CN1127536A - Fiber product processing method - Google Patents
Fiber product processing method Download PDFInfo
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- CN1127536A CN1127536A CN94192838A CN94192838A CN1127536A CN 1127536 A CN1127536 A CN 1127536A CN 94192838 A CN94192838 A CN 94192838A CN 94192838 A CN94192838 A CN 94192838A CN 1127536 A CN1127536 A CN 1127536A
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- 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
-
- 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
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
-
- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3564—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing phosphorus
-
- 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
A fiber product processing method for providing a fiber product with water and oil repellency by treating a fiber product with an at least divalent metal salt, and then treating the resultant product with a hydrophilic functional group-containing fluoropolymer capable of coordinating with that metal. The method is capable of stably providing a fiber product with high initial water and oil repellency and high permanent water and oil repellency.
Description
Utilize the field on the industry
The present invention relates to fiber product processing method.In more detail, relate to fibre, can give the fiber product processing method of anti-water grease resistance of excellent initial and durable anti-water grease resistance when especially the modification of hydrophilic fibre goods is handled.
Prior art
Known that fluorochemical demonstrates the excellent properties as water-and oil-repellent agent.Especially, the finishing agent of making from the polymer of vinyl monomer that contains fluoroalkyl can be for practical.Though this base polymer also has the situation of the homopolymers of the vinyl monomer that contains fluoroalkyl, as a rule, be that copolymer constitutes by being vinyl monomer with various non-fluorine.Non-fluorine used herein is in the vinyl monomer, also comprises showing hydrophilic monomer, for example, has described the water-and oil-repellent agent of making from monomer that contains phosphate and the vinyl monomer that contains perfluoroalkyl in the public clear 62-47466 communique of spy.Yet, under situation about using with the copolymer of the hydrophilic ethylene base monomers such as monomer that contain phosphate, because the polymer that the electrical property of its hydrophily or functional group causes is charged, is difficult to especially be attached on hydrophilic fibre goods such as the nylon, thereby can not gives full play to anti-water oil-resistant characteristic.
The invention main points
The objective of the invention is to give fibre by the stabilisation that the performance of the anti-oil of the anti-water of fluoropolymer is brought into play, especially the hydrophilic fibre goods are with anti-water grease resistance of excellent initial and durable anti-water grease resistance.
One aspect of the present invention provides the processing method of fibre, it is characterized in that fibre handles with the above slaine of divalent earlier, then with contain can with the hydrophily functional group's of this metal-complexing fluoropolymer treated.
Another aspect of the present invention provides the fibre with this disposal methods.
Detailed description of the invention
In this manual, so-called " processing " means the treatment fluid that contains slaine or fluoropolymer is contacted with fibre." processing " comprises dipping, soaks into, pad dyeing method, rubbing method.
The hydrophilic functional group better is the group of selecting from be made up of phosphate and sulfonic group a group.
Fluoropolymer better is the polymer that is made of following:
(a) from the repetitive of fluorine-containing ethylenic monomer derived and
(b) from the repetitive that contains the acidic group monomer derived shown in the following general formula,
R in the formula
1Be hydrogen atom or methyl,
R
2Be following alkylidene of 6 carbon or the alkylidene that replacement is arranged, or the divalent group that is formed by connecting such as these groups and ether, ester group, amide groups,
X is PO or SO
2,
M is hydrogen or alkali metal atom,
When X was PO, p was 1, and n, m are 1 or 2, and n+m=3:X is-SO
2In-time, p is 0, n=m=1 and
(c) if necessary, can exist and never contain that the non-fluorine of any group is the repetitive of monomer derived in phosphate or the sulfonic group,
But composition (b) and total amount (c) for 100 weight portion compositions (a) below 100 weight portions.
Fluorine-containing vinyl monomer (a) is the compound that has Polyfluoroalkyl (especially perfluoroalkyl) or polyfluoroolefins base (especially perfluorinated alkenyl) and polymerism unsaturated double-bond (especially carbon-carbon double bond) simultaneously.As the example of fluorine-containing vinyl monomer (a), can enumerate following compounds:
R in the formula
11Be hydrogen or methyl, R
12Be low alkyl group, X is a divalent organic group, and m is 1～4 integer, and n is 5～21 integer.
