CN102603952A - Resin, resin nanoemulsion and preparation methods thereof - Google Patents
Resin, resin nanoemulsion and preparation methods thereof Download PDFInfo
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- CN102603952A CN102603952A CN2012100529923A CN201210052992A CN102603952A CN 102603952 A CN102603952 A CN 102603952A CN 2012100529923 A CN2012100529923 A CN 2012100529923A CN 201210052992 A CN201210052992 A CN 201210052992A CN 102603952 A CN102603952 A CN 102603952A
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Abstract
The invention discloses resin, resin nanoemulsion and preparation methods thereof. The preparation method of the resin nanoemulsion comprises the following step of: performing emulsion polymerization on styrene, an acrylic ester compound and a methacrylic acid compound in water in the presence of a surfactant, an initiator and a chain transfer agent to obtain a product. The preparation method of the resin comprises the following step of: performing deemulsification on the resin nanoemulsion to obtain the resin. The invention provides the resin which has sufficient charge load capacity (electrical insulation) and thermophysical parameter combination meeting requirements (i.e., the glass transition temperature Tg is not less than 50 DEG C and the softening point Tfs is not greater than 100 DEG C). The resin nanoemulsion provided by the invention can aggregate under pH value adjustment to form clusters of 10-20 mum, and the clusters are fused under normal pressure and at the temperature of not greater than 100 DEG C to form approximately spherical solid particles. The resin and the resin nanoemulsion provided by the invention are suitable for preparing a toner by an aggregation-fusion method.
Description
Technical field
The present invention relates to a kind of resin, resin nano emulsion and preparation method thereof, be specifically related to a kind of gathering-fusion method that is applicable to and prepare laser printer/xerographic printer with the resin of toner, resin nano emulsion and preparation method thereof.
Background technology
Along with popularizing of office automation, the usage quantity of xerographic printer/laser printer increases day by day, and is correspondingly huge as the ink powder demand of its main consumptive material, become a main growth point of the output value and the profit of the industry.
Ink powder (or being called toner, Toner) essentially consist is fluoropolymer resin and pigment, and resin generally accounts for the 80-90% mass percent.Therefore toner is to be the composite organic-inorganic material of main body with the resin, is a kind of aggregate that can charged colouring resin particulate.Other composition also comprises charge adjusting agent (CCA), tensio-active agent, lubricant etc.The effect of resin mainly is parcel dispersive pigment particulate and makes the toner grain have enough static portative poweies and make colorant firm attachment (formation picture and text) ability on the medium of undertaking the printing of.From the elementary heat physical properties, the toner particle should possess necessary bonding characteristic: do not lump when under natural climate condition, storing, when being heated photographic fixing, can soften rapidly and flow, can be rapidly solidified when breaking away from the high-temperature zone, and avoid taking place print through and roll banding phenomenon.Because the main body of toner is a resin, its calorifics behavior mainly depends on resin, and the main determining factor of the thermophysical property of resin is the composition and the structure of resin.
Present toner preparation mainly contains traditional preparation process technology (physics method) [R.J.Gruber and P.C.Julien, Dry Toner Technology.In Handbook of Imaging Materials, A.S.Diamond, Ed.; Marcel Dekker:New York, 1991; P 159] and the technology of preparing (chemical method) [USP 5648193A, 4983488,6582873,65666028,6740463,6528222, EP 0162577,0225476,0302939,0631196] of new development.Prepared by physical method is that to place mixing roll on the resin melt temperature, to mediate by a certain percentage resin, colorant and other composition mixing, the gained melts through extrude, cool off, pulverizing, classification, adding additive obtain finished product.This technical matters is easy, production efficiency is high, and its shortcoming is that the homogeneity of ingredients of toner particle is not very good, the shape regularity is relatively poor, size-grade distribution is wide etc.These are confined to, and problem can be too not outstanding in the black and white printing, but will produce great disadvantageous effect for the quality of colour print.Prepared by physical method process energy consumption is high besides, dust hazard property is bigger.Risen one type of toner technology of preparing that is called chemical method in recent years gradually, chemical method is that " generation " toner grain rather than " grinding " obtain the toner grain.Chemical method is suitable for the particularly preparation of color toner of high-quality toner owing to being easy to control quality product (it is even that the regular spherical in shape or elliposoidal of toner particle shape, size of particles are easy to control, narrow particle size distribution, composition); And the preparation process is that medium does not use high temperature and high-tenacity to pulverize energy-conserving and environment-protective with water.The toner technology of preparing of chemical method has multiple concrete approach, and the gathering-fusion method of one of them (Aggregation/Coalescence Procedure) the most generally adopts.The primary process of gathering the method for melting is: (＜100nm) water base serum prepares ultrafine particle (200-500nm) aqueous-based dispersions of pigment and other composition respectively to (1) emulsion polymerization prepared nano-resin ball.All comprise electrically opposite or identical ionogenic surfactant in these dispersion systems; (2) by a certain percentage several kinds of dispersion systems are mixed (need regulate mixed solution ionic strength or pH value sometimes), induce particle to gather into the colloidal mixed system near shape each other; (3) mildly heating combines powerful the stirring, and colloid is broken up, and forms less cluster structure particle, when reaching needed size, adds other tensio-active agent again to limit it and further reduce or to increase; (4) heat in the resin softening point temperature, impel loose group bunch particulate to merge and form fine and close subsphaeroidal; (5) collect granule, dry, add other necessary composition, obtain toner.
