CN103628317B - A kind of composition of waterproofing and oil-proof agent and processing method, textiles - Google Patents
A kind of composition of waterproofing and oil-proof agent and processing method, textiles Download PDFInfo
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Abstract
The present invention relates to a kind of composition of waterproofing and oil-proof agent and preparation method thereof.Described composition of waterproofing and oil-proof agent by core-shell emulsion and by mass percentage 0.001% ~ 15% crosslinking agent form.Core-shell emulsion comprises the fluoropolymer of 20 ~ 30%, the auxiliary agent of 0.001% ~ 48% and water.Crosslinking agent is polyisocyanates or epoxy.Composition of waterproofing and oil-proof agent of the present invention is applied to textiles, has good waterproof oil-proof result and excellent durability.
Description
Technical field
The present invention relates to textile auxiliary field, specifically a kind of composition of waterproofing and oil-proof agent used for textiles and its preparation method and application.
Background technology
The water and oil-resistant that textiles has normally arranges through water and oil repellent agent and obtains.See " printing and dyeing " nineteen ninety-five the 21st volume the 12nd phase 37-41 page, Fluorine-Contained Oil-Water-Proofing (I): in the paper about the mechanism of waterproof and oilproof performance, author's Kubo unit stretches and points out, water and oil repellent agent is generally fluorine-containing (methyl) acrylate monomer and floride-free chain alkyl (methyl) acrylate monomer is main raw material, adds the fluoropolymer of other monomer copolymerization a small amount of.
The paper stretched of Kubo unit is also introduced, and the mechanism of water and oil repellent agent effect is exactly form thin film at the outer surface of ground, and the surface tension of film lower than general liquid, thus shows and refuses water, refuses oil and anti-pollution function.The low-surface-energy of fluoropolymer itself is the reason that film surface tension force is low.Meanwhile, according to Surface Physical Chemistry principle, the superficial layer of film and extraneous contact, it determines capillary size with extraneous interaction, and the impact of film other parts effects on surface tension force outside desurfacing is very little.Thus, only need fluoropolymer to form superficial layer in waterproof and oilproof agent film, can low-surface-energy be obtained, obtain satisfied treatment effect.Under these conditions, if film other parts are not fluorine-containing, then can reduce the use of fluorine-containing (methyl) acrylate monomer.In addition, because fluorine-containing (methyl) acrylate monomer price is high, production process exists to be polluted and energy resource consumption, needs the consumption as far as possible reducing it.
Core-shell emulsion technology can pass through particle design, make the composition of emulsion particle sheath polymers different from interior nuclear polymer, after film forming, shell is in skin and the extraneous contact of film, kernel is in internal layer and is combined with textiles, kernel fluorine-containing (methyl) acrylate monomer concentration is significantly lower than shell, even do not add, so just can reduce fluorine-containing (methyl) acrylate monomer consumption.The document that this respect is delivered and patent are all a lot, but it is not enough more or less to there are following several respects.
1, specific aim is not strong.Owing to needing the most surface band negative electricity of textiles to be processed, need water and oil repellent agent to be cationic, just can have good effect.And existing technology is much the system of band anion, cationic system cannot be changed into by the adjustment of simple formula.
2, particle design is unreasonable.Be mainly reflected in two aspects, one, although adopt fluorine-containing (methyl) acrylate monomer at the synthesis technique of shell enrichment, because the hydrophily of shell is much smaller than core part, in synthesis and storage process, there is phase reversal, thus impact effect.They are two years old, by the crosslinked form stable making nucleocapsid, the enrichment of fluoropolymer when water and oil repellent agent film forming in superficial layer can be affected, although this defect effectively can be improved by " annealing " technique sometimes, but need a large amount of time and the energy, not there is practical significance.
3, waterproof and oilproof performance durability is poor.Both ways, one, water and oil repellent agent and fiber, particularly with the textiles of cotton composition, binding strength is poor in performance.Its two, most of prior art directly uses as water and oil repellent agent after preparation emulsion, obtains durability in self-crosslinking mode, and can add a small amount of crosslinking agent and improve further.From use practice, such design can not be satisfied the demand.
