JP4763355B2 - Method for producing toner for developing negatively charged electrostatic latent image - Google Patents
Method for producing toner for developing negatively charged electrostatic latent image Download PDFInfo
- Publication number
- JP4763355B2 JP4763355B2 JP2005179350A JP2005179350A JP4763355B2 JP 4763355 B2 JP4763355 B2 JP 4763355B2 JP 2005179350 A JP2005179350 A JP 2005179350A JP 2005179350 A JP2005179350 A JP 2005179350A JP 4763355 B2 JP4763355 B2 JP 4763355B2
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- JP
- Japan
- Prior art keywords
- dispersion
- unit
- emulsion
- charge control
- sulfonic acid
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000006185 dispersion Substances 0.000 claims description 98
- 239000003795 chemical substances by application Substances 0.000 claims description 78
- 239000000178 monomer Substances 0.000 claims description 55
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- 239000000839 emulsion Substances 0.000 claims description 45
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- 239000003086 colorant Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical group OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 230000004931 aggregating effect Effects 0.000 claims description 5
- MIEUQGPIBQNSDB-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid;sodium Chemical group [Na].CC(=C)C(=O)OCCS(O)(=O)=O MIEUQGPIBQNSDB-UHFFFAOYSA-N 0.000 claims description 3
- XBACSBFKXGHTIS-UHFFFAOYSA-N 2-methyl-5-sulfopent-2-enoic acid Chemical group OC(=O)C(C)=CCCS(O)(=O)=O XBACSBFKXGHTIS-UHFFFAOYSA-N 0.000 claims description 3
- QYHGKNBHPLUAJQ-UHFFFAOYSA-N 2-methylidene-4-sulfobutanoic acid Chemical group OC(=O)C(=C)CCS(O)(=O)=O QYHGKNBHPLUAJQ-UHFFFAOYSA-N 0.000 claims description 3
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- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical group [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 238000005185 salting out Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- 125000000129 anionic group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- DEWNCLAWVNEDHG-UHFFFAOYSA-M sodium;2-(2-methylprop-2-enoyloxy)ethanesulfonate Chemical compound [Na+].CC(=C)C(=O)OCCS([O-])(=O)=O DEWNCLAWVNEDHG-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
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- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
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- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
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- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
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- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Developing Agents For Electrophotography (AREA)
Description
本発明は、乾式電子写真法において、静電荷潜像を可視像とする際に用いられる負帯電性静電潜像現像用トナーの製造方法に関する。 The present invention relates to a method for producing a toner for developing a negatively chargeable electrostatic latent image used when a latent electrostatic image is made visible in dry electrophotography.
乾式電子写真法において、静電荷潜像を可視像とする際に用いられるトナーとしては、バインダ樹脂、着色剤、電荷制御剤、必要に応じて磁性粉体、その他添加剤を含むものが使用されている。
トナーの製造方法としては、トナーを構成する成分を含む塊を粉砕する粉砕法が一般的であったが、近年では、粒子を微細かつ均一にでき、高解像度化に容易に対応できることから、エマルジョン凝集法が普及しつつある(例えば、特許文献1参照)。このエマルジョン凝集法では、まず、粉末状の電荷制御剤を水に分散させて電荷制御剤水分散液を調製した後、この電荷制御剤水分散液とバインダ樹脂のエマルジョンと着色剤とを混合して混合液を得る。次いで、混合液に凝集剤を添加して、混合液に含まれる固形物を凝集させ、得られた固形物を濾過により回収した後、洗浄、乾燥する。そして、この方法により得られた乾燥固形物をトナーとして用いる。
In dry electrophotography, the toner used to make the electrostatic latent image visible is used as a toner containing a binder resin, a colorant, a charge control agent, magnetic powder as required, and other additives. Has been.
As a method for producing toner, a pulverization method for pulverizing a lump containing components constituting the toner has been generally used. However, in recent years, particles can be made fine and uniform, and can easily cope with high resolution. The aggregation method is becoming widespread (for example, see Patent Document 1). In this emulsion aggregation method, a powder charge control agent is first dispersed in water to prepare a charge control agent aqueous dispersion, and then the charge control agent aqueous dispersion, a binder resin emulsion, and a colorant are mixed. To obtain a mixture. Next, an aggregating agent is added to the mixed solution to aggregate the solids contained in the mixed solution, and the obtained solids are collected by filtration, and then washed and dried. The dry solid obtained by this method is used as a toner.
一般的に、トナーを静電荷潜像の可視像化(現像)に供する際には、摩擦によりその表面を帯電しておく。トナーに含まれる電荷制御剤は、その際の帯電の電荷を制御するためのものであり、含金属錯体塩系の染料等が広く使用されている。しかしながら、含金属錯体塩系染料はバインダ樹脂との相溶性が低く、バインダ樹脂に均一に付着しにくいという問題を有する。そこで、電荷制御剤として、スルホン酸系単量体単位を含有する共重合体(以下、スルホン酸系共重合体という。)を用いることが提案されている(例えば、特許文献2参照)。スルホン酸系共重合体は樹脂であるからバインダ樹脂との相溶性に優れる。
特許文献2に記載のスルホン酸系共重合体は、ラジカル重合性単量体とスルホン酸系単量体とを、溶液重合、乳化重合、懸濁重合などにより重合した後、溶媒に溶解または分散した固形物を回収することで得られる。
ところで、上記スルホン酸系共重合体を電荷制御剤として用い、エマルジョン凝集法によりトナーを製造する場合には、スルホン酸系共重合体の固形物を水に混合して電荷制御剤分散液を調製し、この電荷制御剤水分散液とバインダ樹脂のエマルジョンと着色剤とを混合して混合液を得る必要がある。しかしながら、スルホン酸系共重合体の固形物は水に再分散しにくいため、トナーの製造に上述したエマルジョン凝集法を適用した場合には、電荷制御剤であるスルホン酸系共重合体がバインダ樹脂に均一に付着したトナーを得ることは困難であった。
本発明は、前記事情を鑑みてなされたものであり、電荷制御剤としてスルホン酸系共重合体を用い、トナーの製造にエマルジョン凝集法を適用した場合でも、電荷制御剤がバインダ樹脂に均一に付着した負帯電性静電潜像現像用トナーを簡便に製造できる負帯電性静電潜像現像用トナーの製造方法を提供することを目的とする。
The sulfonic acid copolymer described in Patent Document 2 is obtained by polymerizing a radical polymerizable monomer and a sulfonic acid monomer by solution polymerization, emulsion polymerization, suspension polymerization or the like, and then dissolving or dispersing in a solvent. It is obtained by recovering the solid matter.
By the way, when the toner is produced by the emulsion aggregation method using the sulfonic acid copolymer as a charge control agent, a solid material of the sulfonic acid copolymer is mixed with water to prepare a charge control agent dispersion. The charge control agent aqueous dispersion, the binder resin emulsion, and the colorant need to be mixed to obtain a mixture. However, since the solid material of the sulfonic acid copolymer is difficult to be redispersed in water, when the emulsion aggregation method described above is applied to the production of the toner, the sulfonic acid copolymer that is a charge control agent is a binder resin. It was difficult to obtain a toner that uniformly adhered to the toner.
The present invention has been made in view of the above circumstances, and even when a sulfonic acid-based copolymer is used as a charge control agent and an emulsion aggregation method is applied to the production of toner, the charge control agent is uniformly applied to the binder resin. It is an object of the present invention to provide a method for producing a negatively chargeable electrostatic latent image developing toner capable of easily producing a negatively charged electrostatic latent image developing toner.
