JPH07224103A - Production of toner resin - Google Patents
Production of toner resinInfo
- Publication number
- JPH07224103A JPH07224103A JP6037524A JP3752494A JPH07224103A JP H07224103 A JPH07224103 A JP H07224103A JP 6037524 A JP6037524 A JP 6037524A JP 3752494 A JP3752494 A JP 3752494A JP H07224103 A JPH07224103 A JP H07224103A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polymerization initiator
- meth
- molecular weight
- polymerization
- 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
- 239000011347 resin Substances 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000178 monomer Substances 0.000 claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001868 water Inorganic materials 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000001506 calcium phosphate Substances 0.000 abstract description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 abstract description 2
- 235000011010 calcium phosphates Nutrition 0.000 abstract description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 abstract 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 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- -1 acrylic ester Chemical class 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- DRBNNXKDUBUOFD-UHFFFAOYSA-N 2-methylprop-2-enoyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC(=O)C(C)=C DRBNNXKDUBUOFD-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-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
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 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
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 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
- 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Developing Agents For Electrophotography (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はトナー用樹脂に用いられ
る高分子量樹脂の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high molecular weight resin used as a resin for toner.
【０００２】[0002]
【従来の技術】従来乾式トナー用樹脂に関しては数多く
の発明がなされている。しかしながら、最近複写機及び
記録装置に対し、処理情報の増大に伴う処理速度の高速
化から、複写スピードの向上が望まれている。そのため
トナー用樹脂としては、従来よりも高い性能のものが要
望されている。スチレンと（メタ）アクリル酸エステル
との共重合体を主成分とするトナー用樹脂としては耐オ
フセット性、耐ブロッキング性及び定着性を高めるため
に、分子量分布の大きい樹脂が有用であることが知られ
ている。そのような樹脂を得る方法としては、低分子量
樹脂及び高分子量樹脂を夫々製造し、得られた樹脂をブ
レンドする方法、あるいは低分子量樹脂を溶解したビニ
ル単量体を重合させる方法等が知られている。又高分子
量樹脂を得るために重合開始剤としては特開平２−３２
１０８号公報及び特開平２−６７３０２号公報には２，
２−ビス（４，４−ジ−ｔ−ブチルペルオキシシクロヘ
キシル）プロパンを用いる方法が開示されている。又特
開昭５８−７２１５５号公報には２，５−ジメチル−
２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン、２，５
−ジメチル−２，５−ジ（ベンゾイルペルオキシ）ヘキ
サン、１，１−ジ−ｔ−ブチルペルオキシ−３，３，５
−トリメチルシクロヘキサン、１，１−ジ−ｔ−オクチ
ルペルオキシ−２−メチルシクロヘキサン等の二官能ペ
ルオキシドを、用いる方法が開示されている。2. Description of the Related Art Conventionally, many inventions have been made on resins for dry toner. However, recently, the copying machine and the recording apparatus are required to improve the copying speed because the processing speed is increased with the increase of the processing information. Therefore, as the toner resin, one having higher performance than ever has been demanded. It has been known that a resin having a large molecular weight distribution is useful as a toner resin containing a copolymer of styrene and a (meth) acrylic acid ester as a main component in order to improve offset resistance, blocking resistance and fixing property. Has been. As a method of obtaining such a resin, a method of producing a low molecular weight resin and a high molecular weight resin, respectively, and blending the obtained resin, or a method of polymerizing a vinyl monomer in which the low molecular weight resin is dissolved is known. ing. Further, as a polymerization initiator for obtaining a high molecular weight resin, JP-A-2-32
No. 108 and JP-A-2-67302 disclose 2,
A method using 2-bis (4,4-di-t-butylperoxycyclohexyl) propane is disclosed. Further, in JP-A-58-72155, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, 2,5
-Dimethyl-2,5-di (benzoylperoxy) hexane, 1,1-di-t-butylperoxy-3,3,5
A method using a bifunctional peroxide such as -trimethylcyclohexane and 1,1-di-t-octylperoxy-2-methylcyclohexane is disclosed.
