CN1958937A - Emulsion water of finishing agent for textile containing fluorin - Google Patents
Emulsion water of finishing agent for textile containing fluorin Download PDFInfo
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- CN1958937A CN1958937A CN 200510061370 CN200510061370A CN1958937A CN 1958937 A CN1958937 A CN 1958937A CN 200510061370 CN200510061370 CN 200510061370 CN 200510061370 A CN200510061370 A CN 200510061370A CN 1958937 A CN1958937 A CN 1958937A
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Abstract
The present invention relates to a fabric finishing agent water emulsion, in particular, it relates to a fabric finishing agent water emulsion containing acrylic perfluoroalkyl ester. Its composition includes (by wt%) 10-40% of comonomer mixture formed from at least (methyl) acrylic perfluoroalkyl ester and (methyl) acrylic straight chain alkyl ester, 10-20% of solvent, 30-70% of deionic water, 1.0-5.0% of emulsifier and small quantity of molecular weight regulating agent.
Description
Technical field
The present invention relates to a kind of emulsion water of finishing agent for textile, relate in particular to a kind of emulsion water of finishing agent for textile that contains perfluoroalkyl acrylate.
Background technology
Utilize the low characteristic of surface energy of perfluoroalkyl acrylate copolymer, can give the surperficial water and oil repellent finish effect of material excellences such as each kind fabric, paper by surface treatment perfluoroalkyl acrylate copolymer, and keep the original good permeability of material.From in form, the water-repellent oil-repellent agent of perfluoroalkyl copolymer is based on the aqueous dispersion emulsion-type.
As everyone knows, the direct film forming of perfluoroalkyl acrylate monomer-polymer, has low-down surface energy, good refusing water and refuse oily effect arranged, and after in polymer, introducing hydrocarbon monomer by a certain percentage, the amplitude that this water and oil repellant effect descends or decays after the copolymer film forming is quite low and slow, perfluoroalkyl acrylate that Here it is the basis that water and oil repellant is used on various materials.The compositing formula of perfluoroalkyl acrylate copolymer is very many, and a lot of foreign patents such as US5344903, US4296224, US4013627, KR9711245, KR9700319 etc. all have and relate to.
But the stability of general perfluoroalkyl acrylate monomer-polymer aqueous emulsion is bad, and film forming is relatively poor, and the crystal property of film is also bad.Simultaneously, all there are defective in the pliability of the washability of aqueous emulsion, film, static electricity resistance.
In addition, when preparation fluorine-containing textile finishing agent copolymer aqueous emulsion, generally be in the aqueous dispersion pre-emulsion, directly to adopt the form of emulsion polymerisation to obtain comonomers such as perfluoroalkyl acrylate, because fluorine-containing alkyl acrylate ester monomer is difficult to dissolving in water, influence carrying out smoothly of emulsification, therefore must add dissolving and the dispersion (US 08048350, EP0898011) that a certain amount of organic cosolvent acetone, isopropyl alcohol etc. help the fluorine ester at aqueous phase, promote that simultaneously the dispersion of different copolymer monomer is fused, the stable emulsion of final formation under auxiliary emulsifier effect.But the use of organic solvent also can cause the increase of final aqueous emulsion VOC value (volatile organic matter) and the decline of aqueous emulsion burning-point, also can cause the adverse effect to environment and technology person's personal safety in the postfinishing process process to a certain extent.
Moreover, because the proportion of perfluoroalkyl acrylate monomer big (having reached about 1.5), only rely on common mechanical stirring device to show as to be difficult to emulsification or emulsification is not thorough with respect to water density.
Summary of the invention
In order to solve above-mentioned technical problem, a purpose of this aspect provides that a kind of to have the emulsion storage stability good, and the filming performance that aqueous emulsion is filmed is good, the fluorine-containing textile finishing agent emulsion of water and oil repellant excellent performance.Another object of the present invention is to solve the technical problem that emulsion is difficult to emulsification, and the preparation method of emulsion of the present invention is provided.
