CN103266482B - Wax-containing water-and-oil repellent agent and textile - Google Patents
Wax-containing water-and-oil repellent agent and textile Download PDFInfo
- Publication number
- CN103266482B CN103266482B CN201310094592.3A CN201310094592A CN103266482B CN 103266482 B CN103266482 B CN 103266482B CN 201310094592 A CN201310094592 A CN 201310094592A CN 103266482 B CN103266482 B CN 103266482B
- Authority
- CN
- China
- Prior art keywords
- monomer
- water
- oil repellent
- repellent agent
- wax
- 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.)
- Active
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention provides a wax-containing water-and-oil repellent agent, preparation technology and application, wherein the wax-containing water-and-oil repellent agent comprises the following components in percentage by mass: fluoropolymer 20%-30%, (modified) polyethylene wax emulsion 3%-40%, surfactant 1-5%, hydrophilic solvent 4-20%, PH adjustment auxiliary agent 0.001-3% and water. The water-and-oil repellent agent provided by the invention has an excellent water-and-oil repelling effect, and an environmental protection property. In-situ polymerization technology is adopted in the invention; compared with prior art, the fluorine-containing material can play a better role of water-and-oil repelling, and the content of elemental fluorine in the decrease the water-and-oil repellent agent can be reduced.
Description
Technical field
The present invention relates to textile auxiliary field, specifically a kind of content of wax water and oil repellent agent used for textiles and its preparation method and application.
Background technology
Many fields require that textiles has waterproof and oilproof performance, and waterproof oil-proof result 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 that to propose water and oil repellent agent be generally fluorine-containing (methyl) acrylate monomer and chain alkyl (methyl) acrylate fluorine-free monomer be main raw material, adds other a small amount of monomer copolymerization and forms.See " Chinese leather " the 38th volume the 9th phase 52-57 page in 2009, at fluorinated acrylate polymer emulsion New research progress (I)---in the paper of the security of synthetic technology and fluorochemical monomer, Yang Qinhuan etc. propose " fluorine-free monomer should be (methyl) acrylate that alkyl carbon chain is greater than 8 ".Visible, water and oil repellent agents a lot of is at present with these materials for raw material, through the aqueous product that emulsion polymerisation obtains.
Because fluorochemical monomer price is high, the water and oil repellent agent price of synthesis is also higher, usually all needs to add some auxiliary substances, so that under the prerequisite ensureing waterproof oil-proof result, reduces the use amount of fluorine-containing material.Chinese patent application as on November 17th, 2004 is open, publication number is CN1546541A discloses a kind of hud typed fluorine-containing (methyl) Acrylic emulsion, it is by comprising monomer, emulsifying agent, initator, pH adjusting agent and water, through ultrasonic wave pre-emulsification, core-shell emulsion polymerization method is adopted to obtain.Owing to have employed nucleocapsid structure, make fluorine monomer be enriched in shell, greatly reduce the consumption of fluorine monomer.And for example on February 6th, 2004 application, application number be 200480003292.9 Chinese invention patent application disclose a kind of water and oil repellent aqueous composition, adopt the wax emulsion after paraffin and modified polyethylene wax emulsification to make auxiliary substance, after it and Fluorine-Contained Oil-Water-Proofing are blended, obtain the water and oil repellent agent of low cost.But for aforesaid prior art, the auxiliary substance added and the undercompounding of Fluorine-Contained Oil-Water-Proofing, under the prerequisite guaranteeing waterproof oil-proof result, the adminicle quality that can add is less, and the use amount of fluorine-containing material is still higher.
Summary of the invention
The present invention aims to provide a kind of content of wax water and oil repellent agent and manufacture method thereof, makes this water and oil repellent agent have the good and feature that fluorine-containing material use amount is low of waterproof oil-proof result.