Summary of the invention
The present invention aims to provide a kind of composition of waterproofing and oil-proof agent and manufacture method thereof, and this composition of waterproofing and oil-proof agent has that waterproof oil-proof result is good, the feature of good economy performance, persistent.
Another object of the present invention is to provide the textiles applying above-mentioned composition of waterproofing and oil-proof agent.
Technical scheme of the present invention is: a kind of composition of waterproofing and oil-proof agent, by core-shell emulsion and by mass percentage 0.001% ~ 15% crosslinking agent form;
Wherein, described core-shell emulsion comprises the fluoropolymer of mass percent 20 ~ 30%, the auxiliary agent of 0.001% ~ 48%, and surplus is water;
Described fluoropolymer is obtained by feature free radical polymerization process by various of monomer, the mass percent of monomer composition is fluorochemical monomer 1% ~ 10%, cationic monomer 0.001% ~ 3%, chain-transferring agent 0.001% ~ 3%, hydroxyl and/or amine-containing monomers 0.001% ~ 5%, many double bond monomers 0.001% ~ 1.5%, chloride monomer 1% ~ 10%, all the other are non-fluorine monomers;
The general formula of described fluorochemical monomer is C
mf
2m+1yC
nh
2noCOCR=CH
2, described Y can not have, and can be-NH-,-NR yet
1-,-NH-SO
2-, NR
1-SO
2-etc., R
1be selected from C
1~ C
4alkyl; R is H, Cl, F or CH
3; Described m be 1,2,3,4,5,6,7,8,9,10,11 or 12, n be 1,2,3 or 4;
Described cationic monomer is selected from containing one or more of the cationic monomers such as tertiary amine, quaternary ammonium or imidazoline group;
Described band amine-containing monomers is selected from containing one or more in the band such as primary amine or secondary amine group amine-containing monomers;
Described many double bond monomers are selected from containing one or more mixing in the monomer of two or more carbon-carbon double bonds;
Described non-fluorine monomer be selected from not fluorine-containing and have the polymerizable material of double bond one or more mixing;
Described feature process makes many double bond monomers be distributed in stratum nucleare; Fluorochemical monomer and chain-transferring agent are distributed in shell; Hydroxyl and/or amine-containing monomers is mainly distributed in shell;
Described free radical is produced by initator thermal decomposition;
Described auxiliary agent is surfactant, solvent and pH adjusting agent;
Described crosslinking agent is polyisocyanates or epoxy, is CATION or positive nonionic or nonionic, and when adding after core-shell emulsion synthesis or use, scene adds.
Preferably, described monomer is as follows:
Described cationic monomer is selected from one or more in (methyl) acrylic acid diformazan (second) amino ethyl ester, (methyl) acrylyl oxy-ethyl-trimethyl salmiac;
Described chain-transferring agent be selected from alkyl hydrosulfide, α-methyl styrene linear dimerization body, mercaprol and mercaptoethanol one or more.The alkyl hydrosulfide of the straight chain of the preferred carbon number more than 12 of described chain-transferring agent;
Described hydroxyl monomer be selected from (methyl) acrylic acid hydroxypropyl (second) ester, (methyl) polyalkylene glycol acrylate ester one or more;
Described band amine-containing monomers be selected from the product of (methyl) acrylamide, glycidyl methacrylate and monoethanolamine, double bond containing urea heterocyclic compound one or more;
Described many double bond monomers are selected from one or more mixing in second (fourth, oneself) glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, divinylbenzene, (methyl) allyl acrylate;
Described chloride monomer be selected from vinyl chloride, dichloroethylene, vinylidene chloride, 3-chlorine-2-hydroxyl-propyl methacrylate one or more;
Described non-fluorine monomer is selected from chain alkyl (methyl) acrylate, and wherein alkyl is linear chain structure, carbon number >=12 that alkyl comprises.
Preferably, described initator is selected from one or more in persulfate, oil-soluble azo-initiator or water-soluble azo class initator; One or more preferably in ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride of described initator.
