CN103572602A - Fluoride-free waterproof agent, preparation method and textile - Google Patents
Fluoride-free waterproof agent, preparation method and textile Download PDFInfo
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Abstract
The invention discloses a fluoride-free waterproof agent. The fluoride-free waterproof agent comprises the following components according to mass percent: 10%-20% of fluoride-free hydrophobic polymer, 10%-20% of (modified) polyethylene wax, 1%-10% of surfactants, 0.001%-10% of auxiliaries and the balance being water, wherein the fluoride-free hydrophobic polymer is formed through free radical polymerization of fluoride-free hydrophobic monomers with hydrocarbon hydrophobic groups and double bonds and functional monomers; the functional monomers are selected from one or more of monomers with a functional group besides double bonds; the (modified) polyethylene wax is selected from polyethylene wax and oxidized polyethylene wax with the softening point of above 100 DEG C; free radicals are generated by thermal decomposition of initiators. The fluoride-free waterproof agent provided by the invention has a good waterproof effect, does not contain fluorine and has an environment-friendly effect. Compared with the prior art, adopting the (modified) polyethylene wax with a high melting point, the fluoride-free waterproof agent has a better waterproof effect.
Description
Technical field
The present invention relates to textile auxiliary field, specifically a kind of used for textiles is without fluoro water proofing agent and its preparation method and application.
Background technology
The water resistance of textiles normally obtains through waterproofing agent arrangement.The waterproofing agent that existing market share is maximum is fluorinated waterproofing agent.Fluorinated waterproofing agent is expensive, fluorine-containing raw material used produce in energy consumption high, pollute heavy, be with fluorine-containing material difficult degradation, have biological accumulation toxicity.Employing is development trend without fluoro water proofing agent.
Application on 03 06th, 2010, the Chinese patent application of application number 201080009570.7 discloses a kind of waterproofing agent, comprises polymer, paraffin and dispersant.This patent adopt fusing point lower than the paraffin of 80 degree as key component, the water proofing property of waterproofing agent and washing durability are limited to.
Summary of the invention
The present invention aims to provide a kind of without fluoro water proofing agent and manufacture method thereof, makes this without fluoro water proofing agent, have better waterproof effect.
For achieving the above object, the invention provides a kind ofly without fluoro water proofing agent, each component and mass percent are as follows:
Floride-free hydrophobic polymer 10-20%, (modification) Tissuemat E 10-20%, surfactant 1-10%, auxiliary agent 0.001-10%, surplus is water;
Described floride-free hydrophobic polymer is formed by radical polymerization by floride-free hydrophobic monomer and function monomer, and the mass percent that described floride-free hydrophobic monomer and function monomer account for floride-free hydrophobic polymer is: floride-free hydrophobic monomer 90-99%, surplus are function monomer;
Described floride-free hydrophobic monomer is with hydrocarbon hydrophobic grouping and two key, and hydrocarbon hydrophobic grouping can be one or more mixing of the hydrophobic alkyl of straight chain, side chain or (many) ring-types;
Described function monomer is selected from one or more of the monomer of the functional group beyond two keys;
Described (modification) Tissuemat E is selected from 100 ℃ of above Tissuemat E, oxidized polyethlene wax of softening point;
Described surfactant is selected from nonionic and cationic surface active agent;
Described auxiliary agent comprises that pH regulates auxiliary agent, secondary solvent;
Described free radical is produced by initator thermal decomposition.
Preferably, the functional group of described function monomer is selected from amino or hydroxyl or carboxyl or ketone carbonyl or epoxy radicals or trialkyl silyl or blocked isocyanate base or one and an above carbon-carbon double bond or has polyoxyethylene fragment or tertiary amine group or quaternary ammonium group or with one or more of chlorine element etc.
Preferably, described function monomer is selected from acrylamide, (methyl) acrylic acid hydroxypropyl (second) ester, (methyl) glycidyl acrylate, vinyltrimethoxy silane, diacetone acrylamide coordinates AH system, ethylene glycol dimethacrylate, trimethylolpropane tris (methyl) acrylate, divinylbenzene, (methyl) dimethylaminoethyl acrylate, (methoxyl group) polyethylene glycol (methyl) acrylate, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, vinyl chloride, vinylidene chloride, one or more in 3-chlorine-2-hydroxyl-propyl methacrylate.