For achieving the above object, first the present invention provides a kind of content of wax water and oil repellent agent, it is characterized in that, each component and mass percent as follows: fluoropolymer 20-30%, polythene wax emulsion or modified polyethylene wax emulsion 3-40%, surfactant 1-5%, hydrophilic solvent 4-20%, pH regulates auxiliary agent 0.001-3%, and surplus is water;
Described fluoropolymer is formed by radical polymerization by fluorochemical monomer, non-fluorine monomer and function monomer, and the mass percent that described fluorochemical monomer, non-fluorine monomer and function monomer account for fluoropolymer is: fluorochemical monomer 20-80%, non-fluorine monomer 10-75%, function monomer 5-10%;
The general formula of described fluorochemical monomer is C
mf
2m+1c
nh
2noCOCR=CH
2or C
mf
2m+1yC
nh
2noCOCR=CH
2, wherein, Y is-NH-,-NR
1-,-NH-SO
2-, NR
1-SO
2-one or more, R
1one or more of C1-C4 alkyl; R represents H, Cl, F or CH
3; The value of m is arbitrary integer of 1-12, and n is arbitrary integer of 1-4;
Described function monomer comprises cross-linking monomer, can also comprise one or more in many double bond monomers, hydrophilic monomer, chloride monomer;
Described polythene wax emulsion or modified polyethylene wax emulsion are selected from the Tissuemat E of softening point more than 100 DEG C, the aqueous emulsion of oxidized polyethlene wax, and solids content is 20 ~ 40%, below particle diameter 100nm, are CATION or nonionic;
Described surfactant is selected from nonionic and cationic surface active agent;
The solubility of described hydrophilic solvent in water is more than 60%, and boiling point is higher than 250 DEG C, and described hydrophilic solvent is single solvent or mixed solvent;
Described pH regulates auxiliary agent to comprise acid or alkali or amino acid, and makes content of wax water and oil repellent agent pH value be between 4 ~ 7;
Described free radical is produced by initator thermal decomposition;
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 cross-linking monomer is selected from containing one or more in the cross-linking monomer of amino or hydroxyl or carboxyl or ketone carbonyl or epoxy radicals or trialkyl silyl or blocked isocyanate base;
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 hydrophilic monomer is selected from molecule the hydrophilic monomer with polyethylene oxide segments, tertiary amine group or quaternary ammonium group;
Described chloride monomer be selected from vinyl chloride or vinylidene chloride or 3-chlorine-2-hydroxyl-propyl methacrylate one or more.
Described cross-linking monomer is selected from one or more in acrylamide, (methyl) acrylic acid hydroxypropyl (second) ester, (methyl) glycidyl acrylate, vinyltrimethoxy silane, diacetone acrylamide cooperation AH system;
Described many double bond monomers be selected from ethylene glycol dimethacrylate, trimethylolpropane tris (methyl) acrylate, divinylbenzene one or more;
Described hydrophilic monomer be selected from (methyl) dimethylaminoethyl acrylate, (methoxyl group) polyethylene glycol (methyl) acrylate, (methyl) acrylyl oxy-ethyl-trimethyl salmiac one or more;
Described hydrophilic solvent be selected from tripropylene glycol, four propylene glycol, tripropylene glycol ether one or more.
Described initator be selected from persulfate, oil-soluble azo-initiator or water-soluble azo class initator one or more.
Described initator be selected from ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride one or more.
A preparation method for water and oil repellent agent, the mode adopting monomer to be polymerized at wax emulsion situ synthesizes described water and oil repellent agent.
Comprise the following steps:
(1) emulgate ingredient is mixed rear emulsification, obtain pre-emulsion, emulgate ingredient does not comprise initator, polythene wax emulsion or modified polyethylene wax emulsion and the boiling point material lower than emulsifying temperature;
(2) high-pressure homogeneous or ultrasonic disperse is carried out to the pre-emulsion that step (1) obtains;
(3) a period of time is stirred after the pre-emulsion obtained step (2) mixes with polythene wax emulsion or modified polyethylene wax emulsion, then initiator for reaction is added, boiling point adds lower than the material of emulsifying temperature is disposable or progressively adds, after reaction terminates, system temperature is down to room temperature, after filtration, obtains target product.
A kind of textiles, adopts above-mentioned water and oil repellent agent to process.