【０００３】[0003]
【発明が解決しようとする課題】特開平２−３２１０８
号公報、特開平２−６７３０２号公報及び特開昭５８−
７２１５５号公報の方法は、何れも懸濁重合により実施
したとき、重合後の単量体の残存が比較的多いため製品
に単量体の臭気が残るという問題がある。又重合後の単
量体を減らすために重合温度を高めようとすると、反応
装置の耐圧性を高めることが必要となり、装置コストの
増加及び熱エネルギーの効率の低下等の問題が生じる。
又同目的で重合開始剤の添加量を多くした場合には、開
始剤分解物の臭気が問題となる。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Japanese Patent Application Laid-Open No. 2-67302 and Japanese Patent Application Laid-Open No. 58-
The methods disclosed in Japanese Patent No. 72155 have a problem in that, when carried out by suspension polymerization, the odor of the monomer remains in the product because the amount of the monomer remaining after the polymerization is relatively large. If the polymerization temperature is increased in order to reduce the amount of monomers after the polymerization, it is necessary to increase the pressure resistance of the reaction apparatus, which causes problems such as an increase in the apparatus cost and a decrease in the heat energy efficiency.
If the amount of the polymerization initiator added is increased for the same purpose, the odor of the decomposition product of the initiator becomes a problem.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記従来
法の問題点を長期にわたって研究した結果、特定のペル
オキシケタールを重合開始剤として用いることにより、
上記の問題点を解決し、本発明を完成するに至った。即
ち、本発明は、スチレンと（メタ）アクリル酸エステル
との単量体混合物より懸濁にてトナー用樹脂を製造する
に際し、重合開始剤として一般式The present inventors have studied the problems of the above conventional method for a long period of time, and as a result, by using a specific peroxyketal as a polymerization initiator,
The above problems have been solved and the present invention has been completed. That is, in the present invention, when a toner resin is produced by suspending a monomer mixture of styrene and a (meth) acrylic acid ester, a general formula as a polymerization initiator is used.
【化２】 で示される化合物を用いることを特徴とするトナー用樹
脂の製造方法に関する。[Chemical 2] The present invention relates to a method for producing a resin for toner, which comprises using the compound represented by
【０００５】本発明において重合開始剤として用いられ
る化２で示される化合物としては、例えば１，１−ジ−
ｔ−ブチルペルオキシ−２−メチルシクロヘキサン、
１，１−ジ−ｔ−ヘキシルペルオキシ−２−メチルシク
ロヘキサン、１，１−ジ−ｔ−アミルペルオキシ−２−
メチルシクロヘキサン等が挙げられる。又、前記重合開
始剤の他に従来から用いられている重合開始剤を併用、
あるいは重合後半に追加使用することもできる。併用あ
るいは追加使用可能な重合開始剤としては、２，５−ジ
メチル−２，５−ジ（２−エチルヘキサノイルペルオキ
シ）ヘキサン、ｔ−ブチルペルオキシピバレート、ｔ−
ブチルペルオキシ−２−エチルヘキサノエート、ベンゾ
イルペルオキシド、ラウロイルペルオキシド、３，５，
５−トリメチルヘキサノイルペルオキシド、１，１−ジ
−ｔ−ブチルペルオキシ−３，３，５−トリメチルシク
ロヘキサン、ｔ−ブチルペルオキシイソプロピルカーボ
ネート等を挙げることができる。併用あるいは追加する
重合開始剤の割合は、（化２）で示される重合開始剤過
酸化結合１モルに対し過酸化結合０．５モル以下が好ま
しい。０．５モルを越えて使用すると、高分子量化と残
存単量体量の低下の効果を両立させることができない。Examples of the compound represented by Chemical formula 2 used as a polymerization initiator in the present invention include 1,1-di-
t-butylperoxy-2-methylcyclohexane,
1,1-di-t-hexylperoxy-2-methylcyclohexane, 1,1-di-t-amylperoxy-2-
Methylcyclohexane and the like can be mentioned. Further, in addition to the polymerization initiator, a conventionally used polymerization initiator is used in combination,
Alternatively, it can be additionally used in the latter half of the polymerization. Examples of the polymerization initiator that can be used together or additionally include 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-butylperoxypivalate, t-
Butyl peroxy-2-ethyl hexanoate, benzoyl peroxide, lauroyl peroxide, 3,5
Examples thereof include 5-trimethylhexanoyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane and t-butylperoxyisopropyl carbonate. The ratio of the polymerization initiator to be used in combination or added is preferably 0.5 mol or less of the peroxide bond to 1 mol of the peroxide bond of the polymerization initiator represented by (Chemical Formula 2). If it is used in excess of 0.5 mol, the effects of increasing the molecular weight and decreasing the amount of residual monomer cannot be achieved at the same time.