Preferably, described auxiliary agent is as follows:
Described surfactant is selected from nonionic and cationic surface active agent;
Described solvent boiling point, higher than 250 DEG C, is selected from solubility in water and is less than 5%, or one or more more than 60% of the solubility in water; Described solvent is preferably from tripropylene glycol butyl ether, tripropylene glycol butyl oxide, 2,2,4-trimethyl-1, one or more of 3-pentanediol mono isobutyrate or mixed acid dibutyl ester (mixture of dibutyl succinate, dibutyl glutarate and dibutyl adipate), tripropylene glycol, four propylene glycol, tripropylene glycol ether etc.;
Described pH regulates auxiliary agent to comprise acid or alkali or amino acid, and composition of waterproofing and oil-proof agent pH value is between 4 ~ 7.
In above-mentioned composition of waterproofing and oil-proof agent, the synthesis technique of core-shell emulsion comprises the steps:
(1) with the non-fluorine monomer of part, many double bond monomers, on a small quantity hydroxyl and/or amine-containing monomers, the chloride monomer of part, and optional a small amount of cationic monomer, part of auxiliary, part initiator and part water are raw material, radical polymerization synthetic kernel emulsion;
(2) by fluorochemical monomer, remain non-fluorine monomer, chain-transferring agent, remaining or whole cationic monomer, tape remaining hydroxyl and/or amine-containing monomers, residue auxiliary agent and part water mix and are emulsified into pre-emulsion.By pre-emulsion, remain chloride monomer and residue initator adds in core emulsion and reacts, after reaction terminates, system temperature is down to room temperature, after filtration, can core-shell emulsion be obtained.
A kind of textiles, adopts above-mentioned composition of waterproofing and oil-proof agent to process.
The processing method of above-mentioned composition of waterproofing and oil-proof agent, is characterized in that comprising the steps:
S1) with the non-fluorine monomer of part, many double bond monomers, on a small quantity hydroxyl and/or amine-containing monomers, the chloride monomer of part, and optional a small amount of cationic monomer, part of auxiliary, part initiator and part water are raw material, radical polymerization synthetic kernel emulsion;
S2) by fluorochemical monomer, remain non-fluorine monomer, chain-transferring agent, remaining or whole cationic monomer, tape remaining hydroxyl and/or amine-containing monomers, residue auxiliary agent and part water mix and are emulsified into pre-emulsion.By pre-emulsion, remain chloride monomer and residue initator adds in core emulsion and reacts, after reaction terminates, system temperature is down to room temperature, after filtration, can core-shell emulsion be obtained;
S3) mixed with crosslinking agent by core-shell emulsion, the mass percent concentration of described crosslinking agent is 0.001% ~ 15%.
The invention has the beneficial effects as follows:
The present invention is intended to by reasonably filling a prescription, the design of technique, provides water and oil repellent agent scheme, overcomes the deficiency of prior art, make the waterproof oil-proof result that the textiles after process reaches economic, efficient and lasting.Specific as follows:
1, electrically aspect presents CATION or positive nonionic, better can be applied to textiles.
2, rational particle design, solves the contradiction between core-shell morphology and fluorine-containing part surface enrichment.
3, adopt the multiple cross-linked mode of chloride monomer and bi-component, improve the fastness of water and oil repellent agent.
Detailed description of the invention
In order to verify the waterproof oil-proof result of textiles after composition of waterproofing and oil-proof agent process of the present invention, investigate by standard method, to compare.Waterproof effect adopts GB GB 4,745 one 1997, and grease proofing effect AATCC-TEST Method l18.1-1992, here is method brief introduction.
Standard GB/T 4,745 one 1997 test method.Intercept the sample of 18x18cm, compress with clamper, and be installed on the firm banking that to become with level with 45° angle, with in the distilled water of 250mL (20 ± 2 DEG C) or deionized water rapidly and reposefully hopper, by the shower nozzle with sample centre distance in 25 ~ 30s, on average and continuously spray towards sample center.Spray complete, rapidly clamper is taken away, make the sample level of facing down into, pat twice lightly, observe sample wetness degree, then use text description and contrast with picture and evaluate its grade.Get 2 mean values.
Rating scale word is:
L level---all wetting by drenching surface.
2 grades---by drenching a surperficial dewetting, namely the summation of fritter wetting surface is about the half of entire area.
3 grades---soak by drenching the surperficial small size only cannot do not had continuously.
4 grades---not wetting by drenching surface, but speckle with droplet.