Wherein, the molecular weight regulator of system mass percent 0 ~ 0.3% can also be comprised in described polymerization system.Described molecular weight regulator can be alkyl hydrosulfide, α-methyl styrene linear dimerization body, mercaptopropionic acid etc.Good selection is the alkyl hydrosulfide of the straight chain of carbon number more than 12.
The invention has the beneficial effects as follows:
The first, adopt modified polyethylene wax or Tissuemat E to be auxiliary element.Modified polyethylene wax or Tissuemat E molecular weight higher relative to paraffin, better to the ilities of fluorine-containing material.
The second, adopt in-situ polymerization mode, wax and fluorine-containing composition are better mixed.Under the prerequisite guaranteeing waterproof oil-proof result, relative to simple blend, such mode can improve the ratio of wax in system, thus reduces Oil repellent.
Detailed description of the invention
In order to verify the waterproof oil-proof result of textiles after water and oil repellent agent process of the present invention, investigate by standard method, to compare.Described standard method adopts GB GB 4745-1997 to investigate waterproof effect, and investigate grease proofing effect with AATCC-TEST Method l18.1-1992, here is method brief introduction.
(1) standard GB/T 4745-1997 test method
Intercept the sample of 18 × 18cm, 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.
（2）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 |
Mechanical stability and the shelf-stability of water and oil repellent agent are also investigated.Mechanical stability adds water and oil repellent agent in 10ml centrifuge tube, in centrifuges with the centrifugal 30min of 3000r/min, observes water and oil repellent agent with or without wild effects such as floating, layering and precipitations.Shelf-stability is that water and oil repellent agent is at room temperature placed 90 days, observes water and oil repellent agent with or without wild effects such as floating, layering and precipitations.
Embodiment 1
Get 15 grams of C
6f
13c
2h
4oCOCH=CH
2, 10 grams of octadecyl acrylate, 2 grams of lauryl acrylates, 1 gram of glycidyl acrylate, 1 gram of hydroxy-ethyl acrylate, 1 gram of acrylyl oxy-ethyl-trimethyl salmiac, 10 gram of four propylene glycol, 56.6 grams of water, 1 gram of octadecyl trimethyl ammonium chloride, 2 grams of stearyl alcohol polyoxyethylene (15) ethers (abbreviation OS-15) and 0.1 gram of acetic acid mix, emulsify at a high speed 20 minutes, obtains pre-emulsion.Emulgate ingredient does not comprise initator, polythene wax emulsion or modified polyethylene wax emulsion and the boiling point material lower than emulsifying temperature; Then by pre-emulsion ultrasonic disperse (also can carry out high-pressure homogeneous), pre-emulsion after ultrasonic disperse and 40 grams of polythene wax emulsions or modified polyethylene wax emulsion are (admittedly containing 33%, nonionic, softening point 130 DEG C, particle diameter 90nm) mix rear stirring 1 hour, then be initiator for reaction, boiling point can disposable add lower than the material of emulsifying temperature or progressively add: logical nitrogen 30 minutes, is warmed up to 62 DEG C simultaneously.Then 0.3 gram of azo-bis-isobutyrate hydrochloride is added, insulation reaction 8 hours.Finally system temperature is down to room temperature, through 300 order filter-cloth filterings, obtains water and oil repellent agent.
Other embodiment
In other embodiment, each component and embodiment 1 are distinguished to some extent, and preparation technology is identical with embodiment 1, below, list the component of each embodiment with subordinate list form.