【０００６】本発明において用いられる（メタ）アクリ
ル酸エステルとしては、メチルアクリレート、エチルア
クリレート、プロピルアクリレート、ｎ−ブチルアクリ
レート、ｓｅｃ−ブチルアクリレート、イソブチルアク
リレート、ｎ−オクチルアクリレート、２−エチルヘキ
シルアクリレート、ラウロイルアクリレート、メチルメ
タクリレート、エチルメタクリレート、プロピルメタク
リレート、ｎ−ブチルメタクリレート、ｓｅｃ−ブチル
メタクリレート、イソブチルメタクリレート、ｎ−オク
チルメタクリレート、２−エチルヘキシルメタクリレー
ト、ラウロイルメタクリレート等が挙げられる。本発明
においてスチレンと（メタ）アクリル酸エステルとはス
チレン１モルに対して（メタ）アクリル酸エステル０．
１〜０．５モルの範囲であることが好ましい。０．１モ
ル未満ではトナーの定着性が低下し、又０．５モルを越
えるとトナーのブロッキングが起こり易くなる。尚、ス
チレンと（メタ）アクリル酸エステルとは必ずしも単量
体のみに限らず、両者よりなる低分子量の樹脂が含まれ
ていてもよい。尚樹脂量は単量体に対して最大で２００
重量％である。２００重量％を越えると樹脂の単量体溶
液の初期粘度が高くなり良好な懸濁状態ができない。又
重合体の重量平均分子量は３００００以下が好ましく３
００００を越えるとトナーの定着性が低下する。Examples of the (meth) acrylic acid ester used in the present invention include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate and lauroyl. Examples thereof include acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate and lauroyl methacrylate. In the present invention, styrene and (meth) acrylic acid ester are (meth) acrylic acid ester of 0.
It is preferably in the range of 1 to 0.5 mol. If it is less than 0.1 mol, the fixing property of the toner will be lowered, and if it exceeds 0.5 mol, blocking of the toner will easily occur. It should be noted that styrene and (meth) acrylic acid ester are not necessarily limited to monomers, and a low molecular weight resin composed of both may be contained. The maximum amount of resin is 200 for the monomer.
% By weight. When it exceeds 200% by weight, the initial viscosity of the monomer solution of the resin becomes high and a good suspension state cannot be obtained. The weight average molecular weight of the polymer is preferably 30,000 or less.
When it exceeds 0000, the fixing property of the toner is deteriorated.
【０００７】本発明において、重合開始剤の使用量は用
いられる単量体の種類、組み合わせにより異なるが通常
単量体１ｋｇに対し、０．００５〜０．２モル好ましく
は０．０１〜０．１モル程度が適当である。０．００５
モル未満では、残存する単量体が増加し、０．２モルを
越えると重合速度の調節が困難になる。In the present invention, the amount of the polymerization initiator used varies depending on the kind and combination of the monomers used, but usually 0.005 to 0.2 mol, preferably 0.01 to 0. About 1 mol is suitable. 0.005
When the amount is less than the molar amount, the amount of the remaining monomers increases, and when the amount exceeds 0.2 mol, it becomes difficult to control the polymerization rate.
【０００８】本発明において重合は懸濁重合に限られ
る。重合温度は５０〜１３０℃が用いられ、一定温度あ
るいはプログラム昇温重合が用いられる。５０℃未満で
は重合速度が低下し、１３０℃を越えると反応槽の圧力
が増加し何れも好ましくない。In the present invention, the polymerization is limited to suspension polymerization. The polymerization temperature is 50 to 130 ° C., and constant temperature or programmed temperature rising polymerization is used. If the temperature is less than 50 ° C, the polymerization rate will decrease, and if it exceeds 130 ° C, the pressure in the reaction tank will increase, which is not preferable.
【０００９】[0009]
【発明の効果】本発明のトナー用樹脂の製造方法は、高
分子量で且つ、残存する単量体が少なく、臭気の少ない
樹脂を得ることができるため工業的利用価値は極めて高
い。INDUSTRIAL APPLICABILITY The method for producing a resin for a toner of the present invention has an extremely high industrial utility value because a resin having a high molecular weight, a small amount of residual monomers and a small odor can be obtained.
