CN1645261A - Production of electric charge regulator and carbon powder containing it for electronic camera - Google Patents

Production of electric charge regulator and carbon powder containing it for electronic camera Download PDF

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Publication number
CN1645261A
CN1645261A CN 200510018175 CN200510018175A CN1645261A CN 1645261 A CN1645261 A CN 1645261A CN 200510018175 CN200510018175 CN 200510018175 CN 200510018175 A CN200510018175 A CN 200510018175A CN 1645261 A CN1645261 A CN 1645261A
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adjusting agent
charge adjusting
azo
complex compound
metallic iron
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CN1323330C (en
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兰泽冠
朱顺全
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Hubei Dinglong Co ltd
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Hubei Dinglong Chemical Co Ltd
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Abstract

A method for preparing charge regulator includes carrying out diazonium and couple reaction for aminophenols and Naphthols AS, then adding methanol, sodium hydroxide, molysite, ammonia chloride and urea directly into reaction liquid, obtaining crude product of azoferre-complex by separating, washing and drying, using pneumatic grinder to grind crude product for obtaining fine product. The electronic photographic carbon powder contains prepared charge regulator and resin.

Description

The preparation method of charge adjusting agent and contain the carbon powder for electro photography of this charge adjusting agent
Technical field
The preparation method of the azo-type metallic iron complex compound class charge adjusting agent finished product that the present invention relates in electrophotographic developer, play a crucial role, and the negative charging carbon powder for electro photography that contains such charge adjusting agent.
Background technology
Charge adjusting agent and resin are two kinds of key components in the carbon dust, the dispersion of charge adjusting agent in resin is extremely important, if it is dispersed bad, just can not homogeneous in the carbon powder particles infiltrate charge adjusting agent, heterogeneityization can appear in the quality of carbon dust, can cause that the speed of electrifying is slow, carried charge is inhomogeneous and variety of issues such as decay, long preservation poor stability.Used aniline black byestuffs, phthalocyanine color and premetallized dye as charge adjusting agent in the past, because cause with the poor compatibility of resin, often can not be in resin in the carbon dust production run dispersion of homogeneous, the carbon dust of producing various defectives can occur on using.For this reason, people have proposed employing azo-type metal complex as charge adjusting agent, though this charge adjusting agent finished product has good compatibility with the resin that the preparation carbon dust is used, can overcome described deficiency, but its preparation method is: separate after diazonium, coupling reaction, obtain the Monoazo compound intermediate, after the conventional production method of use is carried out complex reaction, separate obtaining metal complex once more, use ammoniacal liquor or inorganic ammonium salt to carry out the kation conversion reaction then.Promptly this preparation method need carry out separating for several times, and carries out complex reaction and kation conversion reaction separately, thereby exists chemical reaction step many, production cost height, the shortcoming that labour intensity is big.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of charge adjusting agent and contain the carbon powder for electro photography of this charge adjusting agent, by reducing chemical reaction step the production cost of preparation charge adjusting agent is descended, labour intensity reduces, and prepared charge adjusting agent finished product has good compatibility with the resin that the preparation carbon dust is used, can the preparation speed that electrifies soon, be subjected to continuously long-time use and temperature, humidity effect, the high-performance of stablizing high resolution image carbon dust can be provided for a long time.
Preparation method of the present invention is: it is that preparation is by following chemical formula (I)
Figure A20051001817500051
Chemical formula (I)