R
12Carbon number normally 1～6.X is such as the low alkyl group of the alkylene oxide group of 1～10 carbon, oxygen atom, sulphur atom, 1～6 carbon atom amino that replace or that do not have replacement etc.
The monomer (b) that contains acidic group is an anionic, have can with the functional group of metal-complexing.This functional group is especially phosphate, sulfonic group preferably.As the instantiation of the monomer that contains acidic group (b), can enumerate following compounds:
Acid phosphoric acid-(acrylic acid 2-hydroxy methacrylate) ester,
Acid phosphoric acid-(2-hydroxyethyl methacrylate) ester,
Acid phosphoric acid-(acrylic acid 2-hydroxy propyl ester) ester sodium salt,
Acid phosphoric acid-(methacrylic acid 3-hydroxy propyl ester) ester,
Acid phosphoric acid-(allyl alcohol) ester,
Acid phosphoric acid-(methacrylic acid 3-chloro-2-hydroxy propyl ester) ester,
Acid phosphoric acid-(2-hydroxyethyl vinethene) ester,
Acid phosphoric acid-(3-hydroxypropyl Methacrylamide) ester,
Acid phosphoric acid-(acrylic acid 2-hydroxy methacrylate) ester,
2-acrylamido-2-methyl propane sulfonic acid,
2-methacryl amido-2-ethyl propane sulfonic acid,
2-acrylamido fourth sulfonic acid and
2-(acryloyl group carbonyl oxygen base) ethyl sulfonic acid etc.
Fluorine-containing vinyl monomer (a) and the copolymerization ratio that contains acidic group monomer (b) can produce dysgenic scope at non-confrontational water oil-resistant characteristic.With respect to 100 parts of (weight) fluorine-containing vinyl monomers (a), the amount that contains acidic group monomer (b) below 50 parts (weight), better is 0.2～30 part (weight) normally.
In addition, fluoropolymer can also contain that any non-fluorine is monomer (c) at least a not phosphorous acidic group or the sulfonic group.With respect to 100 parts of (weight) fluorine-containing vinyl monomers (a), non-fluorine is that the amount of monomer (c) is below 100 parts (weight), better is 0～50 part (weight).
Non-fluorine is that the instantiation of monomer (c) comprising:
Ethene, propylene, isobutene, 3-chloro-1-isobutene, butadiene, isoprene, chlorine and dichloroprene, 2,5-dimethyl-1, the halo or the non-halogenated hydrocarbons of rudimentary chain alkenes such as 5-hexadiene, Diisobutylene;
Vinyl or allyl or vinylidene halides such as vinyl chloride or vinylidene chloride, PVF or vinylidene fluoride, allyl bromide, bromoallylene and methylallyl chloride;
Styrene and styrene derivatives such as vinyltoluene, α-Jia Jibenyixi, alpha-cyano methyl styrene, divinylbenzene and N-vinyl card azoles;
Vinyl acetate such as the vinyl acetate of the acid of vinyl acetate, propionate, known commodity " Versatic Acids " by name, isobutyric acid vinyl acetate, senecioic acid vinyl acetate, butanedioic acid vinyl acetate, isodecyl vinyl acetate, stearic acid vinyl ester, divinyl carbonate;
Allyl ester such as allyl acetate and allyl heptanoate;
Halos such as cetyl vinethene, dodecyl vinethene, isobutylvinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, tetraene propoxyl group ethane or do not have the haloalkyl vinethene or the alkyl allyl ether;
Vinyl alkyl ketone such as vinyl ketone;
Acrylic acid, methacrylic acid, α-Lv Bingxisuan, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, unsaturated acids such as senecioic acid, its acid anhydrides and ester thereof, for example vinyl acetate, allyl ester, methyl esters, butyl ester, isobutyl ester, own ester, heptyl ester, the 2-Octyl Nitrite, cyclohexyl, lauryl, the octadecane ester, or acrylic acid and methacrylic acid 2-isocyanato ethyl, dimethyl maleate, ethyl crotonate, maleic acid one methyl esters, monobutyl itaconate, two (acrylic acid) and two (methacrylic acid) diol esters or poly-(alkylidene) diol esters such as two (methacrylic acid) glycol esters or triethyleneglycol ester, methacryloxypropyl trimethoxy monosilane;
