethylene-vinyl acetate copolymer, petroleum resin, paraffin wax, etc. may be used alone or in combination. As the coloring agent, dyes and pigments such as carbon black and phthalocyanine pigments are used alone or in combination. The island-like polymer constituting the present toner does not need to cover all of the surfaces of the spherical polymer particles, but it is sufficient that they are fused and distributed on the surface in the form of islands. In addition, the charge control agent supported on the island-shaped polymer includes nigrosine-based electron-donating dyes, quaternary ammonium salts, etc. in the case of positive toners, and monoazo dyes, electron-accepting agents, etc. in the case of negative polarity toners. Using organic complexes or fatty acid metal salts. ``Furthermore, it is sufficient that the charge control agent is supported at least on the island-like polymer, and more preferably, most or all of the charge control agent is supported on the island-like polymer.
本発明によるトナーは、通常の球状ポリマー粒子の製造
方法により製造された着色剤を含んだ球状ポリマー粒子
である第１の粒子と、該粒子表面に島状に存在するポリ
マーとなる第２の粒子とを以下に示すような方法、すな
わち、ＷＳｌと第２の粒子を混合し、該混合物に対し、
ボールミル、乳鉢等の摩砕機や表面融合装置等により粒
子間の衝撃力や摩擦力等の力学的エネルギーを加える等
の方法によって融合させて製造することができる。The toner according to the present invention includes first particles that are spherical polymer particles containing a colorant produced by a conventional method for producing spherical polymer particles, and second particles that are polymer particles that are present in the form of islands on the surface of the particles. and by the method shown below, that is, by mixing WSL and the second particles, and adding to the mixture,
They can be manufactured by fusing them by applying mechanical energy such as impact force or frictional force between particles using a grinder such as a ball mill or mortar or a surface fusing device.
しかしながら、本発明によるトナーは以下に示す本発明
による製造方法によって製造するのが最も好ましい。す
なわち、重合性単量体、開始剤、着色剤からなるｆ＆を
調整し、これを分散安定剤を含有した水系媒体中に油滴
状に分散保持し、該溶液を上記重合性単量体の重合条件
に付すことにより＠１と第２の粒子を混合物として得、
この混合物を水系媒体から分離した後、上記方法により
第１の粒子に第２の粒子を融合させるという方法である
。However, the toner according to the invention is most preferably manufactured by the manufacturing method according to the invention as described below. That is, f& consisting of a polymerizable monomer, an initiator, and a colorant is prepared, and this is dispersed and maintained in the form of oil droplets in an aqueous medium containing a dispersion stabilizer, and the solution is mixed with the polymerizable monomer. By subjecting it to polymerization conditions, @1 and the second particles are obtained as a mixture,
After this mixture is separated from the aqueous medium, the second particles are fused to the first particles by the method described above.
この製造方法では、第１と！２の粒子の割合は、水系媒
体に添加される電解質及び界面活性剤の量でコントロー
ルされ、電解質の量を多くすると第２の粒子は少なくな
り、界面活性剤の量を多くすると第２の粒子は多くなる
。In this manufacturing method, the first! The ratio of the second particles is controlled by the amount of electrolyte and surfactant added to the aqueous medium; increasing the amount of electrolyte will decrease the number of second particles, and increasing the amount of surfactant will decrease the number of second particles. will increase.
上記重合性単量体としては、前記熱可塑性樹脂に対応す
るものを単独でまたは混合して用いるが、スチレン、メ
タクリル酸エステルが好筐しく、開始剤としてはアゾビ
ス系、ｄ酸化物系の油溶性ラジカル発生剤を用い、好ま
しくは着色剤存在下での安定性、重合性単量体の水相で
の重合を行わせるという観点からアゾビス系を用いるの
が良い。As the above-mentioned polymerizable monomer, those corresponding to the above-mentioned thermoplastic resin are used alone or in combination, but styrene and methacrylic acid ester are preferable, and as the initiator, azobis-based and d-oxide-based oils are used. It is preferable to use a soluble radical generator, preferably an azobis-based one, from the viewpoints of stability in the presence of a colorant and polymerization of a polymerizable monomer in an aqueous phase.
また、分散安定剤としては、リン酸三カルシウムが好ま
しく、水系媒体の３重量％程度で用いるのが好ましい。Moreover, as a dispersion stabilizer, tricalcium phosphate is preferable, and it is preferable to use it in an amount of about 3% by weight of the aqueous medium.
分散にはホモジナイザー等を用いるのが好ましく、５０
００〜１１００００ｒｐ、好ましくは７０００〜８００
０ｒｐｍの攪拌により分散の均−化及び油滴の大きさの
調節を行う。このとき、油滴は数μｍ−数１０μｍの大
きさとなる。It is preferable to use a homogenizer etc. for dispersion.