(in the formula: R 1-R 4Can be the same or different; the alkoxy of the alkyl of expression hydrogen atom, carbon number 1-18 or alkenyl, carbon number 1-18, can have substituent sulfamoyl, mesyl, hydroxyl, carboxyl, carboxylic ester group, acetylamino, benzamido, halogen atom, nitro, can have substituent aryl, R 5Expression hydrogen atom, low alkyl group, lower alkoxy, nitro or halogen atom.X +The expression ammonium ion, hydrogen ion, sodion or three's mixture) Biao Shi azo-type metallic iron complex compound class charge adjusting agent finished product, it is characterized in that earlier amino phenol and azoic coupling component AS series compound being carried out diazonium, coupling reaction, then without separation, directly in coupling reaction liquid, add methyl alcohol, NaOH, molysite, ammonium chloride and urea, carry out complex reaction and kation conversion reaction simultaneously, separate again, washing and dried obtain azo-type metallic iron complex compound class charge adjusting agent crude product, adopt full airslide disintegrating mill that azo-type metallic iron complex compound class charge adjusting agent crude product is pulverized and make azo-type metallic iron complex compound class charge adjusting agent finished product.
Above-mentioned full airslide disintegrating mill adopts the fluidized bed jet mill ultrafine crusher.
NH in the cationic moiety of said azo-type metallic iron complex compound class charge adjusting agent crude product 4 +Containing ratio reach 60%~99%, adopt the laser diffraction granularity tester to record its size-grade distribution to be: D 10=2.000~5.000 μ m, D 50=5.000~15.000 μ m, D 90=15.000~20.000 μ m, said azo-type metallic iron complex compound class charge adjusting agent finished product adopt the laser diffraction granularity tester to record its size-grade distribution: D 10=0.200~1.000 μ m, D 50=1.000~6.000 μ m, D 90=1.000~10.000 μ m.
Said laser diffraction granularity tester adopts Ma Erwen (MASTERSIZER) or Beckman (BECKMAN) laser diffraction granularity tester.
The carbon powder for electro photography that contains the charge adjusting agent of producing by the preparation method of above-mentioned charge adjusting agent, it is characterized in that including said azo-type metallic iron complex compound class charge adjusting agent finished product and carbon dust resin, its consumption is: with respect to the carbon dust resin of 100 weight portions, contain the azo-type metallic iron complex compound class charge adjusting agent finished product of 0.1~10 weight portion.
Said carbon powder for electro photography can also contain colorant and fluidity amendment etc., and its consumption is: with respect to the carbon dust of 100 weight portions resin, contain the colorant of 0.5~10 weight portion and the fluidity amendment of 1~3 weight portion.
The azo-type metallic iron complex compound class charge adjusting agent crude product that adopts above-mentioned preparation method to obtain has good dispersiveness in resin, but be to use the carbon dust of this crude product preparation exist carried charge deficiency, development density low, shortcoming such as bottom ash arranged.In order further to improve the performance of this charge adjusting agent, also must adopt full airslide disintegrating mill that this crude product is pulverized and make azo-type metallic iron complex compound class charge adjusting agent finished product.
Preparation method of the present invention is after diazonium, coupling reaction, without separation, directly carries out complex reaction and kation conversion reaction simultaneously, compare with existing preparation method, reduced chemical reaction step, thereby made the production cost of preparation charge adjusting agent descend, labour intensity reduces.And NH in the cationic moiety of prepared azo-type metallic iron complex compound class charge adjusting agent 4 +Containing ratio reach 60%~99%, in resin, has very good dispersiveness, use the carbon dust of this charge adjusting agent finished product preparation speed that electrifies fast, the long-time defectives such as the carried charge decay also can not occur of using can realize high speed and the long lifetime of carbon dust and the charged stabilization under various environment of duplicating.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1: reduce to 0-5 ℃ add 190ml water, 25g 37% hydrochloric acid, 14.4g 2-amino-4-chlorophenol, stirring and dissolving in the 500ml there-necked flask after, drip 20g 36% sodium nitrite solution, control temperature simultaneously and be not higher than 5 ℃.Sodium nitrite solution dripped the back and obtained diazonium salt solution after 0-5 ℃ of insulation reaction 1-2 hour.In the 1000ml there-necked flask, add 165ml water, 30g 20% sodium hydroxide solution, 26.3g azoic coupling component AS, be cooled to 0-5 ℃ after the stirring and dissolving, add the front then fast and react good diazo salt, react 3-5 hour to the diazo salt disappearance at 5-10 ℃ afterwards, obtain reacting conjugates solution.In conjugates solution, add 100ml methyl alcohol, 30g 20% NaOH, 2.8g ammonium chloride and 15g urea, drip 40.6g 20% liquor ferri trichloridi afterwards, be warming up to 70 ℃ after dripping, back flow reaction is reduced to below 60 ℃ after 2.5 hours, separate then, wash, dry, obtain 43g black powdery azo-type metallic iron complex compound (I), this chemistry of complex structure can be represented with following Chemical formula 1.
