CN106866872A - Water-proofing treatment composition dispersion liquid - Google Patents
Water-proofing treatment composition dispersion liquid Download PDFInfo
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- CN106866872A CN106866872A CN201710144408.XA CN201710144408A CN106866872A CN 106866872 A CN106866872 A CN 106866872A CN 201710144408 A CN201710144408 A CN 201710144408A CN 106866872 A CN106866872 A CN 106866872A
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- proofing treatment
- acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Abstract
The present invention announces a kind of water-proofing treatment combination dispersion liquid, contains：Non-fluorine acrylic polymer, the polymer contains at least C of more than 59wt%14~30The C of the acrylic ester unit of alkyl and at most 40wt%1~12The acrylic ester unit of alkyl, the cross-linking monomer unit also containing more than 1wt%；Contained R [Si (CH3)2O]x‑[Si(CH3)(R1)O]y‑Si(CH3)2Surface activator composition shown in R, wherein, R1It is the monovalent organic group containing polyether group, R is R1Or C1~4Alkyl, x, y be positive integer；Cosolvent；Water.Water-proofing treatment of the invention is good with composition dispersion stability, the not roll banding when bundle cloth was carried out after impregnating fabric, treated textile water-proof performance is excellent, and washability is good, and can preferably keep processing the original feel of fabric, in addition the Continuous maching function admirable of dispersion liquid.
Description
Technical field
The present invention announces a kind of water-proofing treatment composition dispersion liquid, belongs to fabric waterproof treatment auxiliary agent production technical field.
Background technology
Fluoropolymer has without comparable at aspects such as surface-active, Water-proof and oil-proof, antifouling, heat resistance and corrosion resistances
The advantage of plan, can assign product good water-repellent oil-repellent.However, this kind of fluoropolymer usually contains chain fluoroalkyl, especially
It is C8All-fluoroalkyl compound for PFOA or PFOS derivative, have persistence high and cumulative bad in the environment due to it,
In the presence of potential danger, thus especially developed country is severely limited in many countries.In addition, fluoropolymer price
Costly.Therefore, exploitation turns into development trend without fluoro water proofing agent.
Long chain alkane acrylate polymer has water proofing property, is often used to make waterproofing agent.Patent CN201080-
0095707 disclose it is a kind of by acrylic ester monomer, styrene or methyl styrene, vinylidene chloride and/or vinyl chloride, optionally
3- chlorine-2-hydroxyls propyl group (methyl) acrylate and/or glycidyl (methyl) acrylate constitute copolymer, have
The aqueous dispersion of 58 DEG C~80 DEG C paraffin of melting range, dispersant and water composition.Patent CN201310505870X disclose it is a kind of by
Floride-free hydrophobic polymer, (modified) Tissuemat E, surfactant, auxiliary agent and water composition without fluoro water proofing agent.Patent
CN2015105776865 discloses a kind of nothing being made up of fluorine free polymer, polyurethane, paraffin, surfactant, auxiliary agent and water
Fluoro water proofing agent.Patent CN201510729297X discloses a kind of by fluorine free polymer, (modified) Tissuemat E, chemical modification
Shitosan, auxiliary agent and water composition without fluoro water proofing agent.There is xanthochromia due to the presence of paraffin, treated fabric in above-mentioned waterproofing agent
Problem；(modified) Tissuemat E can make xanthochromia problem make moderate progress, but xanthochromia is still present.In addition, above-mentioned waterproofing agent is in upper machine
During production, also there is roll banding phenomenon, waterproof effect also awaits further improvement, and treated fabric feeling is more puckery.
Patent CN2015109014343 disclose one kind by hydrophobic (methyl) acrylate copolymer of core-shell type, help emulsification
The environment-friendly type hydrophobic finishing agent composition of agent, emulsifying agent and organic alcohol solvent composition.Patent CN2014-800636903 is disclosed
It is a kind of by the non-fluorinated polymer with long-chain (methyl) acrylate monomer repeat unit, with one of amide groups and amino or
Both surface active cpds, and the surface conditioning agent that aqueous liquid medium is constituted.Above-mentioned waterproofing agent equally exists roll banding
Phenomenon, treated fabric feeling is more puckery, and waterproof effect also awaits further improvement.
