CN103665279A - Preparation method and application of modified nano TiO2 finishing agent - Google Patents
Preparation method and application of modified nano TiO2 finishing agent Download PDFInfo
- Publication number
- CN103665279A CN103665279A CN201310595984.8A CN201310595984A CN103665279A CN 103665279 A CN103665279 A CN 103665279A CN 201310595984 A CN201310595984 A CN 201310595984A CN 103665279 A CN103665279 A CN 103665279A
- Authority
- CN
- China
- Prior art keywords
- tio
- modified nano
- preparation
- monomer
- finishing composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a preparation method and application of a modified nano TiO2 finishing agent. The preparation method comprises the following steps: adjusting the pH value of a TiO2 water dispersion solution to be 9-12 by ammonia water, and adding a water-soluble cationic initiator so as to obtain an activated and modified TiO2 dispersion solution; adding a monomer and an emulsifier into the activated and modified TiO2 dispersion solution respectively, and ultrasonically grinding a mixed solution; stirring and heating while filling nitrogen gas, dropwise adding methylacrylic acid when the monomer conversion rate is 70%-90%, after dropwise adding, continuously producing a thermal reaction until the reaction is complete, and cooling to obtain the modified nano TiO2 finishing agent. Modified nano TiO2 has two layers of polymers, one layer is a monomer polymer with a bonding effect, and an outer layer of the monomer polymer is a monomer and methylacrylic acid copolymer, so that the modified nano TiO2 not only can be adhered to the fiber surface but also can react with fibers and is better in uniformity and washing durability.
Description
Technical field
The invention belongs to after-finishing of textile products auxiliary agent technical field, relate in particular to a kind of modified Nano TiO
2the preparation method of finishing composition and application thereof.
Background technology
Nano-TiO
2as photocatalyst, ultraviolet light screener etc., be widely used in field of textiles, but TiO
2belong to inorganic materials, natural fiber is without any affinity, and nanoparticle cannot form firmly chemical bond with fiber.At present, under tackiness agent effect, by padding, the postfinishing process such as coating is nano-TiO
2being attached to fabric face, is to make nano-TiO
2the most popular method of modified function textiles.Arrange by this method the fabric fastness to washing forming low, function can not be lasting.Therefore, nano-TiO
2the dispersed of fabric face and with the binding strength of fabric, become TiO
2the subject matter existing while being applied to textile finishing.
Summary of the invention
The present invention, in order to solve the problems of the technologies described above, provides a kind of modified Nano TiO
2the preparation method of finishing composition, makes TiO by the cationic initiator of electrostatic adhesion
2particle surface is activated, by adding the monomer of low Tg at nano-TiO
2surface forms has adhesive effect polymkeric substance, drips with the function monomer reacting with cellulosic fibre in the reaction later stage simultaneously, improves nano-TiO
2and the binding strength between fabric, high efficiency and the persistence of assurance finish fabric function.
In order to solve the problems of the technologies described above, the present invention by the following technical solutions:
A kind of modified Nano TiO
2the preparation method of finishing composition, comprises the steps:
(1) get TiO
2aqueous dispersions, regulates pH value to 9-12, adds TiO
2the water-soluble cationic initiator of weight 1%~5%, obtains TiO
2activation modification dispersion liquid;
(2) add 2~3 times of TiO
2the monomer of weight and 2%~6% TiO
2the emulsifying agent of weight, then ultrasonication;
(3) when passing into nitrogen, while stirring, heat, when monomer conversion is 70%~90%, drip methacrylic acid, dropwise follow-up continuous insulation reaction, to reacting completely, cooling down, obtains modified Nano TiO
2finishing composition;
Described monomer is the mixture of butyl acrylate, Isooctyl acrylate monomer or both compositions.
Monomer conversion adopts the method for conventional test soln solid content to measure.
As preferably, the described TiO of step (1)
2the solid content of aqueous dispersions is 5~25%, TiO
2particle diameter be 120~150nm.
As preferably, the described water-soluble cationic initiator of step (1) is azo diisobutyl amidine hydrochloride, azo two isobutyl imidazoline salt hydrochlorates or mixture that both form.
As preferably, step (1) regulates pH to adopt ammoniacal liquor.