5 grades---not wetting by drenching surface, also without droplet.
AATCC－TEST Method l18.1－1992。First use the experimental liquid of lowest number, carefully drip on sample with 0.05mL liquid, if occurred without infiltration and wetting phenomena in 30 seconds, then and then drip on sample with the experimental liquid of higher number.Experiment is carried out continuously, until experimental liquid in 30 seconds the fountain solution side of dripping or around till sample.The wet goods level of refusing of sample represents with the experimental liquid that can not soak the highest numbering of sample in 30 seconds, and rating is as following table.
Table 1 grease proofness testing standard liquid
| Grease proofing progression | Component | Surface tension (mN/m, 25 DEG C) |
| 1 | White Mineral Oil | 31.2 |
| 2 | White Mineral Oil 65 parts+hexadecane 35 parts | 28.7 |
| 3 | Hexadecane | 27.1 |
| 4 | N-tetradecane | 26.1 |
| 5 | N-dodecane | 25.1 |
| 6 | N-decane | 23.5 |
| 7 | Normal octane | 21.3 |
| 8 | Normal heptane | 19.8 |
Embodiment 1
Get 60.8 grams of lauryl acrylates, 0.5 gram of divinylbenzene, 0.5 gram of hydroxy-ethyl acrylate, 0.1 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 0.1 gram of dimethylaminoethyl methacrylate, 2 grams of octadecyl trimethyl ammonium chloride and 2 grams of peregal O-25s, 0.5 gram of acetic acid, 140 grams of water add flask, high-speed stirred 30 minutes.Then logical nitrogen 30 minutes, is warmed up to 60 degree simultaneously.Add 0.4 gram of azo-bis-isobutyrate hydrochloride, 8 grams of vinyl chloride, insulation reaction 3 hours, obtains core emulsion.
Get 15 grams of C
6f
13sO
2n (CH
3) C
2h
4oCOCH=CH
2, 4 grams of octadecyl acrylates, 2 grams of lauryl acrylates, 0.5 gram of lauryl mercaptan, 3 grams of hydroxy-ethyl acrylates, 0.5 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 1 gram of dimethylaminoethyl methacrylate, 12 grams of mixed acid dibutyl esters and 10 gram of four propylene glycol, 44.9 gram water, 1 gram of maleic acid dodecyl polyoxyethylene (10) ether-ether-ethyl ester support group (trimethyl) ammonium chloride, 2 gram 2, 4, 7, 9-tetramethyl-4, the ethylene oxide adduct (it is 80% that oxirane accounts for mass ratio) of 7-glycol-5-decine, 0.1 gram of acetic acid mixes, emulsify at a high speed 20 minutes, obtain pre-emulsion.Pre-emulsion is added drop-wise in the core emulsion of 62 DEG C of nitrogen replacement, drips the aqueous solution of 0.3 gram of azo-bis-isobutyrate hydrochloride simultaneously, progressively adds 4 grams of vinyl chloride simultaneously.Reinforced 3 hours used times, then insulation reaction 3 hours.Fall system temperature to room temperature, the non-ionic thermal adding 30% concentration unblocks polyisocyanic acid ester aqueous dispersion 150 grams, through 300 order filter-cloth filterings after stirring.
Embodiment 2
Get 60.7 grams of lauryl acrylates, 0.5 gram of glycol diacrylate, 0.6 gram of hydroxyethyl methylacrylate, 0.1 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 0.1 gram of dimethylaminoethyl methacrylate, 8 grams of vinyl chloride, 2 grams of octadecyl trimethyl ammonium chloride and 2 grams of peregal O-25s, 0.5 gram of acetic acid, 140 grams of water add flask, high-speed stirred 30 minutes.Then logical nitrogen 30 minutes, is warmed up to 60 degree simultaneously.Add 0.4 gram of azo-bis-isobutyrate hydrochloride, 8 grams of vinyl chloride, insulation reaction 3 hours, obtains core emulsion.