【００１０】[0010]
【実施例】次に本発明を実施例により更に詳細に説明す
る。尚各例中、部、％は特に断らない限り重量部及び重
量％を示す。又例中の略号は以下の化合物を示す。 ＢｕＭＣ：１，１−ジ−ｔ−ブチルペルオキシ−２−メ
チルシクロヘキサン ＡｍＭＣ：１，１−ジ−ｔ−アミルペルオキシ−２−メ
チルシクロヘキサン ＨｘＭＣ：１，１−ジ−ｔ−ヘキシルペルオキシ−２−
メチルシクロヘキサン ＯｃＭＣ：１，１−ジ−ｔ−オクチルペルオキシ−２−
メチルシクロヘキサン ＰＴＡ ：２，２−ビス（４，４−ジ−ｔ−ブチルペル
オキシシクロヘキシル）プロパン ２５Ｂ ：２，５−ジメチル−２，５−ジ（−ｔ−ブチ
ルペルオキシ）ヘキサン ２５Ｚ ：２，５−ジメチル−２，５−ジ（−ｔ−ベン
ゾイルペルオキシ）ヘキサン ３Ｍ ：１，１−ジ−ｔ−ブチルペルオキシ−３，
３，５−トリメチルシクロヘキサン ＢＰＯ ：ベンゾイルペルオキシド （以上の重合開始剤の内ＢＰＯは単官能ペルオキシド、
ＰＴＡは四官能ペルオキシドであり、その他は二官能ペ
ルオキシドである。） Ｓｔ ：スチレン ＢＡ ：ｎ−ブチルアクリレート ＢＭＡ ：ｎ−ブチルメタクリレートEXAMPLES The present invention will now be described in more detail with reference to Examples. In the examples, parts and% are parts by weight and% by weight unless otherwise specified. The abbreviations in the examples indicate the following compounds. BuMC: 1,1-di-t-butylperoxy-2-methylcyclohexane AmMC: 1,1-di-t-amylperoxy-2-methylcyclohexane HxMC: 1,1-di-t-hexylperoxy-2-
Methylcyclohexane OcMC: 1,1-di-t-octylperoxy-2-
Methylcyclohexane PTA: 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane 25B: 2,5-Dimethyl-2,5-di (-t-butylperoxy) hexane 25Z: 2,5- Dimethyl-2,5-di (-t-benzoylperoxy) hexane 3M: 1,1-di-t-butylperoxy-3,
3,5-Trimethylcyclohexane BPO: Benzoyl peroxide (BPO among the above polymerization initiators is a monofunctional peroxide,
PTA is a tetrafunctional peroxide and the others are difunctional peroxides. ) St: Styrene BA: n-butyl acrylate BMA: n-butyl methacrylate
【００１１】〈実施例 １〉５Ｌオートクレーブにイオ
ン交換水２Ｌ、リン酸カルシウム１０ｇ、ドデシルベン
ゼンスルホン酸ソーダ（日本油脂（株）製、商品名ニュ
ーレックスＲ）０．４ｇ、ＢｕＭＣ １３．０ｇ、Ｓｔ
８００ｇ及びＢＡ ２００ｇ（原料単量体１ｋｇに対
し重合開始剤０．０５モル）を入れ、空間部を窒素置換
した後、攪拌しながら１００℃で３時間重合を行った。
冷却後、内容物を取りだし、塩酸で洗浄し、水洗、乾燥
した。得られた樹脂について、ＧＬＣにより残存単量体
を定量した結果、残存単量体は原料単量体の０．０５％
であった。又ＧＰＣで分子量を測定した結果、数平均分
子量は１３１０００、重量平均分子量は２９８０００で
あった。得られた重合物に単量体の臭気はなく、トナー
用樹脂としては好適である。原料、結果を表１に示す。<Example 1> 2 L of ion-exchanged water, 10 g of calcium phosphate, 0.4 g of sodium dodecylbenzenesulfonate (Nurex Co., Ltd., trade name Nurex R) in a 5 L autoclave, BuMC 13.0 g, St
After adding 800 g and BA 200 g (0.05 mol of a polymerization initiator to 1 kg of the raw material monomer) and replacing the space with nitrogen, polymerization was carried out at 100 ° C. for 3 hours while stirring.
