CN1443807A - Preparation process of dispersing dye microcapsule - Google Patents
Preparation process of dispersing dye microcapsule Download PDFInfo
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- CN1443807A CN1443807A CN 03116242 CN03116242A CN1443807A CN 1443807 A CN1443807 A CN 1443807A CN 03116242 CN03116242 CN 03116242 CN 03116242 A CN03116242 A CN 03116242A CN 1443807 A CN1443807 A CN 1443807A
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- disperse dye
- preparation technology
- microcapsule
- polyisocyanates
- microcapsule disperse
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Abstract
The present invention relates to a technological process for preparing disperse dye microcapsule by utilizing double or polyisocyanate compound as monomer for forming microcapsule wall material, using disperse dye as core material and adopting interfacial polymerization. The polyurea finalkly formed by using said process has no methyl aldehyde, has no pollution, high strength, good slowly-releasing property and small dose of adjuvant. It is specially suitable for high-temp. high-pressure dyeing, thermosol dyeing and multiple transfer printing of polyester fabrics.
Description
Technical field
The invention belongs to fine chemistry industry and light industry field.Specifically a kind of utilize two or polyisocyanate compound as the monomer that forms microcapsule wall material, prepare microcapsule disperse dye by interfacial polymerization.This microcapsule disperse dye is specially adapted to high-temperature pressure dyeing, thermosol dyeing and the repeatedly transfer printing of polyester piece good.
Background technology
Dispersed dye are the strong and water-soluble very little nonionic dyestuffs of a kind of hydrophobicity.Be used for cellulose acetate fibre dyeing the earliest, and be mainly used in the dyeing of trevira now.Since nineteen fifty-three, terylene was used disperse dyeing, the development of dispersed dye was rapid, at present above 2000 kinds.It is one of the fastest dye species of modern development.But because dispersed dye need relatively large dispersion agent in preparation with in using, tensio-active agent such as wetting agent and levelling agent, the dispersion of these auxiliary agents and solublization cause a large amount of dyestuffs to be stranded in the dyeing waste-water, form a large amount of dyeing waste-waters, decolouring is handled and is the devil, and always exists the problem of dust from flying in match color procedure.The pure dispersed dye that do not contain dispersion agent and levelling agent are encapsulated, and the dyestuff of preparation does not have dust, does not have caking, can need not auxiliary agent such as dispersion agent and levelling agent or only use very a spot of wetting agent in dyeing.The dyestuff overwhelming majority of dying on not after the dyeing all remains in the capsule and with capsule shell and enters water lotion, and after leaving standstill by certain hour, capsule shell and residual dye all precipitate.Substantially do not contain COD in the dyeing waste-water, BOD and colourity reclaim easily and reuse.Alleviate environmental pollution, make dyeing realize environmental friendlinessization.
Domestic research to microcapsule disperse dye, Donghua University is once to the melamine micro encapsulation of dispersed dye, employing be situ aggregation method, the wall material is to use melamine resin.In use and preparation process, discharge a small amount of formaldehyde.And textile science institute in Beijing's improves traditional gelatin-Sudan Gum-arabic with the complex coacervation that is separated, and has prepared microcapsule disperse dye.The wall material intensity of this microcapsule disperse dye is not high, non-refractory, and therefore the suitability of this microcapsule is restricted.
The present invention only uses a kind of two or polyisocyanates as wall material monomer, can prepare single microcapsule disperse dye, also can mix the microcapsule disperse dye of another color of preparation by the assembly of two kinds of dispersed dye.In preparation process, organic phase only is made up of wall material monomer and core, and aqueous phase contains emulsifying agent and protective colloid.And release formaldehyde not, be a kind of technology of environment-friendly type.
Summary of the invention
The preparation technology who the purpose of this invention is to provide a kind of microcapsule disperse dye.
The present invention only adopts two or polyisocyanates prepares needed microcapsule disperse dye as wall material monomer.Two or polyisocyanates generates amine with the water reaction earlier, and amine generates polyureas with unreacted isocyanato reaction again.Every in general two or polyisocyanates and composition thereof can be used as wall material monomer.The cyst wall performance that different monomers or monomer mix formation is also different, can be selected as required.
The preparation technology of dispersed dye micro-capsule of the present invention is as follows:
(1) water ingredients: in distilled water, add emulsifying agent, protective colloid on demand, stir
Evenly;
(2) organic phase ingredients: the demand of pressing is with the core dyestuff and wall material monomer is two or polyisocyanates
Mix;
(3) emulsification: under high-speed stirring, organic phase is scattered in water, emulsification 1-10min; Or
The person prepares when piecing together the microcapsule disperse dye that mixes, at first kind of dyestuff organic phase emulsification 1-
Behind the 10min, add another kind of dyestuff organic phase again, reemulsification 1-10min; Use 10-again
30% the NaOH aqueous solution is transferred pH to 7-9; Organic phase is common with inorganic weight ratio mutually
Be 5-20: 80-95, the recommendation ratio is 10-15: 85-90.
