CN1586707A - Color physically foamed micro capsule and preparing method - Google Patents
Color physically foamed micro capsule and preparing method Download PDFInfo
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- CN1586707A CN1586707A CN 200410052920 CN200410052920A CN1586707A CN 1586707 A CN1586707 A CN 1586707A CN 200410052920 CN200410052920 CN 200410052920 CN 200410052920 A CN200410052920 A CN 200410052920A CN 1586707 A CN1586707 A CN 1586707A
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Abstract
The present invention relates to physically foamed color microcapsule and its preparation process. The physically foamed color microcapsule is prepared through limited coagulating polymerization process, and has the polymer of ethylene monomer and acrylate derivative and dispersed dye as wall material and low boiling point solvent as core material.
Description
Technical field:
The invention belongs to fine chemistry industry and field of new.Utilize acrylonitrile, methacrylate and disperse dyes as forming colored foaming microcapsule wall material raw material, low boiling point solvent is a microcapsules core raw material, prepares coloured physical blowing microcapsule by limited aggegation polymerization.This microcapsules are a kind of functional high molecule materials, are specially adapted to coloured intumescent coating finishing technique and coloured Technique of Raised Foaming Printing occasion, also can be used for electrostatic spinning and suede finish.
Background technology:
Blowing microcapsule is a kind of thermal expansivity microcapsules, and it has the thermoplasticity shell, interior bag low boiling point organic solvent.Being generally 5-500 μ m according to its diameter of different purposes does not wait.The rapid gasification of capsule heart liquid (low boiling point organic solvent) produces internal pressure when being heated, and cyst membrane (wall material) is subjected to thermal softening simultaneously, and cyst membrane under the effect of internal pressure (wall material) expands and makes volume increase foaming.When the coupling that is produced in the gasification of wall material thermoplasticity and core was suitable, microballoon then showed good expansion character.Microcapsules after the expansion should have relative morphological stability, are unlikely to retraction after the cooling.When textile printing, adopt suitable adhesive, pigment etc. to mix and just form foaming printing paste with this microballoon.After printing, the drying, through the heat treatment of uniform temperature, microcapsule expansion causes decorative pattern to increase formation third dimension, the very strong pattern of woolen embroidery sense, has special decoration function again.The general physical blowing microcapsule forms the back and is off-white powder, substantially still present milky after the foaming, form coloured physical blowing microcapsule if in preparation process, add disperse dyes, then can present color after the foaming, solve the white core phenomenon that foaming process and colouring process separate operation are caused.Technology is not seen relevant report both at home and abroad in this respect.Relative theory:
(1) preparation principle
The water of being made up of water, dispersant, stabilizing agent and additive reaches the oil phase of being made up of monomer, blowing agent, initator, colouring agent, both mix mutually after strong stirring action, form the oil-in-water type dispersion, oil phase liquid-drop diameter 2-30um, and keep certain stability.The aqueous phase constituent can suppress dissolving and the polymerization of oil phase monomer at aqueous phase.
Rise to the decomposition temperature of initator when temperature after, decompose the free radical trigger monomer polymerization that generates.Before this, monomer, initator, blowing agent, colouring agent are to dissolve each other and form the homogeneous system.Along with the carrying out of polymerisation, polymer is insoluble to blowing agent and precipitating is come out, and this moment, it had certain suction-operated to disperse dyes.Polymer absorption oil phase colouring agent constantly in the oil-water interfaces deposition, form parietal layer, and blowing agent is besieged as core, finally forms coloured physical blowing microcapsule.
(2) foam theory
After heating, the low boiling point solvent vaporization promotes hot retrospective wall shell and outwards expands in coloured physical blowing microcapsule, the microcapsules foaming.After the cooling, dilated wall shell still can keep certain intensity, and its shape is not shunk, and produces the color solid effect.
Summary of the invention:
The object of the invention provides a kind of colored physical blowing microcapsule.
Purpose of the present invention also provides a kind of preparation method of above-mentioned colored physical blowing microcapsule.