Alpha-cyanoacrylate alkane ester, three acryloyls, six hydrogen-s-triazine, vinyltrichlorosilane, vinyl trimethoxy monosilane, vinyl triethoxyl monosilane and N-vinyl-2-Pyrrolidones such as acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, acrylic or methacrylic acid 2-cyano group ethyl ester, methylene glutaronitrile, ethenylidene dintrile, alpha-cyanoacrylate isopropyl ester;
One acrylic acid glycol ester, acrylic acid and hydroxyalkyl methacrylates such as monomethyl propylene ester propylene glycol ester, the acrylate and the methacrylate of poly-(alkylidene) glycol, allyl alcohol, the allyl alcohol acid esters, the isobutene glycol, allyloxyethanol, o-allyl phenol, divinyl methyl alcohol, glycerine α-allyl ether, acrylamide, Methacrylamide, maleic amide and maleimide, N-(cyanoethyl) acrylamide, the N-N-isopropylacrylamide, diacetone acrylamide, N-(methylol) acrylamide and N-(methylol) Methacrylamide, N-(alkoxyl-methyl) acrylamide and N-(alkoxyl-methyl) Methacrylamide, the glyoxal bisacrylamide that contracts, acrylic or methacrylic acid sodium, vinyl sulfonic acid and styrene p-sulfonic acid and alkali metal salt thereof, the amino crotonic nitrile of 3-, one allylamine, vinylpyridine, the acrylic or methacrylic acid glycidyl ester, allyl glycidyl ether, acrolein and methacrylic acid N, N-dimethylamino ethyl ester or N-tert-butyl group amino ethyl ester etc.
The preparation method of fluoropolymer is not particularly limited, and can obtain with methods such as the polymerisation in solution of general use, emulsion polymerisations.Can use radical initiator during polymerization.The molecular weight of fluoropolymer of the present invention normally 1,000～1,000,000.
So-called slaine is handled, and means impregnation of fibers goods in the solution of the salt that contains the above metal of divalent, is used as the phase I processing in the present invention.Preferred metal is chromium, zirconium, titanium, aluminium etc.Preferred metal salt is sulfate, nitrate, chloride etc.Even in the middle of these slaines, from the strong especially this point of anionic functional group's adhesion, especially recommend chromium sulfate basic.
Better embodiment of the present invention is impregnation of fibers goods in the liquid (20～70 ℃ of liquid temperature) at metalline, in this case pH is adjusted to 5～7, is more preferably 5.5～6.5, washes then.The metal saline solution is that slaine content is 0.01～50% (weight) of fibre weight, the aqueous solution or the water slurry of better 0.5～10% (weight).The dip time of fibre more than 10 seconds, better is 1～120 minute normally.PH adjusts and carries out with sodium acetate, sodium formate, sodium bicarbonate etc.
After this, having carried out dry fibre handles with fluoropolymer.With fluoropolymer treated is that second stage among the present invention is handled, and can be when handling with prior art same method for example, is carried out with impregnating method, pad dyeing method or rubbing method etc., then drying.
In addition, after slaine is handled, also can carry out fluoropolymer treated with same body lotion.In this case, after slaine processing, pH adjust, wash, fluoropolymer by solid form to divide be added in the body lotion with 0.01～50% (weight) of fibre weight, better 5～25% (weight), flood then more than 10 seconds, better 1～120 minute.At this moment, if adopt, then effective especially in the processing that certain thickness fibre is arranged with in organic amine such as ammonia, triethylamine or the inorganic bases such as NaOH, potassium hydroxide and the way of fluoropolymer.And in use with the situation of thing under, then behind dipping, add organic acid solns such as inorganic acid solutions such as 0.1～5% hydrochloric acid, sulfuric acid or formic acid, acetate, propionic acid, pH is adjusted to 1～4, better 2.5～3.5.After washing, the dehydration, identical with common fluorine-containing water-and oil-repellent agent processing method.In the body lotion weight ratio of slaine and fluoropolymer be generally 1: 10～10: 1.