As preferably, the described emulsifying agent of step (2) is the mixture of nonionogenic tenside and anion surfactant.In emulsifying agent, the ratio of nonionogenic tenside and anion surfactant is any.
As preferably, described nonionogenic tenside is a kind of in secondary octyl phenol polyethenoxy ether, fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether or fatty alcohol-polyoxyethylene ether, and described anion surfactant is a kind of in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, octyl phenol polyethylene ether maleic acid ester sodium or coco group sodium isethionate.
As preferably, step (3) insulation reaction temperature is 65-70 ℃, and the reaction times is 1.5h~2h.
As preferably, the drop rate of step (3) methacrylic acid is 2ml/h.
The present invention also provides above-mentioned modified Nano TiO
2the application of finishing composition in cellulosic fibre.
By the modified Nano TiO of above-mentioned preparation
2dressing liquid adds water and is mixed with the above-mentioned dressing liquid that concentration is 20~50g/L(20~50g, and adding water to whole liquor capacity is 1L) dressing liquid, then will treat that finish fabric carries out two and soaks two and roll, pick-up 70~100%, drying and shaping in this dressing liquid.
As preferably, drying condition is that 100 ℃ * 2min, sizing condition are 130 ℃ * 1min.
Modified Nano TiO of the present invention
2have two layers of polymers, one deck is the polymkeric substance with the monomer of adhesive effect, and the skin of monomer-polymer is the multipolymer of monomer and methacrylic acid.Therefore not only can stick to fiber surface but also can and fiber-reactive, there is better homogeneity and washing resistance.
Accompanying drawing explanation
Fig. 1 is the tackiness agent of prior art and the scanning electron microscope (SEM) photograph of cellulosic fibre reaction.
Fig. 2 is the embodiment of the present invention 1 modified Nano TiO
2the scanning electron microscope (SEM) photograph of dressing liquid and cellulosic fibre reaction.
Embodiment
Below the present invention is further explained:
Due to nano-TiO
2surface have a lot of hydroxyls, adjust nano-TiO
2the pH value of dispersion liquid is during to 9-11, TiO
2can electrostatic adhesion water-soluble cationic initiator, thus make TiO
2the surface active of particle.Method by in-situ emulsion polymerization realizes monomer at TiO
2the polymerization on surface, forms PBA superpolymer, and this polymkeric substance self has the effect of tackiness agent, can stick to fiber surface, but can not and fiber-reactive.When being 70%~90%, the transformation efficiency of monomer drips methacrylic acid, TiO
2the outside multipolymer that forms monomer and methacrylic acid, like this TiO
2skin just contains the group with fiber-reactive.
embodiment 1
(1) getting solid content is 5% TiO
2aqueous dispersions 10 g, its TiO
2tiO in aqueous dispersions
2particle diameter be 120~150nm.With ammoniacal liquor, regulate aqueous dispersions pH value to 9, then to adding in this aqueous dispersions, account for TiO
2the water-soluble cationic initiator azo-bis-isobutyrate hydrochloride of mass percent 1%, realizes the activation modification to TiO2 surface by azo diisobutyl amidine hydrochloride under stirring at room.
(2) by quality, be TiO respectively
2the butyl acrylate of 2 times and quality are TiO
22% nonionic emulsifying agent secondary octyl phenol polyethenoxy (10) ether TX-10 and anionic emulsifier sodium lauryl sulphate join the TiO described in (1)
2in activation modification dispersion liquid, then, by mixed solution 8min under ultrasonic disintegrator, finally transferred to ready reaction in four-hole boiling flask.
(3) logical nitrogen, heat solution to 65 ℃ in above-mentioned four-hole boiling flask while stirring, speed with 2ml/h when monomer conversion is 70% drips methacrylic acid, dropwise follow-up continuous insulation reaction 1.5h, after cooling down, make the nano-TiO with cellulosic fibre reaction
2dressing liquid.