Preferably, described pH regulates auxiliary agent to comprise acid or alkali or amino acid, and makes without fluoro water proofing agent pH value between 4～7; Described secondary solvent is selected from one or more of ethanol, acetone, isopropyl alcohol, propylene glycol, PEG200, dipropylene glycol, tripropylene glycol, four propylene glycol.
Preferably, described initator is selected from one or more in persulfate, oil-soluble azo-initiator or water-soluble azo class initator.
Preferably, described initator is selected from one or more in ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride.
The above-mentioned preparation method without fluoro water proofing agent, comprises the following steps:
(1) floride-free hydrophobic monomer, (modification) Tissuemat E, surfactant, auxiliary agent and water are mixed and emulsification, obtain pre-emulsion;
(2) pre-emulsion step (1) being obtained is adjusted to reaction temperature, adds function monomer and initiator for reaction, after reaction finishes, system temperature is down to room temperature, obtains target product after filtration.
, adopt above-mentioned processing without fluoro water proofing agent.
The invention has the beneficial effects as follows:
Adopting (modification) Tissuemat E is composition.The relative paraffin of (modification) Tissuemat E molecular weight is higher, and fusing point is also higher, makes without water resistance and the washing fastness of fluoro water proofing agent better.
The specific embodiment
For verify through of the present invention without fluoro water proofing agent, process after the waterproof effect of textiles, can investigate by standard method, so that relatively.Described standard method is to adopt GB GB 4745-1997 to investigate waterproof effect, is method brief introduction below.
National standard < < GB 4745-1997 > > test methods.
The sample of intercepting 18 * 18cm, with clamper, compress, and be installed on and become on the firm banking with 45° angle with level, with the distilled water of 250mL (20 ± 2 ℃) or deionized water rapidly and reposefully in hopper, by with the shower nozzle of sample centre distance in 25～30s, towards sample center, on average and continuously spray.Spray completely, rapidly clamper is taken away, make the sample level of facing down into, pat lightly twice, observe sample wetness degree, then by text description and contrast with picture and evaluate its grade.Get mean value 2 times.
Grading grapholect is:
L level---be subject to drench surface all wetting.
2 grades---drenched a surperficial dewetting, the summation of fritter wetting surface is about half of entire area.
3 grades---being subject to drench surface only has not continuous small size wetting.
4 grades---be subject to drench surface not wetting, but speckle with droplet.
5 grades---be subject to drench surface not wetting, also without droplet.
Mechanical stability and shelf-stability without fluoro water proofing agent have also been investigated.Mechanical stability is to add without fluoro water proofing agent in 10ml centrifuge tube, in centrifuge, with the centrifugal 30min of 3000r/min, observes and without fluoro water proofing agent, to have or not the wild effects such as floating, layering and precipitation.Shelf-stability is at room temperature to place 90 days without fluoro water proofing agent, observes and without fluoro water proofing agent, to have or not the wild effects such as floating, layering and precipitation.
embodiment 1
Get 4 grams of acrylic acid mountain Yu base esters, 4 grams of methacrylic acid mountain Yu base esters, 1 gram of styrene, 5 grams of dipropylene glycol, 10 grams of Ethoqual C/25(ethoxylated quaternaries), 10 grams of Tissuemat Es, 10 grams of oxidized polyethlene wax, 0.1 gram of acetic acid, intensification 130 degree meltings also stir, and add 64 grams of water emulsification 1h, obtain pre-emulsion.Regulate pre-emulsion temperature to 62 degree, add 0.5 gram of glycidyl acrylate, pass into nitrogen gas stirring 30 minutes.Add 0.1 gram of azo-bis-isobutyrate hydrochloride, 0.5 gram of vinyl chloride, insulation reaction 8 hours.Finally system temperature is down to room temperature, through 300 order filter-cloth filterings, obtains without fluoro water proofing agent.
embodiment 2
Get 10 grams of Ethoqual C/25(ethoxylated quaternaries), 10 grams of Tissuemat Es, 10 grams of oxidized polyethlene wax, the 130 degree meltings stirring of heating up, add 64 grams of water emulsification 1h.Add again 4 grams of acrylic acid mountain Yu base esters, 4 grams of methacrylic acid mountain Yu base esters, 1 gram of styrene, 5 grams of dipropylene glycol, 0.1 gram of acetic acid, emulsify at a high speed 30 minutes, obtains pre-emulsion.Regulate pre-emulsion temperature to 62 degree, add 0.5 gram of glycidyl acrylate, pass into nitrogen 30 minutes simultaneously.Add 0.1 gram of azo-bis-isobutyrate hydrochloride, 0.5 gram of vinyl chloride, insulation reaction 8 hours.Finally system temperature is down to room temperature, through 300 order filter-cloth filterings, obtains without fluoro water proofing agent.