Fluoropolymer also can be with various and use with agent, and comprise such as melamine resin, Lauxite, blocked isocyanate, glyoxal etc. with agent.If necessary, can also further heat-treat or calendering processing etc.In addition, also can be used in combination with finishing agent such as the siloxane compound beyond the fluorine based compound.
For the fibre that has carried out slaine processing/fluoropolymer treated of the present invention, can also further handle with other water-and oil-repellent agent, especially good is to handle with fluorine-containing water-and oil-repellent agent.The homopolymers or the copolymer that do not contain anionic functional group's fluorochemical monomer are particularly conducive to the durability that improves fibre.
In the present invention, with regard to the fibre of being supplied with, except that the form of fiber itself, also comprise by fibroplastic silk, fabric, volume thing, nonwoven fabric etc.Fiber also can use natural fabrics such as kapok, wool, silk, and comprises any in the chemical fibre of synthetic fiber such as acrylic compounds, polyamide-based, cellulose family, polyesters.Can also use the blending thing of natural fabric and synthetic fiber.Fibre better is hydrophilic.Especially good hydrophilic fibre goods are polyamide and polyester.In addition, the fabric that the obvious superfine fiber of development in recent years is made, artificial leather etc. also are better fibres of the present invention.Superfine fibre below 1 dawn, better was 1～0.0001 dawn normally, was more preferably for 0.1～0.001 dawn.
Embodiment
Below be embodiment and comparative example, in order to specify the present invention.
WATER RESISTANCE shown in embodiment and the comparative example is measured according to JIS-L-1092-1977, with the numeral shown in the table 1.Grease resistance is then measured with the described method of AATTC TM-118-1975, the different oil of the surface tension shown in the table 2 of dripping, with the highest number of the oil of not seeing any infiltration after 30 seconds as the grease resistance index.
Table 1
The WATER RESISTANCE state
100 surfaces are gone up non-cohesive wetting
Adhesional wetting a little on 90 surfaces
It is wetting that the display part is gone up on 80 surfaces
It is wetting that demonstration is gone up on 70 surfaces
Show wetting on the 50 whole surfaces
Two sides complete wetting all in 0 table
Table 2 grease resistance surface tension experimental liquid 0-1 following person's 1 31.45 atoleines 2 29.6 atoleines/hexadecane=65/35 (volume %) 3 27.3 hexadecanes 4 26.35 n-tetradecanes 5 24.7 n-dodecanes 6 23.5 n-decanes 7 21.4 normal octanes 8 19.75 normal heptanes
In addition, washing resistance is measured according to JIS-L-0217-103, represents with WATER RESISTANCE, the grease resistance of 10 front and back of washing.And when expression WATER RESISTANCE and grease resistance, be with "+" number person, respectively this performance is good slightly in expression respectively, and it is poor slightly to be with "-" number person to represent.
Production Example 1 (fluorinated copolymer preparation)
90.2g (structural formula a) for fluorine-containing vinyl monomer, 10.25g non-fluorine is a monomer methacrylic acid 2-Octyl Nitrite (trade name: ラ イ ト エ ス ヲ Le EH one side society grease system), 2.05g contain acidic group monomer acid phosphoric acid (acrylic acid 2-hydroxy methacrylate) ester (trade name: ラ イ ト エ ス テ Le PM, one side society grease system), 0.1g lauryl mercaptan, 6.23g NONIN HS 240 (trade name: HS-220, Japan's grease (strain) system), 170.8g ion exchange water, 36.75g the mixture that acetone is formed is used ultrasonic emulsification machine emulsification 5 minutes again with homogenizer homogenize one minute.The emulsion that obtains moves in 4 mouthfuls of flasks, adds 0.51g azo diisobutyl miaow hydrochloride, after gas phase is replaced with nitrogen, 55 ℃ of copolymerization 5 hours.The emulsion that obtains is with the dilution of 229.8g ion exchange water, obtains solid content and be 20% fluorinated copolymer emulsion.
Structural formula a:
(n is that 3,4,5,6 compound mol ratio is 5: 3: 2: 1 mixture)
Production Example 2～4 (fluorinated copolymer preparation)
Change non-fluorine and be monomer and contain the kind and the amount ratio of acidic group monomer, use the method identical to carry out, obtain the fluorinated copolymer emulsion with Production Example 1.Its composition is listed in the table 3.
