CN101768861A - Method for endowing polyester fiber with hydrophobic function - Google Patents
Method for endowing polyester fiber with hydrophobic function Download PDFInfo
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- CN101768861A CN101768861A CN200810208040A CN200810208040A CN101768861A CN 101768861 A CN101768861 A CN 101768861A CN 200810208040 A CN200810208040 A CN 200810208040A CN 200810208040 A CN200810208040 A CN 200810208040A CN 101768861 A CN101768861 A CN 101768861A
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Abstract
The invention relates to a method for endowing polyester fiber with a hydrophobic function. When a dispersive dye is used for dyeing processing, the polyester fiber is soaked in a coexisting solution of dihalogenated triazine compound with hydrophilic substituent, a poly-amino compound and a dye solution, and the temperature-raising heat treatment is carried out by a Bath Exhausting Process. After the first stage of heat treatment is finished, the polyester fiber is soaked into the co-existing solution of perfluoroalkyl polyacrylate with water solubility or water dispersion and at least one type of auxiliary which is selected from water silicon softener, water melamine urea derivative and water urethane, and the second stage of drying and high-temperature shaping treatment is carried out by a Dry Heat Continuous Process. The polyester fiber has hydrophobic function with good durability in the processing process, therefore, the purpose of easy maintenance is achieved. The invention uses the common dyeing machines and drying machines, has no need of using synthetic resin and harmful chemicals and has very simple processing method.
Description
Technical field
The invention belongs to the method for the hydrophobic durability that improves the polyester fiber thing, being meant especially dyes on polyester fiber with DISPERSE DYES adds man-hour, the polyester fiber thing is soaked in the coexistence solution of the substituent dihalo compound in triazine class of possess hydrophilic property and polynary amino-compound and dye liquor, adopt " exhaustion method in the bath " to carry out 30 ℃～140 ℃ intensification heat treatment, after heat treatment on phase I finished, usefulness " xeothermic lasting method " was carried out 60 ℃～190 ℃ oven dry, high-temperature process on the second stage again.
Background technology
For a long time, polyester fiber is widely used in suiting, shirt fabric, trousers, skirt, sweater, overcoat, coat classes such as exposure suit, skiing clothes, help clothes; Chandleries such as umbrella, bag, footwear; Cover such as bed sheet, tablecloth, shower curtain, tent, canvas, various Saddle covers dry goods; And underwear class such as socks, underpants, brassiere; In goods, materials and equipments such as fishing net, the oil fence series products.In addition, as a new functional product, the consumer also has higher requirement to the hydrophobic function aspect of polyester fiber, such as, how just can avoid the infiltration of water and rainwater etc.Compare with regenerated fiber with natural fiber, the polyester fiber that dyed with DISPERSE DYES, because washing fastness is good, and, can also suppress because of phenomenons such as making a slit or vent of causing of friction, balling-ups, prevented thick and stiffization of the fiber that causes thus, make polyester fiber have extraordinary characteristic aspect stable in form, such as, hard and soft property, shrink resistance etc., so polyester fiber has purposes widely in dress material, industrial fibre and medical field.Compare with natural fabric, regenerated fiber and string on the other hand, because the inner no hydrophilic group of polyester fiber, so, no hygroscopicity and wet putting, and on fibre structure the low-down weakness of equilibrium water conten rate, and belong to non-conductor again, carry out producing a large amount of static after stoving process and the strong friction.Therefore, generally adopt the macromolecule antistatic class medicament of surface treatment type or having that ionic conductive agent adheres to or the form that is coated on fiber surface reaches the purpose of antistatic.
Processing method for polyester fiber thing hydrophobic property function, at present, the general employing adhered to the method for antistatic agent and added the method for conductor type ion and for the hydrophobic property function in this agent, with synthetic resin integrated technologys such as silicon class and compound, the synthetic pressure of fluorine class water-repelling agent processing on fiber are attached.Therefore, its processing is under hot conditions, and its processing technology is also very complicated, and is even also do not satisfy the requirement of user to hydrophobic function after processing far away, also not high to its evaluation.Reason has 2 points, first for after washing its anti-static effect completely without, produce a large amount of static.Because the antistatic agent that exists with the form of liningization on polyester fibre surface is all come off in water-washing process.And, be the hydrophobic property function, with synthetic resin the silicon class and the fluorine class water-repelling agent composition of media liningization, the influence that is rubbed all comes off, its coefficient of friction also rises gradually along with the variation of temperature and humidity, produces a large amount of static, the reason that has become to adsorb a large amount of dusts.Second is for the hydrophobic property function, compound and be coated on result on the polyester fiber a large amount of water-repelling agents with synthetic resin, causes the problems such as reduction of thick and stiffization, degree of drawing and the snugness of fit of fiber structure.In addition, it is poor to prevent that static and hydrophobicity from adding polytechnic repeatabilities such as adopt man-hour compound, synthetic pressure be attached, in case failure just can't be saved, and because of use harmful chemicals and synthetic resin, its security has also become serious social concern.