00~110000rp, preferably 7000~800rp
Uniform dispersion and adjustment of oil droplet size are performed by stirring at 0 rpm. At this time, the oil droplet has a size of several micrometers to several tens of micrometers.
この後の重合は分散懸濁され念溶液を加熱することによ
り行い、例えば、５０〜８０℃の温度で８〜１６時間維
持することによって行い、この際、該溶液は攪拌機によ
りｌｏｏ〜２００ ｒｐｍで攪拌するのが好ましい。The subsequent polymerization is carried out by heating the dispersed and suspended solution, for example, by maintaining it at a temperature of 50 to 80°C for 8 to 16 hours. Stirring is preferred.
〈作 用〉
一般的にトナーの保存性はそのガラス転移温度に依存し
、高いガラス転移温度をしめずトナーはで保存性は良好
であることが知られている。<Function> In general, the shelf life of toner depends on its glass transition temperature, and it is known that toner has good shelf life without having a high glass transition temperature.
本発明のトナーは、トナーの保存性に主たる寄与をする
トナー表面にガラス転移温度の高いポリマーが島状に存
在し、トナー本体は通常のガラス転移温度のポリマーで
あるために、ガラス転移温度の高いトナーをヒートロー
ル定着に用いた場合にみられるような定着性の低下をと
もなわずに保存性を向上させる。The toner of the present invention has islands of polymer with a high glass transition temperature on the toner surface, which mainly contributes to the shelf life of the toner, and the toner body is made of a polymer with a normal glass transition temperature. To improve storage stability without deteriorating fixing properties as seen when high-quality toner is used for heat roll fixing.
また、表面に存在するポリマーが球状ではなく島状にな
っていることにより、このポリマーが着色されていなく
とも全体としての着色度を低下させることがなく、球状
と島状のポリマーが同種であることから両者の結着性も
良い。In addition, because the polymer present on the surface is not spherical but island-shaped, the overall degree of coloring does not decrease even if this polymer is not colored, and the spherical and island-shaped polymers are of the same type. Therefore, the binding properties between the two are also good.
さらに、帯電制御剤がトナーの表面に担持さｎ、島状ポ
リマーが帯電制御剤を担持していることから、帯電制御
剤の必要な添加量を少量にする。Furthermore, since the charge control agent is supported on the surface of the toner and the island-like polymer supports the charge control agent, the amount of charge control agent required to be added is reduced.
本発明の製造方法において用いられる懸濁重合法では、
水系媒体中に分散保持された各油滴内での重合性単量体
の着色剤の影響下での重合と、水系謀体中に浸出した重
合性単量体の着色剤の影響のない状態での重合が起こる
。その結果、粒径数μｍ〜数ｌＯμｍの球状着色粒子と
数μ風以下の透明微小粒子が混合物として生成する。本
発明の製造方法における第１の粒子は前者の粒子であり
第２の粒子は後者の粒子となるが、着色剤は重合度を低
下させる作用を有するため、嘉２の粒子は第１の粒子よ
りも重合度が高くなり、この重合度に応じて第２の粒子
は第１の粒子よりもガラス転移点が高くまた硬質となる
。これら粒子の混合物に衝撃力や摩擦力等の力学的エネ
ルギーを加えると、粒径の異なる第１と第２の粒子間に
メカノケミカルな作用が生じ合体がおこり、大粒子上に
小粒子が融合する表面融合が生じる。この融合により、
従来第２の粒子である透明微小粒子によって低下させら
れていた着色度が大幅に向上し、さらに島状に融合した
比較的硬い第２の粒子が第１の粒子を保護するようにな
る。In the suspension polymerization method used in the production method of the present invention,
Polymerization of polymerizable monomers within each oil droplet dispersed in an aqueous medium under the influence of a colorant, and a state in which a polymerizable monomer leached into an aqueous medium is not affected by a colorant. Polymerization occurs. As a result, a mixture of spherical colored particles with a particle diameter of several micrometers to several 10 micrometers and transparent microparticles with a diameter of several micrometers or less is produced. In the production method of the present invention, the first particles are the former particles, and the second particles are the latter particles, but since the colorant has the effect of lowering the degree of polymerization, the particles of Ka2 are the first particles. The degree of polymerization is higher than that of the first particles, and depending on this degree of polymerization, the second particles have a higher glass transition point and are harder than the first particles. When mechanical energy such as impact force or frictional force is applied to a mixture of these particles, a mechanochemical action occurs between the first and second particles of different particle sizes, causing coalescence, and the small particles fuse onto the large particles. surface fusion occurs. With this fusion,
The degree of coloring, which was conventionally reduced by the transparent microparticles that are the second particles, is significantly improved, and the second particles, which are relatively hard and fused into an island shape, protect the first particles.