The present invention utilize to adopt vinyl monomer (styrene for example, acrylonitrile, vinylidene chloride, vinyl chloride), acrylate derivative (methyl methacrylate for example, EMA, butyl methacrylate, the methacrylic acid pentyl ester) and disperse dyes (azo disperse dye, anthraquinone type disperse dye or heterocyclic disperse dyes) as forming coloured blowing microcapsule wall material raw material, low boiling point solvent (butane for example, pentane, neopentane, 2-methybutane, n-hexane, normal heptane etc.) be microcapsules core raw material, by the painted coloured physical blowing microcapsule that obtains various colors of limited aggegation polymerization original position.
It is as follows that these microcapsules are generally 10～30 μ m concrete preparation method of the present invention:
(1) batching
Polymerization system is made up of monomer decentralized photo (abbreviation oil phase) and water continuous phase (abbreviation water).Form by the above-mentioned substance weight ratio:
Water: distilled water 500-800, sodium chloride 150-250, ultrafine solids dispersant (white carbon black or Mg (OH)
2Colloid or precipitated calcium carbonate) 90-120, water-soluble polymer dispersant is (as polyvinyl alcohol 1788; The K value is respectively 12,17,20,25,30 polyvinylpyrrolidone; Acid number is respectively 75,105, and 135,185 the adipic acid and the condensation polymer of diethanol amine) 1-5, anion surfactant (for example dodecyl sodium sulfate, lauryl sodium sulfate) 1-5, oxidant (for example potassium bichromate, hydrogen peroxide) 0.15-0.4, and regulate the pH value to 3-4 with concentrated hydrochloric acid solution.
Oil phase: vinyl monomer (styrene for example, acrylonitrile, vinylidene chloride, vinyl chloride) 100-150, acrylate derivative (methyl methacrylate for example, EMA, butyl methacrylate, the methacrylic acid pentyl ester) 15-40, low boiling point solvent (butane for example, pentane, neopentane, the 2-methybutane, n-hexane, normal heptane etc.) 15-40, initator (azodiisobutyronitrile or benzoyl peroxide) 1-2, disperse dyes (azo disperse dye, anthraquinone type disperse dye or heterocyclic disperse dyes) 0.01-0.5.
(2) emulsification
Placed in frozen water and the coolant recirculation pump (0 ℃～-10 ℃) cooling after water, oil phase shaken up respectively 20～30 minutes.Then two-phase is mixed, about 10-30 minute, obtain uniform suspension with 1000-5000 rev/min rotating speed mixing and emulsifying with high shearing mixing emulsor.
(3) reaction
The system that emulsification is good joins in the autoclave that has agitator, seals up lid rapidly, fixes, charge into nitrogen, regulate agitator speed to 200～400 rev/min, slow down programming rate again after the temperature programming to 40 ℃, until 50 ℃, insulation is warmed up to 55 ℃ after half an hour again, is incubated half an hour again, controlling temperature then reacted 8-30 hour about 58 ℃, after system is cooled to about 30 ℃, release, discharging, the washing, suction filtration, dry, sieve.
Wherein, vinyl monomer, series of acrylate and disperse dyes have determined the physical arrangement intensity and the foam performance of parietal layer that this technology forms; Disperse dyes produce microcapsule wall material sometimes and increase north effect, reduce the minimum blowing temperature of capsule; Different low boiling point solvent core materials have played main effect to the minimum blowing temperature of microcapsules.
It is painted to carry out original position when the advantage of this technology is the preparation physical blowing microcapsule, the coloured physical blowing microcapsule color that generally prepares and the color basically identical of disperse dyes, can form specific color after the foaming, increased the vividness of color, the foaming product that also can prepare special colour mixture effect has improved the shortcoming that presents white or gloomy color after conventional physical blowing microcapsule foams.The particle diameter of coloured physical blowing microcapsule of this method preparation mainly concentrates on 10-50 μ m, especially concentrates on 20-30 μ m.
The advantage of this technology is physical blowing microcapsule to be carried out painted, or foaming back forms specific multicolour pattern, has improved the shortcoming that presents white or gloomy color after the conventional physical blowing capsule foaming.
The specific embodiment:
The preparation of embodiment 1 colored physical blowing microcapsule
(1) water weight ratio: distilled water 700, the white carbon black 100 of sodium chloride 200,15%, acid number are 105 adipic acid and diethanol amine condensation polymer 5, dodecyl sodium sulfate 2, and potassium bichromate 0.25, and regulate the pH value to 3-4 with concentrated hydrochloric acid solution.Oil phase weight ratio: add acrylonitrile 123 successively, methyl methacrylate 23, Red-1 200 #0.2, low boiling point solvent pentane 22,1 part of initator azodiisobutyronitrile.