本発明の負帯電性静電潜像現像用トナーの製造方法は、ラジカル重合性単量体単位99.5〜80質量%およびスルホン酸系単量体単位0.5〜20質量%を含むスルホン酸系共重合体の乳化重合エマルジョンである負電荷制御剤乳化分散液(A)と、バインダ樹脂のエマルジョンであるバインダ樹脂乳化分散液(B)と、着色剤が水中に分散した着色剤分散液(C)および/または離型剤が水中に分散した離型剤分散液(D)とを配合し、混合して混合液を調製する混合工程と、該混合液に含まれる固形物を凝集させて回収する回収工程とを有し、混合工程では、負電荷制御剤乳化分散液(A)中の固形分が、前記混合液に含まれる固形物中の0.5〜10質量%になるように配合し、
前記スルホン酸系共重合体に含まれるラジカル重合性単量体単位が、スチレン系単量体単位、メタクリル酸アルキルエステル単位、アクリル酸アルキルエステル単位から選ばれる1種以上であり、スルホン酸系単量体単位が、2−アクリルアミド−2−メチルプロパンスルホン酸単位、スチレンスルホン酸ナトリウム単位、スルホエチルアクリル酸単位、スルホエチルメタクリル酸単位、スルホエチルメタクリル酸ナトリウム単位から選ばれる1種以上であることを特徴とする。
本発明の負帯電性静電潜像現像用トナーの製造方法においては、スチレン系単量体単位が、スチレン、α−メチルスチレンから選ばれる1種以上であることが好ましい。
The method for producing a negatively chargeable electrostatic latent image developing toner of the present invention comprises a sulfone containing 99.5 to 80% by mass of a radical polymerizable monomer unit and 0.5 to 20% by mass of a sulfonic acid monomer unit. A negative charge control agent emulsion dispersion (A) which is an emulsion polymerization emulsion of an acid copolymer, a binder resin emulsion dispersion (B) which is an emulsion of a binder resin, and a colorant dispersion in which a colorant is dispersed in water (C) and / or a release agent dispersion liquid (D) in which a release agent is dispersed in water, and mixing to prepare a mixed liquid, and aggregating solids contained in the mixed liquid It possesses a recovery step of recovering Te, in the mixing step, so that the solid content in the negative charge control agent emulsified dispersion (a) becomes 0.5 to 10% by weight of the solids in the contained in the liquid mixture Blended with
The radical polymerizable monomer unit contained in the sulfonic acid copolymer is at least one selected from a styrene monomer unit, a methacrylic acid alkyl ester unit, and an acrylic acid alkyl ester unit. The monomer unit is at least one selected from 2-acrylamido-2-methylpropanesulfonic acid unit, sodium styrenesulfonate unit, sulfoethylacrylic acid unit, sulfoethylmethacrylic acid unit, and sodium sulfoethylmethacrylate unit. It is characterized by.
In the method for producing a negatively chargeable electrostatic latent image developing toner of the present invention, the styrene monomer unit is preferably at least one selected from styrene and α-methylstyrene.
本発明の負帯電性静電潜像現像用トナーの製造方法によれば、エマルジョン凝集法によるトナーの製造であるにもかかわらず、電荷制御剤がバインダ樹脂に均一に付着した負帯電性静電潜像現像用トナーを簡便に製造できる。
本発明の負帯電性静電潜像現像用トナーの製造方法において、負電荷制御剤乳化分散液(A)のスルホン酸系共重合体に含まれるラジカル重合性単量体単位がスチレン系単量体単位および/またはアクリル系単量体単位であり、スルホン酸系単量体単位が2−アクリルアミド−2−メチルプロパンスルホン酸単位である場合には、重合しやすい上に、好ましい軟らかさの共重合体を得ることができる。
また、本発明の負帯電性静電潜像現像用トナーの製造方法において、負電荷制御剤乳化分散液(A)のスルホン酸系共重合体におけるラジカル重合性単量体単位の含有量が99.5〜80質量%、スルホン酸系単量体単位の含有量が0.5〜20質量%である場合には、得られるトナーに適度な帯電性を付与することができる。
また、混合工程にて、負電荷制御剤乳化分散液(A)中の固形分が、前記混合液に含まれる固形物中の0.1〜15質量%になるように配合する場合にも、得られるトナーに適度な帯電性を付与することができる。
According to the method for producing a negatively chargeable electrostatic latent image developing toner of the present invention, the charge control agent is uniformly adhered to the binder resin even though the toner is produced by an emulsion aggregation method. A toner for developing a latent image can be easily produced.
In the method for producing a negatively chargeable electrostatic latent image developing toner of the present invention, the radical polymerizable monomer unit contained in the sulfonic acid copolymer of the negative charge control agent emulsified dispersion (A) is a styrene monomer. In the case where the sulfonic acid monomer unit is a 2-acrylamido-2-methylpropane sulfonic acid unit, it is easy to polymerize and has a preferred softness. A polymer can be obtained.
In the method for producing a negatively chargeable electrostatic latent image developing toner of the present invention, the content of the radically polymerizable monomer unit in the sulfonic acid copolymer of the negative charge control agent emulsified dispersion (A) is 99. When the content of the sulfonic acid monomer unit is 0.5 to 20% by mass and the content of the sulfonic acid monomer unit is 0.5 to 20% by mass, appropriate chargeability can be imparted to the obtained toner.
Moreover, also when mix | blending so that the solid content in a negative charge control agent emulsion dispersion liquid (A) may be 0.1-15 mass% in the solid substance contained in the said liquid mixture in a mixing process, Appropriate chargeability can be imparted to the resulting toner.
本発明の負帯電性静電潜像現像用トナー(以下、トナーと略す。)の製造方法は、負電荷制御剤乳化分散液(A)とバインダ樹脂乳化分散液(B)と着色剤分散液(C)および/または離型剤分散液(D)とを配合し、混合して混合液を調製する混合工程と、混合工程により調製された混合液に含まれる固形物を凝集させて回収する回収工程とを有する。
以下、各工程について説明する。
The method for producing a negatively chargeable electrostatic latent image developing toner (hereinafter abbreviated as “toner”) of the present invention comprises a negative charge control agent emulsified dispersion (A), a binder resin emulsified dispersion (B), and a colorant dispersion. (C) and / or mold release agent dispersion (D) are mixed and mixed to prepare a mixed solution, and solids contained in the mixed solution prepared by the mixing step are aggregated and recovered. A recovery step.
Hereinafter, each step will be described.
(混合工程)
混合工程にて配合される(A)〜(D)成分について説明する。
負電荷制御剤乳化分散液(A)は、ラジカル重合性単量体単位とスルホン酸系単量体単位を含むスルホン酸系共重合体の乳化重合エマルジョンである。ここで、乳化重合エマルジョンとは、乳化重合によって得られたエマルジョンのことである。また、スルホン酸系共重合体は負電荷制御剤として機能するものである。
(Mixing process)
The components (A) to (D) blended in the mixing step will be described.
The negative charge control agent emulsion dispersion (A) is an emulsion polymerization emulsion of a sulfonic acid copolymer containing a radical polymerizable monomer unit and a sulfonic acid monomer unit. Here, the emulsion polymerization emulsion is an emulsion obtained by emulsion polymerization. The sulfonic acid copolymer functions as a negative charge control agent.