When adopting the toner technology of preparing of gathering-fusion method; For the convenience of technology with simple; The softening temperature of resin (refer in particular to here: initial softening temperature Tfs/2.5Kg adds stone roller) is preferably in below 100 ℃ that (because gather the method for melting is medium with water; If the Tfs of resin surpasses 100 ℃, then need use the high-pressure reactor operation just can reach loose bunch and be fused into subsphaeroidal purpose).On the other hand; Practical toner product will have the particularly stability of thermal environment of environmental stability; This just needs the second-order transition temperature (Tg) of toner resin to want enough high (generally should be not less than 50 ℃; Otherwise when storing or printing continuously summer, be easy to generate the particle agglomeration phenomenon, make toner mis-behave even inefficacy).
As stated, be suitable for most assembling-resin of fusion method should have relatively than high glass transition temperature (Tg＞50 ℃) and relatively low softening temperature (Tfs＜100 ℃).Yet the second-order transition temperature of polymkeric substance and the softening temperature normally relevant and softening temperature of forward are the index amplitude with the second-order transition temperature increase and rise; Specifically more some says, common polymkeric substance (homopolymerization or multipolymer) if second-order transition temperature above 50 ℃ then softening temperature can be much larger than 100 ℃.Therefore, a kind ofly be suitable for gathering the obtaining of resin that the particular thermal physical parameter requires that have of melting method powder process and depend on careful selection monomer type, well-designed proportioning components and appropriately adopt compound method etc.
Summary of the invention
The purpose of this invention is to provide a kind of resin, resin nano emulsion and preparation method thereof, prepare toner applicable to gathering-fusion method.
The preparation method of a kind of resin nano emulsion provided by the present invention comprises the steps:
Under the condition that tensio-active agent, initiator and chain-transfer agent exist, vinylbenzene, acrylic ester compound and methacrylic compounds are carried out letex polymerization and are promptly got product in water.
Among the above-mentioned preparation method, said acrylic ester compound can be the alkyl ester of C1～C6; Said methacrylic compounds can be the methylacrylic acid or derivatives thereof that contains polar functional group.
Among the above-mentioned preparation method, said methacrylic compounds specifically can be methylacrylic acid, methacrylonitrile, Jia Jibingxisuanβ-Qiang Yizhi or methylacrylic acid β-carboxylic ethyl ester.
Among the above-mentioned preparation method, said tensio-active agent can be X 2073, dodecane sulfonate, dodecyl carboxylate salt, dodecyl trialkylamine, polyoxyethylene glycol (PEG 800～20000), Si Ban or tween etc.; Said initiator can be Potassium Persulphate, ammonium persulphate or Sodium Persulfate etc.; Said chain-transfer agent can be aliphatics mercaptan, like Dodecyl Mercaptan.
Among the above-mentioned preparation method, the ratio of quality and the number of copies of said vinylbenzene, acrylic ester compound and methacrylic compounds can be (7～15): (1～2): (0.1～1) specifically can be 11: 2: 1 or 12: 2: 1;
The composition of said emulsion polymerization systems is following, is the quality percentage composition:
Vinylbenzene, acrylic ester compound and methacrylic compounds 15%～25%, tensio-active agent 0.3%～1%, initiator 0.05%～0.6%, chain-transfer agent 0.01%～1%, surplus is a water; Specifically can be vinylbenzene, acrylic ester compound and methacrylic compounds 19.78%; Tensio-active agent 0.59%; Initiator 0.1%, water or vinylbenzene, acrylic ester compound and the methacrylic compounds 20.38% of chain-transfer agent 0.49% and surplus, tensio-active agent 0.59%; Initiator 0.1%, the water of chain-transfer agent 0.49% and surplus.
Among the above-mentioned preparation method, the temperature of said letex polymerization can be 60 ℃～90 ℃, specifically can be 70 ℃, and the time can be 4 hours～and 10 hours, specifically can be 5 hours; Said polyreaction can be in the pH value under 9～10 the condition carries out.
The present invention also further provides the resin nano emulsion by method for preparing.