Figure A20051001817500071
Chemical formula 1.
(in Chemical formula 1, X 1 +Expression ammonium ion, hydrogen ion, sodion or three's mixture)
By found that of ultimate analysis, NH in the cationic moiety of complex compound (I) 4 +Containing ratio be 83.6%.Complex compound (I) is recorded its size-grade distribution with the Ma Erwen particle size analyzer is: D 10=3.960 μ m, D 50=10.360 μ m, D 90=22.740 μ m.Then complex compound (I) is adopted the fluidized bed jet mill ultrafine crusher to pulverize and obtain charge adjusting agent finished product (I), record its size-grade distribution with the Ma Erwen particle size analyzer and be: D 10=0.444 μ m, D 50=1.402 μ m, D 90=4.780 μ m.
It (can also be styrene resin that carbon dust adopts styrene acrylic resin with resin, acrylic resin, epoxy resin, vinyl resins, polyester resin etc.), colorant adopts carbon black (also can use known most of dyestuff and pigment), fluidity amendment adopts paraffin, (I) uses styrene acrylic resin respectively with the charge adjusting agent finished product, carbon black and paraffin are according to mass unit 93 portions of resin 5 carbon blacks: 1 paraffin: 1 charge adjusting agent carries out proportioning, after fully mixing, heating and melting is mixing, the usual method crushing and classification is used in the cooling back, obtaining volume average particle size and be 9 microns negative charging carbon dust, is that the iron powder of 90-130 micron mixes in bowl mill and obtains developer with these carbon dusts with weight ratio 3: 97 and diameter then.
Use developer in duplicating machine, to duplicate five thousand sheets continuously, measure the carbon dust carried charge and test the copy effect and obtain the result it is as shown in the table.
Embodiment 2: add 190ml water, 25g 37% hydrochloric acid, 14.4g 2-amino-4-chlorophenol in the 500ml there-necked flask, reduce to 0-5 ℃ after the stirring and dissolving, drip 20g 36% sodium nitrite solution, control temperature simultaneously and be not higher than 5 ℃.Sodium nitrite solution dripped the back and obtained diazonium salt solution after 0-5 ℃ of insulation reaction 1-2 hour.In the 1000ml there-necked flask, add 165ml water, 30g 20% sodium hydroxide solution, 29.3g Naphthol AS-OL, be cooled to 0-5 ℃ after the stirring and dissolving, add the front then fast and react good diazo salt, react 3-5 hour to the diazo salt disappearance at 5-10 ℃ afterwards, obtain reacting conjugates solution.In conjugates solution, add 100ml methyl alcohol, 30g 20% NaOH, 2.8g ammonium chloride and 15g urea, drip 40.6g 20% liquor ferri trichloridi afterwards, be warming up to 70 ℃ after dripping, back flow reaction is reduced to below 60 ℃ after 2.5 hours, separate then, wash, dry, obtain 41.5g black powdery azo-type metallic iron complex compound (II), this chemistry of complex structure can be represented with following Chemical formula 2.
Chemical formula 2
(in Chemical formula 2, X 2 +Expression ammonium ion, hydrogen ion, sodion or three's mixture)
By found that of ultimate analysis, NH in the cationic moiety of complex compound 3 4 +Containing ratio be 64.8%.Complex compound (II) is recorded its size-grade distribution with the Ma Erwen particle size analyzer is: D 10=3.720 μ m, D 50=9.950 μ m, D 90=22.120 μ m.Adopt the fluidized bed jet mill ultrafine crusher to pulverize in complex compound (II) then and obtain charge adjusting agent finished product (II), this finished product records its size-grade distribution with the Ma Erwen particle size analyzer and is: D 10=0.390 μ m, D 50=1.503 μ m, D 90=4.546 μ m.
Press the identical mode of embodiment 1, select identical raw material for use and use identical ratio that charge adjusting agent finished product (II) is made developer.
Use developer in duplicating machine, to duplicate five thousand sheets continuously, measure the carbon dust carried charge and test the copy effect and obtain the result it is as shown in the table.
The charge adjusting agent kind Evaluation for carbon dust
Carried charge (microcoulomb/gram) Carried charge (microcoulomb/gram) Image quality Image quality Environmental stability
Starting stage The 5th thousand sheets Starting stage The 5th thousand sheets
Embodiment 1 Charge adjusting agent finished product (I) ????-24.8 ????-24.5 Outstanding Outstanding Outstanding
Embodiment 2 Charge adjusting agent finished product (II) ????-22.7 ????-22.5 Outstanding Outstanding Outstanding

