CN103194904B - Water-repellent and oil-repellent fabric finishing agent, as well as preparation method and applications thereof - Google Patents
Water-repellent and oil-repellent fabric finishing agent, as well as preparation method and applications thereof Download PDFInfo
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- CN103194904B CN103194904B CN201310153485.3A CN201310153485A CN103194904B CN 103194904 B CN103194904 B CN 103194904B CN 201310153485 A CN201310153485 A CN 201310153485A CN 103194904 B CN103194904 B CN 103194904B
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Abstract
The invention discloses a water-repellent and oil-repellent fabric finishing agent, as well as a preparation method and applications thereof. The preparation method comprises the steps of: preparing a mixed monomer from tridecafluorooctyl acrylate, butyl acrylate, metyl methacrylate or methyl acrylate as well as hydroxyalkyl acrylate, and bis(acryloxypropyl) tetramethyl disiloxane, and initiating radical copolymerization with waterborne initiator under the action of a compound emsulsifying agent to obtain a fluorine-containing copolymer emulsion type water-repellent and oil-repellent finishing agent with excellent stability. According to the water-repellent and oil-repellent fabric finishing agent, a slightly crosslinked net structure is introduced in a fluorine-containing prepolymer, a compact polymer film and dense fluoroalkyl covering are formed on the surfaces of fibers in an adhering manner when the fabric is in finishing, so that a relatively good fluoroalkyl shielding effect can be favorably provided for the fibers, thereby achieving the excellent water-repellent and oil-repellent finishing effect, and having no influence on the fabric finishing handfeeling. The fabric finishing agent is simple and convenient in preparation technique, mild in reaction conditions, and suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of hindlimb unload of textiles, particularly a kind of fabric finishing agent, preparation method and application thereof.
Background technology
Find in fabric post-treatment process, carry out arranging the two thin performance-hydro-oleophobicity can giving fabric excellence to fabric with containing fluoroalkyle compound, develop a series of water-refusing oil-refusing finishing agent thus, organic fluorine material research field has greatly been enriched in these researchs, and become one of them important branch, obtain the very big concern of domestic and international researcher.Through 60 years of researches development, fluorine-containing textile finishing agent commercialization occupy very large market.
Fluorinated acrylate polymer finishing agent is a kind of most widely used fluorine-containing textile finishing agent, and its active ingredient is mainly containing C
8~ C
10perfluoroalkyl acrylate or methacrylate polymers.Wherein, carbon chain lengths is that the perfluoro capryl derivative of eight carbon has very excellent low-surface-energy and water and oil repellant effect.Therefore, in nearest decades, perfluoro capryl polymer-type fabric finishing agent is able to extensive use.But, because long carbon chain perfluor compound is difficult to degraded, there is animal migration and cumulative toxicity, European Union has completely forbidden and has produced and use perfluorinated octyl sulfuryl amine derivative (PFOS), forbidding scope not only comprises perfluorinated octyl sulfuryl amine, also comprises containing a series of compounds of perfluoro capryl, auxiliary agent and material.The U.S. and Japan are also about to stop producing the auxiliary agent containing PFO base sulfonyl compound and goods.Produce and big export country as fabric, PFOS has sizable market in China, in the face of the trend of whole world forbidding PFOS, develops the focus of attention that short fluorocarbon chain substitute has become current fluorine-containing textile finishing agent.
Prior art why widely use carbon chain lengths be the perfluoro capryl derivative of eight carbon as water-refusing oil-refusing finishing agent, be because polymer is not enough to provide excellent low-surface-energy when the carbon chain lengths of side chain fluoroalkyl is less than six carbon.Study carefully its essential reason, be because fluoroalkyl carbochain in short-term polymer lateral chain very effective fluoroalkyl shielding action can not be provided.
The present invention is to contain 3,3,4 of six fluorine carbon atoms, 4,5,5,6,6,7,7,8,8,8-ten trifluoro octyl acrylate and other not fluorinated acrylate copolymerization, making prepolymer form lightly crosslinked structure by adding two (acryloxypropyl) tetramethyl disiloxane, obtaining a kind of fluorinated copolymer type water-refusing oil-refusing finishing agent, being applied to the water and oil repellant effect that textile finishing can provide very excellent.Compared with conventional fluorinated copolymer emulsion fabric finishing agent, in fluorinated copolymer emulsion-type finishing agent provided by the invention, two (acryloxypropyl) tetramethyl disiloxane makes prepolymer lightly crosslinked when emulsion polymerisation, therefore, by emulsion applications in textile finishing time, finishing agent can form fine and close fluoropolymer structure at fiber surface, in this one polymer layer containing fluoroalkyl due to cross-linked structure dense accumulation, thus the shielding action of fluoroalkyl low-surface-energy can be effectively provided, show excellent water and oil repellent finish effect; Meanwhile, the wearability such as soft, the feel that do not affect finish fabric of the silicon oxygen bond cross-bridge of introducing.