Get 15 grams of C
mf
2m+1c
2h
4oCOCH=CH
2(monomer is m is 6, 8, the mixture of 10, m be 8 account for 70% ~ 85%, m be 10 account for 15% ~ 25%, all the other to be m be 6 component), 4 grams of octadecyl acrylates, 2 grams of lauryl acrylates, 0.5 gram of lauryl mercaptan, 1.5 grams of hydroxyethyl methylacrylates, 0.5 gram of acrylamide, 0.5 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 1 gram of dimethylaminoethyl methacrylate, 10 grams of dipropylene glycol, 56.9 gram water, 1 gram of maleic acid dodecyl polyoxyethylene (10) ether-ether-ethyl ester support group (trimethyl) ammonium chloride, 2 gram 2, 4, 7, 9-tetramethyl-4, the ethylene oxide adduct (it is 80% that oxirane accounts for mass ratio) of 7-glycol-5-decine, 0.1 gram of acetic acid mixes, emulsify at a high speed 20 minutes, obtain pre-emulsion.Pre-emulsion is added drop-wise in the core emulsion of 62 DEG C of nitrogen replacement, drips the aqueous solution of 0.3 gram of azo-bis-isobutyrate hydrochloride simultaneously, progressively adds 4 grams of vinyl chloride simultaneously.Reinforced 3 hours used times, then insulation reaction 3 hours.System temperature falls to room temperature, 300 order filter-cloth filterings.When use, scene adds 50 grams of nonionic water and dispersibles polyisocyanates and stir.
Embodiment 3
Get 60.8 grams of lauryl acrylates, 0.5 gram of divinylbenzene, 0.5 gram of hydroxy-ethyl acrylate, 0.2 gram of dimethylaminoethyl methacrylate, 2 grams of octadecyl trimethyl ammonium chloride and 2 grams of peregal O-25s, 1 gram of acetic acid, 140 grams of water add flask, high-speed stirred 30 minutes.Then logical nitrogen 30 minutes, is warmed up to 60 degree simultaneously.Add 0.4 gram of azo-bis-isobutyrate hydrochloride, 8 grams of vinylidene chlorides, insulation reaction 3 hours, obtains core emulsion.
Get 15 grams of C
6f
13sO
2n (CH
3) C
2h
4oCOCH=CH
2, 4 grams of octadecyl acrylates, 2 grams of lauryl acrylates, 0.5 gram of lauryl mercaptan, 3 grams of hydroxy-ethyl acrylates, 1.5 grams of dimethylaminoethyl methacrylates, 12 grams of mixed acid (succinic acid, glutaric acid and adipic acid) dibutyl ester and 10 gram of four propylene glycol, 44.9 gram water, 1 gram of maleic acid dodecyl polyoxyethylene (10) ether-ether-ethyl ester support group (trimethyl) ammonium chloride, 2 gram 2, 4, 7, 9-tetramethyl-4, the ethylene oxide adduct (it is 80% that oxirane accounts for mass ratio) of 7-glycol-5-decine, 1.5 grams of acetic acid mix, emulsify at a high speed 20 minutes, obtain pre-emulsion.Then pre-emulsion is carried out high-pressure homogeneous.Pre-emulsion after high-pressure homogeneous is added drop-wise in the core emulsion of carrying out nitrogen replacement 62 DEG C, drips the aqueous solution of 0.3 gram of azo-bis-isobutyrate hydrochloride simultaneously, and progressively adds 4 grams of vinylidene chlorides.Drip and add 3 hours gas used times, then insulation reaction 3 hours.Fall after system temperature to room temperature through 300 order filter-cloth filterings.25 grams of glycerine three-glycidyl esters are added when use.
Comparative example 1 stratum nucleare does not add vinyl chloride and divinylbenzene.
Get 69.3 grams of lauryl acrylates, 0.5 gram of hydroxy-ethyl acrylate, 0.1 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 0.1 gram of dimethylaminoethyl methacrylate, 2 grams of octadecyl trimethyl ammonium chloride and 2 grams of peregal O-25s, 0.5 gram of acetic acid, 140 grams of water add flask, high-speed stirred 30 minutes.Then logical nitrogen 30 minutes, is warmed up to 60 degree simultaneously.Add 0.4 gram of azo-bis-isobutyrate hydrochloride, insulation reaction 3 hours, obtains core emulsion.