The content of the invention
It is an object of the invention to provide a kind of water-proofing treatment composition dispersion liquid, the dispersion liquid not fluoride, comprising
Silicon-containing compound, its water resistance is excellent, and washability is good, and the original feel of fabric is maintained substantially.
To achieve these goals, present invention employs following technical scheme：
A kind of water-proofing treatment composition dispersion liquid, not including fluorochemical, comprising silicon-containing compound, contains：
1) non-fluorine acrylic polymer, the polymer contain at least 59wt% (wt% is mass percent, under
C more than together)14~30The C of the acrylic ester unit of alkyl and at most 40wt%1~12The acrylic ester unit of alkyl, also contains
The cross-linking monomer unit of more than 1wt%；
2) surface activator composition shown in contained (1)
R-[Si(CH3)2O]x-[Si(CH3)(R1)O]y-Si(CH3)2R formulas (1)
Wherein, R1It is the monovalent organic group containing polyether group, R is R1Or C1~4Alkyl, x, y be positive integer；
3) cosolvent；
4) water.
Described C14~30The acrylate of alkyl is preferably (methyl) octadecyl acrylate, (methyl) acrylic acid 22
One kind or its mixture in ester etc., described C1~12The acrylate of alkyl is preferably (methyl) dodecyl acrylate, (first
Base) one kind in tert-butyl acrylate etc. or its mixture.
Described cross-linking monomer is selected from N hydroxymethyl acrylamide, methacrylic acid urea groups ester, DAAM, third
One kind in olefin(e) acid hydroxyl ethyl ester, glycidyl acrylate, 3- chlorine-2-hydroxyl-propyl methacrylates etc..
Further, described cross-linking monomer is preferably hydroxy-ethyl acrylate.
Described surface activator composition preferably comprises H (OCH2CH2)nOCH2CH2CH2Si(CH3)2O[Si(CH3)2O]mSi(CH3)2CH2CH2CH2O(CH2CH2O)nH、(CH3)3SiO[Si(CH3)2O]x[Si(CH3)(CH2CH2CH2O(CH2CH2O)nH)
O]ySi(CH3)3In one kind, wherein m, x, y be positive integer, n is the integer more than or equal to 4.
Described cosolvent is selected from one kind or its mixing in acetone, isopropanol, triethylene glycol, DPG, glycerine etc..
Further, described cosolvent is preferably triethylene glycol.
Disperseed with composition dispersion liquid and fluoropolymer it is a further object of the present invention to provide a kind of foregoing water-proofing treatment
The compound emulsion of liquid.
It is yet another object of the invention to provide a kind of method of fabric treating, the method includes using water-proofing treatment of the invention
With composition dispersion liquid or its fabric is processed with the compound emulsion of fluoropolymer dispersion liquid the step of.
Another object of the present invention be to provide it is a kind of by water-proofing treatment composition dispersion liquid of the invention or its with it is fluorine-containing
The treated textile article of the compound emulsion of polymer dispersion liquid.
Water-proofing treatment of the invention composition dispersion liquid, not including fluorochemical, comprising silicon-containing compound, containing non-
Perfluoroalkyl acrylate esters polymer, silicon-containing surfactant composition, cosolvent and water.
Non-fluorine acrylic polymer contains at least C of more than 59wt%14~18The acrylic ester unit of alkyl and at most
The C of 40wt%1~12The acrylic ester unit of alkyl, the cross-linking monomer unit also containing more than 1wt%.
The C14~30The acrylic ester unit of alkyl such as (methyl) tetradecyl acrylate, (methyl) Process Conditions of Cetane Acrylate,
(methyl) octadecyl acrylate, (methyl) Behenyl acrylate etc., wherein being preferably (methyl) octadecyl acrylate, (methyl)
One kind in Behenyl acrylate etc. mixes its mixture.
Described C1~12The acrylic ester unit of alkyl such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (first
Base) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) the just own ester of acrylic acid, 2-Ethylhexyl Methacrylate, (first
Base) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) isodecyl acrylate, (methyl) dodecyl acrylate, (first
Base) cyclohexyl acrylate, (methyl) phenyl acrylate, isobornyl acrylate etc., wherein being preferably (methyl) acrylic acid 12
One kind in ester, (methyl) tert-butyl acrylate.