(4) by nano-TiO prepared and cellulosic fibre reaction
2dressing liquid is mixed with the dressing liquid that concentration is 20~50g/L, then will treat that finish fabric carries out two and soaks two and roll in this dressing liquid, pick-up 70~100%, and 100 ℃ * 2min is dried, 130 ℃ * 1min sizing.
embodiment 2
(1) getting solid content is 10% TiO
2aqueous dispersions 10 g, its TiO
2tiO in aqueous dispersions
2particle diameter be 120~150nm.With ammoniacal liquor, regulate aqueous dispersions pH value to 10, then to adding in this aqueous dispersions, account for respectively TiO
2mass percent is 3% water-soluble cationic initiator azo-bis-isobutyrate hydrochloride and the mixture of azo two isobutyl imidazoline salt hydrochlorates, under stirring at room, by azo diisobutyl amidine hydrochloride and azo two isobutyl imidazoline salt hydrochlorates, realizes the activation modification to TiO2 surface.
(2) by quality, be TiO respectively
2the butyl acrylate of 3 times and quality are TiO
24% nonionic emulsifying agent fatty alcohol-polyoxyethylene ether OP-9 and anionic emulsifier Sodium dodecylbenzene sulfonate join the TiO described in (1)
2in activation modification dispersion liquid, then, by mixed solution 10 min under ultrasonic disintegrator, finally transferred to ready reaction in four-hole boiling flask.
(3) logical nitrogen, heat solution to 65 ℃ in above-mentioned four-hole boiling flask while stirring, speed with 2ml/h when monomer conversion is 80% drips methacrylic acid, dropwise follow-up continuous insulation reaction 2h, after cooling down, make the nano-TiO with cellulosic fibre reaction
2dressing liquid.
(4) by nano-TiO prepared and cellulosic fibre reaction
2dressing liquid is mixed with the dressing liquid that concentration is 20~50g/L, then will treat that finish fabric carries out two and soaks two and roll in this dressing liquid, pick-up 70~100%, and 100 ℃ * 2min is dried, 130 ℃ * 1min sizing.
embodiment 3
(1) getting solid content is 15% TiO
2aqueous dispersions 15g, its TiO
2tiO in aqueous dispersions
2particle diameter be 120~150nm.With ammoniacal liquor, regulate aqueous dispersions pH value to 11, then to adding in this aqueous dispersions, account for respectively TiO
2mass percent is 3% water-soluble cationic initiator azo-bis-isobutyrate hydrochloride and the mixture of azo two isobutyl imidazoline salt hydrochlorates, under stirring at room, by azo diisobutyl amidine hydrochloride and azo two isobutyl imidazoline salt hydrochlorates, realizes the activation modification to TiO2 surface.
(2) by quality, be TiO respectively
2the butyl acrylate of 2 times and quality are TiO
24% nonionic emulsifying agent polyoxyethylene nonylphenol ether NP-9 and anionic emulsifier octyl phenol polyethylene ether maleic acid ester sodium join the TiO described in (1)
2in activation modification dispersion liquid, then, by mixed solution 10 min under ultrasonic disintegrator, finally transferred to ready reaction in four-hole boiling flask.
(3) logical nitrogen, heat solution to 65 ℃ in above-mentioned four-hole boiling flask while stirring, speed with 2ml/h when monomer conversion is 90% drips methacrylic acid, dropwise follow-up continuous insulation reaction 2h, after cooling down, make the nano-TiO with cellulosic fibre reaction
2dressing liquid.
(4) by nano-TiO prepared and cellulosic fibre reaction
2dressing liquid is mixed with the dressing liquid that concentration is 20~50g/L, then will treat that finish fabric carries out two and soaks two and roll in this dressing liquid, pick-up 70~100%, and 100 ℃ * 2min is dried, 130 ℃ * 1min sizing.
embodiment 4
(1) getting solid content is 25% TiO
2aqueous dispersions 10g, its TiO
2tiO in aqueous dispersions
2particle diameter be 120~150nm.With ammoniacal liquor, regulate aqueous dispersions pH value to 12, then to adding in this aqueous dispersions, account for respectively TiO
2mass percent is 5% water-soluble cationic initiator azo-bis-isobutyrate hydrochloride and the mixture of azo two isobutyl imidazoline salt hydrochlorates, under stirring at room, by azo diisobutyl amidine hydrochloride and azo two isobutyl imidazoline salt hydrochlorates, realizes the activation modification to TiO2 surface.