Compared with prior art, its beneficial effect of technical scheme provided by the invention is:
1, between fluorinated copolymer performed polymer, lightly crosslinked network is formed by silicon oxygen bond, for the fluoroalkyl of more intensive covering can be provided after fiber and other material surface treatment, the fine and close lightly crosslinked structure of main chain is also more conducive to fluoroalkyl perpendicular to ground outwardly, this is conducive to the fluoroalkyl shielding action that polymer provides excellent, thus provides better water and oil repellant effect;
2, the fluoroalkyl adopted is short fluorine alkyl group, does not belong to perfluorinated octyl sulfuryl amine derivative (PFOS) and forbids scope;
3, the lightly crosslinked key introduced is soft silicon oxygen bond, does not affect the wearability such as the feel of finish fabric;
4, emulsion polymerisation is adopted to realize the combined polymerization of ten trifluoro octyl acrylate, butyl acrylate, (methyl) methyl acrylate and hydroxyalkyl acrylates, the fluorinated copolymer emulsion fabric finishing agent that directly obtained silicon oxygen bond is crosslinked, reaction process is easy, reaction condition is gentle, is applicable to suitability for industrialized production.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, there is provided a kind of materials safety, simple process, be suitable for suitability for industrialized production, the original wearability of fabric and feel can be kept, effectively can improve again the finishing agent of the water and oil repellant effect of fabric, preparation method and application thereof.
To achieve the above object of the invention, the technical solution adopted in the present invention is to provide a kind of fabric water-refusing oil-refusing finishing agent, and it is the polymer emulsion that a kind of silicon oxygen bond is cross-linked, and has following structure:
Wherein, Rf is-(CH
2)
2(CF
2)
6f; R is-CH
2-Huo – CH
2cH
2-; R ' is H Huo – CH
3; M=5 ~ 12; N=2 ~ 4; O=20 ~ 35; P=2 ~ 5; Q=10 ~ 25.
A preparation method for fabric water-refusing oil-refusing finishing agent as above, comprises the steps:
1, by weight, 1 ~ 3 part of nonionic surface active agent and 1 ~ 3 portion of anion surfactant are joined in 270 parts of water, in 8000 ~ 11000 revs/min of emulsified process of speed conditions 1 ~ 15 minute in high-speed shearing emulsion machine; Add 30 part of ten trifluoro octyl acrylate monomer, 40 ~ 50 parts of Butyl Acrylate Monomers, 20 ~ 25 parts of methyl methacrylates or methyl acrylate methyl monomers, 2 ~ 4 parts of hydroxyalkyl acrylates monomers and 0.5 ~ 2 part of two (acryloxypropyl) tetramethyl disiloxane again, mixed liquor stir process 15 ~ 30 minutes under the rotating speed of 8000 ~ 11000 revs/min, obtains mix monomer pre-emulsion;
2, the mix monomer pre-emulsion obtained is being stirred and N
2protection, temperature is under the condition of 50 ~ 90 DEG C, and adding 8 ~ 10 parts of mass concentrations is the initiator solution of 5 ~ 20%, reacts 2 ~ 12 hours, obtains the polymer emulsion that a kind of silicon oxygen bond is crosslinked, i.e. fabric water-refusing oil-refusing finishing agent after cooling.
Nonionic surface active agent of the present invention is the one in AEO-9, this dish-60, Tween-80.Described anion surfactant is SDS.Described hydroxyalkyl acrylates is any one in hydroxymethyl acrylate and hydroxy ethyl methacrylate.Described aqueous initiator is any one in ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate.
A preferred version of the present invention is: in step 1, the addition of two (acryloxypropyl) tetramethyl disiloxane is 1 ~ 1.5 part.Reaction temperature in step 2 is 70 ~ 80 DEG C.
Technical solution of the present invention also comprises a kind of application of fabric water-refusing oil-refusing finishing agent as above, its method is: it is 5 ~ 20% that the fabric water-refusing oil-refusing finishing agent prepared is diluted to polymer residual, obtain textile finishing working solution, padding machine carries out water and oil repellent finish to fabric, process conditions are: pick-up 90 ~ 110%, preliminary drying temperature 90 ~ 110 DEG C, preliminary drying time 1 ~ 3 min, baking temperature 160 DEG C ~ 180 DEG C, bakes time 2 ~ 5min.