(4) encapsulated: as, to react a small amount of catalysis of adding after 0.5-3 hour in room temperature with under stirring
Agent is or/and the small molecules amine reacts 5-30min again;
(5) discharging, filtration, washing, modulation.
Wherein, the character of isocyanates has determined this technology to form capsular release performance, has also determined the physical structure intensity of capsule cortex.Two and the polyisocyanates of considering in technology of the present invention comprises that aromatics is two, polyisocyanates, and aliphatic series is two, polyisocyanates and their mixture.Its mainstream product has: 2, the 4-tolylene diisocyanate, 2, the two isocyanic ester of 6-methyl, 4,4 '-diphenylmethane group two (isocyanic ester), 4,4 '-methylene-bis (2-TI), polymethylene bis isocyanic ester (as the two isocyanic ester of hexa-methylene), and the polymethylene polyisocyanates etc.
The ratio of the dispersed dye core in the organic phase and two or polyisocyanates is also determining to form the wall thickness of microcapsule.In other words, employed amount two or polyisocyanates will determine that the cyst wall of formed microcapsule is thick in this technology.Core dyestuff weight ratio two to the wall material or polyisocyanates is 1: 1-5, the recommendation ratio is 1: 1-3.
Described emulsifying agent can be a non-ionic type, also can be negatively charged ion or cationic, and its hydrophile-lipophile balance value (HLB) is preferably between the 10-16.The emulsifying agent that can select is very wide.As polyglycol ether 600, polyethers 2040, nonionogenic tensides such as polyethers F-68; Anion surfactant or their suitable mixtures such as sodium lauryl sulphate; Bromination benzene is inserted cats products such as alkylammonium.Recommend to use the mixture of nonionogenic tenside or nonionic and anion surfactant as emulsifying agent, as polyethers 2040.With the microcapsule disperse dye good dispersity of this emulsifying agent preparation, narrow diameter distribution, particle diameter is more easy to control.The emulsifying agent consumption is 0.1% to 5.0% (weight) of total system, and recommending consumption is 2.0% to 3.0% of total system.
Also has protective colloid at aqueous phase; the protective colloid that can select is as follows: methylcellulose gum, polyvinyl alcohol, polyacrylamide and lignosulfonic acid salt, and as polyvinyl alcohol 1788, polyvinyl alcohol 1799; gelatin, polyvinylpyrrolidone water-soluble polymers or their mixtures such as (PVP).For total system consumption is 0.1% to 5.0% weight, and recommending consumption is to be 1.0% to 2.0%.The protective colloid of recommending to use is a polyvinyl alcohol, and the hydroxyl in the polyvinyl alcohol helps to form the wall equipment structure of cross-linked network, increases the intensity of wall.
In case of necessity, can catalyzer be added system in preceding 20 minutes to 30 minutes in the reaction end, purpose is to remove free isocyano group, and described catalyzer is a dibutyl tin laurate, and consumption is 0% to 0.01% of total system weight.
Described small molecules amine is the general molecular formula with RnNHm, wherein R=C
1-C
4Alkyl, n=0～2, m=3～1.As n-Butyl Amine 99, dimethylamine, diethylamine, ammonia etc.Add system at last stage reaction, purpose is thoroughly to remove free isocyano group, and consumption is 0.01% to 0.1% of total liquid measure.
Technological advantage of the present invention is the carbamide resin wall material that forms, and is formaldehydeless, pollution-free, the intensity height, and slow-releasing is good, and the auxiliary agent of use is few, and cost is low and easy and simple to handle.
Embodiment
To help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1
To contain and disperse deep blue S-3BG is 9g; 4; the organic phase of two isocyanic ester (MDI) 18g of 4-ditane joins among the water 300mL that contains 2% polyethers 2040,1% protective colloid polyvinyl alcohol 1788, and (the dynamo-electric company limited of Shanghai prestige space) goes up with 9000rpm emulsification 10min in BME100L type high-shear emulsion machine.The NaOH of adding 25% regulates the pH value to 7-8.Add a little n-Butyl Amine 99 behind the reaction 150min, reaction 30min.Examine under a microscope after the filtration, can obtain 2 μ m-10 μ m left and right sides microcapsule disperse dyes, wherein have about 50% all to concentrate on about 4 μ m.