ラジカル重合性単量体としては、例えば、スチレン、α−メチルスチレン等のスチレン系単量体、メタクリル酸アルキルエステル、アクリル酸アルキルエステル等のアクリル系単量体、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、アクリロニトリルなどが挙げられる。
スルホン酸系単量体としては、例えば、2−アクリルアミド−2−メチルプロパンスルホン酸、スチレンスルホン酸ナトリウム、スルホエチルアクリル酸、スルホエチルメタクリル酸、スルホエチルメタクリル酸ナトリウム等のスルホアルキル(メタ)アクリル酸系単量体などが挙げられる。
ラジカル重合性単量体およびスルホン酸系単量体はそれぞれ1種類であってもよいし、2種類以上を組み合わせてもよい。
Examples of the radical polymerizable monomer include styrene monomers such as styrene and α-methylstyrene, acrylic monomers such as alkyl methacrylate and alkyl acrylate, vinyl acetate, vinyl propionate, and chloride. Examples thereof include vinyl and acrylonitrile.
Examples of the sulfonic acid monomer include sulfoalkyl (meth) acryl such as 2-acrylamido-2-methylpropanesulfonic acid, sodium styrenesulfonate, sulfoethylacrylic acid, sulfoethylmethacrylic acid, and sodium sulfoethylmethacrylate. Examples include acid monomers.
Each of the radical polymerizable monomer and the sulfonic acid monomer may be one kind or a combination of two or more kinds.
上記単量体の中でも、重合しやすい上に、好ましい軟らかさの共重合体を得ることができることから、ラジカル重合性単量体がスチレン系単量体および/またはアクリル酸系単量体であり、かつ、スルホン酸系単量体が2−アクリルアミド−2−メチルプロパンスルホン酸であることが好ましい。 Among the above monomers, the radical polymerizable monomer is a styrene monomer and / or an acrylic acid monomer because it is easy to polymerize and a copolymer having a preferable softness can be obtained. In addition, the sulfonic acid monomer is preferably 2-acrylamido-2-methylpropanesulfonic acid.
スルホン酸系共重合体においては、ラジカル重合性単量体単位の含有量が99.5〜80質量%およびスルホン酸系単量体単位の含有量が0.5〜20質量%であることが好ましく、ラジカル重合性単量体単位の含有量が99〜85質量%およびスルホン酸系単量体単位の量が1〜15質量%であることが好ましい(ただし、ラジカル重合性単量体単位とスルホン酸系単量体単位との合計が100質量%である。)。ラジカル重合性単量体単位の含有量が99.5質量%を超えると(スルホン酸系単量体単位の含有量が0.5質量%未満であると)、得られるトナーが充分に帯電しないことがある。また、ラジカル重合性単量体単位の含有量が80質量%未満である(スルホン酸系単量体単位の含有量が20質量%を超える)場合においても、充分な帯電性を確保することができなくなる。 In the sulfonic acid copolymer, the content of the radically polymerizable monomer unit is 99.5 to 80% by mass and the content of the sulfonic acid monomer unit is 0.5 to 20% by mass. Preferably, the content of the radical polymerizable monomer unit is 99 to 85% by mass and the amount of the sulfonic acid monomer unit is 1 to 15% by mass (provided that the radical polymerizable monomer unit and The total with the sulfonic acid monomer units is 100% by mass). When the content of the radical polymerizable monomer unit exceeds 99.5% by mass (when the content of the sulfonic acid monomer unit is less than 0.5% by mass), the resulting toner is not sufficiently charged. Sometimes. Further, even when the content of the radical polymerizable monomer unit is less than 80% by mass (the content of the sulfonic acid monomer unit exceeds 20% by mass), sufficient chargeability can be ensured. become unable.
負電荷制御剤乳化分散液(A)は、ラジカル重合性単量体とスルホン酸系単量体とを乳化重合することにより得られる。
その際に使用する重合開始剤としては、例えば、過酸化ベンゾイル、t−ブチルパーベンゾエート、ジシクロヘキシルパーオキサイド、ジクミルパーオキサイド、アゾビスイソブチロニトリル、アゾビスメチルブチロニトリル、アゾビスジメチルバレロニトリル、ペルオキソ二硫酸ナトリウム、ペルオキソ二硫酸カリウム、ペルオキソ二硫酸アンモニウムなどが挙げられる。
乳化剤としては特に制限されず、例えば、モノアルキルサクシネートスルホン酸ジナトリウム塩、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩、アルキルジフェニルエーテルジスルホン酸ナトリウム、メタクリロイロキシエチルスルホン酸ナトリウムなどが挙げられる。
また、乳化重合の際には、ラジカル重合性単量体とスルホン酸系単量体とをそれぞれ別々に添加することが好ましい。スルホン酸系単量体は水に溶解しやすいため、別々に添加することによりラジカル重合性単量体との共重合性を高めることができる。
この乳化重合により得られた負電荷制御剤乳化分散液(A)中のスルホン酸系共重合体含有量は10〜40質量%であることが好ましい。
The negative charge control agent emulsion dispersion (A) is obtained by emulsion polymerization of a radical polymerizable monomer and a sulfonic acid monomer.
Examples of the polymerization initiator used in this case include benzoyl peroxide, t-butyl perbenzoate, dicyclohexyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobismethylbutyronitrile, azobisdimethylvalero. Nitrile, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate and the like can be mentioned.
The emulsifier is not particularly limited, and examples thereof include monoalkyl succinate sulfonic acid disodium salt, polyoxyethylene polycyclic phenyl ether sulfate ester salt, alkyl diphenyl ether disulfonate sodium salt, and sodium methacryloyloxyethyl sulfonate.
In the emulsion polymerization, it is preferable to add the radical polymerizable monomer and the sulfonic acid monomer separately. Since the sulfonic acid monomer is easily dissolved in water, the copolymerization with the radical polymerizable monomer can be enhanced by adding it separately.
The sulfonic acid copolymer content in the negative charge control agent emulsion dispersion (A) obtained by this emulsion polymerization is preferably 10 to 40% by mass.
バインダ樹脂乳化分散液(B)は、バインダ樹脂のエマルジョンのことである。バインダ樹脂としては、例えば、ポリスチレン、ポリ−p−クロルスチレン、ポリビニルトルエンなどのスチレンおよびその置換体の単独重合体;スチレン−p−クロルスチレン共重合体、スチレン−ビニルトルエン共重合体、スチレン−ビニルナフタリン共重合体、スチレンアクリル酸エステル共重合体、スチレン−メタクリル酸エステル共重合体、スチレン−α−クロルメタクリル酸メチル共重合体、スチレン−アクリロニトリル共重合体、スチレン−ビニルメチルエーテル共重合体、スチレン−ビニルエーテル共重合体、スチレン−ビニルメチルケトン共重合体、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、スチレン−アクリロニトリル−インデン共重合体などのスチレン系共重合体;ポリ塩化ビニル、フェノール樹脂、天然変性フェノール樹脂、天然樹脂変性マレイン酸樹脂、アクリル樹脂、メタクリル樹脂、ポリ酢酸ビニル、シリコーン樹脂、ポリエステル、ポリウレタン、ポリアミド、フラン樹脂、エポキシ樹脂、キシレン樹脂、ポリビニルブチラール、テルペン樹脂、クマロインデン樹脂、石油系樹脂などが挙げられる。
これらの中でも、ポリスチレン、(メタ)アクリル酸エステルの単独重合体もしくはこれらの共重合体、ビスフェノール型ジオールおよびグリコールからなる群から選ばれた少なくとも1つのジオール成分と、フタル酸、イソフタル酸、テルフタル酸などのジカルボン酸またはトリメリット酸とから合成されるポリエステルが好ましい。
The binder resin emulsified dispersion (B) is an emulsion of a binder resin. Examples of the binder resin include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene- Vinyl naphthalene copolymer, styrene acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Styrene copolymers such as styrene-vinyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride , Fenault Resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester, polyurethane, polyamide, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaroindene resin And petroleum resins.