(2) by quality, be TiO respectively
2the butyl acrylate of 2 times and quality are TiO
26% nonionic emulsifying agent fatty alcohol-polyoxyethylene ether OP-10 and anionic emulsifier coco group sodium isethionate join the TiO described in (1)
2in activation modification dispersion liquid, then, by mixed solution 10 min under ultrasonic disintegrator, finally transferred to ready reaction in four-hole boiling flask.
(3) logical nitrogen, heat solution to 65 ℃ in above-mentioned four-hole boiling flask while stirring, speed with 2ml/h when monomer conversion is 90% drips methacrylic acid, dropwise follow-up continuous insulation reaction 2h, after cooling down, make the nano-TiO with cellulosic fibre reaction
2dressing liquid.
(4) by nano-TiO prepared and cellulosic fibre reaction
2dressing liquid is mixed with the dressing liquid that concentration is 20~50g/L, then will treat that finish fabric carries out two and soaks two and roll in this dressing liquid, pick-up 70~100%, and 100 ℃ * 2min is dried, 130 ℃ * 1min sizing.
test result:
1, stereoscan photograph:
Fig. 1 is the common adhesive of prior art and the scanning electron microscope (SEM) photograph of cellulosic fibre reaction, and in figure, nanoparticle is piled up, skewness.
Fig. 2 is modified Nano TiO of the present invention
2the scanning electron microscope (SEM) photograph of dressing liquid and cellulosic fibre reaction, in figure, nanoparticle is evenly distributed, and fiber self-crosslinking.
Contrast by Fig. 1 and Fig. 2 can be found out, nano-TiO of the present invention
2be evenly distributed on cellulosic fibre, better with respect to prior art in the dispersiveness of fabric face, more firm with the combination of fabric.
2, the scope of UPF value (Ultraviolet Protection Factor, i.e. ultraviolet protection index) sees table:
UPF scope | Protection classification | Ultraviolet transmittance | UPF grade |
15-24 | Good ultraviolet resistance | 6.7-4.2 | 15,20 |
25-39 | Good ultraviolet resistance | 4.1-2.6 | 25,30,35 |
40-50,50+ | Excellent ultraviolet resistance | ≤2.5 | 40,45,50,50+ |
The UPF value contrast of the present invention and prior art:
Contrast 1: do not add nano-TiO
2fabric;
Contrast 2: add prior art nano-TiO
2fabric;
The present invention: embodiment 1~4.
? | Contrast 1 | Contrast 2 | Embodiment 1(is optimum) | Embodiment 2 | Embodiment 3 | Embodiment 4 |
Not washing | 18 | 48 | 116 | 110 | 112 | 108 |
HL5 | 16 | 31 | 102 | 95 | 100 | 99 |
HL10 | 15 | 26 | 98 | 90 | 96 | 89 |
HL20 | 12 | 22 | 96 | 82 | 90 | 83 |
From upper table data, can find out, not add nano-TiO
2fabric, a little less than its UPF value (uvioresistant performance), through HL20(5 home washings) after, UPF value decreases; Add prior art nano-TiO
2fabric, its UPF value is strengthened to some extent, but through after washing repeatedly, UPF value is reduction obviously; Through the present invention, make nano-TiO by oneself
2fabric after arrangement, its UPF value increases rapidly, and after 20 home washings, UPF value does not obviously reduce, and illustrates through the present invention and makes nano-TiO by oneself
2fabric after arrangement has washing resistance.
Claims (9)
1. a modified Nano TiO
2the preparation method of finishing composition, is characterized in that: comprise the steps:
(1) get TiO
2aqueous dispersions, regulates pH value to 9-12, adds TiO
2the water-soluble cationic initiator of weight 1%~5%, obtains TiO
2activation modification dispersion liquid;
(2) add 2~3 times of TiO
2the monomer of weight and 2%~6% TiO
2the emulsifying agent of weight, then ultrasonication;
(3) when passing into nitrogen, while stirring, heat, when monomer conversion is 70%~90%, drip methacrylic acid, dropwise follow-up continuous insulation reaction, to reacting completely, cooling down, obtains modified Nano TiO
2finishing composition;
Described monomer is the mixture of butyl acrylate, Isooctyl acrylate monomer or both compositions.