In order to reach first purpose of the present invention, the present invention has adopted following technical scheme:
A kind of fluorine-containing textile finishing agent aqueous emulsion, percentage in the aqueous emulsion gross weight, this aqueous emulsion comprises 10～40% copolymerized monomer mixtures of being made up of (methyl) perfluoroalkyl acrylate and (methyl) acrylic acid straight chained alkyl ester at least, 10～20% solvent and 30～70% deionized water, and the emulsifying agent and a spot of molecular weight regulator that account for copolymerized monomer mixture quality 1.0～5.0%.
As preferably, above-mentioned (methyl) perfluoroalkyl acrylate accounts for 30～70% at copolymerized monomer mixture, preferably accounts for 40～60%; (methyl) perfluoroalkyl acrylate molecular formula is CF
3CF
2(CF
2CF
2) nCH
2CH
2-OCOCH=CH
2Or CF
3CF
2(CF
2CF
2) nCH
2CH
2OCOC (CH
3)=CH
2, (methyl) perfluoroalkyl acrylate is that the different fluorine ester of 2～6 integers constitutes by the n number, wherein n is that 2～5 (methyl) perfluoroalkyl acrylate of forming account for gross weight 90～100%.
As preferably, above-mentioned (methyl) acrylic acid straight chained alkyl ester is selected from a kind of in butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid certain herbaceous plants with big flowers ester, (methyl) dodecyl acrylate, (methyl) Process Conditions of Cetane Acrylate, (methyl) octadecyl acrylate or several, and its consumption is 10～40% of a copolymerized monomer mixture quality.
As preferably, above-mentioned copolymerized monomer mixture contains 2-hydroxy-cyclohexyl acrylate, can add or not add chain-transferring agent less in the emulsion.As preferred, copolymerized monomer mixture also comprises simultaneously: promote the acrylate monomer of emulsion washability, its consumption is 0～5% of a copolymerized monomer mixture quality; Can improve other functional monomer of emulsion film forming character, its consumption be the copolymerized monomer mixture quality the copolymerized monomer mixture quality 0～20%.
As preferably, the acrylate monomer of promoting the emulsion washability can be selected from N hydroxymethyl acrylamide, (methyl) acrylic acid-N-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, acrylic acid diacetone ester, acrylic acid hydroxyl diacetone ester and 3-chlorine, the mixture of one or more in the 2-hydroxy acrylic acid propyl ester.
As preferably, can improve optional one or more the mixture in vinylidene chloride, acrylic acid cyclohexyl ester, acrylic acid-2-hydroxyl cyclohexyl ester, epihydric alcohol acrylic ester and acrylic acid polyoxyethylene ester of the functional monomer of emulsion film forming character.
As preferably, emulsifying agent is by the quaternary cationics that contains chain alkyl and have compound composition of non-ionic surface active agent of polyoxyethylene segment, and wherein cationic surfactant accounts for 20～60% of emulsifying agent total amount; Compound cationic surfactant and non-ionic surface active agent HLB value between 8～18, preferred 8～12.
As preferably, cationic surfactant is selected from cetyl trimethyl chlorine (bromine) and changes a kind of or its mixture that amine and octadecyl trimethyl chlorine (bromine) are changed amine.
As preferably, non-ionic surface active agent is selected from one or more of alkyl polyoxyethylene base ether, alkylphenol polyoxyethylene, and alkyl is 4～18 chain alkyl polyoxy ethyl alkene, and the alkyl of alkylphenol-polyethenoxy base ether is 4～20, and preferred 6～12.
As preferably, solvent is selected from a kind of or several mixture in acetone, isopropyl alcohol, propylene glycol, dipropylene glycol and the butanone.As preferred again, solvent is a double solvents, and wherein main solvent is acetone, dipropylene glycol or isopropyl alcohol, and main solvent accounts for 60～95% in the solvent gross mass.As most preferably, solvent is selected from a kind of in acetone/isopropanol, acetone/isopropanol/oxolane, acetone/isopropanol/dipropylene glycol, dipropylene glycol/butanone and isopropyl alcohol/acetone double solvents.