| Sequence number | Pre-emulsion component | Wax emulsion, boiling point are lower than the material of emulsifying temperature and initator |
| Embodiment 2 | 3.2 grams of C 8F 17C 2H 4OCOCH=CH 2, 0.8 gram of C 10F 21C 2H 4OCOCH=CH 2, 14 grams of methacrylic acid 20 diester, 0.6 gram of glycidyl methacrylate, 0.4 gram of hydroxyethyl methylacrylate, 4 grams of tripropylene glycols, 71.9 grams of water, 0.4 gram of octadecyl benzyl dimethyl ammonium chloride, 0.6 gram of stearyl alcohol polyoxyethylene (25) ether (paregal O), 0.1 gram of acetic acid | 3 grams of polythene wax emulsions (admittedly containing 30%, sun/nonionic, softening point 140 DEG C, particle diameter 85nm), 1 gram of vinylidene chloride, 0.15 gram of azo-bis-isobutyrate hydrochloride |
| Embodiment 3 | 24 grams of C 6F 13SO 2N(CH 3)CH 2CH 2OCOCH=CH 2, 3 grams of octadecyl methacrylates, 1 gram of vinyltrimethoxy silane, 1 gram of dimethylaminoethyl methacrylate, 10 grams of tripropylene glycol ether, 17 grams of water, 1 gram of dodecylbenzyl alkyl dimethyl ammonium chloride, 2 grams of polyoxyethylene (20) sorbitan list hard acid ester (polysorbate60), 0.2 gram of citric acid | 40 grams of polythene wax emulsions (admittedly containing 31%, sun/nonionic, softening point 138 DEG C, particle diameter 88nm), 1 gram of vinyl chloride, 0.3 gram of azo-bis-isobutyrate hydrochloride |
| Embodiment 4 | 12.5 gram C 8F 17SO 2N(CH 3)CH 2CH 2OCOCH=CH 2, 10 grams of octadecyl acrylates, 1 gram of vinyltrimethoxy silane, 0.5 gram of ethylene glycol dimethacrylate, 1 gram of 3-chlorine-2-hydroxyl-propyl methacrylate, 8 grams of tripropylene glycols, 35 grams of water, 1 gram of dioctadecyl dimethyl ammonium chloride, 2 grams of polyoxyethylene (20) sorbitan list hard acid ester (polysorbate60), 2 grams of sorbitanmonolaureate (span 20), 0.2 gram of oxalic acid | 30 grams of polythene wax emulsions (admittedly containing 31%, sun/nonionic, softening point 138 DEG C, particle diameter 88nm), 0.25 gram of azo-bis-isobutyrate hydrochloride |
| Embodiment 5 | 12.5 gram C 6F 13C 2H 4OCOCH=CH 2, 5 grams of C 4F 9C 2H 4OCOCH=CH 2, 5 grams of Behenyl acrylate, 1 gram of glycidyl acrylate, 0.5 gram of methoxy poly (ethylene glycol) (750) methacrylate, 10 grams of tripropylene glycols, 30 grams of water, 0.5 gram of octadecyl trimethyl ammonium chloride, 2 grams of polyoxyethylene (20) sorbitan mono-oleic acid ester (Tween 80), 0.2 gram of lactic acid | 30 grams of polythene wax emulsions (admittedly containing 31%, sun/nonionic, softening point 138 DEG C, particle diameter 88nm), 1 gram of vinyl chloride, 0.25 gram of azo-bis-isobutyrate hydrochloride |
comparative example 1
Water and oil repellent agent is by fluorine-containing latex and polythene wax emulsion is blended forms.
Get 15 grams of C
6f
13c
2h
4oCOCH=CH
2, 10 grams of octadecyl acrylate, 2 grams of lauryl acrylates, 1 gram of glycidyl acrylate, 1 gram of hydroxy-ethyl acrylate, 1 gram of acrylyl oxy-ethyl-trimethyl salmiac, 10 gram of four propylene glycol, 56.6 grams of water, 1 gram of octadecyl trimethyl ammonium chloride, 2 grams of stearyl alcohol polyoxyethylene (15) ethers (abbreviation OS-15) and 0.1 gram of acetic acid mix, emulsify at a high speed 20 minutes, obtains pre-emulsion.Then pre-emulsion is carried out ultrasonic disperse.Pre-emulsion after ultrasonic disperse leads to nitrogen 30 minutes, is warmed up to 62 DEG C simultaneously.Then 0.3 gram of azo-bis-isobutyrate hydrochloride is added, insulation reaction 8 hours.Finally system temperature is down to room temperature, adds 40 grams of polythene wax emulsions (identical with embodiment), stir 20 minutes, through 300 order filter-cloth filterings, obtain water and oil repellent agent.
comparative example 2
Water and oil repellent agent is the polythene wax emulsion of comparative example 1.
comparative example 3
Water and oil repellent agent is by fluorine-containing latex and paraffin wax emulsions is blended forms.