また、融合時に上記混合物中に帯電制御剤を存在させる
ことによって融合粒子表面に帯電性が付与され、特に第
２の粒子により形成される島状ポリマー表面に多くの帯
電制御剤が担持されるようになる。あるいは、これに代
えて融合後に帯電制御剤を付着させるようにしても、島
状の融合部が突き出ているために、より効率的に島状ポ
リマー表面に帯電制御剤が担持される。In addition, the presence of a charge control agent in the mixture at the time of fusion imparts chargeability to the surface of the fused particles, and in particular, a large amount of charge control agent is supported on the surface of the island-shaped polymer formed by the second particles. become. Alternatively, even if the charge control agent is attached after fusion, the charge control agent is more efficiently carried on the surface of the island-like polymer because the island-like fused portions protrude.
以下実施例によりこの発明を説明するが、これによりこ
の発明が限定されるものではない。EXAMPLES This invention will be explained below with reference to Examples, but the invention is not limited thereto.
〈実施例〉
容ｉ５００ｍｌのフラスコ内でイオン交換水１００重量
部、リン酸三カルシウム３重量部、塩化ナトリウム１０
重量部、ラウリル硫酸ナトリウム０．０１重量部を溶解
分散させた後、スチレン４０重量部、カーボンブラック
２．８重量部、アゾビスイソブチロニトリ／Ｌ’０．２
８重量部をあらかじめ混合して調整した液を注入し、ホ
モジナイザーにて上記注入した混合液を平均粒径２０μ
ｍの油滴状に分散した。その後、液温７５℃で９時間重
合反応を窒素雰囲気下で行い、この後、濾過、稀塩酸に
よる分散剤の分解除去、水洗、乾燥を行い固体粒子を得
た。<Example> In a flask with a volume of 500 ml, 100 parts by weight of ion-exchanged water, 3 parts by weight of tricalcium phosphate, and 10 parts by weight of sodium chloride.
After dissolving and dispersing 0.01 part by weight of sodium lauryl sulfate, 40 parts by weight of styrene, 2.8 parts by weight of carbon black, and azobisisobutyronitrile/L'0.2
Inject a liquid prepared by mixing 8 parts by weight in advance, and use a homogenizer to reduce the injected mixture to an average particle size of 20 μm.
It was dispersed in the form of oil droplets of m. Thereafter, a polymerization reaction was carried out in a nitrogen atmosphere at a liquid temperature of 75° C. for 9 hours, followed by filtration, decomposition and removal of the dispersant with dilute hydrochloric acid, washing with water, and drying to obtain solid particles.
この粒子は顕微鏡観察により、第１図に示すように粒径
約２０μｍの黒色球状ポリマー粒子１と粒径約１〜３μ
ｍの透明球状ポリマー粒子２からなることがわかった。By microscopic observation, these particles were found to be black spherical polymer particles 1 with a particle size of about 20 μm and particle sizes of about 1 to 3 μm, as shown in Figure 1.
It was found that it consisted of transparent spherical polymer particles 2 of m.
この粒子の色調は灰色であった。分級によりこれら粒子
を分離し、それぞれのガラス転移温度を測定したところ
、黒色球状粒子が８７℃、透明球状粒子が９６℃であっ
た。The color of the particles was gray. When these particles were separated by classification and the glass transition temperature of each was measured, it was found to be 87°C for the black spherical particles and 96°C for the transparent spherical particles.
分離前の粒子の混合物をボールミルにより融合処理した
ところ、粒子の色調は灰色から黒色へと変化し、顕微鏡
観察によりこの粒子は第２図に示すように、黒色球状ポ
リマー粒子１表面に透明球状ポリマー粒子２が島状に融
合し、島状ポリマー３を形成している事がわかった。When the mixture of particles before separation was fused using a ball mill, the color tone of the particles changed from gray to black, and microscopic observation revealed that the particles had a transparent spherical polymer on the surface of the black spherical polymer particles 1, as shown in Figure 2. It was found that the particles 2 were fused in an island shape to form an island polymer 3.
また、融合処理をする前に混合物中にニグロシンを０．
２重量部添加して得られた粒子を、鉄粉キャリヤーとの
摩擦により帯電させたところ、帯電量が約１１μｃ ７
ｇの安定した正帯電性を示した。In addition, 0.0% of nigrosine was added to the mixture before the fusion process.
When the particles obtained by adding 2 parts by weight were charged by friction with an iron powder carrier, the amount of charge was approximately 11 μc 7
It showed stable positive chargeability of g.
また、融合処理した後、ニグロシンのメタノール溶液中
に粒子を分散し乾燥することにより帯電性付与を行った
ところ、上記と同様の帯電方法によって約２０μｃ／ｇ
の安定した正帯電性を示した。In addition, after the fusion treatment, the particles were dispersed in a methanol solution of nigrosine and dried to impart chargeability.
It showed stable positive chargeability.