In order to reach second purpose of the present invention, the present invention has adopted following technical scheme:
A kind of preparation method of fluorine-containing textile finishing agent aqueous emulsion, this method comprises the steps:
A, with copolymerized monomer mixture, emulsifying agent, solvent and deionized water mix and stir 10～30min and obtain pre-emulsion;
B, resulting pre-emulsion is handled 1～10min in ultrasonic wave, high pressure homogenisers or emulsifier, obtain stable monomer emulsions;
C, above-mentioned monomer emulsions is placed reactor; add respectively and account for the chain-transferring agent of copolymerized monomer mixture quality 0～1%, the initator that accounts for copolymerized monomer mixture quality 0.05～1% and pH regulator agent under nitrogen protection; be warming up to 50～80 ℃ of initiation reaction polymerizations; 1～4 hour reaction time; be incubated 1～6 hour then; when the monomer total conversion is cooled to room temperature in 96% above time cooling, filter and obtain described fluorine-containing textile finishing agent aqueous emulsion.
As preferably, used chain-transferring agent is a lauryl mercaptan.Used initator is water soluble starter, is selected from potassium peroxydisulfate or sodium peroxydisulfate, ammonium persulfate or azo-bis-isobutyrate hydrochloride.
Among the present invention, the certain proportion perfluoroalkyl acrylate can guarantee to have low surface energy behind the emulsion film forming, and the introducing of a certain proportion of chain alkyl acrylate then can improve the film forming of emulsion copolymers, promotes the crystal property of film simultaneously.In copolymer mixture, add an amount of functional monomer and then be the character that to improve behind the emulsion film forming, and this improvement focuses mostly on self-emulsifying is being provided, increase the aspects such as pliability, static electricity resistance of washability, film.Prepared fluorine-containing textile finishing agent aqueous emulsion has good water and oil repellant performance, good Size Distribution and stability of emulsion for the white emulsion or the translucent emulsion of band blue-fluorescence.Fabric still can keep good hand feeling, original gas permeability and good whiteness after this emulsion arrangement.
The water and oil repellant fluorine-containing textile finishing agent aqueous emulsion of the present invention preparation has adopted the method for composite auxiliary solvent, and by ultrasonic wave or high pressure homogenisers or the pre-emulsification treatment of emulsifier.Adopt the aqueous emulsion of this method preparation to have excellent storage stability, emulsion particle is evenly distributed, and dilution stability is good, has outstanding water and oil repellant effect, can be used for the water and oil repellent finish of various material such as fabric, leather, paper.
Water and oil repellant fluorine-containing textile finishing agent aqueous emulsion of the present invention, the finishing condition that is used for textile finishing is: polymer emulsion is diluted, make the diluting emulsion solid content 1～8%, can select different dilution ratios for use according to the difference that is organized material, recommending the ratio that is suitable for as terylene, nylon fabrics is 1～3%, it is 1～3% that the terylene fabric is recommended the ratio that is suitable for, and it is 2～8% that COTTON FABRIC is recommended the ratio that is suitable for, and the fluorine that adheres on the fabric accounts for 0.5～4% of fabric gross weight by mass ratio.Can allocate a small amount of melmac or pollopas as required in dilution, alkyl polyoxyethylene pyridyl ethers compound (NP-40, NP-50) is to increasing the washability and the surperficial facilitation of fabric.Fabric adopts and to dip technology, and the two-part temperature bakes finishing technique, dips the back 100～130 ℃ of dried 1～3 minute, bakes 1～3 minute at 150～180 ℃, and the water and oil repellant effect is had good facilitation.