embodiment 3
Get 4 grams of acrylic acid mountain Yu base esters, 4 grams of methacrylic acid mountain Yu base esters, 1 gram of styrene, 5 grams of dipropylene glycol, 10 grams of Ethoqual C/25(ethoxylated quaternaries), the 85 degree meltings stirring of heating up, add 64 grams of water emulsification 1h.Then emulsion is dropped in 130 degree wax liquid, wax liquid is comprised of 10 grams of Tissuemat Es and 10 grams of oxidized polyethlene wax, and emulsify at a high speed 30 minutes, obtains pre-emulsion.Regulate pre-emulsion temperature to 62 degree, add 0.5 gram of glycidyl acrylate, 0.1 gram of acetic acid passes into nitrogen 30 minutes simultaneously.Add 0.1 gram of azo-bis-isobutyrate hydrochloride, 0.5 gram of vinyl chloride, insulation reaction 8 hours.Finally system temperature is down to room temperature, through 300 order filter-cloth filterings, obtains without fluoro water proofing agent.
Other embodiment
In other embodiment, each component and embodiment 1 distinguish to some extent, and preparation technology is identical with embodiment 1, below, with subordinate list form, list the component of each embodiment.
comparative example 1
Without fluoro water proofing agent, by floride-free hydrophobic polymer and paraffin, formed.
Get 4 grams of acrylic acid mountain Yu base esters, 4 grams of methacrylic acid mountain Yu base esters, 1 gram of styrene, 5 grams of dipropylene glycol, 10 grams of Ethoqual C/25(ethoxylated quaternaries), intensification 85 degree meltings also stir, add 64 grams of water emulsifications 30 minutes, then high-pressure homogeneous, obtain the pre-emulsion that particle diameter is less than 100nm.Pre-emulsion adds in 20 grams of fusing points, 63～68 degree paraffin of 85 degree, and emulsify at a high speed 30 minutes is then high-pressure homogeneous, obtains stable pre-emulsion.Regulate pre-emulsion temperature to 62 degree, add 0.5 gram of glycidyl acrylate, 0.1 gram of acetic acid, passes into nitrogen gas stirring 30 minutes.Add 0.1 gram of azo-bis-isobutyrate hydrochloride, 0.5 gram of vinyl chloride, insulation reaction 8 hours.Finally system temperature is down to room temperature, through 300 order filter-cloth filterings, obtains without fluoro water proofing agent.
comparative example 2
Without fluoro water proofing agent, it is wax emulsion.
Get 6.6 grams of Ethoqual C/25(ethoxylated quaternaries), 10 grams of Tissuemat Es, 10 grams of oxidized polyethlene wax, the 130 degree meltings stirring of heating up, add 64 grams of water emulsification 1h, obtain wax emulsion.
comparative example 3
Without fluoro water proofing agent, it is floride-free hydrophobic polymer.
Get 8 grams of acrylic acid mountain Yu base esters, 8 grams of methacrylic acid mountain Yu base esters, 2 grams of styrene, 5 grams of dipropylene glycol, 6.6 grams of Ethoqual C/25(ethoxylated quaternaries), the 85 degree meltings stirring of heating up, add 64 grams of water emulsifications 30 minutes, then high-pressure homogeneous, obtain pre-emulsion.Regulate pre-emulsion temperature to 62 degree, add 1 gram of glycidyl acrylate, 0.2 gram of acetic acid, passes into nitrogen gas stirring 30 minutes.Add 0.2 gram of azo-bis-isobutyrate hydrochloride, 1 gram of vinyl chloride, insulation reaction 8 hours.Finally system temperature is down to room temperature, through 300 order filter-cloth filterings, obtains without fluoro water proofing agent.