Table 3
Numeral is represented with weight % in the table.※ ラ イ ト エ ス テ Le S: a grease factory of side society system methacrylic acid stearyl ester.
| (structural formula a) for fluorochemical monomer | Non-fluorine is a monomer | Contain the acidic group monomer | |||
| ライト エステルEH | ライトエス テルS※ | ライトエス テルPM | 2-acrylamido-2-methyl propane sulfonic acid | ||
| Production Example 1 | ??88 | ??10 | ??- | ????2 | ????- |
| Production Example 2 | ??85 | ??10 | ??- | ????5 | ????- |
| Production Example 3 | ??88 | ??10 | ??- | ????- | ????2 |
| Production Example 4 | ??70 | ??- | ??25 | ????5 | ????- |
Slaine Processing Test cloth is made example 1
6. dye test is used, and nylon 6 silks are the chromium sulfate basic (trade name: バ イ Network ロ system F of 5% (weight) containing with respect to test cloth weight, Beyer Co., Ltd's system) dipping in 30 ℃ of aqueous solution (bath raio 10: 1), after carrying out rotation in 120 minutes and handle with dyeing test machine (move well dye machine industry (strain) system), add the sodium formate and the sodium bicarbonate that are respectively 0.2% (weight) with respect to test cloth weight and neutralize.Be further rotated at 40 ℃ then and handled 20 minutes, wash after the dehydration, make sample in drying at room temperature then.
Embodiment 1～4
The fluorinated copolymer emulsion of preparation with the running water dilution, makes solid concentration reach 1% respectively in the Production Example 1～4, further adds 3% isopropyl alcohol, makes treatment fluid.Slaine Processing Test cloth is made the test cloth of preparing in the example 1 and is flooded in above-mentioned treatment fluid, does with the ironer strand, and making hydroscopicity is 25%, 110 ℃ of dryings 3 minutes, 160 ℃ of further heat treatments 1 minute.WATER RESISTANCE, the grease resistance of 10 front and back of working sample washing.The results are shown in Table 4 for it.
Comparative example 1～4
Except that with not carrying out dye test that slaine handles, carry out the processing same with embodiment 1～4 with nylon 6 silks.WATER RESISTANCE, the grease resistance of 10 front and back of working sample washing.The results are shown in Table 4 for it.
Table 4
WATER RESISTANCE grease resistance embodiment 1 L0 100+ 6
L10 80 2 embodiment 2 L0 100+ 7
L10 100 3 embodiment 3 L0 100 6
L10 50 2 embodiment 4 L0 100+ 8
L10 100 3 comparative examples 1 L0 50 5
L10 00 comparative examples 2 L0 50 5
L10 00 comparative examples 3 L0 00
L10 00 comparative examples 4 L0 100 5
L10????50???????0
Embodiment 5～6
Carry out making in the example 1 until the identical technical process of nylon 6 silk neutralisation treatment with slaine Processing Test cloth, discharge body lotion then, containing with respect to test cloth weight is dipping in 50 ℃ of dilution waters (bath raio 10: 1) of emulsion (being expressed as embodiment 5 or 6 respectively) of 15% Production Example 1 or 2, carries out rotation processing in 60 minutes.In same body lotion, add be 3% formic acid with respect to test cloth weight after, further carry out rotation in 20 minutes and handle at 40 ℃.Wash, dewater after discharging body lotion, 110 ℃ of dryings 3 minutes, further 160 ℃ of heat treatments 1 minute.WATER RESISTANCE, grease resistance to 10 front and back of resulting sample determination washing.Its result is listed in the table 5 as embodiment 5 and 6 respectively.
Embodiment 7～8
Fluorine is that water-and oil-repellent agent テ Star Network ス ガ-De TG-5431 (ダ イ キ Application industry (strain) system) dilutes with running water, and making solid concentration is 1%, further adds 3% isopropyl alcohol, makes treatment fluid.The test cloth that embodiment 5 and 6 is obtained floods in this treatment fluid, does with ironer strand, and making hydroscopicity is 25%, 110 ℃ of dryings 3 minutes, further 160 ℃ of heat treatments 1 minute.WATER RESISTANCE, grease resistance to 10 front and back of resulting sample determination washing.Its result lists in the table 5 as embodiment 7 and 8 respectively.