Usual C14And the long chain acrylate of the above can assign polymer water-repellancy, and C12And following short chain propylene
Acid esters can adjust the filming performance and film forming feel of polymer, improve the water resistance of polymer.
The non-fluorine acrylic polymer also cross-linking monomer unit containing active group, the monomer is not fluorine-containing.Hand over
Receipts or other documents in duplicate body is usually the monomer for having reaction active groups containing carbon-carbon double bond and at least one, and the group with reactivity is such as
Oh group, epoxide group, isocyanate groups or blocked isocyanate groups, amino etc., but can not be the work of anionic
Property group, such as carboxyl.Such monomer has hydroxy-ethyl acrylate, 3- chlorine-2-hydroxyl-propyls methacrylate, allyl alcohol, alkene
Propyl hydroxy ethylether, N hydroxymethyl acrylamide, glycidyl acrylate, allyl iso cyanurate, isocyanates propylene
Acetoacetic ester, (methyl) acrylamide, methacrylic acid urea groups ester, DAAM etc..
Non-fluorine acrylic polymer can also be containing except C14~18The acrylate of alkyl, C1~12The acrylic acid of alkyl
Other non-fluorine monomer units beyond ester and cross-linking monomer, such as styrene, chlorostyrene, AMS, vinyl chloride, partially
Vinyl chloride etc..
Cross-linking monomer unit and other monomeric units are connected or by by heat by chemical bond with treatment fabric formation
Pressure acts on bonding or by improve the characteristic of film forming matter the to form stronger attachment stronger with treatment fabric, improves treatment
The washing fastness of fabric.
Surface activator composition contains the compound shown in formula (1)
R-[Si(CH3)2O]x-[Si(CH3)(R1)O]y-Si(CH3)2R formulas (1)
Wherein, R1It is that, to the monovalent organic group containing polyether group, R is R1Or C1~4Alkyl, x, y be positive integer.Contain
There are the monovalent organic group such as-CH of polyether group2CH2CH2O(CH2CH2O)nH、-CH2CH2COO(CH2CH2O)nH、-CH2CH
(CH3)COO(CH2CH2O)nH、-CH2CH2COO(CH(CH3)CH2O)l(CH2CH2O)nH、-CH2CH2CH2NHCH2CH(CH3)COO
(CH2CH2O)nH、-CH2CH2CH2NHCH2CH(CH3)COO(CH(CH3)CH2O)l(CH2CH2O)nH、-CH2CH2CH2N[(CH2)6]
[CH2CH(CH3)COO(CH2CH2O)nH], wherein n, l are the integer more than or equal to 4.Surfactant as shown in formula (1) can be with
By containing hydrogen silicone oil and CH2=CHCH2O(CH2CH2O)nH、CH2=CHCOO (CH2CH2O)nH、CH2=C (CH3)COO(CH2CH2O)nH
Prepared through Si―H addition reaction Deng hydroxyl monomer, or by amido silicon oil and CH2=C (CH3)COO(CH2CH2O)nThe hydroxyl monomer such as H
Prepared through Michael addition reaction.Surfactant shown in formula (1) can be added before polymerisation, be played to combination of monomers
The effect of thing emulsification；Can also after polymerization add, play a part of auxiliary stabilization polymeric latex particle.In addition, formula (1)
Shown surfactant cooperates with non-fluorine acrylic polymer, further increases the water resistance of composition,
And can effectively overcome prick cloth when roll banding phenomenon.Its addition typically constitutes from the 1%~10% of polymer quality fraction.
Surface activator composition preferably comprises H (OCH2CH2)nOCH2CH2CH2Si(CH3)2O[Si(CH3)2O]mSi
(CH3)2CH2CH2CH2O(CH2CH2O)nH、(CH3)3SiO[Si(CH3)2O]x[Si(CH3)(CH2CH2CH2O(CH2CH2O)nH)O]ySi(CH3)3In one kind, wherein m, x, y be positive integer, n is the integer more than or equal to 4.