2. modified Nano TiO according to claim 1
2the preparation method of finishing composition, is characterized in that: the described TiO of step (1)
2the solid content of aqueous dispersions is 5~25%, TiO
2particle diameter be 120~150nm.
3. modified Nano TiO according to claim 1
2the preparation method of finishing composition, is characterized in that: the described water-soluble cationic initiator of step (1) is the mixture of azo diisobutyl amidine hydrochloride, azo two isobutyl imidazoline salt hydrochlorates or both compositions.
4. modified Nano TiO according to claim 1
2the preparation method of finishing composition, is characterized in that: step (1) regulates pH to adopt ammoniacal liquor.
5. modified Nano TiO according to claim 1
2the preparation method of finishing composition, is characterized in that: the described emulsifying agent of step (2) is the mixture of nonionogenic tenside and anion surfactant.
6. modified Nano TiO according to claim 5
2the preparation method of finishing composition, it is characterized in that: described nonionogenic tenside is a kind of in secondary octyl phenol polyethenoxy ether, fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether or fatty alcohol-polyoxyethylene ether, described anion surfactant is a kind of in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, octyl phenol polyethylene ether maleic acid ester sodium or coco group sodium isethionate.
7. modified Nano TiO according to claim 1
2the preparation method of finishing composition, is characterized in that: step (3) insulation reaction temperature is 65 ℃, and the reaction times is 1.5h~2h.
8. modified Nano TiO according to claim 1
2the preparation method of finishing composition, is characterized in that: the drop rate of step (3) methacrylic acid is 2ml/h.
9. modified Nano TiO claimed in claim 1
2the application of finishing composition in cellulosic fibre.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310595984.8A CN103665279A (en) | 2013-11-25 | 2013-11-25 | Preparation method and application of modified nano TiO2 finishing agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310595984.8A CN103665279A (en) | 2013-11-25 | 2013-11-25 | Preparation method and application of modified nano TiO2 finishing agent |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103665279A true CN103665279A (en) | 2014-03-26 |
Family
ID=50304131
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310595984.8A Pending CN103665279A (en) | 2013-11-25 | 2013-11-25 | Preparation method and application of modified nano TiO2 finishing agent |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103665279A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106978722A (en) * | 2017-04-28 | 2017-07-25 | 河南工程学院 | The preparation method of PET non-woven fabrics with photocatalytic degradation function |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1628195A (en) * | 2002-05-01 | 2005-06-15 | 那侬纺织有限公司 | Hydrophilic finish for fibrous substrates |
CN101280517A (en) * | 2007-08-22 | 2008-10-08 | 浙江传化股份有限公司 | Non-ironing crease-proofing agent and preparation thereof |
CN101302265A (en) * | 2008-06-30 | 2008-11-12 | 天津大学 | Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof |
CN101629031A (en) * | 2009-08-17 | 2010-01-20 | 湖北大学 | Photocatalytic functional coating and preparation method thereof |
CN101768853A (en) * | 2009-12-29 | 2010-07-07 | 浙江三元电子科技有限公司 | Method for preparing finishing agent of modified nano titanium dioxide coating layer of electromagnetic shielding fabric |
CN103147290A (en) * | 2013-03-07 | 2013-06-12 | 中国科学院上海应用物理研究所 | Functional nano textile and preparation method thereof |
CN103396520A (en) * | 2013-08-05 | 2013-11-20 | 陕西科技大学 | Core-shell structure nanometer titanium dioxide/ fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof |
-
2013
- 2013-11-25 CN CN201310595984.8A patent/CN103665279A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1628195A (en) * | 2002-05-01 | 2005-06-15 | 那侬纺织有限公司 | Hydrophilic finish for fibrous substrates |
CN101280517A (en) * | 2007-08-22 | 2008-10-08 | 浙江传化股份有限公司 | Non-ironing crease-proofing agent and preparation thereof |
CN101302265A (en) * | 2008-06-30 | 2008-11-12 | 天津大学 | Polymethyl methacryate/titanic oxide composite nano-microsphere and preparation thereof |
CN101629031A (en) * | 2009-08-17 | 2010-01-20 | 湖北大学 | Photocatalytic functional coating and preparation method thereof |