Comparative example 5
Fluorine is that water-and oil-repellent agent テ Star Network ス ガ-De TG-5431 (ダ イ キ Application industry (strain) system) dilutes with running water, and making solid concentration is 1%, further adds 3% isopropyl alcohol, makes treatment fluid.The dye test of non-processor is flooded in this treatment fluid with nylon 6 silks, do with ironer strand, making hydroscopicity is 25%, 110 ℃ of dryings 3 minutes, further 160 ℃ of heat treatments 1 minute.WATER RESISTANCE, grease resistance to 10 front and back of resulting sample determination washing.The results are shown in Table 5 for it.
Table 5
The WATER RESISTANCE grease resistance
Embodiment 5 L0 100+ 6
L10???????100???????3
Embodiment 6 L0 100+ 5
L10???????100???????2
Embodiment 7 L0 100+ 6
L10???????100???????3
Embodiment 8 L0 100+ 5
L10???????100???????2
Comparative example 5 L0 100+ 6
L10 80 0 annotates) L0: not washing
After L10:10 the washing
Slaine Processing Test cloth is made example 2
Remove with zirconium basic sulphate (trade name: ジ Le コ Application, ロ-ム ﹠amp; Ha-ス society system) replaces outside the chromium sulfate basic, carry out making the identical processing of example 1 with slaine Processing Test cloth.
Embodiment 9
Make the test cloth of preparing in the example 2 except that fluorinated copolymer emulsion, the above-mentioned slaine Processing Test cloth of use, carry out processing similarly to Example 1 of Production Example 4 preparations.WATER RESISTANCE, grease resistance to 10 front and back of sample determination washing.The results are shown in Table 6 for it.Table 6
WATER RESISTANCE grease resistance embodiment 9 L0 100+ 7
L10??????90???????3
The invention effect
According to the present invention, can give fibre, especially the hydrophilic fibre goods are with anti-water grease resistance of the initial stage of excellence, also can be easily and give stably that tolerance comprises washing and the durable anti-water grease resistance of the long-term use examined etc. of rubbing.
Claims (6)
1. fiber product processing method, it is characterized in that fibre with the above slaine of divalent handle the back with contain can with the hydrophilic functional group's of this metal-complexing fluoropolymer treated.
2. the processing method of claim 1, wherein the above metal of divalent is selected from one group that is made up of chromium, titanium, zirconium and aluminium.
3. the processing method of claim 1, wherein the hydrophilic functional group is selected from one group that is made up of phosphate and sulfonic group.
4. the process of claim 1 wherein the copolymer that fluoropolymer is made up of following ingredients:
(a) from the repetitive of fluorine-containing ethylenic monomer derived and
(b) from the repetitive that contains the acidic group monomer derived shown in the following general formula,
R in the formula
1Be hydrogen atom or methyl,
R
2Be following alkylidene of 6 carbon or the alkylidene that replacement is arranged, or the divalent group that is formed by connecting such as these groups and ether, ester group, amide groups,
X is PO or SO
2,
M is hydrogen or alkali metal atom,
When X was PO, p was 1, and n, m are 1 or 2, and n+m=3; X is-SO
2In-time, p is 0, n=m=1 and
(c) if necessary, can exist and never contain that the non-fluorine of any group is the repetitive of monomer derived in phosphate or the sulfonic group,
But composition (b) and total amount (c) for 100 weight portion compositions (a) below 100 weight portions.
5. the fibre of using the described method of claim 1 to handle.