Among these, at least one diol component selected from the group consisting of polystyrene, (meth) acrylic acid ester homopolymers or copolymers thereof, bisphenol type diols and glycols, and phthalic acid, isophthalic acid, terphthalic acid Polyesters synthesized from dicarboxylic acids or trimellitic acids such as are preferred.
バインダ樹脂乳化分散液(B)は、乳化重合により得られる。また、各種重合法により得られたバインダ樹脂の固形物を分散媒中に乳化分散させることによっても得られる。バインダ樹脂乳化分散液(B)中の乳化剤としては特に制限されず、例えば、負電荷制御剤乳化分散液(A)に含まれる乳化剤と同じものが挙げられる。
バインダ樹脂乳化分散液(B)中のバインダ樹脂含有量は10〜50質量%であることが好ましい。
The binder resin emulsion dispersion (B) is obtained by emulsion polymerization. It can also be obtained by emulsifying and dispersing a binder resin solid obtained by various polymerization methods in a dispersion medium. The emulsifier in the binder resin emulsion dispersion (B) is not particularly limited, and examples thereof include the same emulsifiers as those contained in the negative charge control agent emulsion dispersion (A).
The binder resin content in the binder resin emulsion dispersion (B) is preferably 10 to 50% by mass.
着色剤分散液(C)は、着色剤が水中に分散した液であり、具体的には、懸濁分散液であってもよいし、乳化分散液であってもよい。ただし、着色剤の分散性を向上させるためには、乳化剤(界面活性剤)を含んだ乳化分散液が好ましい。乳化剤としては、着色剤の種類に応じて、カチオン性、アニオン性、非イオン性のいずれかが適宜選択される。 The colorant dispersion (C) is a liquid in which a colorant is dispersed in water. Specifically, the colorant dispersion (C) may be a suspension dispersion or an emulsification dispersion. However, in order to improve the dispersibility of the colorant, an emulsified dispersion containing an emulsifier (surfactant) is preferable. As the emulsifier, either cationic, anionic, or nonionic is appropriately selected according to the type of the colorant.
着色剤分散液(C)中の着色剤としては、例えば、カーボンブラック、ランプブラック、鉄黒、群青、ニグロシン染料、アニリンブルー、フタロシアニンブルー、フタロシアニングリーン、ハンザイエローG、ローダミン6G、カルコオイルブルー、クロムイエロー、キナクリドン、ベンジジンイエロー、ローズベンガル、トリアリールメタン系染料、モノアゾ系、ジスアゾ系染顔料などを単独で、あるいは混合して使用できる。
着色剤分散液(C)中の着色剤含有量は5〜30質量%であることが好ましい。
Examples of the colorant in the colorant dispersion (C) include carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, calco oil blue, Chrome yellow, quinacridone, benzidine yellow, rose bengal, triarylmethane dyes, monoazo dyes, disazo dyes and the like can be used alone or in combination.
The colorant content in the colorant dispersion (C) is preferably 5 to 30% by mass.
離型剤分散液(D)は、離型剤が水中に分散した液であり、具体的には、懸濁分散液であってもよいし、乳化分散液であってもよい。ただし、離型剤の分散性を向上させるためには、乳化剤(界面活性剤)を含んだ乳化分散液が好ましい。乳化剤としては、離型剤の種類に応じて、カチオン性、アニオン性、非イオン性のいずれかが適宜選択される。 The release agent dispersion (D) is a liquid in which the release agent is dispersed in water. Specifically, the release agent dispersion (D) may be a suspension dispersion or an emulsification dispersion. However, in order to improve the dispersibility of the release agent, an emulsified dispersion containing an emulsifier (surfactant) is preferable. As the emulsifier, either cationic, anionic or nonionic is appropriately selected depending on the type of the release agent.
離型剤分散液(D)中の離型剤としては、例えば、ポリエチレンワックス、ポリプロピレンワックス、高級脂肪酸ビスアミド系ワックス、カルナバワックスなどの天然ワックスなどが挙げられる。
離型剤分散液(D)中の離型剤含有量は5〜30質量%であることが好ましい。
Examples of the release agent in the release agent dispersion (D) include natural waxes such as polyethylene wax, polypropylene wax, higher fatty acid bisamide wax, and carnauba wax.
The release agent content in the release agent dispersion (D) is preferably 5 to 30% by mass.
混合工程においては、負電荷制御剤乳化分散液(A)中の固形分が前記混合液に含まれる固形物中の0.1〜15質量%になるように各成分を配合することが好ましい。このように配合することにより、得られるトナーに含まれる負電荷制御剤乳化分散液(A)の固形分の量を0.1〜15質量%、特に0.5〜10質量%にすることができる。トナーに含まれる負電荷制御剤乳化分散液(A)の固形分の量が前記範囲外にあると、トナーが適度な帯電性を有することができず、乾式電子写真法により形成した画像の特性が低くなる傾向にある。すなわち、トナーに含まれる負電荷制御剤乳化分散液(A)の固形分の量が0.1質量%より少ないと、トナー帯電の立ち上がりが悪い、トナー飛散が多い、トナーのボタ落ちが生じるなどの問題が起きることがある。一方、10質量%より多くなると、トナーの吸湿性が強くなり、帯電量の経時変化が大きくなる。
なお、ここでいう各成分とは、(A)〜(D)成分のみを配合する場合にはこれらの成分のことであり、後述する他の成分(E)をさらに配合する場合には(A)〜(E)成分のことである。
In the mixing step, each component is preferably blended so that the solid content in the negative charge control agent emulsified dispersion (A) is 0.1 to 15% by mass in the solid contained in the mixed solution. By blending in this way, the solid content of the negative charge control agent emulsified dispersion (A) contained in the obtained toner can be 0.1 to 15% by mass, particularly 0.5 to 10% by mass. it can. If the amount of the solid content of the negative charge control agent emulsified dispersion (A) contained in the toner is outside the above range, the toner cannot have an appropriate chargeability, and the characteristics of an image formed by dry electrophotography Tend to be lower. That is, if the amount of the solid content of the negative charge control agent emulsified dispersion (A) contained in the toner is less than 0.1% by mass, the toner charge rises poorly, the toner scatters a lot, and the toner drops off. Problems may occur. On the other hand, if it exceeds 10% by mass, the hygroscopicity of the toner becomes strong and the change with time in the charge amount becomes large.
In addition, each component here is these components, when mix | blending only (A)-(D) component, and when further mix | blending the other component (E) mentioned later (A) ) To (E).
また、混合工程においては、上記(A)〜(D)成分以外に、他の成分(E)を配合してもよい。他の成分(E)としては、例えば、トナーを二成分系現像剤として用いる場合には、キャリアを含む分散液などが挙げられる。ここで、キャリアとしては、カスケード現像方式を実施する場合には樹脂コートしたガラスビーズやスチール球等が挙げられ、磁気ブラシ現像方式を実施する場合にはフェライトや微粉鉄、あるいはいわゆるバインダ型キャリア等が挙げられる。 Moreover, in a mixing process, you may mix | blend another component (E) other than the said (A)-(D) component. Examples of the other component (E) include a dispersion liquid containing a carrier when a toner is used as a two-component developer. Here, examples of the carrier include resin-coated glass beads and steel balls when the cascade development method is performed, and ferrite, fine iron, or a so-called binder type carrier when the magnetic brush development method is performed. Is mentioned.