(2) after being shaken up, water, oil phase placed in frozen water and the coolant recirculation pump (8 ℃) cooling respectively 20～30 minutes.Then two-phase is mixed, about 10-30 minute, obtain uniform suspension with 2500 rev/mins rotating speed mixing and emulsifying with high shearing mixing emulsor.
(3) reaction
The system that emulsification is good joins in the autoclave that has agitator, seals up lid rapidly, fixes, and charges into nitrogen, applies certain first pressing 0.35MPa.Regulate agitator speed to 300 rev/min, slow down programming rate again after the temperature programming to 40 ℃, until 50 ℃, insulation is warmed up to 55 ℃ after half an hour again, is incubated half an hour again, controlling temperature then reacted 24 hours about 58 ℃, after system is cooled to about 30 ℃, release, discharging, the washing, suction filtration, dry, sieve.
| Coloured physical blowing microcapsule sample | No disperse dyes | Disperse yellow E-2G | Red-1 200 # | Disperse Green | ||||
| Concentrated blowing temperature (℃) | ???????155 | ??????153 | ????????109 | ???????149 | ||||
| Steady bubble Wen Cheng (℃) | ???????12 | ??????27 | ????????56 | ???????26 | ||||
| Phenomenon | The broken in a large number bubble of the simultaneous of a large amount of foaming, foaming effect is not good | In the time of 155 ℃, be accompanied by brokenly bubble, but not serious | A large amount of foaming back steady bubble effect is very good in the time of 109 ℃, do not have a large amount of broken bubble phenomenons, bubble is the contraction of gradual slow | The back steady bubble effect of comprehensively bubbling is fine, only be attended by a small amount of broken bubble, do not have a large amount of broken bubble phenomenons | ||||
| Foaming height (cm) | Elemental height | The foaming maximum height | Elemental height | The foaming maximum height | Elemental height | The foaming maximum height | Elemental height | The foaming maximum height |
| ???0.3 | ???1.6 | ???0.3 | ???1.7 | ???0.25 | ???2.2 | ???0.25 | ???1.6 | |
| Expansion ratio | ??????5.3 | ??????5.7 | ???????8.8 | ???????6.4 | ||||
Annotate: core is a pentane, and Disperse Green is to be made into by the ratio of disperseing blue E-4R and disperse yellow E-2G in 1: 1.
Red-1 200 # (azo disperse dye) disperse yellow E-2G disperses blue E-4R (anthraquinone type disperse dye).
Claims (3)
1, a kind of colored physical blowing microcapsule is characterized in that the polymer of vinyl monomer and acrylate derivative and disperse dyes are that wall material and low boiling point solvent are the colored physical blowing microcapsule of core.
2, the preparation method of colored physical blowing microcapsule as claimed in claim 1 is characterized in that by following method preparation:
(1) distilled water, sodium chloride, ultrafine solids dispersant, water-soluble polymer dispersant, anion surfactant, oxidant are mixed by following weight ratio: 500-800: 150-250: 90-120: 1-5: 1-5: 0.15-0.4, regulate mixed liquor with concentrated hydrochloric acid and make water to pH3-4;
Vinyl monomer, acrylate derivative, low boiling point solvent, initator and disperse dyes are mixed into oil phase by following weight ratio: 100-150: 15-40: 15-40: 1-2: 0.01-0.5;
(2) above-mentioned water is become suspended emulsion with the oil phase mixing and emulsifying, with room temperature to 60 ℃ reaction 20-30 hour, reactant was through washing, filtration, dried and screened under nitrogen protection;
Described ultrafine solids dispersant is white carbon black, precipitated calcium carbonate or magnesium hydroxide colloid; Described water-soluble polymer dispersant is the condensation polymer of polyvinyl alcohol, polyvinylpyrrolidone or ethanedioic acid and diethanol amine; Described anion surfactant is dodecyl sodium sulfate, lauryl sodium sulfate; Described oxidant is potassium bichromate or hydrogen peroxide; Described acrylate is methyl methacrylate, EMA, butyl methacrylate or methacrylic acid pentyl ester; Described low boiling point solvent is butane, pentane, neopentane, Alpha-Methyl butane, n-hexane or normal heptane; Described initator is azodiisobutyronitrile or benzoyl peroxide; Described disperse dyes are azo disperse dye, anthraquinone type disperse dye or heterocyclic disperse dyes.