Surfactant of the surface activator composition also containing other silicon-containing surfactants or non-silicon non-fluorine, other contain
Silicon surface active agent preferred cationic type or amphoteric surfactant, the preferred nonionic of surfactant of non-silicon non-fluorine, sun
Ionic or amphoteric surfactant.The non-fluorine-type nonionic surfactant of non-silicon usually contains non-perfluoroalkyl polyether and/or polyhydroxy
The hydrophilic section of group and the hydrophobic section of non-fluorine alkyl, hydrophilic section and hydrophobic section are by connections, polyethers such as ester strong, ehter bond, nitrogen-atoms
Group and polyhydroxy group are connected by ehter bond.Nonionic surfactant can be listed below：This disk series (S-80, S-40
Deng), TWEEN Series (T-60, T-20 etc.), AEO/polyethenoxy ether (AEO-5, AEO-9, AEO-15, isomery
Alcohol ether E-1306 etc.), aliphatic acid polyethenoxy/polyoxypropylene ester (LAE-9, polyoxyethylene oleate A-105, SG-100 etc.),
Aliphatic amine polyoxyethylene ether (AC-1810, AC-1820 etc.).Non-silicon non-fluorine cationic surfactant usually contains quaternary ammonium salt sun
The hydrophilic section of ionic group and the hydrophobic section of non-fluorine alkyl, such as hexadecyltrimethylammonium chloride, octadecyl trimethyl chlorination
Ammonium etc..Non-silicon non-fluorine amphoteric surfactant such as betaine type amphoteric surfactant etc..
Cosolvent is selected from organic solvent miscible with water, such as acetone, isopropanol, glycerine, ethylene glycol, propane diols, fourth two
Alcohol, DPG, diethylene glycol, triethylene glycol, tripropylene glycol, 5- decine -4,7- glycol -2,4,7,9- tetramethyls, 3- methoxies
One kind or its mixing in base -3- methyl-1-butanols etc., its consumption are preferably more than the 3% of monomer mass consumption.Described helps
Solvent is preferably triethylene glycol.
Water-proofing treatment composition dispersion liquid of the invention can directly be prepared by emulsion polymerization, it is also possible to by molten
Liquid copolymerization method obtains non-fluorine acrylic polymer and adds water emulsification removing solvent and obtain, and preferably directly passes through emulsion polymerization
Method is obtained.
Emulsion polymerization is in the presence of emulsifying agent, monomer is emulsified in water, then heats to 50~95 DEG C of reaction temperature
Degree stirring polyase 13~15h.Polymerization can use oil-soluble initiator or water soluble starter.Oil-soluble initiator such as azo
Azodiisobutyronitrile, benzoyl peroxide, the di-tert-butyl peroxide of peroxide etc..Water soluble starter such as persulfuric acid
Potassium, ammonium persulfate, sodium peroxydisulfate, azo diisobutyl ether hydrochloride, hydrogen peroxide, 3- carboxyl acrylic peroxide etc..Relatively
In the monomer of 100 mass parts, initiator amount is 0.05~5wt%.When from oil-soluble initiator, preferably initiator is added
To enter emulsified again in monomer；But during from water soluble starter, preferably after monomer emulsification, add initiator.In addition, adopting
When using water soluble starter, but when containing cationic emulsifier in emulsifying agent, initiator preferred cationic type or nonionic.
In order to be uniformly dispersed, the good dispersion liquid of storage stability, preferably emulsify laggard stepping horizontal high voltage in monomer
Homogeneous, ultrasonication or height press through the treatment such as film.Above-mentioned processing equipment can produce the crushing energy of intensity, monomer droplets to enter one
Step miniaturization, and stability enhancing.
Chain-transferring agent can also be added in polymerization system, to adjust the size of polymer molecular weight.Chain-transferring agent may be selected from
Alkyl thiol compound such as butanethiol, octyl mercaptan, 2 mercapto ethanol, lauryl mercaptan etc., or sodium hypophosphite, sulfurous acid
The inorganic salts such as hydrogen sodium, wherein preferably lauryl mercaptan.Its consumption elects the 0.1~3% of monomer mass consumption as.
PH conditioning agents, such as acetic acid, sodium acetate, acetic acid can also be added before polymerization or in the backward system that is polymerized as needed
Ammonium, hydrochloric acid, phosphoric acid, potassium dihydrogen phosphate, disodium hydrogen phosphate etc..
Water-proofing treatment composition dispersion liquid of the invention can be used alone, it is also possible to match somebody with somebody with other water-proofing treatment liquid
Conjunction is used.Other water-proofing treatment liquid can be that floride-free water-proofing treatment liquid can also be fluorine-containing water-proofing treatment liquid, but should ensure that with
The treatment fluid of dispersion liquid of the invention compounding is kept always on ionic, otherwise may compositional liquor may precipitate.