(回収工程)
回収工程において、混合液に含まれる固形物を凝集させる方法としては、例えば、凝集剤を添加する塩析法、異なる電荷の乳化分散液を混合するヘテロ凝集、乳化破壊を生じるpHに調節するpH調節法、乳化破壊を生じる温度に調節する温度調節法、混合液を真空乾燥器内に噴霧するスプレードライ法などを適用することができる。
これらの中でも塩析法が簡便であるため好ましい。塩析法を適用する場合の凝集剤としては、例えば、硫酸アルミニウム、硝酸カルシウム、硫酸亜鉛、硫酸マグネシウム、ポリ塩化アルミニウムなどが挙げられる。凝集剤の添加量は、混合液中の分散媒を100質量%とした際の0.05〜10質量%であることが好ましく、0.075〜2質量%であることがより好ましい。
(Recovery process)
In the recovery step, the solids contained in the mixed solution may be aggregated by, for example, a salting-out method in which a flocculant is added, heteroaggregation in which emulsion dispersions of different charges are mixed, or a pH that is adjusted to a pH that causes emulsion breakage An adjustment method, a temperature adjustment method for adjusting the temperature to cause emulsification breakage, a spray drying method in which a mixed solution is sprayed into a vacuum dryer, and the like can be applied.
Among these, the salting out method is preferable because it is simple. Examples of the flocculant when applying the salting-out method include aluminum sulfate, calcium nitrate, zinc sulfate, magnesium sulfate, and polyaluminum chloride. The addition amount of the flocculant is preferably 0.05 to 10% by mass, more preferably 0.075 to 2% by mass, based on 100% by mass of the dispersion medium in the mixed liquid.
混合液を凝集して得た固形物は回収後に、洗浄、乾燥することが好ましい。洗浄方法としては、例えば、多量の水で洗い流す方法などが挙げられ、乾燥方法としては、例えば、熱風乾燥法、赤外線照射乾燥法、真空乾燥法などが挙げられる。 The solid obtained by aggregating the mixed solution is preferably washed and dried after recovery. Examples of the cleaning method include a method of rinsing with a large amount of water, and examples of the drying method include a hot air drying method, an infrared irradiation drying method, and a vacuum drying method.
上記回収工程により回収された固形物をトナーとして用いる。固形物をそのままトナーとして用いてもよいが、解砕し、分級して所定範囲の粒径のものを選別して用いることが好ましい。
得られたトナーの帯電量は10〜40μC/gであることが好ましく、15〜35μC/gであることがより好ましい。トナーの帯電量が10μC/g未満であると、トナーを記録シートの所定の部分に転写することが困難になり、画像を形成した際に背景部分が汚れやすくなる。また、トナーの帯電量が40μC/gを超えると、画像濃度が低下する傾向にある。
The solid matter recovered by the recovery step is used as toner. The solid material may be used as the toner as it is, but it is preferable to use the solid material after pulverizing and classifying it to select a particle having a predetermined particle size.
The charge amount of the obtained toner is preferably 10 to 40 μC / g, and more preferably 15 to 35 μC / g. When the charge amount of the toner is less than 10 μC / g, it becomes difficult to transfer the toner to a predetermined portion of the recording sheet, and the background portion is easily stained when an image is formed. Further, when the charge amount of the toner exceeds 40 μC / g, the image density tends to decrease.
上述したように、トナーの製造方法における負電荷制御剤分散液(A)は、スルホン酸系共重合体の乳化重合エマルジョンであり、スルホン酸系共重合体が均一に分散した液である。そのため、負電荷制御剤乳化分散液(A)と、バインダ樹脂乳化分散液(B)と、着色剤分散液(C)および/または離型剤分散液(D)とを配合し、混合することにより、均一な混合液を調製できる。また、スルホン酸系共重合体の乳化重合エマルジョンを固形物化せずに、そのまま用いるため、混合液を容易に調製できる。したがって、この混合液に含まれる固形物を凝集させて回収することにより、電荷制御剤がバインダ樹脂に均一に付着したトナーを簡便に製造できる。そして、このようなトナーを用いれば、画質に優れた画像を形成できる。 As described above, the negative charge control agent dispersion liquid (A) in the toner production method is an emulsion polymerization emulsion of a sulfonic acid copolymer, and is a liquid in which the sulfonic acid copolymer is uniformly dispersed. Therefore, the negative charge control agent emulsion dispersion (A), the binder resin emulsion dispersion (B), the colorant dispersion (C) and / or the release agent dispersion (D) are blended and mixed. Thus, a uniform mixed solution can be prepared. Moreover, since the emulsion polymerization emulsion of a sulfonic acid copolymer is used as it is without being solidified, a mixed solution can be easily prepared. Therefore, a toner in which the charge control agent uniformly adheres to the binder resin can be easily produced by aggregating and collecting the solids contained in the mixed solution. If such toner is used, an image having excellent image quality can be formed.
以下、実施例に基づいて本発明を具体的に説明する。
[調製例1]負電荷制御剤乳化分散液(A−1)の調製
攪拌機、コンデンサ、温度計、窒素導入管を備えた3Lフラスコに、純水1000g、乳化剤としてモノアルキルサクシネートスルホン酸ジナトリウム塩(日本乳化剤製ニューコール293)8g、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩(日本乳化剤製ニューコール707−SF)2gを仕込み、30分間窒素置換した。
次いで、上記フラスコにペルオキソ二硫酸カリウム(KPS)2gを仕込み、攪拌して溶解させた。その後、窒素導入下70℃に昇温し、スチレン280gおよびアクリル酸−2−エチルヘキシル(2−EHA)80gの単量体混合物と、2−アクリルアミド−2−メチルプロパンスルホン酸(AAPS)40gを純水600gに溶解した水溶液とを、3時間かけて、それぞれ別々にフラスコ内に滴下した。その後、80℃のまま3時間重合し、残存モノマーを低減させる目的で、KPS0.3gをあらたに添加し、85℃に昇温し、2時間反応させて負電荷制御剤乳化分散液(A−1)を得た。
Hereinafter, the present invention will be specifically described based on examples.
[Preparation Example 1] Preparation of negative charge control agent emulsified dispersion (A-1) In a 3 L flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 1000 g of pure water and disodium monoalkyl succinate sulfonate as an emulsifier 8 g of a salt (Nippon Emulsifier Newcor 293) and 2 g of a polyoxyethylene polycyclic phenyl ether sulfate salt (Nippon Emulsifier Newcor 707-SF) were charged, and the atmosphere was replaced with nitrogen for 30 minutes.
Next, 2 g of potassium peroxodisulfate (KPS) was charged into the flask and dissolved by stirring. Thereafter, the temperature was raised to 70 ° C. under introduction of nitrogen, and a monomer mixture of 280 g of styrene and 80 g of 2-ethylhexyl acrylate (2-EHA) and 40 g of 2-acrylamido-2-methylpropanesulfonic acid (AAPS) were purified. An aqueous solution dissolved in 600 g of water was separately dropped into the flask over 3 hours. Thereafter, polymerization was continued at 80 ° C. for 3 hours, and for the purpose of reducing the residual monomer, 0.3 g of KPS was newly added, the temperature was raised to 85 ° C., and the mixture was reacted for 2 hours to give a negative charge control agent emulsion dispersion (A- 1) was obtained.