Get 15 grams of C
6f
13sO
2n (CH
3) C
2h
4oCOCH=CH
2, 4 grams of octadecyl acrylates, 2 grams of lauryl acrylates, 0.5 gram of lauryl mercaptan, 3 grams of hydroxy-ethyl acrylates, 0.5 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 1 gram of dimethylaminoethyl methacrylate, 12 grams of mixed acid dibutyl esters and 10 gram of four propylene glycol, 44.9 gram water, 1 gram of maleic acid dodecyl polyoxyethylene (10) ether-ether-ethyl ester support group (trimethyl) ammonium chloride, 2 gram 2, 4, 7, 9-tetramethyl-4, the ethylene oxide adduct (it is 80% that oxirane accounts for mass ratio) of 7-glycol-5-decine, 0.1 gram of acetic acid mixes, emulsify at a high speed 20 minutes, obtain pre-emulsion.Pre-emulsion is added drop-wise in the core emulsion of 62 DEG C of nitrogen replacement, drips the aqueous solution of 0.3 gram of azo-bis-isobutyrate hydrochloride simultaneously, progressively adds 4 grams of vinyl chloride simultaneously.Reinforced 3 hours used times, then insulation reaction 3 hours.Fall system temperature to room temperature, the non-ionic thermal adding 30% concentration unblocks polyisocyanic acid ester aqueous dispersion 150 grams, through 300 order filter-cloth filterings after stirring.
Comparative example 2 shell does not add lauryl mercaptan, and adds divinylbenzene.
Get 60.8 grams of lauryl acrylates, 0.5 gram of divinylbenzene, 0.5 gram of hydroxy-ethyl acrylate, 0.1 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 0.1 gram of dimethylaminoethyl methacrylate, 2 grams of octadecyl trimethyl ammonium chloride and 2 grams of peregal O-25s, 0.5 gram of acetic acid, 140 grams of water add flask, high-speed stirred 30 minutes.Then logical nitrogen 30 minutes, is warmed up to 60 degree simultaneously.Add 0.4 gram of azo-bis-isobutyrate hydrochloride, 8 grams of vinyl chloride, insulation reaction 3 hours, obtains core emulsion.
Get 15 grams of C
6f
13sO
2n (CH
3) C
2h
4oCOCH=CH
2, 4 grams of octadecyl acrylates, 2 grams of lauryl acrylates, 0.5 gram of divinylbenzene, 3 grams of hydroxy-ethyl acrylates, 0.5 gram of acrylyl oxy-ethyl-trimethyl salmiac, the hydrochloric acid corrective of 1 gram of dimethylaminoethyl methacrylate, 12 grams of mixed acid dibutyl esters and 10 gram of four propylene glycol, 44.9 gram water, 1 gram of maleic acid dodecyl polyoxyethylene (10) ether-ether-ethyl ester support group (trimethyl) ammonium chloride, 2 gram 2, 4, 7, 9-tetramethyl-4, the ethylene oxide adduct (it is 80% that oxirane accounts for mass ratio) of 7-glycol-5-decine, 0.1 gram of acetic acid mixes, emulsify at a high speed 20 minutes, obtain pre-emulsion.Pre-emulsion is added drop-wise in the core emulsion of 62 DEG C of nitrogen replacement, drips the aqueous solution of 0.3 gram of azo-bis-isobutyrate hydrochloride simultaneously, progressively adds 4 grams of vinyl chloride simultaneously.Reinforced 3 hours used times, then insulation reaction 3 hours.Fall system temperature to room temperature, the non-ionic thermal adding 30% concentration unblocks polyisocyanic acid ester aqueous dispersion 150 grams, through 300 order filter-cloth filterings after stirring.
Comparative example 3
In embodiment 1, polyisocyanate component is not added.
The composition of embodiment 1-3 and comparative example 1-3 or emulsion running water are diluted to 3%, get terylene woven fabric one to soak one and roll, 100 DEG C of oven dry, 180 DEG C of heat treatment 30 seconds, waterproof oil-proof result is measured after cool to room temperature, then after standard wash 10 times, then carry out waterproof and oilproof performance mensuration, the results are shown in Table 2.