Water-proofing treatment composition dispersion liquid of the invention can be acted on processed fabric using conventional method.It is logical
It is often as follows：By dispersion liquid dilute with water, then it is that treatment fluid is attached on fabric by methods such as dip coated, spraying coatings, knits
Thing through overvoltage prick, high temperature drying processed after fabric.In addition, can also be compounded in treatment fluid into blocked isocyanate crosslinking
Agent emulsion, pricks in pressure and crosslinking is produced after high-temperature process, washability is further improved.Softness can also as needed be added
Other auxiliary agents such as agent, preservative.Composition can be generally diluted to 0.03~3% mass concentration.
The fabric that can be processed with fabric waterproof composition for treating dispersion liquid of the invention, can be listed below：Natural fiber
Fabric (cotton fibre, fiber crops, animal fur etc.), synthetic fabrics (polyester fiber, Fypro, polyster fibre, polyvinyl alcohol,
Polyacrylonitrile, polyvinyl chloride, polypropylene etc.), semisynthetic fibre fabric (artificial silk, acetate fiber etc.), inorganic fibre fabric (glass
Glass fiber, carbon fiber, asbestos fibre etc.), or their composite fibre fabric.
The present invention is by adopting the above-described technical solution, have the advantages that：
Water-proofing treatment of the invention composition dispersion liquid good emulsion stability, when bundle cloth was carried out after impregnating fabric not
Roll banding, treated textile water-proof performance is excellent, and washability is good, and can preferably keep processing the original feel of fabric, separately
The Continuous maching function admirable of outer dispersion liquid.
Specific embodiment
Sample preparation
Dispersion liquid is diluted to 0.5% concentration, then test fabric cloth is processed, then pressed with press
Prick, 150 DEG C of temperature heat treatment cloth 2 minutes, that is, obtain test sample afterwards.
Method of testing
(1) waterproofing tests
Waterproofing property evaluation standard is pressed GB/T 4745-1997 textile fabrics surface moisture resistance and determines dip experiment execution, refers to table 1；
The waterproofing property evaluation standard of table 1：GB/T 4745-1997 textile fabrics surface moisture resistance determines dip experiment.
| Classification of waterproof | State |
| 5 | Surface is without moistening |
| 4 | Surface moistens on a small quantity |
| 3 | Surface portion is moistened |
| 2 | Surface wettability |
| 1 | Surface all moistens |
(2) washing fastness test
Washed by the decantation test method in GB 12799-91 oil resistant water resistant protective garment safety and sanitation performance requirements,
Then waterproofing tests are carried out again.
(3) Continuous maching performance test
The dispersion liquid that 1Kg concentration is 0.5% is prepared, by pending Cloth Cutting into 20cm × 20cm sizes, according to sample
Preparation method first piece cloth is processed, afterwards at after the same method successively to the 2nd~6 cloth
Reason.And every cloth water resistance is tested, by the Continuous maching of waterproof property evaluation dispersion liquid.
The synthesis of surfactant shown in formula (1)
H(OCH2CH2)nOCH2CH2CH2Si(CH3)2O[Si(CH3)2]mSi(CH3)2CH2CH2CH2O(CH2CH2O)nH (surfaces
Activating agent a) is by HSi (CH3)2O[Si(CH3)2O]mSiH and CH2=CHCH2O(CH2CH2O)nH Si―H addition reactions are formed, and wherein m is about
It is that 30, n is about 15.
(CH3)3SiO[Si(CH3)2O]x[Si(CH3)(CH2CH2CH2O(CH2CH2O)nH)O]ySi(CH3)3(surfactant
B) by (CH3)3SiO[Si(CH3)2O]x[SiH(CH3)O]ySi(CH3)3With CH2=CHCH2O(CH2CH2O)nH Si―H addition reactions are formed,
Wherein x is about 25, y and is about 7, n and is about 15.