[調製例2]負電荷制御剤乳化分散液(A−2)の調製
アクリル酸−2−エチルヘキシル(2−EHA)80gの代わりにアクリル酸−n−ブチル80gを混合したこと以外は調製例1と同様にして負電荷制御剤乳化分散液(A−2)を得た。
[Preparation Example 2] Preparation of negative charge control agent emulsified dispersion (A-2) Preparation Example 1 except that 80 g of acrylic acid-n-butyl was mixed instead of 80 g of 2-ethylhexyl acrylate (2-EHA) In the same manner as above, a negative charge control agent emulsified dispersion (A-2) was obtained.
[調製例3]負電荷制御剤乳化分散液(A−3)の調製
モノアルキルサクシネートスルホン酸ジナトリウム塩8gの代わりにアルキルジフェニルエーテルジスルホン酸ナトリウム(日本乳化剤製ニューコール271A)8gを混合したこと以外は調製例1と同様にして負電荷制御剤乳化分散液(A−3)を得た。
[Preparation Example 3] Preparation of negative charge control agent emulsified dispersion (A-3) 8 g of sodium alkyldiphenyl ether disulfonate (New Coal 271A manufactured by Nippon Emulsifier) was mixed instead of 8 g of monoalkyl succinate sulfonic acid disodium salt. Except for the above, a negative charge control agent emulsified dispersion (A-3) was obtained in the same manner as in Preparation Example 1.
[調製例4]負電荷制御剤乳化分散液(A−4)の調製
モノアルキルサクシネートスルホン酸ジナトリウム塩8gの代わりにメタクリロイロキシエチルスルホン酸ナトリウム(日本乳化剤製アントックスMS−2N)1gを用い、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩(日本乳化剤製ニューコール707−SF)の量を3gとしたこと以外は調製例1と同様にして負電荷制御剤乳化分散液(A−4)を得た。
[Preparation Example 4] Preparation of emulsified dispersion of negative charge control agent (A-4) 1 g of sodium methacryloyloxyethyl sulfonate (Antox MS-2N manufactured by Nippon Emulsifier) instead of 8 g of monoalkyl succinate sulfonic acid disodium salt And a negative charge control agent emulsified dispersion (A-4) in the same manner as in Preparation Example 1 except that the amount of polyoxyethylene polycyclic phenyl ether sulfate ester (Nippon Emulsifier Newcor 707-SF) was changed to 3 g. )
[調製例5]負電荷制御剤乳化分散液(A−5)の調製
スチレンの量を318g、2−アクリルアミド−2−メチルプロパンスルホン酸の量を1gに変更したこと以外は調製例1と同様にして負電荷制御剤乳化分散液(A−5)を得た。
[Preparation Example 5] Preparation of negative charge control agent emulsified dispersion (A-5) Same as Preparation Example 1, except that the amount of styrene was changed to 318 g and the amount of 2-acrylamido-2-methylpropanesulfonic acid was changed to 1 g. Thus, a negative charge control agent emulsified dispersion (A-5) was obtained.
[調製例6]負電荷制御剤乳化分散液(A−6)の調製
スチレンの量を220g、2−アクリルアミド−2−メチルプロパンスルホン酸の量を100gに変更したこと以外は調製例1と同様にして負電荷制御剤乳化分散液(A−6)を得た。
[Preparation Example 6] Preparation of negative charge control agent emulsified dispersion (A-6) Same as Preparation Example 1, except that the amount of styrene was changed to 220 g and the amount of 2-acrylamido-2-methylpropanesulfonic acid was changed to 100 g. Thus, a negative charge control agent emulsified dispersion (A-6) was obtained.
[調製例7]負電荷制御剤乳化分散液(A−7)の調製
サリチル酸系金属錯体(オリエント化学工業製ボントロンE−84)10g、非イオン性界面活性剤(三洋化成工業製ノニポール400)5g、イオン交換水190gを混合し、ホモジナイザ(IKA製ウルトラタラックスT25)を用いて、20分間分散させて負電荷制御剤乳化分散液(A−7)を得た。
[Preparation Example 7] Preparation of negative charge control agent emulsified dispersion (A-7) 10 g of salicylic acid metal complex (Bontron E-84 manufactured by Orient Chemical Industries), 5 g of nonionic surfactant (Nonipol 400 manufactured by Sanyo Chemical Industries) In addition, 190 g of ion-exchanged water was mixed and dispersed for 20 minutes using a homogenizer (Ultra Turrax T25 manufactured by IKA) to obtain a negative charge control agent emulsified dispersion (A-7).
[調製例8]バインダ樹脂乳化分散液(B−1)の調製
攪拌機、コンデンサ、温度計、窒素導入管を備えた3Lフラスコに、純水930g、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム(日本乳化剤製ニューコール271A)10gを仕込み、30分間窒素置換した。
次いで、上記フラスコにペルオキソ二硫酸カリウム(KPS)2gを仕込み、攪拌して溶解させた。その後、窒素導入下80℃に昇温し、スチレン280gおよびアクリル酸−n−ブチル120gの単量体混合物を仕込み、攪拌した。その後、フラスコ内を80℃に昇温し3時間重合した。その後、残存モノマーを低減させる目的で、KPS0.3gをあらたに添加し、85℃に昇温し、2時間反応させてバインダ樹脂乳化分散液(B−1)を得た。
[Preparation Example 8] Preparation of Binder Resin Emulsion Dispersion (B-1) Into a 3 L flask equipped with a stirrer, condenser, thermometer and nitrogen introduction tube, 930 g of pure water and sodium alkyldiphenyl ether disulfonate as an emulsifier (New from Japan Emulsifier) Cole 271A) was charged with 10 g, and the atmosphere was replaced with nitrogen for 30 minutes.
Next, 2 g of potassium peroxodisulfate (KPS) was charged into the flask and dissolved by stirring. Thereafter, the temperature was raised to 80 ° C. under nitrogen introduction, and a monomer mixture of 280 g of styrene and 120 g of acrylic acid-n-butyl was charged and stirred. Thereafter, the inside of the flask was heated to 80 ° C. and polymerized for 3 hours. Thereafter, for the purpose of reducing the residual monomer, 0.3 g of KPS was newly added, heated to 85 ° C., and reacted for 2 hours to obtain a binder resin emulsion dispersion (B-1).
[調製例9]バインダ樹脂乳化分散液(B−2)の調製
単量体混合物に、アクリル酸8gをさらに含有させたものを用いたこと以外は調製例8と同様にしてバインダ樹脂乳化分散液(B−2)を得た。
[Preparation Example 9] Preparation of Binder Resin Emulsion Dispersion (B-2) Binder Resin Emulsion Dispersion as in Preparation Example 8 except that a monomer mixture further containing 8 g of acrylic acid was used. (B-2) was obtained.