The specific embodiment
Embodiment 1
With perfluoroalkyl acrylate (the perfluor carbon number is 6,8,10 or 12) 10g, octadecyl methacrylate 5g, N hydroxyacrylamide 0.8g, butyl methacrylate 4g, butanone 3g, dipropylene glycol 7g, OP-101.03g, 16 trimethyl amine bromide 1.33g, potassium peroxydisulfate 0.6g, lauryl mercaptan 0.1g, deionized water 65g, place the 100ml there-necked flask that has paddle, thermometer, return duct, logical nitrogen device, at 40 ℃ of following emulsification 30min, be warming up to 65 ℃ under stirring, initiated polymerization 5 hours obtains the white emulsion of blueing look fluorescence.Be diluted to 2g/100ml concentration, handled in 2 minutes through 120 ℃ of oven dry 2 minutes and 160 ℃ of training bakings, refuse 60 grades in water through the white cotton of test and refuse 6 grades of oil, white plain weave silk ribbon cotton is refused 90 grades in water and is refused 7 grades of oil (the WATER REPELLENCY test is tested with reference to AATCC118-1998 with reference to standard GB 4745-1984, oil repellent)
Embodiment 2
With perfluoroalkyl acrylate 10g, octadecyl methacrylate 6g, N hydroxy ethyl methacrylate 0.5g, butyl acrylate 1g, acetone 8g, isopropyl alcohol 2g, TX-11 and TX-13 are respectively 0.7 and 0.3g, hexadecyl trimethyl ammonium bromide 0.6g, deionized water 55g, lauryl mercaptan 0.1g, glacial acetic acid 0.05g in container in 40 ℃ through the pre-emulsification of ultrasonic wave 3 minutes, after emulsion placed have paddle, thermometer, return duct, in the 100ml there-necked flask of logical nitrogen device, at 40 ℃ of following emulsification 10min, stir the aqueous solution that adds azo diisobutyl amidino groups hydrochloride 0.25g down, be warming up to 60 ℃, initiated polymerization obtains the white emulsion of blueing look fluorescence in 65 ℃ of insulation reaction 4 hours.Emulsion was handled through 120 ℃ of oven dry, 160 ℃ of training bakings in 2 minutes through being diluted to 2g/100ml in 1.5 minutes, refused 100 grades in water with white plain weave polyester-mixed cotton cloth test and refused 5 grades of oil; Be diluted to 5g/100ml and handled in 1.5 minutes,, refuse water 90+ level and refuse 5 grades of oil with white cotton test through 120 ℃ of oven dry, 170 ℃ of training bakings in 2 minutes.
Embodiment 3
With perfluoroalkyl acrylate 10g, octadecyl acrylate 5g, N hydroxy ethyl methacrylate 0.5g, 2 hydroxy-cyclohexyl acrylate 0.5g, butyl acrylate 1g, acetone 9g, isopropyl alcohol 2g, NP-8 and NP-10 are respectively 0.6 and 0.4g, hexadecyl trimethyl ammonium bromide 0.5g, deionized water 55g, glacial acetic acid 0.05 in container in 40 ℃ through the pre-emulsification of ultrasonic wave 5 minutes, after emulsion placed have paddle, thermometer, the condensing reflux pipe, in the 100ml there-necked flask of logical nitrogen device, at 40 ℃ of following emulsification 10min, stir the aqueous solution that adds azo diisobutyl amidino groups hydrochloride 0.25g down, the vinylidene chloride 1g that adds metering, be warming up to 50 ℃ of reactions 2 hours, in 65 ℃ of insulation reaction 4 hours, obtain the white emulsion of blueing look fluorescence again.Emulsion was handled through 120 ℃ of oven dry, 160 ℃ of training bakings in 2 minutes through being diluted to 2g/100ml in 1.5 minutes, refused 100 grades in water with white plain weave polyester-mixed cotton cloth test and refused 5 grades of oil; Be diluted to 5g/100ml and handled in 1.5 minutes,, refuse 100 grades in water and refuse 5 grades of oil with white cotton test through 120 ℃ of oven dry, 170 ℃ of training bakings in 2 minutes.