The present invention also provides a kind of preparation method of resin, comprises the steps: to prepare according to the method described above the resin nano emulsion; Said resin nano emulsion promptly gets said resin through going emulsifying effect; As the resin balls gathering being separated out, after collection, drying, get final product through adding an amount of mineral acid or salt.
The present invention further provides the resin by method for preparing.
The invention provides and have enough electric charge carrying capacity (electrical insulating property), have the combination of satisfactory thermophysical parameter the resin of (be second-order transition temperature Tg be not less than 50 ℃, softening temperature Tfs be not higher than 100 ℃); Nano-resin emulsion provided by the invention can regulate in the pH value bunch group that forms 10～20 μ m takes place down to assemble, at normal pressure be no more than under 100 ℃ the temperature bunch group and merge the subsphaeroidal solid particle of formation; Resin provided by the invention and resin nano emulsion are suitable for gathering-fusion method and prepare toner.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
The preparation and the application thereof of embodiment 1, resin and resin nano emulsion
Potassium Persulphate (0.5 gram), sodium hydrogencarbonate (0.42 gram) and methylacrylic acid-β-carboxylic ethyl ester (6.8 gram) are dissolved in 140 and restrain and be put in the water in the Erlenmeyer flask as A liquid, and be for use; In 1 liter of three mouthfuls of reaction flask, add X 2073 (3 gram), deionized water (260 gram), vinylbenzene (78 gram), Bing Xisuandingzhi (15.4 gram) and Dodecyl Mercaptan (2.5 gram); The A liquid that adds 28 grams again; Behind the mixing pH value is adjusted to 9, uses high-speed emulsifying machine (transferring to 10000rpm) to handle mixed solution 5 minutes then; Reaction flask device for mechanical whisking appliance (stir speed (S.S.) 800rpm), the oil bath heating is after temperature reaches 70 degree; Drip A liquid remaining in the Erlenmeyer flask, dropwise in 2 hours that (in this reaction system, the quality percentage composition of each component is following: vinylbenzene, methylacrylic acid-β-carboxylic ethyl ester and Bing Xisuandingzhi are 19.78%; Potassium Persulphate is 0.10%; X 2073 is 0.59%, and Dodecyl Mercaptan is 0.49%, and surplus is a water; The ratio of quality and the number of copies of vinylbenzene, Bing Xisuandingzhi and methylacrylic acid-β-carboxylic ethyl ester is 12: 2: 1); Drip off back insulation 5 hours, stopped reaction is chilled to room temperature and promptly gets nano-resin ball emulsion.
Get the partial tree fat liquor, add CaCl
2The strong solution breakdown of emulsion through suction filtration, washing, drying, gets powdery resin:
Tg=55 ℃; Tfs=92 ℃, can know that the resin of the present invention's preparation has higher second-order transition temperature and lower softening temperature, be fit to the preparation toner.
The synthetic resins of getting the above-mentioned preparation of part carries out the toner preparation; The preparation general step is following: under the room temperature; With the above-mentioned resin emulsion that makes (150 gram), polyethylene wax water miscible liquid (10%; 10 grams), sooty water dispersion liquid (5%, 40 gram), charge adjusting agent zinc salicylate (1 gram) and emulsifying agent X 2073 (5 gram) mixing and stirring; PH value to 1～2 of regulation system, and powerful the stirring (2000～5000rpm) 3～6 hours, obtain bunch group of 10～20 μ m; Stirred 5～10 hours elevated temperature to 95～98 ℃, and a bunch group is fused into the subsphaeroidal solid particle of shape; Cool off, filter, dry, obtain the toner that is applicable to that Laser Printing or xerox are used.
The preparation of embodiment 2, resin and resin nano emulsion
The preparation method is identical with embodiment 1, and difference is: the consumption of methylacrylic acid-β-carboxylic ethyl ester is 10.8 grams, and the consumption of Bing Xisuandingzhi is 15.2 grams; Thereby in this polymerization reaction system; The quality percentage composition of each component is following: vinylbenzene, methylacrylic acid-β-carboxylic ethyl ester and Bing Xisuandingzhi are 20.38%, and Potassium Persulphate is 0.10%, and X 2073 is 0.59%; Dodecyl Mercaptan is 0.49%, and surplus is a water; The ratio of quality and the number of copies of vinylbenzene, Bing Xisuandingzhi and methylacrylic acid-β-carboxylic ethyl ester is 11: 2: 1; Gained resin:
Tg=51 ℃; Tfs=81 ℃.
Embodiment 3, resin and and the preparation of resin nano emulsion
The preparation method is identical with embodiment 1, and difference is: replace methylacrylic acid-β-carboxylic ethyl ester with methacrylic-beta-hydroxy ethyl ester (6.8 gram); Gained resin:
Tg=54 ℃; Tfs=90 ℃.
Can know that by the foregoing description resin provided by the invention and resin emulsion have higher glass transition temperature and softening temperature, be suitable for gathering and melt legal system and be equipped with toner.