[調製例10]バインダ樹脂乳化分散液(B−3)の調製
攪拌機、コンデンサ、温度計、窒素導入管を備えた3Lフラスコに、純水930g、乳化剤としてアルキルジフェニルエーテルジスルホン酸ナトリウム(日本乳化剤製ニューコール271A)10gを仕込み、30分間窒素置換した。
次いで、上記フラスコにペルオキソ二硫酸カリウム(KPS)2gを仕込み、攪拌して溶解させた。その後、窒素導入下80℃に昇温し、スチレン340gとアクリル酸−n−ブチル60gとn−ドデシルメルカプタン(花王製チオカルコール20)12gの混合液を仕込み、攪拌した。その後、フラスコ内を80℃に昇温し5時間重合した。その後、残存モノマーを低減させる目的で、KPS0.3gをあらたに添加し、85℃に昇温し、2時間反応させ、さらにKPS0.3gを添加し、85℃に昇温し、2時間反応させてバインダ樹脂乳化分散液(B−3)を得た。
[Preparation Example 10] Preparation of Binder Resin Emulsified Dispersion (B-3) In a 3 L flask equipped with a stirrer, condenser, thermometer and nitrogen introduction tube, 930 g of pure water and sodium alkyldiphenyl ether disulfonate as an emulsifier (New from Japan Emulsifier) Cole 271A) was charged with 10 g, and the atmosphere was replaced with nitrogen for 30 minutes.
Next, 2 g of potassium peroxodisulfate (KPS) was charged into the flask and dissolved by stirring. Thereafter, the temperature was raised to 80 ° C. under introduction of nitrogen, and a mixed solution of 340 g of styrene, 60 g of n-butyl acrylate and 12 g of n-dodecyl mercaptan (Kao thiocalcol 20) was charged and stirred. Thereafter, the flask was heated to 80 ° C. and polymerized for 5 hours. Thereafter, for the purpose of reducing the residual monomer, 0.3 g of KPS is newly added, the temperature is raised to 85 ° C., the reaction is performed for 2 hours, and further 0.3 g of KPS is added, the temperature is raised to 85 ° C., and the reaction is performed for 2 hours. Thus, a binder resin emulsion dispersion (B-3) was obtained.
[調製例11]バインダ樹脂乳化分散液(B−4)の調製
混合液に、メタクリル酸8gをさらに含有させたものを用いたこと以外は調製例10と同様にしてバインダ樹脂乳化分散液(B−4)を得た。
[Preparation Example 11] Preparation of Binder Resin Emulsified Dispersion (B-4) Binder Resin Emulsion Dispersion (B-4) was prepared in the same manner as Preparation Example 10 except that the mixture was further mixed with 8 g of methacrylic acid. -4) was obtained.
[調製例12]着色剤分散液(C−1)の調製
カーボンブラック(デグサ製NIPEX150)50g、非イオン性界面活性剤(三洋化成工業製ノニポール400)5g、イオン交換水200gを混合し、ホモジナイザ(IKA製ウルトラタラックスT25)を用いて、20分間分散させて着色剤分散液(C−1)を得た。
[Preparation Example 12] Preparation of Colorant Dispersion (C-1) 50 g of carbon black (NIPEX 150 manufactured by Degussa), 5 g of nonionic surfactant (Nonipol 400 manufactured by Sanyo Chemical Industries), and 200 g of ion-exchanged water were mixed together. (IKA Ultra Turrax T25) was used for dispersion for 20 minutes to obtain a colorant dispersion (C-1).
[調製例13]着色剤分散液(C−2)の調製
カーボンブラック50gの代わりに銅フタロシアニン顔料(大日本インキ化学工業製FASTOGEN BLUE TGRC.I.B 15:3)50gを混合したこと以外は調製例12と同様にして着色剤分散液(C−2)を得た。
[Preparation Example 13] Preparation of Colorant Dispersion (C-2) Copper phthalocyanine pigment (FASTOGEN BLUE TGRC.IB 15: 3, manufactured by Dainippon Ink and Chemicals, Inc.) instead of 50 g of carbon black was mixed. A colorant dispersion (C-2) was obtained in the same manner as in Preparation Example 12.
[調製例14]離型剤分散液(D−1)の調製
パラフィンワックス(日本精蝋製HNP0190)50g、カチオン性界面活性剤(花王製サニゾールB50)5g、イオン交換水200gを混合し、95℃に加熱した後、ホモジナイザ(IKA製ウルトラタラックスT25)を用いて、20分間分散させて離型剤分散液(D−1)を得た。
[Preparation Example 14] Preparation of mold release agent dispersion (D-1) 50 g of paraffin wax (HNP0190 manufactured by Nippon Seiwa), 5 g of cationic surfactant (Sanisol B50 manufactured by Kao) and 200 g of ion-exchanged water were mixed. After heating to ° C., a release agent dispersion (D-1) was obtained by dispersing for 20 minutes using a homogenizer (Ultra Turrax T25 manufactured by IKA).
(製造例1〜12)
1Lフラスコ中に、上述のようにして得た負電荷制御剤乳化分散液(A−1〜7)、バインダ樹脂乳化分散液(B−1〜4)、着色剤分散液(C−1,2)、離型剤分散液(D−1)を表1および表2に示す量で配合し、攪拌しながら45℃に昇温して混合した。
次いで、上記フラスコ中に10質量%の凝集剤である硝酸カルシウム水溶液30gを2時間かけて添加した後、95℃まで昇温し、その温度で2時間保持した。その後、室温に冷却し、純水500gで洗浄しながら、ヌッチェで吸引濾過(ろ紙:ADVANTEC製FILTER PAPER 5C)して固形物を回収した後、回収した固形物を45℃で20時間送風乾燥した。
次いで、乾燥した固形物を解砕機(岩谷産業製ミルサー600)により解砕した後、分級機(日本ニューマティック工業MDS)により分級して、平均粒径7μmのトナーを得た。
(Production Examples 1-12)
In a 1 L flask, the negative charge control agent emulsified dispersion (A-1 to 7), the binder resin emulsified dispersion (B-1 to 4), and the colorant dispersion (C-1 and 2) obtained as described above. ), The release agent dispersion (D-1) was blended in the amounts shown in Tables 1 and 2, and the mixture was heated to 45 ° C. and mixed with stirring.
Next, after adding 30 g of a calcium nitrate aqueous solution as a 10 mass% flocculant to the flask over 2 hours, the temperature was raised to 95 ° C. and kept at that temperature for 2 hours. Then, after cooling to room temperature and washing with 500 g of pure water, the solid matter was recovered by suction filtration with a Nutsche (filter paper: FILTER PAPER 5C manufactured by ADVANTEC), and then the recovered solid matter was blown and dried at 45 ° C. for 20 hours. .
Next, the dried solid was pulverized by a pulverizer (Milcer 600 manufactured by Iwatani Corporation) and then classified by a classifier (Nippon Pneumatic Industrial MDS) to obtain a toner having an average particle diameter of 7 μm.
製造例1〜12のトナーについて、以下の方法により帯電量を測定した。
まず、トナー100質量%に対してアエロジルR972(日本アエロジル製シリカ粒子)0.5質量%を添加して均一に攪拌した。次いで、このシリカ付きトナー100質量部にキャリア(パウダーテック社製F−150)3質量部を混合した後、20℃、65%RHの雰囲気下で60分間摩擦帯電させた。そして、帯電量を、東芝ケミカル製ブローオフ粉体帯電量測定装置(TB−203)により測定した。その結果を表1および表2に示す。
For the toners of Production Examples 1 to 12, the charge amount was measured by the following method.
First, 0.5% by mass of Aerosil R972 (Nippon Aerosil silica particles) was added to 100% by mass of the toner and stirred uniformly. Next, 100 parts by mass of this silica-coated toner was mixed with 3 parts by mass of a carrier (F-150 manufactured by Powdertech Co., Ltd.), and then frictionally charged in an atmosphere of 20 ° C. and 65% RH for 60 minutes. Then, the charge amount was measured with a blow-off powder charge amount measuring device (TB-203) manufactured by Toshiba Chemical. The results are shown in Tables 1 and 2.