Embodiment 4
With perfluoroalkyl acrylate 20g, octadecyl methacrylate 10g, N hydroxy ethyl methacrylate 0.6g, hydroxy ethyl methacrylate 0.3g, acrylic acid cyclohexyl ester 2g, acetone 16g, isopropyl alcohol 4g, oxolane 2g, TX-8 and TX-13 are respectively 1.6 and 0.4g, hexadecyl trimethyl ammonium bromide 1.0g, deionized water 100g, lauryl mercaptan 0.2g, glacial acetic acid 0.2g in container in 40 ℃ of stirring and dissolving, while hot through high pressure homogenisers emulsification 1 minute, after emulsion placed have paddle, thermometer, return duct, in the 250ml there-necked flask of logical nitrogen device, the aqueous solution that under 40 ℃ of stirrings, adds azo diisobutyl amidino groups hydrochloride 0.4g, heat up 65 ℃, initiated polymerization insulation reaction 5 hours obtains the white emulsion of blueing look fluorescence.Emulsion was handled through 120 ℃ of oven dry, 160 ℃ of training bakings in 2 minutes through being diluted to 2g/100ml in 1.5 minutes, refused 100 grades in water with white plain weave polyester-mixed cotton cloth test and refused 3 grades of oil; Be diluted to 5g/100ml and handled in 1.5 minutes,, refuse 100 grades in water and refuse 5 grades of oil with white cotton test through 120 ℃ of oven dry, 170 ℃ of training bakings in 2 minutes.
Embodiment 5
Perfluoroalkyl acrylate 10g, octadecyl methacrylate 5g, N hydroxyacrylamide 0.8g, butyl methacrylate 4g, butanone 8g, polyoxyethylene nonylphenol ether (EO=40) 1.0g, 16 trimethyl amine bromide 1.0g, deionized water 65g are mixed; in 40 ℃ of mechanical agitation emulsifications; nitrogen protection adds potassium peroxydisulfate 0.6g down; be warming up to 65 ℃ of reactions 5 hours; the a small amount of cold glue in emulsion bottom, emulsion is filtered steady in a long-term.
Claims (13)
1. fluorine-containing textile finishing agent aqueous emulsion, it is characterized in that percentage in the aqueous emulsion gross weight, this aqueous emulsion comprises 10～40% copolymerized monomer mixtures of being made up of (methyl) perfluoroalkyl acrylate and (methyl) acrylic acid straight chained alkyl ester at least, 10～20% solvent and 30～70% deionized water, and the emulsifying agent and a spot of molecular weight regulator that account for copolymerized monomer mixture quality 1.0～5.0%.
2. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 1 is characterized in that (methyl) perfluoroalkyl acrylate accounts for 30～70% at copolymerized monomer mixture, preferably accounts for 40～60%; (methyl) perfluoroalkyl acrylate molecular formula is CF
3CF
2(CF
2CF
2)
nCH
2CH
2OCOCH=CH
2Or CF
3CF
2(CF
2CF
2)
nCH
2CH
2OCOC (CH
3)=CH
2, (methyl) perfluoroalkyl acrylate is that the different fluorine ester of 2～6 integers constitutes by the n number, wherein n is that 2～5 (methyl) perfluoroalkyl acrylate of forming account for gross weight 90～100%.
3. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 1 or 2, it is characterized in that (methyl) acrylic acid straight chained alkyl ester is selected from a kind of in butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid certain herbaceous plants with big flowers ester, (methyl) dodecyl acrylate, (methyl) Process Conditions of Cetane Acrylate, (methyl) octadecyl acrylate or several, its consumption is 10～40% of a copolymerized monomer mixture quality.
4. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 1 is characterized in that copolymerized monomer mixture also comprises: promote the acrylate monomer of emulsion washability, its consumption is 0～5% of a copolymerized monomer mixture quality; Can improve other functional monomer of emulsion film forming character, its consumption be the copolymerized monomer mixture quality the copolymerized monomer mixture quality 0～20%.
5. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 4, it is characterized in that the acrylate monomer of promoting the emulsion washability can be selected from N hydroxymethyl acrylamide, (methyl) acrylic acid-N-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, acrylic acid diacetone ester, acrylic acid hydroxyl diacetone ester and 3-chlorine, the mixture of one or more in the 2-hydroxy acrylic acid propyl ester.