6. the fibre of claim 5, wherein the fiber of fibre is polyamide or polyester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP181256/93 | 1993-07-22 | ||
| JP18125693A JP3284672B2 (en) | 1993-07-22 | 1993-07-22 | Textile processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1127536A true CN1127536A (en) | 1996-07-24 |
| CN1084814C CN1084814C (en) | 2002-05-15 |
Family
ID=16097526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94192838A Expired - Fee Related CN1084814C (en) | 1993-07-22 | 1994-07-18 | Fiber product processing method |
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| Country | Link |
|---|---|
| EP (1) | EP0710738B1 (en) |
| JP (1) | JP3284672B2 (en) |
| KR (1) | KR100322937B1 (en) |
| CN (1) | CN1084814C (en) |
| DE (1) | DE69426025T2 (en) |
| TW (1) | TW278104B (en) |
| WO (1) | WO1995003445A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104088155A (en) * | 2014-06-25 | 2014-10-08 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm, preparation method thereof and lithium ion battery |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU7361200A (en) | 1999-09-10 | 2001-04-10 | Nano-Tex, Llc | Water-repellent and soil-resistant finish for textiles |
| US20070197717A1 (en) * | 2004-04-09 | 2007-08-23 | Akihiko Ueda | Polymer for masonry treatment and treating agent |
| WO2006108240A1 (en) * | 2005-04-14 | 2006-10-19 | Feltex Australia Pty Ltd | Method of treating carpet |
| KR101003266B1 (en) | 2008-09-30 | 2010-12-21 | 재단법인대구경북디자인센터 | Process Of Water-Repellent Treatment for Polyester Fabrics Using TiO2-Sol |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3467612A (en) * | 1967-05-12 | 1969-09-16 | Domenick Donald Gagliardi | Textile-treating compositions containing fluorinated acrylic polymers and polyvalent metal salts of weak acids |
| NL7505229A (en) * | 1974-05-07 | 1975-11-11 | Hoechst Ag | METHOD AND MEANS FOR THE DIRT-REPELLENT AND ANTISTATIC FINISHING OF FIBER MATERIAL. |
| JPS5576171A (en) * | 1978-12-01 | 1980-06-09 | Kanebo Ltd | Process of hydrophilic fiber structure |
| JPS569474A (en) * | 1979-07-03 | 1981-01-30 | Teijin Ltd | Antistatic process of polyamide synthetic fiber |
| JPS5747373A (en) * | 1980-09-05 | 1982-03-18 | Dainippon Ink & Chem Inc | Organic fluorine-containing water-repelling and oil-repelling agent having strong adhesivity |
| JPS61103912A (en) * | 1984-10-25 | 1986-05-22 | Nitto Electric Ind Co Ltd | Aqueous emulsion of resin |
| JP2766491B2 (en) * | 1988-12-15 | 1998-06-18 | 三菱レイヨン株式会社 | Thermosetting coating composition |
| US5084306A (en) * | 1990-10-23 | 1992-01-28 | Monsanto Company | Process for coating fabrics with fluorochemicals |
| JPH0598568A (en) * | 1991-10-09 | 1993-04-20 | Senka Kk | Treatment of animal hair fiber |
-
1993
- 1993-07-22 JP JP18125693A patent/JP3284672B2/en not_active Expired - Fee Related
-
1994
- 1994-07-18 KR KR1019960700104A patent/KR100322937B1/en not_active IP Right Cessation
- 1994-07-18 CN CN94192838A patent/CN1084814C/en not_active Expired - Fee Related
- 1994-07-18 DE DE69426025T patent/DE69426025T2/en not_active Expired - Fee Related
- 1994-07-18 EP EP94921106A patent/EP0710738B1/en not_active Expired - Lifetime
- 1994-07-18 WO PCT/JP1994/001171 patent/WO1995003445A1/en active IP Right Grant
- 1994-07-28 TW TW083106910A patent/TW278104B/zh active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104088155A (en) * | 2014-06-25 | 2014-10-08 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm, preparation method thereof and lithium ion battery |
| CN104088155B (en) * | 2014-06-25 | 2016-05-04 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm and preparation method thereof, and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0710738A4 (en) | 1996-07-31 |
| KR960704106A (en) | 1996-08-31 |
| JPH0734384A (en) | 1995-02-03 |
| DE69426025T2 (en) | 2001-05-17 |
| DE69426025D1 (en) | 2000-11-02 |
| JP3284672B2 (en) | 2002-05-20 |
| EP0710738B1 (en) | 2000-09-27 |
| EP0710738A1 (en) | 1996-05-08 |
| WO1995003445A1 (en) | 1995-02-02 |
| TW278104B (en) | 1996-06-11 |
| CN1084814C (en) | 2002-05-15 |
| KR100322937B1 (en) | 2002-06-20 |
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