3, preparation method as claimed in claim 2 is characterized in that described emulsification is that described water and oil phase were cooled off 20-30 minute, uses mulser mixing and emulsifying 10-30 minute in ice or coolant circulation pump.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410052920 CN1253243C (en) | 2004-07-16 | 2004-07-16 | Color physically foamed micro capsule and preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410052920 CN1253243C (en) | 2004-07-16 | 2004-07-16 | Color physically foamed micro capsule and preparing method |
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| CN1586707A true CN1586707A (en) | 2005-03-02 |
| CN1253243C CN1253243C (en) | 2006-04-26 |
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| CN 200410052920 Expired - Fee Related CN1253243C (en) | 2004-07-16 | 2004-07-16 | Color physically foamed micro capsule and preparing method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113611A (en) * | 2011-11-17 | 2013-05-22 | 罗李华 | Granule foaming agent |
| CN105777959A (en) * | 2016-03-18 | 2016-07-20 | 深圳市心流行科技有限公司 | Nanoparticle functional textile material and manufacturing method thereof |
| CN108658612A (en) * | 2018-05-18 | 2018-10-16 | 赵顺全 | A kind of preparation method of refratory insulating brick |
| CN109647300A (en) * | 2019-01-18 | 2019-04-19 | 唐山开滦化工科技有限公司 | It is a kind of can physical blowing microcapsules and preparation method thereof |
| CN109762220A (en) * | 2019-01-04 | 2019-05-17 | 中策橡胶集团有限公司 | A kind of Tire tread rubber composition and its preparation method and application with microcellular structure |
| CN109777634A (en) * | 2019-01-25 | 2019-05-21 | 关汉杰 | A kind of chance Water blown capsule and preparation method thereof |
| CN112779814A (en) * | 2020-12-25 | 2021-05-11 | 宜兴市佳普林新材料有限公司 | High-permeability thermal sublimation transfer paper coating |
-
2004
- 2004-07-16 CN CN 200410052920 patent/CN1253243C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113611A (en) * | 2011-11-17 | 2013-05-22 | 罗李华 | Granule foaming agent |
| CN105777959A (en) * | 2016-03-18 | 2016-07-20 | 深圳市心流行科技有限公司 | Nanoparticle functional textile material and manufacturing method thereof |
| CN108658612A (en) * | 2018-05-18 | 2018-10-16 | 赵顺全 | A kind of preparation method of refratory insulating brick |
| CN108658612B (en) * | 2018-05-18 | 2021-02-02 | 山东银山耐火材料有限公司 | Preparation method of refractory heat-insulating brick |
| CN109762220A (en) * | 2019-01-04 | 2019-05-17 | 中策橡胶集团有限公司 | A kind of Tire tread rubber composition and its preparation method and application with microcellular structure |
| CN109647300A (en) * | 2019-01-18 | 2019-04-19 | 唐山开滦化工科技有限公司 | It is a kind of can physical blowing microcapsules and preparation method thereof |
| CN109777634A (en) * | 2019-01-25 | 2019-05-21 | 关汉杰 | A kind of chance Water blown capsule and preparation method thereof |
| CN112779814A (en) * | 2020-12-25 | 2021-05-11 | 宜兴市佳普林新材料有限公司 | High-permeability thermal sublimation transfer paper coating |
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| Publication number | Publication date |
|---|---|
| CN1253243C (en) | 2006-04-26 |
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| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shanghai Anoky Textile Chemicals Co. Ltd. Assignor: Donghua University Contract fulfillment period: 2006.6.30 to 2016.6.30 contract change Contract record no.: 2008310000016 Denomination of invention: Color physically foamed micro capsule and preparing method Granted publication date: 20060426 License type: Exclusive license Record date: 2008.9.8 |
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Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2006.6.30 TO 2016.6.30 Name of requester: SHANGHAI ANNUOQI SPINNING CHEMICAL CO.,LTD. Effective date: 20080908 |
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
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