Mechanism of the present invention is: adopt ten trifluoro octyl acrylate, butyl acrylate, methyl methacrylate or methyl acrylate, hydroxyalkyl acrylates and two (acryloxypropyl) tetramethyl disiloxane monomer to carry out emulsion copolymerization, reaction equation is as follows:
Wherein, Rf is-(CH
2)
2(CF
2)
6f; R is-CH
2-Huo – CH
2cH
2-; R ' is H Huo – CH
3; M=5 ~ 12; N=2 ~ 4; O=20 ~ 35; P=2 ~ 5; Q=10 ~ 25.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of ten trifluoro octyl acrylate co-polymer membranes in the fluorinated copolymer emulsion fabric finishing agent that is cross-linked of the silicon oxygen bond prepared by the embodiment of the present invention 1 technical scheme;
Fig. 2 is the latex particle size resolution chart of the fluorinated copolymer emulsion fabric finishing agent emulsion that the silicon oxygen bond prepared by the embodiment of the present invention 1 technical scheme is cross-linked;
Fig. 3 is the latex particle size resolution chart of the fluorinated copolymer emulsion fabric finishing agent emulsion that the silicon oxygen bond prepared by the embodiment of the present invention 2 technical scheme is cross-linked;
Fig. 4 is the latex particle size resolution chart not adding the fluorinated copolymer emulsion of crosslinking agent prepared by the embodiment of the present invention 3 technical scheme.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
1, two (acryloxypropyl) tetramethyl disiloxane synthesis
Be the there-necked flask of 500ml at capacity, add 67.5 grams of allyl methacrylates and 150 grams of toluene, after being heated to 75 DEG C, add 0.1ml commercially available Karst catalyst (3000ppm), logical nitrogen.Drip 30 grams of tetramethyl disiloxanes at a slow speed, 1.5 ~ 2h drips off, and drips off rear insulation reaction 3h.Stop reaction, cooling, at 75 DEG C, vacuum rotary steam is except desolventizing, and distillation time is 80min, obtains colourless transparent liquid product and is two (acryloxypropyl) tetramethyl disiloxane of addition compound product.
Tetramethyl disiloxane and allyl acrylate hydrosilylation prepare two (acryloxypropyl) tetramethyl disiloxane, react as shown in the formula:
2, ten trifluoro octyl acrylate copolymer emulsion finishing agent preparations
By weight, 0.6 gram of emulsifying agent SDS and 0.6 gram emulsifying agent AEO-9 is joined in 80 grams of water, stir under 8000 revs/min of rotating speeds after 1 minute in high-speed shearing emulsion machine, add ten trifluoro octyl acrylate 9.5 grams, butyl acrylate 13.2 grams, methyl methacrylate 6.3 grams, hydroxy ethyl methacrylate 1.0 grams and two (acryloxypropyl) tetramethyl disiloxane 0.3 gram, mixed liquor stirs 15 minutes to obtain mix monomer pre-emulsion under the rotating speed of 11000 revs/min.
Thermometer is being housed, in the reactor of constant pressure funnel and reflux condensing tube, is adding mix monomer pre-emulsion, stir, after being heated to 75 DEG C, adding 8 parts of mass concentrations is the ammonium persulfate aqueous solution of 10%.At 75 ~ 80 DEG C, insulation reaction is after 2 hours, stops reaction, cooling reactant liquor, the fluorinated copolymer emulsion that discharging obtains blueing light, translucent silicon oxygen bond is cross-linked.Emulsion dries film forming at 120 DEG C, the surperficial attenuate total reflection infrared spectrum of test polymer film, and result is see accompanying drawing 1; In Fig. 1,2960cm-1 place is methylene-CH
2-stretching vibration absworption peak, 1730cm
-1strong absorption vibration be-C=O, 1450cm
-1place is methylene-CH
2the stretching vibration absworption peak that-flexural vibrations absorb; 1210cm
-1with 1060cm
-1place belongs to the characteristic absorption peak of Si-O-Si main chain.1160 cm
-1place is-CF
2vibration absorption peak.Meanwhile, original in 1640 cm in acrylate monomer
-1the C=C double bond vibration peak at place disappears, and illustrates that monomer there occurs free radical copolymerization.