Get 15 grams of C
6f
13c
2h
4oCOCH=CH
2, 10 grams of octadecyl acrylate, 2 grams of lauryl acrylates, 1 gram of glycidyl acrylate, 1 gram of hydroxy-ethyl acrylate, 1 gram of acrylyl oxy-ethyl-trimethyl salmiac, 10 gram of four propylene glycol, 56.6 grams of water, 1 gram of octadecyl trimethyl ammonium chloride, 2 grams of stearyl alcohol polyoxyethylene (15) ethers (abbreviation OS-15) and 0.1 gram of acetic acid mix, emulsify at a high speed 20 minutes, obtains pre-emulsion.Then pre-emulsion is carried out ultrasonic disperse.Pre-emulsion after ultrasonic disperse leads to nitrogen 30 minutes, is warmed up to 62 DEG C simultaneously.Then 0.3 gram of azo-bis-isobutyrate hydrochloride is added, insulation reaction 8 hours.Finally system temperature is down to room temperature, adds 40 grams of paraffin wax emulsions (admittedly containing 33%, fusing point 68 DEG C-70 DEG C, nonionic, particle diameter 500nm), stir 20 minutes, through 300 order filter-cloth filterings, obtain water and oil repellent agent.
comparative example 4
Water and oil repellent agent is the paraffin wax emulsions of comparative example 3.
comparative example 5
Water and oil repellent agent is made up of fluorine-containing latex.
Get 15 grams of C
6f
13c
2h
4oCOCH=CH
2, 10 grams of octadecyl acrylate, 2 grams of lauryl acrylates, 1 gram of glycidyl acrylate, 1 gram of hydroxy-ethyl acrylate, 1 gram of acrylyl oxy-ethyl-trimethyl salmiac, 10 gram of four propylene glycol, 56.6 grams of water, 1 gram of octadecyl trimethyl ammonium chloride, 2 grams of stearyl alcohol polyoxyethylene (15) ethers (abbreviation OS-15) and 0.1 gram of acetic acid mix, emulsify at a high speed 20 minutes, obtains pre-emulsion.Then pre-emulsion is carried out ultrasonic disperse.Pre-emulsion after ultrasonic disperse leads to nitrogen 30 minutes, is warmed up to 62 DEG C simultaneously.Then 0.3 gram of azo-bis-isobutyrate hydrochloride is added, insulation reaction 8 hours.Finally system temperature is down to room temperature, through 300 order filter-cloth filterings, obtains water and oil repellent agent.
The water and oil repellent agent running water of embodiment 1-5 and comparative example 1-5 is diluted to 3%, gets terylene woven fabric one and soak one and roll, 100 DEG C of oven dry, 180 DEG C of heat treatment 30 seconds, measures waterproof oil-proof result after cool to room temperature, the results are shown in Table 2.