また、いずれの方法によっても島状ポリマー３に帯電制
御剤がより高い密度で担持されていた。In addition, the charge control agent was supported on the island-shaped polymer 3 at a higher density by either method.
これらトナー粒子はいずれも保存安定性が良好であり、
融合粒子の剥がれ等は全く生じなかった。All of these toner particles have good storage stability;
No peeling of the fused particles occurred.
尚、上記懸濁重合法により粒子を合成する際にニグロシ
ン１に０．２重量部添加して得られた粒子をのニグロシ
ンを添加しなければならなかった。In addition, when synthesizing particles by the above-mentioned suspension polymerization method, it was necessary to add 0.2 parts by weight of nigrosine to nigrosine 1 to obtain particles.
〈発明の効果〉
本発明のトナーを用いることにより、保存性が良く、帯
電制御剤の添加量が少ないため安価で、かつ定着性も損
うことのないトナーが実現された。<Effects of the Invention> By using the toner of the present invention, a toner that has good storage stability, is inexpensive because the amount of charge control agent added is small, and has no loss in fixability was realized.
また、本発明のトナーの製造方法を用いることにより、
従来懸濁重合法において問題となっていた透明微粒子の
問題が解決され、同時に保存性の良いトナーも製造でき
るようになった。Furthermore, by using the toner manufacturing method of the present invention,
The problem of transparent fine particles, which had been a problem in the conventional suspension polymerization method, has been solved, and at the same time it has become possible to produce toner with good shelf life.
さらに、帯電制御剤のｇＳ７ＩＯ量を少なくできるため
に、安価なトナーを製造することができる。Furthermore, since the amount of gS7IO of the charge control agent can be reduced, an inexpensive toner can be manufactured.
筐た、本製造方法によりマイクロカプセルトナーと同様
の構造を有するトナーが合成されるために、従来生産性
の低かったマイクロカプセルトナーの製造方法に替わり
、生産性の良いマイクロカプセルトナーの製造方法’ｋ
ｌ供することができる。In addition, since this manufacturing method synthesizes toner having a structure similar to that of microcapsule toner, it is a highly productive method for manufacturing microcapsule toner, replacing the conventional manufacturing method of microcapsule toner, which had low productivity. k
can be provided.
第１図は実施例に示す懸濁′！ＩＬ合により得られた融
合前の粒子を示す図、第２図は実施例に示す融合後の粒
子を示す図である。
１・・・黒色球状ポリマー粒子
２・・・透明球状ポリマー粒子
３・・・島状ポリマーFigure 1 shows the suspension shown in the example. FIG. 2 is a diagram showing particles before fusion obtained by IL synthesis, and FIG. 2 is a diagram showing particles after fusion shown in Examples. 1... Black spherical polymer particles 2... Transparent spherical polymer particles 3... Island-shaped polymer
Claims (1)
成り、 該島状ポリマーは上記球状ポリマー粒子を形成するポリ
マーよりもガラス転移温度が高い同種のポリマーよりな
り、かつ帯電制御剤を担持していることを特徴とするト
ナー。 ２、懸濁重合法により、同種のポリマーよりなる、着色
剤を含有する第１の球状ポリマー粒子と該第１の粒子よ
り小さくガラス転移温度の高い第２の球状ポリマー粒子
を混合物として同時に合成する工程と、 該混合物に力学的エネルギーを加えて上記第１の粒子に
上記第２の粒子を島状に融合させる工程とを含む請求項
１記載のトナーの製造方法。[Scope of Claims] 1. Consisting of spherical polymer particles containing a colorant and island-like polymers present on the surface of the spherical polymer particles, the island-like polymers having a higher glass transition than the polymer forming the spherical polymer particles. A toner comprising a polymer of the same type having a high temperature and carrying a charge control agent. 2. Simultaneously synthesize a mixture of first spherical polymer particles containing a colorant and second spherical polymer particles smaller than the first particles and having a higher glass transition temperature by a suspension polymerization method. 2. The method for producing a toner according to claim 1, further comprising the step of: applying mechanical energy to the mixture to fuse the second particles to the first particles in an island shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1300068A JPH03158864A (en) | 1989-11-16 | 1989-11-16 | Toner and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1300068A JPH03158864A (en) | 1989-11-16 | 1989-11-16 | Toner and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03158864A true JPH03158864A (en) | 1991-07-08 |
Family
ID=17880314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1300068A Pending JPH03158864A (en) | 1989-11-16 | 1989-11-16 | Toner and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03158864A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017015767A (en) * | 2015-06-26 | 2017-01-19 | キヤノン株式会社 | Manufacturing method of toner particles |
-
1989
- 1989-11-16 JP JP1300068A patent/JPH03158864A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017015767A (en) * | 2015-06-26 | 2017-01-19 | キヤノン株式会社 | Manufacturing method of toner particles |
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