The latex particle size of test finishing agent emulsion and domain size distribution, result is see accompanying drawing 2.As seen from Figure 2, the latex particle size difference integrated distribution of the fluorinated copolymer emulsion that 1% crosslinking agent obtains is added at 0.137 μm.In the silicon oxygen bond cross-linking type fluorine-containing copolymer emulsion obtained, prepolymer structure is:
Wherein, Rf is-(CH
2)
2(CF
2)
6f; M=5 ~ 12; N=2 ~ 4; O=20 ~ 35; P=2 ~ 5; Q=10 ~ 25.
3, textile finishing application
It is 5% that the fluorinated copolymer emulsion that the silicon oxygen bond obtained of preparation is crosslinked is diluted to polymer residual, as fabric finishing agent working solution finishing of cotton textiles, two leaching two ginning cloth on padding machine, pick-up is 90%, at 105 DEG C of preliminary drying 1min, 175 DEG C bake 2min.
4, performance test
With reference to GB4745-84 " textile fabric surface moisture-resistant assay method ", trickle instrument carries out trickle test, and after arranging, cotton fabric waterproofing scoring is 100, and fabric face is without the adhesion globule, and oil repellent can reach 2 grades.Test the style of finish fabric, its result is see table 1.
The pure bending rigidity of the different finishing agent finishing of cotton textiles of table 1
Embodiment 2
1, ten trifluoro octyl acrylate copolymer emulsion finishing agent preparations
By weight, 0.6 gram of emulsifying agent SDS and 0.6 gram emulsifying agent AEO-9 is joined in 80 grams of water, stir under 8000 revs/min of rotating speeds after 1 minute in high-speed shearing emulsion machine, add ten trifluoro octyl acrylate 9.2 grams, butyl acrylate 13.0 grams, methyl methacrylate 6.1 grams, hydroxy ethyl methacrylate 1.0 grams and two (acryloxypropyl) tetramethyl disiloxane 0.45 gram, mixed liquor stirs 15 minutes to obtain mix monomer pre-emulsion under the rotating speed of 11000 revs/min.
Thermometer is being housed, in the reactor of constant pressure funnel and reflux condensing tube, is adding mix monomer pre-emulsion, stir, after being heated to 75 DEG C, adding 10 parts of mass concentrations is the sodium persulfate aqueous solution of 20%.。At 75 ~ 80 DEG C, insulation reaction is after 4 hours, stops reaction, cooling reactant liquor, and discharging obtains blueing light and the crosslinked fluorinated copolymer emulsion of translucent silicon oxygen bond, and record latex particle size and the domain size distribution of emulsion, result is see accompanying drawing 3.As seen from Figure 3, the latex particle size difference integrated distribution of the fluorinated copolymer emulsion that 1.5% crosslinking agent obtains is added at 0.153 μm.Data show, along with crosslinking agent addition increases, ten trifluoro octyl acrylate copolymer emulsions particle diameter increase, simultaneously domain size distribution broadens.
2, textile finishing application
It is 5% that the fluorinated copolymer emulsion that the silicon oxygen bond obtained of preparation is crosslinked is diluted to polymer residual, as textile finishing working solution, utilize this working solution two leaching two ginning cloth on padding machine, pick-up is 90%, at 105 DEG C of preliminary drying 1min, 175 DEG C bake 2min.
3, performance test
With reference to GB4745-84 " textile fabric surface moisture-resistant assay method ", trickle instrument carries out trickle test, and after arranging, cotton fabric waterproofing scoring is 100, and fabric face is without the adhesion globule, and oil repellent can reach 2 grades.The finish fabric style result data that test obtains is see table 1.
Embodiment 3:
1, ten trifluoro octyl acrylate copolymer emulsion finishing agent preparations
By weight, 0.6 gram of emulsifying agent SDS and 0.6 gram emolsifier span-60 is joined in 80 grams of water, stir under 9000 revs/min of rotating speeds after 1 minute in high-speed shearing emulsion machine, add ten trifluoro octyl acrylate 9.5 grams, butyl acrylate 13.2 grams, methyl methacrylate 6.3 grams and hydroxy ethyl methacrylate 1.0 grams, mixed liquor stirs 25 minutes to obtain mix monomer pre-emulsion under the rotating speed of 10000 revs/min.