Table 2 waterproof and oilproof performance and stability
| Numbering | Waterproof | Grease proofing | Mechanical stability | Shelf-stability |
| Embodiment 1 | 5 | 5 | Stable | Stable |
| Embodiment 2 | 5 | 5- | Stable | Stable |
| Embodiment 3 | 5- | 5 | Stable | Stable |
| Embodiment 4 | 5- | 5 | Stable | Stable |
| Embodiment 5 | 5 | 5 | Stable | Stable |
| Comparative example 1 | 4～5- | 3 | Stable | 1% floating thing |
| Comparative example 2 | 3～4 | 0～1 | Stable | Stable |
| Comparative example 3 | 4～5- | 3- | Layering | Layering |
| Comparative example 4 | 4 | 0～1 | Stable | Stable |
| Comparative example 5 | 5 | 5 | Stable | Stable |
The present invention also provides the application on the textile of a kind of above-mentioned water and oil repellent agent.Applying step comprises: first above-mentioned water and oil repellent agent is diluted to 0.1-10% mass fraction, is then applied on textiles; Then remove unnecessary liquid, finally carry out drying process.The combination of coating, spraying, roller coat, pad dyeing, impregnating method and these methods can be passed through, water and oil repellent agent is applied on textiles.After testing, attachment fluoropolymer on the textile accounts for the mass ratio of textiles is 0.01%-10%.In described drying process, drying condition is difference to some extent according to the difference of textiles kind, should ensure that the crosslinked group brought by cross-linking monomer in fluoropolymer fully reacts simultaneously, to reach best waterproof oil-proof result and durability, usually to need at 100 DEG C-200 DEG C dry 1-90 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 (7)
1. a content of wax water and oil repellent agent, is characterized in that, each component and mass percent as follows:
Fluoropolymer 20-30%, polythene wax emulsion or modified polyethylene wax emulsion 3-40%, surfactant 1-5%, hydrophilic solvent 4-20%, pH regulates auxiliary agent 0.001-3%, and surplus is water;
Described fluoropolymer is formed by radical polymerization by fluorochemical monomer, non-fluorine monomer and function monomer, and the mass percent that described fluorochemical monomer, non-fluorine monomer and function monomer account for fluoropolymer is: fluorochemical monomer 20-80%, non-fluorine monomer 10-75%, function monomer 5-10%;
The general formula of described fluorochemical monomer is C
mf
2m+1c
nh
2noCOCR=CH
2or C
mf
2m+1yC
nh
2noCOCR=CH
2, wherein, Y is-NH-,-NR
1-,-NH-SO
2-, NR
1-SO
2-one or more, R
1one or more of C1-C4 alkyl; R represents H, Cl, F or CH
3; The value of m is arbitrary integer of 1-12, and n is arbitrary integer of 1-4;
Described function monomer comprises cross-linking monomer, can also comprise one or more in many double bond monomers, hydrophilic monomer, chloride monomer;
Described polythene wax emulsion or modified polyethylene wax emulsion are selected from the Tissuemat E of softening point more than 100 DEG C, the aqueous emulsion of oxidized polyethlene wax, and solids content is 20 ~ 40%, below particle diameter 100nm, are CATION or nonionic;
Described surfactant is selected from nonionic and cationic surface active agent;
The solubility of described hydrophilic solvent in water is more than 60%, and boiling point is higher than 250 DEG C, and described hydrophilic solvent is single solvent or mixed solvent;
Described pH regulates auxiliary agent to comprise acid or alkali or amino acid, and makes content of wax water and oil repellent agent pH value be between 4 ~ 7;
Described free radical is produced by initator thermal decomposition;
Described non-fluorine monomer is selected from chain alkyl (methyl) acrylate, and wherein alkyl is linear chain structure, carbon number >=12 that alkyl comprises.
2. water and oil repellent agent according to claim 1, it is characterized in that, described cross-linking monomer is selected from containing one or more in the cross-linking monomer of amino or hydroxyl or carboxyl or ketone carbonyl or epoxy radicals or trialkyl silyl or blocked isocyanate base;
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 hydrophilic monomer is selected from molecule the hydrophilic monomer with polyethylene oxide segments, tertiary amine group or quaternary ammonium group;
Described chloride monomer be selected from vinyl chloride or vinylidene chloride or 3-chlorine-2-hydroxyl-propyl methacrylate one or more.
3. water and oil repellent agent according to claim 2, it is characterized in that, described cross-linking monomer is selected from one or more in acrylamide, (methyl) acrylic acid hydroxypropyl (second) ester, (methyl) glycidyl acrylate, vinyltrimethoxy silane, diacetone acrylamide cooperation AH system;
Described many double bond monomers be selected from ethylene glycol dimethacrylate, trimethylolpropane tris (methyl) acrylate, divinylbenzene one or more;
Described hydrophilic monomer be selected from (methyl) dimethylaminoethyl acrylate, (methoxyl group) polyethylene glycol (methyl) acrylate, (methyl) acrylyl oxy-ethyl-trimethyl salmiac one or more.