Embodiment 1
By 70 mass parts octadecyl acrylates, 27 mass parts dodecyl acrylates, 3 mass parts hydroxy-ethyl acrylates, 5 matter
Amount part triethylene glycol, 4 mass parts AEO-9, the E-1306 of 2 mass parts, 1 mass parts AC-1810,3 mass parts octadecyl front threes
Ammonium chloride, 5 mass of surface activating agent a, 0.5 mass parts acetic acid and 210 mass parts water add reactor, are warming up to 40~45
DEG C carry out pre-emulsification.Then high-pressure homogeneous 30 minutes under the pressure of 30MPa, homogenizing fluid is transferred to reactor, opens stirring.
Formation adds reactor with solution during 0.5 mass parts initiator A IBA to be incorporated the water of 2 mass parts.Then heat to 70~
75 DEG C of reaction 5h, obtain water-proofing treatment composition dispersion liquid of the invention.
Embodiment 2
Using technique same as Example 1, Ju Ti Pei Fang refers to table 2.
Embodiment 3
By 60 mass parts octadecyl methacrylates, the diester of methacrylic acid 20 of 10 mass parts, 10 mass parts methyl
Dodecyl acrylate, 10 mass parts Tert-butyl Methacrylates, 3 mass parts hydroxy-ethyl acrylates, 10 mass parts triethylene glycols,
5.5 mass parts AEO-9,3 mass parts E-1306,1.5 mass parts AC-1810,0.5 mass parts acetic acid and 210 mass parts water are added
Reactor, being warming up to 40~45 DEG C carries out pre-emulsification.Then high-pressure homogeneous 30 minutes under the pressure of 30MPa, homogenizing fluid is turned
Reactor is moved to, stirring is opened.Formation is added anti-with solution during 0.5 mass parts initiator A IBA to be incorporated the water of 2 mass parts
Answer kettle.70 DEG C of beginning clock reactions are then heated to, and starts to be passed through the vinyl chloride of 7 mass parts in rear 1h in reaction.Continue poly-
Reaction 5h is closed, then adds the surfactant a such as 1 mass parts, obtain water-proofing treatment composition dispersion liquid of the invention.
Embodiment 4~6
Using technique same as Example 3, the addition opportunity of Ju Ti Pei Fang and surfactant a, b refers to table 2.
The technical recipe table of table 2 (being mass fraction in table)
AIBA is azo diisobutyl amidine hydrochloride；" preceding " is added before referring to reaction, and " afterwards " refers to addition after reaction.
Comparative example 1~6
Wherein comparative example 1~3 and 5 uses technique same as Example 1, and comparative example 4 and 6 is using same as Example 3
Technique, the addition opportunity of Ju Ti Pei Fang and surfactant a, b refers to table 3.
The technical recipe table of table 3 (being mass fraction in table)
AIBA is azo diisobutyl amidine hydrochloride；" preceding " is added before referring to reaction, and " afterwards " refers to addition after reaction.
The Continuous maching of table 4 is evaluated
Embodiment 7
By 40 mass parts perfluorooctylethyl group acrylate, 20 mass parts octadecyl methacrylates, 10 mass parts first
Base Behenyl acrylate, 10 mass parts lauryl methacrylates, 10 mass parts Tert-butyl Methacrylates, 3 mass parts third
Olefin(e) acid hydroxyl ethyl ester, 10 mass parts triethylene glycols, 5.5 mass parts AEO-9,3 mass parts E-1306,1.5 mass parts AC-1810,0.5
Mass parts acetic acid and 210 mass parts water add reactor, and being warming up to 40~45 DEG C carries out pre-emulsification.Then in the pressure of 30MPa
Under high-pressure homogeneous 30 minutes, homogenizing fluid is transferred to reactor, open stirring.0.5 mass parts initiator A IBA is incorporated into 2 mass
Formed in the water of part with solution, add reactor.70 DEG C of beginning clock reactions are then heated to, and is started in rear 1h in reaction
It is passed through the vinyl chloride of 7 mass parts.Continue polymerisation 5h, obtain water-proofing treatment fluoro-containing composition dispersion liquid.
The compound property of table 5 and fluorine-containing water repellent
Note：Development of evil in febrile disease 528A is the fluorine-containing water repellent of development of evil in febrile disease group production, and great Jin 581 is the fluorine-containing waterproof of big King Company production
Agent.