Table two waterproof and oilproof performance
| Numbering | Waterproof | Grease proofing | Waterproof after washing 10 times | Grease proofing after washing 10 times |
| Embodiment 1 | 5 | 5 | 5 | 5 |
| Embodiment 2 | 5 | 4～5 | 5 | 4～5 |
| Embodiment 3 | 5 | 4～5 | 5 | 4～5 |
| Comparative example 1 | 4～5 | 2～3 | 4～5 | 2～3 |
| Comparative example 2 | 5 | 3～4 | 5 | 3～4 |
| Comparative example 3 | 4 | 2～3 | 3 | 2 |
Water and oil repellent agent of the present invention can provide waterproof oil-proof result for cotton, terylene, polyamide fibre and their blended textile.Applying step is: first water and oil repellent agent is diluted to 0.1 ~ 10% mass fraction water-based system, preferably uses running water, deionized water etc. to pass through the water of purification and sofening treatment; Then with the combination of coating, spraying, roller coat, pad dyeing, impregnating method and these methods, be applied on textiles to be processed; Then remove unnecessary liquid with roll, after testing, the fluoropolymer being attached to textiles accounts for the mass ratio about 0.01% ~ 10% of textiles; Finally carry out drying process, drying condition is variant according to textiles kind difference, should ensure that in fluoropolymer, fluorine-containing shell fully moves simultaneously, and at surface enrichment, then crosslinking agent and active group fully react, reach best waterproof oil-proof result and durability, usually need under 100 DEG C ~ 200 DEG C conditions, dry 1 minute ~ 90 minutes.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some changes, improvements and modifications, these changes, improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. a composition of waterproofing and oil-proof agent, by core-shell emulsion and by mass percentage 0.001% ~ 15% crosslinking agent form; It is characterized in that,
Described core-shell emulsion comprises the fluoropolymer of mass percent 20 ~ 30%, the auxiliary agent of 0.001% ~ 48%, and surplus is water; Described fluoropolymer is obtained by feature free radical polymerization process by various of monomer, the mass percent of monomer composition is fluorochemical monomer 1% ~ 10%, cationic monomer 0.001% ~ 3%, chain-transferring agent 0.001% ~ 3%, hydroxyl and/or amine-containing monomers 0.001% ~ 5%, many double bond monomers 0.001% ~ 1.5%, chloride monomer 1% ~ 10%, all the other are non-fluorine monomers; The general formula of described fluorochemical monomer is C
mf
2m+1yC
nh
2noCOCR=CH
2, described Y can not have, and can be-NH-,-NR yet
1-,-NH-SO
2-, NR
1-SO
2-, R
1be selected from C
1~ C
4alkyl; R is H, Cl, F or CH
3; Described m be 1,2,3,4,5,6,7,8,9,10,11 or 12, n be 1,2,3 or 4;
Described feature process makes many double bond monomers be distributed in stratum nucleare; Fluorochemical monomer and chain-transferring agent are distributed in shell; Hydroxyl and/or amine-containing monomers is mainly distributed in shell;
Described free radical is produced by initator thermal decomposition;
Described auxiliary agent is surfactant, solvent and pH adjusting agent;
Described crosslinking agent is polyisocyanates or epoxy, is CATION or positive nonionic or nonionic, and when adding after core-shell emulsion synthesis or use, scene adds;
Described cationic monomer be selected from dimethylaminoethyl methacrylate, acrylyl oxy-ethyl-trimethyl salmiac one or both;
Described chain-transferring agent selects the alkyl hydrosulfide of the straight chain of carbon number more than 12;
Described hydroxyl monomer be selected from hydroxy-ethyl acrylate, hydroxyethyl methylacrylate one or both;
Described band amine-containing monomers is selected from acrylamide;
Described many double bond monomers are selected from one or both mixing in glycol diacrylate, divinylbenzene;
Described chloride monomer be selected from vinyl chloride, dichloroethylene, vinylidene chloride, 3-chlorine-2-hydroxyl-propyl methacrylate one or more;
Described non-fluorine monomer is selected from chain alkyl (methyl) acrylate, and wherein alkyl is linear chain structure, carbon number >=12 that alkyl comprises;
Described initator be selected from ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride one or more;
Described surfactant is selected from nonionic and cationic surface active agent;