4. water and oil repellent agent according to claim 3, is characterized in that, described hydrophilic solvent be selected from tripropylene glycol, four propylene glycol, tripropylene glycol ether one or more.
5. water and oil repellent agent according to claim 1, is characterized in that, described initator be selected from persulfate, oil-soluble azo-initiator or water-soluble azo class initator one or more.
6. water and oil repellent agent according to claim 5, is characterized in that, described initator be selected from ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride one or more.
7. a textiles, is characterized in that, adopts the water and oil repellent agent according to any one of claim 1-4 to process.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310094592.3A CN103266482B (en) | 2013-03-23 | 2013-03-23 | Wax-containing water-and-oil repellent agent and textile |
| CN201410558384.9A CN104294597B (en) | 2013-03-23 | 2013-03-23 | A kind of preparation method of content of wax water and oil repellent agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310094592.3A CN103266482B (en) | 2013-03-23 | 2013-03-23 | Wax-containing water-and-oil repellent agent and textile |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410558384.9A Division CN104294597B (en) | 2013-03-23 | 2013-03-23 | A kind of preparation method of content of wax water and oil repellent agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103266482A CN103266482A (en) | 2013-08-28 |
| CN103266482B true CN103266482B (en) | 2015-02-04 |
Family
ID=49010136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310094592.3A Active CN103266482B (en) | 2013-03-23 | 2013-03-23 | Wax-containing water-and-oil repellent agent and textile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103266482B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572603A (en) * | 2013-10-24 | 2014-02-12 | 广东德美精细化工股份有限公司 | Fluoride-free waterproof agent for textile, preparation method thereof and textile |
| CN103572602A (en) * | 2013-10-24 | 2014-02-12 | 广东德美精细化工股份有限公司 | Fluoride-free waterproof agent, preparation method and textile |
| CN103628317B (en) * | 2013-12-02 | 2015-09-30 | 广东德美精细化工股份有限公司 | A kind of composition of waterproofing and oil-proof agent and processing method, textiles |
| TWI491721B (en) * | 2014-01-20 | 2015-07-11 | Jinex Corp Ltd | Fluorine-free water repellent, preparation thereof, and applications thereof |
| CN105220473B (en) * | 2014-06-06 | 2018-06-26 | 戴李宗 | A kind of water-proof aagent and its application |
| CN105369621A (en) * | 2015-10-30 | 2016-03-02 | 无锡市长安曙光手套厂 | Textile fluoride-free waterproofing agent and preparation method thereof and textile |
| CN106634431B (en) * | 2016-12-20 | 2019-06-25 | 山东东宏管业股份有限公司 | A kind of clinkery epoxy powder coating and preparation method thereof with super-drainage structure |
| CN107653681B (en) * | 2017-10-24 | 2019-10-25 | 广东德美精细化工集团股份有限公司 | High-effective water-proof oil-proofing agent and preparation method comprising telechelic polymer |
| CN109056329A (en) * | 2018-06-26 | 2018-12-21 | 福建荣宏光电科技有限公司 | A kind of architectural engineering impregnated carbon fiber glue caking agent and its preparation process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153675A (en) * | 1997-09-12 | 2000-11-28 | Nippon Mektron, Limited | Fluorinated water-and oil-repellent agents with improved freeze-thaw stability |
| CN1993443A (en) * | 2004-06-04 | 2007-07-04 | 优迈特株式会社 | Method for producing water-and-oil repellent agent |
| CN102149738A (en) * | 2008-09-15 | 2011-08-10 | 大金工业株式会社 | Water- and oil-repellent composition |
| US8216952B2 (en) * | 2006-10-20 | 2012-07-10 | Matsumoto Yushi-Seiyaku Co., Ltd. | Fabric treating agent, process for producing fabric, and fabric for vehicle interior materials |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711241A (en) * | 1993-06-22 | 1995-01-13 | Kao Corp | Water-repellent composition and water repellent article and method for water repelling treatment |