By embodiment 1-7 and comparative example 1-3 without fluoro water proofing agent, with running water, to be diluted to solids content be 1%, get terylene woven fabric one and soak one and roll, 100 ℃ of oven dry, 180 ℃ of heat treatment 30 seconds, measures waterproof effect after cool to room temperature.
| Numbering | Waterproof | Waterproof after washing 10 times | Mechanical stability | Shelf-stability |
| Embodiment 1 | 5 | 5- | Stable | Stable |
| Embodiment 2 | 5- | 4+ | Stable | Stable |
| Embodiment 3 | 5 | 5- | Stable | Stable |
| Embodiment 4 | 5- | 5- | Stable | Stable |
| Embodiment 5 | 5 | 5 | Stable | Stable |
| Embodiment 6 | 5- | 4+ | Stable | Stable |
| Embodiment 7 | 5- | 4+ | Stable | Stable |
| Comparative example 1 | 4- | 3 | Stable | A small amount of precipitation |
| Comparative example 2 | 3 | 1 | Stable | Stable |
| Comparative example 3 | 4 | 2- | Stable | Stable |
The present invention also provides a kind of above-mentioned application on textiles without fluoro water proofing agent.Applying step comprises: first, by the above-mentioned aqueous solution that is diluted to 0.1-10% mass fraction without fluoro water proofing agent, be then applied on textiles; Then remove unnecessary liquid, be finally dried processing.Can, by the combination of coating, spraying, roller coat, pad dyeing, impregnating method and these methods, will be applied on textiles without fluoro water proofing agent.After testing, the mass ratio that accounts for textiles without fluoro water proofing agent composition being attached on textiles is 0.01%-10%.In described dry processing, drying condition is difference to some extent according to the difference of textiles kind, should guarantee fully to react without the functional group being brought by function monomer in fluoro water proofing agent, to reach best waterproof effect and durability, conventionally need at 100 ℃-200 ℃, be dried 0.1-90 minutes simultaneously.
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 change, improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. without a fluoro water proofing agent, it is characterized in that, each component and mass percent are as follows:
Floride-free hydrophobic polymer 10-20%, (modification) Tissuemat E 10-20%, surfactant 1-10%, auxiliary agent 0.001-10%, surplus is water;
Described floride-free hydrophobic polymer is formed by radical polymerization by floride-free hydrophobic monomer and function monomer, and the mass percent that described floride-free hydrophobic monomer and function monomer account for floride-free hydrophobic polymer is: floride-free hydrophobic monomer 90-99%, surplus are function monomer;
Described floride-free hydrophobic monomer is with hydrocarbon hydrophobic grouping and two key, and hydrocarbon hydrophobic grouping can be one or more mixing of the hydrophobic alkyl of straight chain, side chain or (many) ring-types;
Described function monomer is selected from one or more of the monomer of the functional group beyond two keys;
Described (modification) Tissuemat E is selected from 100 ℃ of above Tissuemat E, oxidized polyethlene wax of softening point;
Described surfactant is selected from nonionic and cationic surface active agent;
Described auxiliary agent comprises that pH regulates auxiliary agent, secondary solvent;
Described free radical is produced by initator thermal decomposition.
2. according to claim 1 without fluoro water proofing agent, it is characterized in that, the functional group of described function monomer is selected from amino or hydroxyl or carboxyl or ketone carbonyl or epoxy radicals or trialkyl silyl or blocked isocyanate base or one and an above carbon-carbon double bond or has polyoxyethylene fragment or tertiary amine group or quaternary ammonium group or with one or more of chlorine element etc.
3. according to claim 2 without fluoro water proofing agent, it is characterized in that, described function monomer is selected from acrylamide, (methyl) acrylic acid hydroxypropyl (second) ester, (methyl) glycidyl acrylate, vinyltrimethoxy silane, diacetone acrylamide coordinates AH system, ethylene glycol dimethacrylate, trimethylolpropane tris (methyl) acrylate, divinylbenzene, (methyl) dimethylaminoethyl acrylate, (methoxyl group) polyethylene glycol (methyl) acrylate, (methyl) acrylyl oxy-ethyl-trimethyl salmiac, vinyl chloride, vinylidene chloride, one or more in 3-chlorine-2-hydroxyl-propyl methacrylate.
4. according to claim 1 without fluoro water proofing agent, it is characterized in that, described pH regulates auxiliary agent to comprise acid or alkali or amino acid, and makes without fluoro water proofing agent pH value between 4～7;
Described secondary solvent is selected from one or more of ethanol, acetone, isopropyl alcohol, propylene glycol, PEG200, dipropylene glycol, tripropylene glycol, four propylene glycol.
5. according to claim 1 without fluoro water proofing agent, it is characterized in that, described initator is selected from one or more in persulfate, oil-soluble azo-initiator or water-soluble azo class initator.
6. according to claim 5 without fluoro water proofing agent, it is characterized in that, described initator is selected from one or more in ammonium persulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride.