CN101768853A (en) * | 2009-12-29 | 2010-07-07 | 浙江三元电子科技有限公司 | Method for preparing finishing agent of modified nano titanium dioxide coating layer of electromagnetic shielding fabric |
CN103147290A (en) * | 2013-03-07 | 2013-06-12 | 中国科学院上海应用物理研究所 | Functional nano textile and preparation method thereof |
CN103396520A (en) * | 2013-08-05 | 2013-11-20 | 陕西科技大学 | Core-shell structure nanometer titanium dioxide/ fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
吴明华等: "纳米TiO2粒子静电吸附引发剂及其原位锚固丙烯酸丁酯聚合", 《高分子学报》, no. 5, 31 May 2009 (2009-05-31), pages 445 - 450 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106978722A (en) * | 2017-04-28 | 2017-07-25 | 河南工程学院 | The preparation method of PET non-woven fabrics with photocatalytic degradation function |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104672403B (en) | A kind of environmentally friendly silicone acrylic emulsion and preparation method thereof | |
CN101250244B (en) | Polymer hollow microsphere and preparation method thereof | |
CN102432733B (en) | A kind of cation type emulsion for basalt fibre treating compound and preparation method thereof | |
CN103554346B (en) | Graphene oxide modified polyacrylate prepares the method for pigment printing binding agent | |
CN102766241A (en) | Core-shell structured nano-silica/polyacrylate emulsion and its preparation method | |
CN102391411A (en) | Low-temperature self-crosslinking polyacrylate pigment printing binding agent and preparation method thereof | |
CN102060954A (en) | Acrylic emulsion as well as preparation method and application thereof | |
CN103232826B (en) | Heat-stabilized acrylate adhesive used for waterproof coiled material blank base cloth, and preparation method thereof | |
CN106367031A (en) | High thermal conductivity composite phase change microcapsule and preparation method thereof | |
CN105294925A (en) | Electrostatic flocking adhesive for high fastness carpet and preparation method thereof | |
CN102786629A (en) | Preparation of core-shell fluoroacrylate-containing copolymer fabric finishing agent and application thereof in cowboy clothing | |
CN104311716A (en) | Organic silicon modified styrene-acrylate microemulsion reinforcing agent as well as preparation method and application thereof | |
CN102634306A (en) | Starch adhesive for nano material modified wood and preparation method of starch adhesive | |
CN101967257A (en) | Pure acrylic emulsion modified by inorganic nanoparticles and preparation method thereof | |
CN103360872A (en) | Transfer printing paper coating agent and production method thereof | |
CN102995488A (en) | Method for preparing cationic rosin/C9 petroleum resin sizing agent | |
CN104744642A (en) | Method for preparing nano-titanium dioxide modified color fixing agent emulsion | |
CN107700216A (en) | A kind of preparation method of nano modification fluorine-containing textile finishing agent | |
CN103387645A (en) | Fluorine-containing copolymer grafted modified nano TiO2 compound particle and preparation method thereof | |
CN106988134A (en) | A kind of printing adhesive and preparation method thereof, print paste and clothes | |
CN107488246A (en) | A kind of micro- tertiary acrylate and vinyl acetate emulsion of crosslinking and preparation method and application | |
CN101263166B (en) | Method of preparing vinylchloride-based copolymer and vinylchloride plastisol composition including vinylchloride-based copolymer prepared using the method | |
CN106592226A (en) | Environment-friendly type textile sizing agent having strong stability and preparation method | |
CN103665279A (en) | Preparation method and application of modified nano TiO2 finishing agent | |
CN103965816A (en) | Low-VOC (Volatile Organic Compound) high-performance emulsion adhesive for non-woven fabric material and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C41 | Transfer of patent application or patent right or utility model | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20160304 Address after: 226300 Jiangsu city of Nantong province Tongzhou District Industrial Park building sun Zhihao Applicant after: JIANGSU GOLDSUN TEXTILE TECHNOLOGY CO., LTD. Address before: 226300 Jiangsu city of Nantong province Tongzhou District Industrial Park building sun Zhihao Applicant before: Jiangsu gold Cloth capable of reflecting sun infrared and ultraviolet rays industry Co., Ltd |
|
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140326 |