スルホン酸系共重合体の乳化重合エマルジョンである負電荷制御剤乳化分散液(A)を、バインダ樹脂乳化分散液(B)と着色剤分散液(C)と離型剤分散液(D)とに配合して得た製造例1〜11のトナーは、スルホン酸系共重合体がスチレン−アクリル共重合体に均一に付着していた。しかも、負電荷制御剤乳化剤分散液(A)の配合量が特定の範囲内で、スルホン酸系共重合体におけるラジカル重合性単量体単位およびスルホン酸系単量体単位の含有量が特定の範囲である製造例1〜7のトナーは、適度な帯電性を有していた。しかし、負電荷制御剤乳化剤分散液(A)の配合量が少ない製造例8のトナーは帯電性が低く、負電荷制御剤乳化剤分散液(A)の配合量が多い製造例9のトナーは帯電性が高すぎた。また、負電荷制御剤乳化分散液(A)中のスルホン酸系共重合体におけるラジカル重合性単量体単位およびスルホン酸系単量体単位の含有量が特定の範囲にない製造例10,11のトナーも帯電性が低かった。
これに対し、負電荷制御剤乳化分散液(A)として含金属錯体塩系染料を用いた製造例12のトナーは、負電荷制御剤がバインダ樹脂に均一に付着していなかった上に、帯電性も低かった。
A negative charge control agent emulsion dispersion (A) which is an emulsion polymerization emulsion of a sulfonic acid copolymer, a binder resin emulsion dispersion (B), a colorant dispersion (C), and a release agent dispersion (D) In the toners of Production Examples 1 to 11 obtained by blending with the toner, the sulfonic acid copolymer was uniformly attached to the styrene-acrylic copolymer. Moreover, the amount of the negative charge control agent emulsifier dispersion (A) is within a specific range, and the content of the radical polymerizable monomer unit and the sulfonic acid monomer unit in the sulfonic acid copolymer is specific. The toners of Production Examples 1 to 7, which are in the range, had appropriate chargeability. However, the toner of Preparation Example 8 with a small amount of the negative charge control agent emulsifier dispersion (A) has a low charging property, and the toner of Preparation Example 9 with a large amount of the negative charge control agent emulsifier dispersion (A) is charged. Sex was too high. Further, Production Examples 10 and 11 in which the content of the radical polymerizable monomer unit and the sulfonic acid monomer unit in the sulfonic acid copolymer in the negative charge control agent emulsified dispersion (A) are not within a specific range. The toner of this example also had low chargeability.
In contrast, in the toner of Production Example 12 using the metal-containing complex salt dye as the negative charge control agent emulsified dispersion (A), the negative charge control agent was not uniformly adhered to the binder resin, The nature was also low.
また、負電荷制御剤乳化分散液(A−1)から回収したスルホン酸系共重合体の固形物の水への再分散性について以下のようにして調べた。
まず、負電荷制御剤乳化分散液(A−1)を、50℃の真空乾燥機内により、水分が1%以下になるまで乾燥してスルホン酸系共重合体の固形物を得た。次いで、得られたスルホン酸系共重合体の固形物5gを、非イオン系界面活性剤(三洋化成工業製ノニポール400)をイオン交換水190に溶解した乳化剤水溶液に添加した。そして、ホモジナイザ(IKA製ウルトラタラックスT25)を用いて、20分間分散させた。その結果、スルホン酸系共重合体は水中に分散せず、ホモジナイザの攪拌を停止すると、直ちに沈降した。つまり、スルホン酸系共重合体の固形物は水に再分散しにくい。そのため、電荷制御剤としてスルホン酸系共重合体の固形物を用い、トナーの製造にエマルジョン凝集法を適用した場合には、電荷制御剤がバインダ樹脂に均一に付着したトナーを得ることは困難である。したがって、電荷制御剤としてスルホン酸系共重合体を用い、トナーの製造にエマルジョン凝集法を適用する際には、本発明は極めて有効である。
Further, the redispersibility of the sulfonic acid copolymer recovered from the negative charge control agent emulsified dispersion (A-1) in water was examined as follows.
First, the negative charge control agent emulsified dispersion (A-1) was dried in a vacuum dryer at 50 ° C. until the water content became 1% or less to obtain a sulfonic acid copolymer solid. Next, 5 g of the obtained sulfonic acid copolymer solid was added to an emulsifier aqueous solution in which a nonionic surfactant (Nonipol 400 manufactured by Sanyo Chemical Industries) was dissolved in ion-exchanged water 190. And it was made to disperse | distribute for 20 minutes using the homogenizer (The Ultra-Turrax T25 made from IKA). As a result, the sulfonic acid copolymer was not dispersed in water, and immediately settled when stirring of the homogenizer was stopped. That is, the solid material of the sulfonic acid copolymer is difficult to redisperse in water. Therefore, when a solid material of a sulfonic acid copolymer is used as the charge control agent and the emulsion aggregation method is applied to the production of the toner, it is difficult to obtain a toner in which the charge control agent uniformly adheres to the binder resin. is there. Therefore, the present invention is extremely effective when a sulfonic acid copolymer is used as the charge control agent and the emulsion aggregation method is applied to the production of the toner.
Claims (2)
該混合液に含まれる固形物を凝集させて回収する回収工程とを有し、
混合工程では、負電荷制御剤乳化分散液(A)中の固形分が、前記混合液に含まれる固形物中の0.5〜10質量%になるように配合し、
前記スルホン酸系共重合体に含まれるラジカル重合性単量体単位が、スチレン系単量体単位、メタクリル酸アルキルエステル単位、アクリル酸アルキルエステル単位から選ばれる1種以上であり、スルホン酸系単量体単位が、2−アクリルアミド−2−メチルプロパンスルホン酸単位、スチレンスルホン酸ナトリウム単位、スルホエチルアクリル酸単位、スルホエチルメタクリル酸単位、スルホエチルメタクリル酸ナトリウム単位から選ばれる1種以上であることを特徴とする負帯電性静電潜像現像用トナーの製造方法。 Emulsion dispersion of negative charge control agent which is an emulsion polymerization emulsion of sulfonic acid copolymer containing 99.5 to 80% by mass of radical polymerizable monomer unit and 0.5 to 20% by mass of sulfonic acid monomer unit (A), binder resin emulsion dispersion (B) which is an emulsion of binder resin, colorant dispersion (C) in which a colorant is dispersed in water and / or release agent dispersion in which a release agent is dispersed in water A mixing step of blending and mixing the liquid (D) to prepare a mixed liquid;
Possess a recovery step of recovering by aggregating the solids contained in the mixture,
In the mixing step, the solid content in the negative charge control agent emulsified dispersion (A) is blended so as to be 0.5 to 10% by mass in the solid contained in the mixed solution,
The radical polymerizable monomer unit contained in the sulfonic acid copolymer is at least one selected from a styrene monomer unit, a methacrylic acid alkyl ester unit, and an acrylic acid alkyl ester unit. The monomer unit is at least one selected from 2-acrylamido-2-methylpropanesulfonic acid unit, sodium styrenesulfonate unit, sulfoethylacrylic acid unit, sulfoethylmethacrylic acid unit, and sodium sulfoethylmethacrylate unit. And a method for producing a negatively chargeable electrostatic latent image developing toner.
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