| US7094743B2 (en) * | 2003-07-29 | 2006-08-22 | 3M Innovative Properties Company | Composition, wipe and method for cleaning, protecting and imparting gloss to a substrate |
| JP5439743B2 (en) * | 2007-10-11 | 2014-03-12 | ユニマテック株式会社 | Water and oil repellent |
| CN102666772B (en) * | 2009-11-13 | 2016-05-04 | 旭硝子株式会社 | Waterproofing/oilproofing agent composition, the article of being processed by it and their manufacture method |
-
2013
- 2013-03-23 CN CN201310094592.3A patent/CN103266482B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153675A (en) * | 1997-09-12 | 2000-11-28 | Nippon Mektron, Limited | Fluorinated water-and oil-repellent agents with improved freeze-thaw stability |
| CN1993443A (en) * | 2004-06-04 | 2007-07-04 | 优迈特株式会社 | Method for producing water-and-oil repellent agent |
| US8216952B2 (en) * | 2006-10-20 | 2012-07-10 | Matsumoto Yushi-Seiyaku Co., Ltd. | Fabric treating agent, process for producing fabric, and fabric for vehicle interior materials |
| CN102149738A (en) * | 2008-09-15 | 2011-08-10 | 大金工业株式会社 | Water- and oil-repellent composition |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平7-11241A 1995.01.13 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103266482A (en) | 2013-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103266482B (en) | Wax-containing water-and-oil repellent agent and textile | |
| CN104294597B (en) | A kind of preparation method of content of wax water and oil repellent agent | |
| TWI610948B (en) | Fluorine-contained composition and fluorine-contained polymer | |
| EP3164426B1 (en) | Fluorine-containing water-repellent composition | |
| CN103572604B (en) | A kind of water and oil repellent agent and its preparation method and application | |
| CN103572603A (en) | Fluoride-free waterproof agent for textile, preparation method thereof and textile | |
| CN103572602A (en) | Fluoride-free waterproof agent, preparation method and textile | |
| CN105765025A (en) | Water-based surface treatment agent | |
| CN103628317B (en) | A kind of composition of waterproofing and oil-proof agent and processing method, textiles | |
| CA2097238A1 (en) | Fluorine containing aqueous composition having water repellent and oil repellent properties | |
| CN102149738A (en) | Water- and oil-repellent composition | |
| CN105369621A (en) | Textile fluoride-free waterproofing agent and preparation method thereof and textile | |
| KR102189119B1 (en) | Surface treatment agent | |
| KR102197951B1 (en) | Copolymer, and surface treatment agent | |
| EP2762504A1 (en) | Water-repellent and oil-repellent composition | |
| CN104024292A (en) | Fluorine-containing composition and fluorine-containing polymer | |
| CN102822218A (en) | Graft copolymer and repellent composition | |
| TWI625339B (en) | Surface treatment agent and method of producing the same | |
| CN109162098A (en) | A kind of short fluorocarbon chain waterproof and oilproof of resistance to disperse dyes dispersion liquid | |
| CN108699426A (en) | Surface conditioning agent | |
| CN106637976A (en) | High-efficiency fluorine-free waterproof agent for cotton fabrics subjected to low-temperature dyeing and finishing processing | |
| CN105658689A (en) | Fluorine-containing polymer and treatment agent | |
| CN110527014A (en) | A kind of free-floride cationic polyacrylate waterproofing agent and preparation method thereof | |
| CN106884327A (en) | Fabric waterproof composition for treating dispersion liquid | |
| CN106866872A (en) | Water-proofing treatment composition dispersion liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160426 Address after: Jinjiang Economic Development Zone in Fujian province 362261 (five yuan) Hin Yangxin Road No. 33 Patentee after: Fujian Province Jinjiang Dymatic Chemical Co., Ltd. Address before: 528300, Shunde Foshan hi tech Zone, Guangdong hi tech Industrial Zone, Gui Gui South Road Patentee before: Guangdong Demei Fine Chemical Co., Ltd. |