Specific embodiment of the invention is these are only, but technical characteristic of the invention is not limited thereto.It is any with this hair
It is to solve essentially identical technical problem based on bright, realizes essentially identical technique effect, done ground simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (10)
1. a kind of water-proofing treatment composition dispersion liquid, not including fluorochemical, comprising silicon-containing compound, it is characterised in that
Contain：
1) non-fluorine acrylic polymer, the polymer contains at least C of more than 59wt%14~30The acrylate list of alkyl
Unit and the at most C of 40wt%1~12The acrylic ester unit of alkyl, the cross-linking monomer unit also containing more than 1wt%；
2) surface activator composition shown in contained (1)
R-[Si(CH3)2O]x-[Si(CH3)(R1)O]y-Si(CH3)2R formulas (1)
Wherein, R1It is the monovalent organic group containing polyether group, R is R1Or C1~4Alkyl, x, y be positive integer；
3) cosolvent；
4) water.
2. fabric waterproof composition for treating dispersion liquid according to claim 1, it is characterised in that：Described C14~30Alkyl
Acrylate be preferably one kind or its mixture in (methyl) octadecyl acrylate, (methyl) Behenyl acrylate etc.,
Described C1~12The acrylate of alkyl is preferably the one kind in (methyl) dodecyl acrylate, (methyl) tert-butyl acrylate etc.
Or its mixture.
3. water-proofing treatment according to claim 1 composition dispersion liquid, it is characterised in that：Described cross-linking monomer is selected from
N hydroxymethyl acrylamide, methacrylic acid urea groups ester, DAAM, hydroxy-ethyl acrylate, glycidyl
One kind in ester, 3- chlorine-2-hydroxyl-propyl methacrylates etc..
4. water-proofing treatment according to claim 3 composition dispersion liquid, it is characterised in that：Described cross-linking monomer is preferred
It is hydroxy-ethyl acrylate.
5. water-proofing treatment according to claim 1 composition dispersion liquid, it is characterised in that：Described surfactant group
Compound preferably comprises H (OCH2CH2)nOCH2CH2CH2Si(CH3)2O[Si(CH3)2O]mSi(CH3)2CH2CH2CH2O(CH2CH2O)nH、(CH3)3SiO[Si(CH3)2O]x[Si(CH3)(CH2CH2CH2O(CH2CH2O)nH)O]ySi(CH3)3In one kind, wherein m,
X, y are positive integer, and n is the integer more than or equal to 4.
6. water-proofing treatment according to claim 1 composition dispersion liquid, it is characterised in that：Described cosolvent is selected from third
One kind or its mixing in ketone, isopropanol, triethylene glycol, DPG, glycerine etc..
7. water-proofing treatment according to claim 6 composition dispersion liquid, it is characterised in that：Described cosolvent is preferably
Triethylene glycol.
8. a kind of water-proofing treatment comprising described in any one of claim 1~7 compound emulsion of composition dispersion liquid, its feature
It is：The compound emulsion also includes fluoropolymer dispersion liquid.
9. a kind of method that fabric waterproof is processed, it is characterised in that：The processing method is included with any one of claim 1~8 institute
The step of water-proofing treatment composition dispersion liquid stated is processed fabric.
10. a kind of by any one of the claim 1~8 water-proofing treatment treated textile article of composition dispersion liquid.
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| CN110685154A (en) * | 2018-07-05 | 2020-01-14 | 京准化工技术(上海)有限公司 | Washable fluoride-free waterproof processing finishing agent |
| CN112029294A (en) * | 2020-09-11 | 2020-12-04 | 宁波俊瑆玩具科技有限公司 | Waterproof particle and application thereof |
| CN114316118A (en) * | 2020-09-30 | 2022-04-12 | 四川赛华睿科技有限责任公司 | Oil-repellent agent and oil-repellent paper product |
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| CN110485159A (en) * | 2017-10-24 | 2019-11-22 | 广东德美精细化工集团股份有限公司 | The preparation method of high-efficient, no-freon waterproofing agent comprising telechelic polymer |
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| CN109281172A (en) * | 2018-08-15 | 2019-01-29 | 浙江理工大学 | Hud typed free-floride water-proof aagent and its preparation method and application |
| CN112029294A (en) * | 2020-09-11 | 2020-12-04 | 宁波俊瑆玩具科技有限公司 | Waterproof particle and application thereof |
| CN114316118A (en) * | 2020-09-30 | 2022-04-12 | 四川赛华睿科技有限责任公司 | Oil-repellent agent and oil-repellent paper product |
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