After cooling, the contents were taken out, washed with hydrochloric acid, washed with water and dried. The residual monomer of the obtained resin was quantified by GLC, and the residual monomer was found to be 0.05% of the raw material monomer.
Met. As a result of measuring the molecular weight by GPC, the number average molecular weight was 131,000 and the weight average molecular weight was 298,000. The obtained polymer has no monomer odor and is suitable as a resin for toner. The raw materials and the results are shown in Table 1.
【００１２】〈実施例 ２〜１０及び比較例１〜１０〉
表１，表２に示す単量体及び重合開始剤を使用した以外
は実施例１に準じて実施した。その結果は表１、表２の
通りである。実施例２〜５及び７〜１０で得られた重合
物は単量体の臭気はなかったが、実施例６、実施例１〜
５及び７〜９で得られた重合物にはスチレン臭及びブチ
ルアクリレート臭があった。又比較例１０で得られた重
合物にはスチレン臭及びブチルメタクリレート臭があっ
た。又比較例６で得られた重合物には重合開始剤の分解
物の臭気が認められた。実施例１〜５と比較例１〜４、
実施例７，８と比較例９及び実施例１０と比較例１０の
結果から重合開始剤として従来の多官能ペルオキシドを
用いる方法は、比較的高い分子量体が得られるが残存す
る単量体が多いことが判る。又実施例１と比較例５の結
果から重合開始剤としてＯｃＭＣを用いたものは、分子
量も小さく又残存する単量体が多いことが判る。又比較
例１と比較例６の結果から重合開始剤の添加量を増加さ
せたとき残存単量体を低下させることはできるが分子量
も同時に低下してしまうと共に重合開始剤の分解物が多
く残ることが判る。又実施例１〜５と比較例７，８の結
果から２５Ｂ及び２５Ｚは使用量を増しても尚残存単量
体が多く残ることが判る。又実施例９から従来の重合開
始剤を併用しても残存単量体が少なく高分子量体が得ら
れることが判る。<Examples 2 to 10 and Comparative Examples 1 to 10>
The procedure of Example 1 was repeated except that the monomers and polymerization initiators shown in Tables 1 and 2 were used. The results are shown in Tables 1 and 2. The polymers obtained in Examples 2 to 5 and 7 to 10 had no monomer odor, but Examples 6 and 1 to
The polymers obtained in Nos. 5 and 7 to 9 had a styrene odor and a butyl acrylate odor. The polymer obtained in Comparative Example 10 had a styrene odor and a butyl methacrylate odor. Further, the polymer obtained in Comparative Example 6 had an odor of the decomposition product of the polymerization initiator. Examples 1 to 5 and Comparative Examples 1 to 4,
From the results of Examples 7 and 8 and Comparative Example 9 and Example 10 and Comparative Example 10, the conventional method of using a polyfunctional peroxide as a polymerization initiator gives a relatively high molecular weight product, but many monomers remain. I understand. From the results of Example 1 and Comparative Example 5, it can be seen that the one using OcMC as the polymerization initiator has a small molecular weight and a large amount of residual monomers. Further, from the results of Comparative Example 1 and Comparative Example 6, when the addition amount of the polymerization initiator is increased, the residual monomer can be decreased, but the molecular weight is decreased at the same time, and many decomposition products of the polymerization initiator remain. I understand. Further, from the results of Examples 1 to 5 and Comparative Examples 7 and 8, it is understood that 25B and 25Z still have a large amount of residual monomer even if the amount used is increased. Further, it can be seen from Example 9 that even if the conventional polymerization initiator is used in combination, the residual monomer is small and a high molecular weight product is obtained.
【００１３】〈実施例 １１〉表１に示すように実施例
１において、Ｓｔ ８００ｇ及びＢＡ ２００ｇの代わ
りに、溶液重合法により製造した重量平均分子量１１０
００のＳｔ／ＢＡ（８：２）共重合体１０００ｇをＳｔ
８００ｇとＢＡ ２００ｇの単量体混合物に溶解した
溶液を用い、ＢｕＭＣの使用量を１９．５ｇに変えた他
は実施例１に準じて実施した。その結果は表１に示すよ
うに残存単量体は０．０２％であった。又ＧＰＣで分子
量を測定した結果、ピークは２山になり高分子量側の重
量平均分子量は３３５０００であった。得られた重合物
に単量体の臭気はなかった。<Example 11> As shown in Table 1, in Example 1, instead of St 800 g and BA 200 g, a weight average molecular weight of 110 produced by a solution polymerization method was used.