Thermometer is being housed, in the reactor of constant pressure funnel and reflux condensing tube, add mix monomer pre-emulsion, stir, after being heated to 75 DEG C, adding 8 parts of mass concentrations is the ammonium persulfate aqueous solution of 10%, and at 75 ~ 80 DEG C, insulation reaction is after 2 hours, stops reaction, cooling reactant liquor, discharging must without crosslinked fluorinated copolymer emulsion, and the latex particle size of test emulsion and domain size distribution, result is see accompanying drawing 4.As seen from Figure 4, the fluorine-containing latex particle diameter obtained when not adding crosslinking agent is less, and integrated distribution is at 0.125 μm.What obtain without prepolymer formula in crosslinked fluorinated copolymer emulsion is:
Wherein, Rf=-(CH
2)
2(CF
2)
6f; M=5 ~ 12; N=2 ~ 4; O=20 ~ 35; P=2 ~ 5; Q=10 ~ 25.
2, textile finishing application
It is 5% that the crosslinked fluorinated copolymer emulsion-type finishing agent of the nothing obtained of preparation is diluted to polymer residual, and as dressing liquid finishing of cotton textiles, two leaching two ginning cloth on padding machine, pick-up is 105%, and be 105 DEG C of preliminary drying 2min in temperature, 175 DEG C bake 3min.
3, performance test
Reference GB4745-84 " textile fabric surface moisture-resistant assay method ", trickle instrument carries out trickle test, and after arranging, cotton fabric waterproofing scoring is 90, and fabric face has the minute quantity adhesion globule, and oil repellent can reach 2 grades.The Fabric Hand Test result of finish fabric is see table 1.
COTTON FABRIC after fluorine-contained finishing agent arranges has very excellent refuses water effect, and wherein the water grade of refusing of fluorine-contained finishing agent finish fabric promotes by adding crosslinking agent in finishing agent, and oil repellent can then remain unchanged.
From arranging front and back Fabric Style test result in table 1, compared with untreated former cloth, the COTTON FABRIC bending stiffness after fluorine-contained finishing agent provided by the invention arranges and delayed square increase all to some extent, the Bending Deformation of fabric and the less able of reply.Simultaneously, compare with the fluorine-contained finishing agent of cross-linking agent-free, adding of siliceous crosslinking agent makes the softness of fabric be improved, wherein best containing the finishing agent effect of organosilicon cross-linking agent of 1%, finish fabric have well refuse water effect while feel improve.
Claims (9)
1. a fabric water-refusing oil-refusing finishing agent, is characterized in that it is the polymer emulsion that a kind of silicon oxygen bond is cross-linked, has following structure:
Wherein, Rf is-(CH
2)
2(CF
2)
6f; R is-CH
2-Huo – CH
2cH
2-; R ' is H Huo – CH
3; M=5 ~ 12; N=2 ~ 4; O=20 ~ 35; P=2 ~ 5; Q=10 ~ 25.
2. a preparation method for fabric water-refusing oil-refusing finishing agent as claimed in claim 1, is characterised in that and comprises the steps:
(1) by weight, 1 ~ 3 part of nonionic surface active agent and 1 ~ 3 portion of anion surfactant are joined in 270 parts of water, in 8000 ~ 11000 revs/min of emulsified process of speed conditions 1 ~ 15 minute in high-speed shearing emulsion machine; Add 30 part of ten trifluoro octyl acrylate monomer, 40 ~ 50 parts of Butyl Acrylate Monomer, 20 ~ 25 parts of methyl methacrylates or methyl acrylate methyl monomer, 2 ~ 4 parts of hydroxymethyl acrylates or hydroxy ethyl methacrylate monomers and 0.5 ~ 2 part of two (acryloxypropyl) tetramethyl disiloxane again, mixed liquor stir process 15 ~ 30 minutes under the rotating speed of 8000 ~ 11000 revs/min, obtains mix monomer pre-emulsion;
(2) the mix monomer pre-emulsion obtained is being stirred and N
2protection, temperature is under the condition of 50 ~ 90 DEG C, and adding 8 ~ 10 parts of mass concentrations is the initiator solution of 5 ~ 20%, reacts 2 ~ 12 hours, obtains the polymer emulsion that a kind of silicon oxygen bond is crosslinked, i.e. fabric water-refusing oil-refusing finishing agent after cooling.
3. the preparation method of a kind of fabric water-refusing oil-refusing finishing agent according to claim 2, is characterized in that: described nonionic surface active agent is the one in AEO-9, this dish-60, Tween-80.
4. the preparation method of a kind of fabric water-refusing oil-refusing finishing agent according to claim 2, is characterized in that: described anion surfactant is SDS.