Embodiment 2
The organic phase that will contain the blue 2BLN of dispersion of 0.8g and 6.2g liquefied mdi joins among the water 300mL that contains 2% polyethers 2040 and 1%PVA, on BME100L type high-shear emulsion machine with 9000rpm emulsification 10min.Add percentage concentration and be 25% the NaOH aqueous solution and regulate the pH value, add 1.6g DISPERSE YELLOW E-3RL and the 12.4g liquefied mdi that stirs behind the emulsification 10min to 7-8.Add a little n-Butyl Amine 99 behind the reaction 150min and react 30min again.Can obtain green microcapsule disperse dye, diameter 4 μ m-8 μ m.
Embodiment 3
The organic phase that will contain the liquefied mdi of the blue 2BLN of dispersion of 3.5g and 45.5g joins the aqueous phase 9000rpm emulsification 20min that contains 28g polyethers 2040,7g polyvinyl alcohol and 665g water, the percentage concentration that adds 12mL is that 25% aqueous solution NaOH regulates the pH value to 7-8, adds a little n-Butyl Amine 99 reaction 30min behind the reaction 150min.Can make the microcapsule disperse dye of 3 μ m-15 μ m.
Claims (9)
1. the preparation technology of a microcapsule disperse dye, it is characterized in that a kind of utilize two or polyisocyanate compound as the monomer that forms microcapsule wall material, generate amine with the water reaction earlier, amine generates polyureas with unreacted isocyanate reaction again, and preparation technology is as follows for this interfacial polymerization:
(1) water ingredients: in distilled water, add emulsifying agent, protective colloid on demand, stir;
(2) organic phase ingredients: two or polyisocyanates mixes with core dyestuff and wall material monomer by demand;
(3) emulsification: under high-speed stirring, organic phase is scattered in water, emulsification 1-10min; When perhaps the microcapsule disperse dye that mixes is pieced together in preparation, behind first kind of dyestuff organic phase emulsification 1-10min, add another kind of dyestuff organic phase again, reemulsification 1-10min; Transfer pH to 7-9 with the NaOH aqueous solution of 10-30% then; Organic phase is generally 5-20 with inorganic weight ratio mutually: 80-95;
(4) encapsulated: as under room temperature and mild stirring, to react adding catalyzer and/or small molecules amine after 0.5-3 hour, react 5-30min again;
(5) discharging, filtration, washing, modulation; Wherein, core dyestuff weight ratio two to the wall material or polyisocyanates is 1: 1-5; the usage quantity of emulsifying agent is 0.1% to 5.0% of total system weight; the employed amount of protective colloid is 0.1% to 5.0% a weight of total system; small molecules amine consumption is 0.01% to 0.1% of total liquid measure, and catalyst levels is 0% to 0.01% of total system weight.
2. the preparation technology of a kind of microcapsule disperse dye as claimed in claim 1, it is characterized in that described two or polyisocyanates comprises tolylene diisocyanate, 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 80%2, the mixture of 4-and 20%2,6-tolylene diisocyanate isomer, ditane-4,4 '-vulcabond and polymethylene polyisocyanic acid phenyl ester are at interior aromatics two or polyisocyanates, aliphatic vulcabond or polyisocyanates or other polyisocyanates.
3. the preparation technology of a kind of microcapsule disperse dye as claimed in claim 1 is characterized in that described emulsifying agent is the emulsifying agent of the mixture of non-ionic type, anionic, cationic tensio-active agent or nonionic and anion surfactant.
4. the preparation technology of a kind of microcapsule disperse dye as claimed in claim 1 is characterized in that its hydrophile-lipophile balance value of described emulsifying agent HLB is between 10-16.
5. as the preparation technology of claim 3 or 4 described a kind of microcapsule disperse dyes, it is characterized in that described emulsifying agent is a polyglycol ether 600, polyethers 2040, polyethers F-68, sodium lauryl sulphate or bromination benzene are inserted alkylammonium.
6. the preparation technology of a kind of microcapsule disperse dye as claimed in claim 1 is characterized in that described protective colloid is methylcellulose gum, polyvinyl alcohol, polyacrylamide or lignosulfonic acid salt, gelatin or polyvinylpyrrolidone water-soluble polymers,
7. the preparation technology of a kind of microcapsule disperse dye as claimed in claim 1 is characterized in that described small molecules amine has the general formula of RnNHm, wherein R=C
1-C
4Alkyl, n=0～2, m=3～1.
8. the preparation technology of a kind of microcapsule disperse dye as claimed in claim 7 is characterized in that described small molecules amine is a n-Butyl Amine 99, dimethylamine, diethylamine or ammonia.