1000 g of St / BA (8: 2) copolymer of
The procedure of Example 1 was repeated except that a solution prepared by dissolving 800 g of BA and 200 g of BA in a monomer mixture was used and the amount of BuMC used was changed to 19.5 g. As a result, as shown in Table 1, the residual monomer content was 0.02%. As a result of measuring the molecular weight by GPC, the peak had two peaks and the weight average molecular weight on the high molecular weight side was 335,000. The obtained polymer had no monomer odor.
【００１４】〈比較例 １１〉表２に示すように実施例
１１においてＢｕＭＣの代わりにＰＴＡ ２１．０ｇを
使用した以外は実施例１１に準じて実施した。その結果
は表２に示すように残存単量体は４．８０％であった。
又ＧＰＣで分子量を測定した結果ピークは２山になり高
分子量側の重量平均分子量は３８５０００であった。得
られた重合物にはスチレン臭及びブチルアクリレート臭
があった。実施例１１及び比較例１１より本発明の方法
は、低分子量共重合体の存在下においても、残存モノマ
ーが少ないことが判る。Comparative Example 11 As shown in Table 2, the procedure of Example 11 was repeated except that 21.0 g of PTA was used instead of BuMC in Example 11. As a result, as shown in Table 2, the residual monomer content was 4.80%.
As a result of measuring the molecular weight by GPC, two peaks were obtained and the weight average molecular weight on the high molecular weight side was 385,000. The obtained polymer had a styrene odor and a butyl acrylate odor. From Example 11 and Comparative Example 11, it can be seen that the method of the present invention has less residual monomer even in the presence of the low molecular weight copolymer.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【表２】 [Table 2]
【００１７】表１、表２を比較することにより本発明の
重合開始剤を用いてスチレンと（メタ）アクリル酸エス
テルとを懸濁重合して得られた樹脂はトナー用として優
れた性質を持つことが明らかになった。By comparing Tables 1 and 2, the resin obtained by suspension polymerization of styrene and (meth) acrylic acid ester using the polymerization initiator of the present invention has excellent properties for toner. It became clear.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｇ 9/087 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location G03G 9/087
Claims (1)
との単量体混合物より懸濁重合によりトナー用樹脂を製
造するに際し、重合開始剤として一般式 【化１】 で示される化合物を用いることを特徴とするトナー用樹
脂の製造方法。1. When a toner resin is produced by suspension polymerization from a monomer mixture of styrene and a (meth) acrylic acid ester, a compound represented by the general formula: A method for producing a resin for toner, which comprises using the compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6037524A JPH07224103A (en) | 1994-02-14 | 1994-02-14 | Production of toner resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6037524A JPH07224103A (en) | 1994-02-14 | 1994-02-14 | Production of toner resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07224103A true JPH07224103A (en) | 1995-08-22 |
Family
ID=12499937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6037524A Pending JPH07224103A (en) | 1994-02-14 | 1994-02-14 | Production of toner resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07224103A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955234A (en) * | 1996-10-09 | 1999-09-21 | Canon Kabushiki Kaisha | Toner for developing electrostatic image, and image forming method |
| JP2007065633A (en) * | 2005-08-01 | 2007-03-15 | Canon Inc | toner |
| JP2010202811A (en) * | 2009-03-05 | 2010-09-16 | Sekisui Plastics Co Ltd | Styrene-acrylic resin particle for shrink inhibitors |
-
1994
- 1994-02-14 JP JP6037524A patent/JPH07224103A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955234A (en) * | 1996-10-09 | 1999-09-21 | Canon Kabushiki Kaisha | Toner for developing electrostatic image, and image forming method |
| JP2007065633A (en) * | 2005-08-01 | 2007-03-15 | Canon Inc | toner |
| JP2010202811A (en) * | 2009-03-05 | 2010-09-16 | Sekisui Plastics Co Ltd | Styrene-acrylic resin particle for shrink inhibitors |
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