5. the preparation method of a kind of fabric water-refusing oil-refusing finishing agent according to claim 2, is characterized in that: described hydroxyalkyl acrylates is any one in hydroxymethyl acrylate and hydroxy ethyl methacrylate.
6. the preparation method of a kind of fabric water-refusing oil-refusing finishing agent according to claim 2, is characterized in that: described initator is any one in ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate.
7. the preparation method of a kind of fabric water-refusing oil-refusing finishing agent according to claim 2, is characterized in that: in step (1), the addition of two (acryloxypropyl) tetramethyl disiloxane is 1 ~ 1.5 part.
8. the preparation method of a kind of fabric water-refusing oil-refusing finishing agent according to claim 2, is characterized in that: the reaction temperature in step (2) is 70 ~ 80 DEG C.
9. the application of a fabric water-refusing oil-refusing finishing agent as claimed in claim 1, it is 5 ~ 20% that the fabric water-refusing oil-refusing finishing agent prepared is diluted to polymer residual, obtain textile finishing working solution, padding machine carries out water and oil repellent finish to fabric, process conditions are: pick-up 90 ~ 110%, preliminary drying temperature 90 ~ 110 DEG C, preliminary drying time 1 ~ 3 min, baking temperature 160 DEG C ~ 180 DEG C, bakes time 2 ~ 5min.
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| CN103396698B (en) * | 2013-07-19 | 2014-08-20 | 浙江理工大学 | Blue-ray curing formula and textile digital functional finishing method utilizing same |
| CN103408692A (en) * | 2013-08-08 | 2013-11-27 | 中科院广州化学有限公司 | Aqueous dispersion crosslinkable random fluoropolymer and constructed super-amphiphobic coat through aqueous dispersion crosslinkable random fluoropolymer |
| CN103643518A (en) * | 2013-11-27 | 2014-03-19 | 常熟市赵市圣丹龙制衣厂 | Preparation method for fabric water-oil repellent finishing agent |
| CN103726308A (en) * | 2013-12-17 | 2014-04-16 | 江苏金太阳纺织科技有限公司 | Oil-repellent finishing liquid for woolen sweater and preparation method for oil-repellent finishing liquid |
| CN103981710B (en) * | 2014-04-21 | 2016-07-06 | 孙德庆 | A kind of fabric finishing agent and preparation method thereof |
| CN104074052B (en) * | 2014-05-21 | 2016-10-12 | 巨化集团技术中心 | A kind of fluorine-silicon copolymer waterproof oil-proof finishing agent aqueous liquid dispersion |
| CN104594045B (en) * | 2015-01-29 | 2016-11-02 | 苏州大学 | A kind of fabric water-refusing oil-refusing finishing agent and preparation method thereof |
| CN106555336B (en) * | 2016-11-23 | 2019-09-27 | 苏州联胜化学有限公司 | A kind of fluorine-containing water-refusing oil-refusing finishing agent and preparation method thereof |
| CN106758239A (en) * | 2016-12-15 | 2017-05-31 | 苏州益可泰电子材料有限公司 | Textile finishing liquid and preparation method thereof |
| CN107177983A (en) * | 2017-05-22 | 2017-09-19 | 如皋市下原科技创业服务有限公司 | A kind of fabric water and oil repellent finish technique |
| CN109464849A (en) * | 2018-12-20 | 2019-03-15 | 合肥合意环保科技工程有限公司 | A kind of two-ply foam coating air filting material, preparation method and application |
| CN112029032B (en) * | 2020-08-26 | 2022-02-01 | 盐城工学院 | Preparation method of durable fabric waterproof finishing agent and product thereof |
| CN115652637B (en) * | 2022-10-25 | 2024-02-02 | 苏州大学 | Fluorine-free oil-repellent coated fabric and preparation method thereof |
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| CN101349010A (en) * | 2008-08-28 | 2009-01-21 | 苏州大学 | Silk broadcloth anti-water anti-oil dressing agent, preparation method and uses thereof |
| CN102094329A (en) * | 2009-12-09 | 2011-06-15 | 北京服装学院 | Fluorine and silicon containing water and oil repellent finishing agent, preparation and application thereof |
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Effective date of registration: 20181211 Address after: 215228 No. 12 Tanqiu Silk Factory Road, Shengze Town, Wujiang City, Jiangsu Province Patentee after: Jiangsu Hua Jia Holdings Group Limited Address before: 215123 199 Ren Yan Road, Suzhou Industrial Park, Suzhou, Jiangsu Patentee before: Soochow University |