9. the preparation technology of a kind of microcapsule disperse dye as claimed in claim 1 is characterized in that the catalyzer that added in preceding 20 minutes to 30 minutes in the reaction end is a dibutyl tin laurate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116242 CN1215126C (en) | 2003-04-08 | 2003-04-08 | Preparation process of dispersing dye microcapsule |
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|---|---|---|---|
| CN 03116242 CN1215126C (en) | 2003-04-08 | 2003-04-08 | Preparation process of dispersing dye microcapsule |
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| CN1443807A true CN1443807A (en) | 2003-09-24 |
| CN1215126C CN1215126C (en) | 2005-08-17 |
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| CN 03116242 Expired - Fee Related CN1215126C (en) | 2003-04-08 | 2003-04-08 | Preparation process of dispersing dye microcapsule |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085469A (en) * | 2010-12-15 | 2011-06-08 | 郑州大学 | Method for preparing big-diameter granules from micro and nano powder by means of interfacial polymerization |
| CN102146219A (en) * | 2011-01-19 | 2011-08-10 | 山西大学 | Preparation method of reactive dye microcapsule |
| CN102146218A (en) * | 2011-01-19 | 2011-08-10 | 山西大学 | Preparation method of reactive dye microcapsule |
| CN103331133A (en) * | 2013-06-07 | 2013-10-02 | 深圳大学 | Epoxy microcapsule with polyurea as wall material and preparation method thereof |
| CN107206344A (en) * | 2015-01-23 | 2017-09-26 | 弗门尼舍有限公司 | The method for preparing the microcapsules without melamino-formaldehyde |
| CN109881507A (en) * | 2019-02-27 | 2019-06-14 | 温州优巴信息技术有限公司 | It is a kind of by low temperature plasma and the high-precision digital printing technology of isocyanates microcapsules technology |
| CN110172261A (en) * | 2019-05-10 | 2019-08-27 | 浙江梅盛实业股份有限公司 | A kind of preparation method of microcapsule disperse dye and the dyeing of artificial leather |
| WO2021174614A1 (en) * | 2020-03-04 | 2021-09-10 | Tcl华星光电技术有限公司 | Microcapsule-type dye and preparation method therefor, and application method therefor |
-
2003
- 2003-04-08 CN CN 03116242 patent/CN1215126C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085469A (en) * | 2010-12-15 | 2011-06-08 | 郑州大学 | Method for preparing big-diameter granules from micro and nano powder by means of interfacial polymerization |
| CN102085469B (en) * | 2010-12-15 | 2013-01-02 | 郑州大学 | Method for preparing big-diameter granules from micro and nano powder by means of interfacial polymerization |
| CN102146219A (en) * | 2011-01-19 | 2011-08-10 | 山西大学 | Preparation method of reactive dye microcapsule |
| CN102146218A (en) * | 2011-01-19 | 2011-08-10 | 山西大学 | Preparation method of reactive dye microcapsule |
| CN102146218B (en) * | 2011-01-19 | 2013-04-24 | 山西大学 | Preparation method of reactive dye microcapsule |
| CN102146219B (en) * | 2011-01-19 | 2013-04-24 | 山西大学 | Preparation method of reactive dye microcapsule |
| CN103331133A (en) * | 2013-06-07 | 2013-10-02 | 深圳大学 | Epoxy microcapsule with polyurea as wall material and preparation method thereof |
| WO2014194600A1 (en) * | 2013-06-07 | 2014-12-11 | 深圳大学 | Epoxy microcapsule with polyurea as wall material and preparation method thereof |
| CN103331133B (en) * | 2013-06-07 | 2015-06-24 | 深圳大学 | Epoxy microcapsule with polyurea as wall material and preparation method thereof |
| CN107206344A (en) * | 2015-01-23 | 2017-09-26 | 弗门尼舍有限公司 | The method for preparing the microcapsules without melamino-formaldehyde |
| CN109881507A (en) * | 2019-02-27 | 2019-06-14 | 温州优巴信息技术有限公司 | It is a kind of by low temperature plasma and the high-precision digital printing technology of isocyanates microcapsules technology |
| CN110172261A (en) * | 2019-05-10 | 2019-08-27 | 浙江梅盛实业股份有限公司 | A kind of preparation method of microcapsule disperse dye and the dyeing of artificial leather |
| WO2021174614A1 (en) * | 2020-03-04 | 2021-09-10 | Tcl华星光电技术有限公司 | Microcapsule-type dye and preparation method therefor, and application method therefor |
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| Publication number | Publication date |
|---|---|
| CN1215126C (en) | 2005-08-17 |
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Granted publication date: 20050817 Termination date: 20120408 |