Summary of the invention
The objective of the invention is to, the polyester fiber thing is given or improved hydrophobic function, improve its water system soil resistance and the hydrophobic durability when being rubbed.
For solving above-mentioned problem, the technical scheme that adopts among the present invention is; The method of endowing polyester fiber with hydrophobic function during with disperse dyeing, it is characterized in that: the polyester fiber thing is soaked in the coexistence solution of the substituent dihalo compound in triazine class of possess hydrophilic property and polynary amino-compound and dye liquor, adopts " exhaustion method in the bath " this polyester fiber thing to be carried out 30 ℃～140 ℃ intensification heat treatment; Then, for making the polyester fiber thing have hydrophobicity, be soaked in once more in the coexistence solution of perfluoroalkyl polyacrylate with water-soluble or water dispersible and at least a auxiliary agent of from water-based silicon class softener, water-based melamine urea derivative and water-based urethane, selecting, carry out 60 ℃～190 ℃ oven dry heat treatment in 2～30 minutes with " xeothermic lasting method ".
Described " exhaustion method in the bath " heat treatment refers to, and heats up gradually with 40～60 fens clock times, and bath temperature is risen to 30 ℃～140 ℃, then, keeps 10～60 minutes heat treatment process method between 100 ℃～140 ℃.Emphasize that here the reason that heats up gradually is, in dyeing course for fear of the dyeing non-uniform phenomenon of DISPERSE DYES and since the substituent dihalo compound in triazine class of possess hydrophilic property add water decomposition and agglutination phenomenon, cause to be coated on uniformly the problem on the polyester fibre surface, in temperature-rise period, definitely to avoid sharply heating up or uneven intensification phenomenon, specifically, reasonably programming rate is below 2 ℃/minute.
Described " exhaustion method in the bath " is in bath raio is dye liquor below 1: 30, weight in described polyester fiber structures thing is 100%, the DISPERSE DYES of input 0.1%～5% and 0.1%～10% substituent dihalo compound in triazine class of possess hydrophilic property and 0.01%～10% polynary amino-compound, after in this coexistence solution, soaking this polyester fiber, carry out 30 ℃～140 ℃ phase I intensification heat treatment.For making dyeing and reaction reach better evenly effect, from acetic acid, malic acid and citric acid, to select a kind of adding in the coexistence solution at least, the pH value of solution is reached between 3.5～6.5.
Heat treatment as second stage, for better improving the hydrophobic function of polyester fiber thing, this polyester fiber thing be soaked in the perfluoroalkyl polyacrylate of water-soluble or water dispersible with hydrophobic function with from water-based silicon class softener, in the mixed solution of at least a auxiliary agent of selecting in water-based melamine urea derivative and the water-based urethane, specifically use amount separately is 100% for the weight in described polyester fiber structures thing, percentage with perfluoroalkyl polyacrylate weight of water-soluble or water dispersible is 0.1%～10%, from water-based silicon class softener, the use amount of at least a auxiliary agent of selecting in water-based melamine urea derivative and the water-based urethane is 0.1%～10% of a polyester fiber structures thing weight.After pushing by predetermined water absorption rate, adopt that " continuing dry heating method " dries, high-temperature heat treatment in 60 ℃～190 ℃ temperature.
Adopt in the present invention and have the DISPERSE DYES of following chemical structural formula: benzeneazo class (monoazo and two azos), different ring type azo class (thiazolylazo, benzothiazole azo) anthraquinone class, condensation system (quinoral, styryl, cumarin) etc.
Contain 2 in the substituent above-mentioned dihalo compound in triazine class of described possess hydrophilic property, 6-dihalo-4-Y-1,3, the 5-pyrrolotriazine derivatives, with general formula (1) expression,
In the formula, X refers to chlorine, the halogen radical of electing in fluorine and the bromine class, Y refers to virtue amino, aryloxy group, aromatic thiohydroxy, alkylamino, alkoxyl, alkylthio group, triazine amino, triazine hydroxyl, the triazine sulfenyl of being replaced by a kind of base of electing in sulfo group, carboxyl, hydroxy and the mercaptan base class at least, or triazine ammonia stilbene amino.Above-described sulfo group, carboxyl, hydroxy, and the hydrogen atom in the mercapto also can be replaced by alkali metal atom or alkaline earth metal atom.