7. the preparation method without fluoro water proofing agent according to claim 1, is characterized in that, comprises the following steps:
(1) floride-free hydrophobic monomer, (modification) Tissuemat E, surfactant, auxiliary agent and water are mixed and emulsification, obtain pre-emulsion;
(2) pre-emulsion step (1) being obtained is adjusted to reaction temperature, adds function monomer and initiator for reaction, after reaction finishes, system temperature is down to room temperature, obtains target product after filtration.
8. a textiles, is characterized in that, adopts processing without fluoro water proofing agent described in any one in claim 1-5.
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| CN103835133A (en) * | 2014-03-18 | 2014-06-04 | 浙江理工大学 | Method for preparing fluorine-free super-hydrophobic textile surface |
| CN105088796A (en) * | 2015-09-11 | 2015-11-25 | 无锡市长安曙光手套厂 | Textile fluoride-free water-proofing agent, preparation method and application thereof |
| CN105178007A (en) * | 2015-10-15 | 2015-12-23 | 丹阳市宇晟纺织新材料有限公司 | Manufacturing method of waterproof acupuncture cotton |
| CN105671970A (en) * | 2016-03-16 | 2016-06-15 | 广州恒锦化工科技有限公司 | Fluoride-free water-proofing agent for textiles and preparation method of fluoride-free water-proofing agent |
| CN106087420A (en) * | 2016-06-07 | 2016-11-09 | 苏州联胜化学有限公司 | A kind of without fluoro water proofing agent and preparation method thereof |
| CN106661303A (en) * | 2014-07-04 | 2017-05-10 | 昂高知识产权有限公司 | Fluorine-free water-repellent composition |
| CN106637976A (en) * | 2016-11-29 | 2017-05-10 | 广东德美高新材料有限公司 | High-efficiency fluorine-free waterproof agent for cotton fabrics subjected to low-temperature dyeing and finishing processing |
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| CN108486874A (en) * | 2018-04-04 | 2018-09-04 | 佛山慧创正元新材料科技有限公司 | One kind floride-free waterproof coating gluing finishing agent used for textiles and preparation method thereof |
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| CN103835133B (en) * | 2014-03-18 | 2015-10-28 | 浙江理工大学 | A kind of method preparing floride-free super-hydrophobic fabric face |
| CN103835133A (en) * | 2014-03-18 | 2014-06-04 | 浙江理工大学 | Method for preparing fluorine-free super-hydrophobic textile surface |
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| CN105088796A (en) * | 2015-09-11 | 2015-11-25 | 无锡市长安曙光手套厂 | Textile fluoride-free water-proofing agent, preparation method and application thereof |
| CN105178007A (en) * | 2015-10-15 | 2015-12-23 | 丹阳市宇晟纺织新材料有限公司 | Manufacturing method of waterproof acupuncture cotton |
| CN106958146A (en) * | 2016-01-08 | 2017-07-18 | 东丽纤维研究所（中国）有限公司 | A kind of textile of process water repellent processing |
| CN105671970A (en) * | 2016-03-16 | 2016-06-15 | 广州恒锦化工科技有限公司 | Fluoride-free water-proofing agent for textiles and preparation method of fluoride-free water-proofing agent |
| CN107447523A (en) * | 2016-06-01 | 2017-12-08 | 东丽纤维研究所（中国）有限公司 | A kind of textile handled by water repellent |
| CN107447523B (en) * | 2016-06-01 | 2021-03-05 | 东丽纤维研究所（中国）有限公司 | Textile subjected to water repellent treatment |
| CN106087420A (en) * | 2016-06-07 | 2016-11-09 | 苏州联胜化学有限公司 | A kind of without fluoro water proofing agent and preparation method thereof |
| CN107587346A (en) * | 2016-07-08 | 2018-01-16 | 东丽酒伊织染（南通）有限公司 | A kind of floride-free water repellent fabric and its manufacture method |
| CN106637976A (en) * | 2016-11-29 | 2017-05-10 | 广东德美高新材料有限公司 | High-efficiency fluorine-free waterproof agent for cotton fabrics subjected to low-temperature dyeing and finishing processing |
| CN106637976B (en) * | 2016-11-29 | 2019-05-07 | 广东德美高新材料有限公司 | The cotton fabric high-efficient, no-freon waterproofing agent processed through low-temperature dyeing and finishing |
| CN109988264B (en) * | 2017-12-29 | 2022-03-04 | 乳源东阳光氟有限公司 | Fluorine-free waterproof agent and preparation method and application thereof |
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Application publication date: 20140212 |