6. as claim 4 or 5 described a kind of fluorine-containing textile finishing agent aqueous emulsions, it is characterized in that to improve optional one or more the mixture in vinylidene chloride, cyclohexyl acrylate, acrylic acid-2-hydroxyl cyclohexyl, epihydric alcohol acrylic ester and acrylic acid polyoxyethylene ester of the functional monomer of emulsion film forming character.
7. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 1, it is characterized in that emulsifying agent by quaternary cationics that contains chain alkyl and compound composition of non-ionic surface active agent that has the polyoxyethylene segment, wherein cationic surfactant accounts for 20～60% of emulsifying agent total amount; Compound cationic surfactant and non-ionic surface active agent HLB value between 8～18, preferred 8～12.
8. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 7 is characterized in that cationic surfactant is selected from a kind of or its mixture that cetyl trimethyl chlorine (bromine) is changed amine and octadecyl trimethyl chlorine (bromine) change amine.
9. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 7, it is characterized in that non-ionic surface active agent is selected from one or more of alkyl polyoxyethylene base ether, alkylphenol polyoxyethylene, alkyl is 4～18 chain alkyl polyoxy ethyl alkene, the alkyl of alkylphenol-polyethenoxy base ether is 4～20, preferred 6～12.
10. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 1 is characterized in that solvent is selected from a kind of or several mixture in acetone, isopropyl alcohol, propylene glycol, dipropylene glycol and the butanone.
11. a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 10, it is characterized in that solvent is a double solvents, wherein main solvent is acetone, dipropylene glycol or isopropyl alcohol, main solvent accounts for 60～95% in the solvent gross mass, double solvents is a kind of in acetone/isopropanol, acetone/isopropanol/oxolane, acetone/isopropanol/dipropylene glycol, dipropylene glycol/butanone and isopropyl alcohol/acetone double solvents preferably.
12. the preparation method of a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 1 is characterized in that this method comprises the steps:
A, with copolymerized monomer mixture, emulsifying agent, solvent and deionized water mix and stir 10～30min and obtain pre-emulsion;
B, resulting pre-emulsion is handled 1～10min in ultrasonic emulsator or high pressure homogenisers, obtain stable monomer emulsions;
C, above-mentioned monomer emulsions is placed reactor; add respectively and account for the chain-transferring agent of copolymerized monomer mixture quality 0～1%, the initator that accounts for copolymerized monomer mixture quality 0.05～1% and pH regulator agent under nitrogen protection; be warming up to 50～80 ℃ of initiation reaction polymerizations; 1～4 hour reaction time; be incubated 1～6 hour then; when the monomer total conversion is cooled to room temperature in 96% above time cooling, filter and obtain described fluorine-containing textile finishing agent aqueous emulsion.
13. the preparation method of a kind of fluorine-containing textile finishing agent aqueous emulsion as claimed in claim 12, it is characterized in that used chain-transferring agent is a lauryl mercaptan, initator is a water soluble starter, is selected from potassium peroxydisulfate or sodium peroxydisulfate, ammonium persulfate or azo-bis-isobutyrate hydrochloride.