Claims (6)

1, a kind of preparation method of charge adjusting agent, it is that preparation is by following chemical formula (I)
Figure A2005100181750002C1
... ... chemical formula (I)
(in the formula: R 1-R 4Can be the same or different; the alkoxy of the alkyl of expression hydrogen atom, carbon number 1-18 or alkenyl, carbon number 1-18, can have substituent sulfamoyl, mesyl, hydroxyl, carboxyl, carboxylic ester group, acetylamino, benzamido, halogen atom, nitro, can have substituent aryl, R 5Expression hydrogen atom, low alkyl group, lower alkoxy, nitro or halogen atom.X +The expression ammonium ion, hydrogen ion, sodion or three's mixture) Biao Shi azo-type metallic iron complex compound class charge adjusting agent finished product, it is characterized in that earlier amino phenol and azoic coupling component AS series compound being carried out diazonium, coupling reaction, then without separation, directly in coupling reaction liquid, add methyl alcohol, NaOH, molysite, ammonium chloride and urea, carry out complex reaction and kation conversion reaction simultaneously, separate again, washing and dried obtain azo-type metallic iron complex compound class charge adjusting agent crude product, adopt full airslide disintegrating mill that azo-type metallic iron complex compound class charge adjusting agent crude product is pulverized and make azo-type metallic iron complex compound class charge adjusting agent finished product.
2,, it is characterized in that said full airslide disintegrating mill adopts the fluidized bed jet mill ultrafine crusher by the preparation method of the described a kind of charge adjusting agent of claim 1.
3,, it is characterized in that NH in the cationic moiety of said azo-type metallic iron complex compound class charge adjusting agent crude product by the preparation method of the described a kind of charge adjusting agent of claim 1 4 +Containing ratio reach 60%~99%, adopt the laser diffraction granularity tester to record its size-grade distribution to be: D 10=2.000~5.000 μ m, D 50=5.000~15.000 μ m, D 90=15.000~20.000 μ m, said azo-type metallic iron complex compound class charge adjusting agent finished product adopt the laser diffraction granularity tester to record its size-grade distribution: D 10=0.200~1.000 μ m, D 50=1.000~6.000 μ m, D 90=1.000~10.000 μ m.
4,, it is characterized in that said laser diffraction granularity tester adopts Ma Erwen (MASTERSIZER) or Beckman (BECKMAN) laser diffraction granularity tester by the preparation method of the described a kind of charge adjusting agent of claim 3.
5, a kind of carbon powder for electro photography that contains the charge adjusting agent of producing by the preparation method of the described charge adjusting agent of claim 1, it is characterized in that including said azo-type metallic iron complex compound class charge adjusting agent finished product and carbon dust resin, its consumption is: with respect to the carbon dust resin of 100 weight portions, contain the azo-type metallic iron complex compound class charge adjusting agent finished product of 0.1~10 weight portion.
6, by the described a kind of carbon powder for electro photography of claim 5, it is characterized in that to contain colorant and fluidity amendment etc., its consumption is: with respect to the carbon dust resin of 100 weight portions, contain the colorant of 0.5~10 weight portion and the fluidity amendment of 1~3 weight portion.
CNB2005100181756A 2005-01-20 2005-01-20 Production of electric charge regulator and carbon powder containing it for electronic camera Expired - Fee Related CN1323330C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100421032C (en) * 2005-11-07 2008-09-24 湖北鼎龙化学股份有限公司 Charge regulator and its preparing method and carbon powder for containing same charge regulator
CN100485539C (en) * 2007-04-12 2009-05-06 湖北鼎龙化学股份有限公司 Charge adjusting agent and carbon powder
CN102346390A (en) * 2011-10-28 2012-02-08 湖北鼎龙化学股份有限公司 Charge regulator and preparation method thereof, and carbon powder
CN101630129B (en) * 2009-08-05 2012-09-26 湖北鼎龙化学股份有限公司 Azo series charge regulator dispersoid and preparation method thereof and carbon powder
CN107254191A (en) * 2017-06-29 2017-10-17 广西新晶科技有限公司 A kind of azo bivalent metallic ion complex and its purposes in toner
CN108604071A (en) * 2016-02-16 2018-09-28 花王株式会社 Electrophoto-graphic toner