Claims (10)
1. the preparation method of a resin nano emulsion comprises the steps:
Under the condition that tensio-active agent, initiator and chain-transfer agent exist, vinylbenzene, acrylic ester compound and methacrylic compounds are carried out letex polymerization and are promptly got product in water.
2. method according to claim 1 is characterized in that: said acrylic ester compound is the alkyl ester of C1～C6; Said methacrylic compounds is the methylacrylic acid or derivatives thereof that contains polar functional group.
3. method according to claim 2 is characterized in that: said methacrylic compounds is methylacrylic acid, methacrylonitrile, Jia Jibingxisuanβ-Qiang Yizhi or methylacrylic acid β-carboxylic ethyl ester.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: said tensio-active agent is X 2073, dodecane sulfonate, dodecyl carboxylate salt, dodecyl trialkylamine, polyoxyethylene glycol, Si Ban or tween; Said initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate; Said chain-transfer agent is an aliphatics mercaptan.
5. according to arbitrary described method among the claim 1-4, it is characterized in that: the ratio of quality and the number of copies of said vinylbenzene, acrylic ester compound and methacrylic compounds is (7～15): (1～2): (0.1～1);
The composition of said emulsion polymerization systems is following, is the quality percentage composition:
Vinylbenzene, acrylic ester compound and methacrylic compounds 15%～25%, tensio-active agent 0.3%～1%, initiator 0.05%～0.6%, chain-transfer agent 0.01%～1%, surplus is a water.
6. according to arbitrary described method among the claim 1-5, it is characterized in that: the temperature of said letex polymerization is 60 ℃～90 ℃, and the time is 4 hours～10 hours; Said polyreaction is to carry out under 9～10 the condition in the pH value.
7. the resin nano emulsion that arbitrary said method prepares among the claim 1-6.
8. the preparation method of a resin comprises the steps:
Prepare the resin nano emulsion according to arbitrary said method among the claim 1-7; Said resin nano emulsion promptly gets said resin through going emulsifying effect.
9. the resin of the said method of claim 8 preparation.
10. said resin nano emulsion of claim 7 or the said resin of claim 9 application in the preparation toner.
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| CN201210052992.3A CN102603952B (en) | 2012-03-02 | 2012-03-02 | Resin, resin nanoemulsion and preparation methods thereof |
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| CN201210052992.3A CN102603952B (en) | 2012-03-02 | 2012-03-02 | Resin, resin nanoemulsion and preparation methods thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104360584A (en) * | 2014-11-27 | 2015-02-18 | 邯郸汉光办公自动化耗材有限公司 | Preparation method and application of nano charge control agent dispersion liquid |
| CN105777969A (en) * | 2016-04-19 | 2016-07-20 | 宁波佛来斯通新材料有限公司 | Preparation method for water-base resin for chemical toner and preparation method for chemical toner |
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| JP2002131981A (en) * | 2000-10-24 | 2002-05-09 | Konica Corp | Method for manufacturing toner and method for image formation by using the same |
| CN1427017A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气股份有限公司 | Preparation method of acrylic acid latex having agglomeration action |
| CN101125905A (en) * | 2007-09-04 | 2008-02-20 | 王建新 | Emulsion polymerization macromolecule resin and its preparing process |
| CN101699353A (en) * | 2009-10-29 | 2010-04-28 | 湖北鼎龙化学股份有限公司 | Colored carbon power and producing method thereof |
| CN102243452A (en) * | 2011-07-06 | 2011-11-16 | 邯郸汉光办公自动化耗材有限公司 | Method for preparing color toner |
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2012
- 2012-03-02 CN CN201210052992.3A patent/CN102603952B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002131981A (en) * | 2000-10-24 | 2002-05-09 | Konica Corp | Method for manufacturing toner and method for image formation by using the same |
| CN1427017A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气股份有限公司 | Preparation method of acrylic acid latex having agglomeration action |
| CN101125905A (en) * | 2007-09-04 | 2008-02-20 | 王建新 | Emulsion polymerization macromolecule resin and its preparing process |
| CN101699353A (en) * | 2009-10-29 | 2010-04-28 | 湖北鼎龙化学股份有限公司 | Colored carbon power and producing method thereof |
| CN102243452A (en) * | 2011-07-06 | 2011-11-16 | 邯郸汉光办公自动化耗材有限公司 | Method for preparing color toner |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104360584A (en) * | 2014-11-27 | 2015-02-18 | 邯郸汉光办公自动化耗材有限公司 | Preparation method and application of nano charge control agent dispersion liquid |
| CN105777969A (en) * | 2016-04-19 | 2016-07-20 | 宁波佛来斯通新材料有限公司 | Preparation method for water-base resin for chemical toner and preparation method for chemical toner |
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| CN102603952B (en) | 2014-04-16 |
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