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| CN102060956A (en) * | 2010-11-16 | 2011-05-18 | 巨化集团公司 | Method for preparing water-oil repellent fluorine-containing textile finishing agent |
| CN102352000A (en) * | 2011-07-14 | 2012-02-15 | 浙江大学 | Method for synthesis of organic-inorganic composite hydrophobic/oleophobic surface treatment agent |
| CN102587141A (en) * | 2012-01-18 | 2012-07-18 | 常州化工研究所有限公司 | Fluoride-contained textile finishing agent and preparation method thereof |
| CN102597101A (en) * | 2009-11-09 | 2012-07-18 | 纳幕尔杜邦公司 | Fluoropolymer emulsions |
| CN102653580A (en) * | 2011-03-01 | 2012-09-05 | 河北工业大学 | Preparation method of Janus-structure composite emulsion particle |
| CN101889035B (en) * | 2007-12-07 | 2013-03-13 | 纳幕尔杜邦公司 | Fluoropolymer emulsions |
| CN103524670A (en) * | 2013-09-27 | 2014-01-22 | 昆山培新服装有限公司 | Preparation and dyeing process of water-and-oil-repellent finishing agent for cotton fabrics |
| CN103757915A (en) * | 2013-11-01 | 2014-04-30 | 巨化集团技术中心 | Novel environment-friendly oil and water repellent agent for leather |
| CN105085793A (en) * | 2014-05-20 | 2015-11-25 | 东莞市长安东阳光铝业研发有限公司 | Fluorinated textile finishing agent composition and preparation method therefor |
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| CN101889035B (en) * | 2007-12-07 | 2013-03-13 | 纳幕尔杜邦公司 | Fluoropolymer emulsions |
| CN102597101A (en) * | 2009-11-09 | 2012-07-18 | 纳幕尔杜邦公司 | Fluoropolymer emulsions |
| CN102597101B (en) * | 2009-11-09 | 2014-09-17 | 纳幕尔杜邦公司 | Fluoropolymer emulsions |
| CN102060956B (en) * | 2010-11-16 | 2012-10-17 | 巨化集团公司 | Method for preparing water-oil repellent fluorine-containing textile finishing agent |
| CN102060956A (en) * | 2010-11-16 | 2011-05-18 | 巨化集团公司 | Method for preparing water-oil repellent fluorine-containing textile finishing agent |
| CN102653580B (en) * | 2011-03-01 | 2016-02-17 | 河北工业大学 | A kind of preparation method of Janus-structure composite emulsion particle |
| CN102653580A (en) * | 2011-03-01 | 2012-09-05 | 河北工业大学 | Preparation method of Janus-structure composite emulsion particle |
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| CN102587141A (en) * | 2012-01-18 | 2012-07-18 | 常州化工研究所有限公司 | Fluoride-contained textile finishing agent and preparation method thereof |
| CN103524670A (en) * | 2013-09-27 | 2014-01-22 | 昆山培新服装有限公司 | Preparation and dyeing process of water-and-oil-repellent finishing agent for cotton fabrics |
| CN103757915A (en) * | 2013-11-01 | 2014-04-30 | 巨化集团技术中心 | Novel environment-friendly oil and water repellent agent for leather |
| CN105085793A (en) * | 2014-05-20 | 2015-11-25 | 东莞市长安东阳光铝业研发有限公司 | Fluorinated textile finishing agent composition and preparation method therefor |
| CN105085793B (en) * | 2014-05-20 | 2019-06-25 | 东莞东阳光科研发有限公司 | A kind of fluorine-containing textile finishing agent composition and preparation method thereof |
| CN106008794A (en) * | 2016-06-23 | 2016-10-12 | 无锡市金五星针纺有限公司 | Fluorine-containing textile finishing agent and preparation method thereof |
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| CN106995512A (en) * | 2017-04-18 | 2017-08-01 | 南通纺织丝绸产业技术研究院 | A kind of close and distant convertible fabric finishing liquor of property in intelligent surface and preparation method thereof |
| CN108570854A (en) * | 2018-05-07 | 2018-09-25 | 佛山慧创正元新材料科技有限公司 | A kind of resistance to waterproofing agent used for textiles and preparation method thereof washed by force |
| CN108611858A (en) * | 2018-05-07 | 2018-10-02 | 佛山慧创正元新材料科技有限公司 | A kind of resistance to waterproof coating gluing finishing agent used for textiles and preparation method thereof washed by force |
| CN111270522A (en) * | 2020-04-14 | 2020-06-12 | 北京邦维高科特种纺织品有限责任公司 | Vinyl chloride acrylonitrile copolymer fabric and its production process |
| CN111286982A (en) * | 2020-04-14 | 2020-06-16 | 北京邦维高科特种纺织品有限责任公司 | Water-repellent and oil-repellent finishing agent, preparation method and application thereof, and water-repellent and oil-repellent treatment method |
| CN114410188A (en) * | 2022-02-18 | 2022-04-29 | 兰州城市学院 | Organic-inorganic nano composite coating |
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