Described solvent is selected from tripropylene glycol butyl ether, tripropylene glycol butyl oxide, 2,2,4-trimethyl-1, one or more of 3-pentanediol mono isobutyrate, the mixture be made up of dibutyl succinate, dibutyl glutarate and dibutyl adipate three, tripropylene glycol, four propylene glycol, tripropylene glycol ether;
Described pH regulates auxiliary agent to comprise acid or alkali or amino acid, and makes composition of waterproofing and oil-proof agent pH value be between 4 ~ 7;
The synthesis technique of core-shell emulsion comprises the steps:
(1) with the non-fluorine monomer of part, many double bond monomers, on a small quantity hydroxyl and/or amine-containing monomers, the chloride monomer of part, and optional a small amount of cationic monomer, part of auxiliary, part initiator and part water are raw material, radical polymerization synthetic kernel emulsion;
(2) by fluorochemical monomer, remain non-fluorine monomer, chain-transferring agent, remaining or whole cationic monomer, tape remaining hydroxyl and/or amine-containing monomers, residue auxiliary agent and part water mix and are emulsified into pre-emulsion; By pre-emulsion, remain chloride monomer and residue initator adds in core emulsion and reacts, after reaction terminates, system temperature is down to room temperature, after filtration, can core-shell emulsion be obtained.
2. a textiles, is characterized in that, adopts composition of waterproofing and oil-proof agent according to claim 1 to process.
3. the processing method of composition of waterproofing and oil-proof agent according to claim 1, is characterized in that comprising the steps:
S1) with the non-fluorine monomer of part, many double bond monomers, on a small quantity hydroxyl and/or amine-containing monomers, the chloride monomer of part, and optional a small amount of cationic monomer, part of auxiliary, part initiator and part water are raw material, radical polymerization synthetic kernel emulsion;
S2) by fluorochemical monomer, remain non-fluorine monomer, chain-transferring agent, remaining or whole cationic monomer, tape remaining hydroxyl and/or amine-containing monomers, residue auxiliary agent and part water mix and are emulsified into pre-emulsion; By pre-emulsion, remain chloride monomer and residue initator adds in core emulsion and reacts, after reaction terminates, system temperature is down to room temperature, after filtration, can core-shell emulsion be obtained;
S3) mixed with crosslinking agent by core-shell emulsion, the mass percent concentration of described crosslinking agent is 0.001% ~ 15%.
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| CN104074076B (en) * | 2014-06-11 | 2016-08-24 | 周文叶 | A kind of color fixing agent for polyester carpet digit printing and application thereof |
| CN107223144B (en) * | 2015-02-13 | 2021-02-02 | 3M创新有限公司 | Fluorine-free fiber treatment composition comprising oligomers containing isocyanate-derived ethylenically unsaturated monomers and method of treatment |
| CN106758252B (en) * | 2016-11-29 | 2019-08-30 | 绍兴德美新材料有限公司 | Type water and oil repellent agent easy to maintain and preparation method thereof, textile |
| CN110685150A (en) * | 2018-07-05 | 2020-01-14 | 京准化工技术(上海)有限公司 | High-washing-resistance fluorine-containing waterproof processing agent for textiles |
| CN113527597A (en) * | 2020-04-16 | 2021-10-22 | 东莞东阳光科研发有限公司 | Preparation method of fluorine-containing emulsion, fluorine-containing surface protective agent and application thereof |
| CN114351464A (en) * | 2022-01-11 | 2022-04-15 | 桐乡市钜成涂装科技有限公司 | Chlorine-free durable waterproof and oil-proof agent and preparation method thereof |
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| JP2000160148A (en) * | 1998-11-30 | 2000-06-13 | Daikin Ind Ltd | Solvent-type water- and oil-repellent composition, and its production |
| US6767638B2 (en) * | 2002-05-16 | 2004-07-27 | Meadwestvaco Corporation | Core-shell polymeric compositions |
| TWI226346B (en) * | 2003-08-21 | 2005-01-11 | Jintex Corp Ltd | Nano fluorinated water-and oil-repellent and process for producing the same |
| JP2005146102A (en) * | 2003-11-14 | 2005-06-09 | Daikin Ind Ltd | Manufacturing method of water and oil repellant composition |
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