Family Cites Families (6)

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CN1097211C (en) * 1990-06-15 2002-12-25 佳能株式会社 Pattern forming device, component parts and facsimile apparatus
US5508139A (en) * 1993-03-25 1996-04-16 Canon Kabushiki Kaisha Magnetic toner for developing electrostatic image
US5439770A (en) * 1993-04-20 1995-08-08 Canon Kabushiki Kaisha Toner for developing electrostatic image, image forming apparatus and process cartridge
JP3392479B2 (en) * 1993-09-29 2003-03-31 保土谷化学工業株式会社 Method for producing metal complex dye and electrophotographic toner containing the dye
US7094513B2 (en) * 2002-12-06 2006-08-22 Orient Chemical Industries, Ltd. Charge control agent and toner for electrostatic image development
JP4344580B2 (en) * 2003-10-15 2009-10-14 オリヱント化学工業株式会社 Method for producing charge control agent

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100421032C (en) * 2005-11-07 2008-09-24 湖北鼎龙化学股份有限公司 Charge regulator and its preparing method and carbon powder for containing same charge regulator
CN100485539C (en) * 2007-04-12 2009-05-06 湖北鼎龙化学股份有限公司 Charge adjusting agent and carbon powder
CN101630129B (en) * 2009-08-05 2012-09-26 湖北鼎龙化学股份有限公司 Azo series charge regulator dispersoid and preparation method thereof and carbon powder
CN102346390A (en) * 2011-10-28 2012-02-08 湖北鼎龙化学股份有限公司 Charge regulator and preparation method thereof, and carbon powder
CN102346390B (en) * 2011-10-28 2013-05-01 湖北鼎龙化学股份有限公司 Charge regulator and preparation method thereof, and carbon powder
CN108604071A (en) * 2016-02-16 2018-09-28 花王株式会社 Electrophoto-graphic toner
CN108604071B (en) * 2016-02-16 2022-03-15 花王株式会社 Toner for electrophotography
CN107254191A (en) * 2017-06-29 2017-10-17 广西新晶科技有限公司 A kind of azo bivalent metallic ion complex and its purposes in toner

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