The polynary amino-compound that is adopted among the present invention is, the molecular weight that can from cocoon, feather, raw silk, obtain be below 20000 low macromolecule water-solubility add the water decomposition silk.
When using DISPERSE DYES to dye to polyester fiber, put into substituent dihalo compound in triazine class of possess hydrophilic property represented in the above-mentioned general formula 1 in the dye liquor and polynary amino-compound after implementing the electron replacement reaction under the acid bath condition, together form ions binding with DISPERSE DYES with fiber structure, reach the liningization effect, chlorotriazine ring (general formula 1) becomes nonionic simultaneously.
In the heat treatment of second stage, in the molecule of perfluoroalkyl polyacrylate, water-based silicon class softener, water-based melamine urea derivative and the water-based urethane of described water-soluble or water dispersible, preferably contain water-soluble transposing base such as sulfo group, carboxyl, hydroxy.These compounds and the chlorotriazine ring that is coated on as nonionic on the polyester fiber form total combination and ions binding under heat treated effect, finally can make the polyester fiber thing have hydrophobic function.
Advantage of the present invention is: do not use harmful substances such as synthetic resin and organic solvent, thereby avoid consuming the huge energy, reduce the generation of carbon dioxide and nitrogen oxide, prevented because the phenomenon that the generation of a large amount of heat worsens working environment, be a kind of harmless to operating environment, the cost of available cheapness carries out the processing method of functional processing.The present invention does not need to introduce the equipment of advanced costliness, utilizes current production devices just can carry out functional processing, can save cost of investment.With in the past with synthetic resin carry out compound and the lining method for processing compare, the present invention can improve the hydrophobic durability of friction in the washing, and can prevent to cause the phenomenon of a large amount of dust absorption again, and then provide polyester fiber thing with hydrophobic function with snugness of fit to the user because of the generation of static.
Therefore, except the dress material field, can enlarge the purposes of polyester fiber in various fields such as industry, industry goods, materials and equipments.Specifically can be used for general dress material, cap, the exposure suit class, skiing clothes class, leisure clothing class, the anorak class, the uniform class, Bed with special provision for nursing list class, doctor and nurse use gown of a doctor, cooking teacher clothing class, bag, footwear, gloves, tent, the various plastics and the cloth of defence water/rain/water system liquid, the antifouling purposes of water systems such as tablecloth, open-air clothes and sportswear etc. need lightweight clothing class, socks, underpants, protecting abdomen uses, underpants, brassiere, the long filament socks, suiting, other also has fields such as lingerie.
The specific embodiment
Except special declaration, be concentration expressed in percentage by weight among the present invention.
It should be understood by one skilled in the art that embodiment of the present invention and embodiment all just are used to illustrate the purpose of the present invention and the specific embodiment, under the prerequisite that does not deviate from spiritual essence of the present invention, can carry out various variations the present invention.
Describe preferred forms of the present invention below in detail.Dye on polyester fiber with DISPERSE DYES and to add man-hour, the polyester fiber thing is soaked in the coexistence solution of the substituent dihalo compound in triazine class of possess hydrophilic property and polynary amino-compound and dye liquor, adopts " exhaustion method in the bath " to carry out 30 ℃～140 ℃ intensification heat treatment.After heat treatment on phase I finishes, in order to improve the hydrophobic function of polyester fiber thing, be soaked in once more in the coexistence solution of perfluoroalkyl polyacrylate with water-soluble or water dispersible and at least a auxiliary agent of from water-based silicon class softener, water-based melamine urea derivative and water-based urethane, selecting, then, carry out oven dry, high-temperature heat treatment on 60 ℃～190 ℃ the second stage with " xeothermic lasting method ".By this process, make the polyester fiber thing have fabulous hydrophobicity of durability and snugness of fit.Prevent absorption (anti-fouling effect) phenomenon of dust in drying course by the generation that suppresses static, in addition, by improving the rub resistance in water-washing process, make hydrophobic effect keep (water system anti-fouling effect) for a long time, finally make the polyester fiber thing reach the purpose of easy maintenance.
Substituent dihalo compound in triazine class of possess hydrophilic property and polynary amino-compound are after implementing electronics transposing reaction in the heat treatment of phase I under the acid bath condition, together form ions binding with DISPERSE DYES with fiber structure, reach the liningization effect, the chlorotriazine ring becomes nonionic simultaneously.As the heat treatment on the second stage, the perfluoroalkyl polyacrylate of water-soluble or water dispersible and at least a compound of from water-based silicon class softener, water-based melamine urea derivative and water-based urethane, selecting as auxiliary agent and usefulness, these compounds and the chlorotriazine ring that is coated on as nonionic on the polyester fiber, under heat treated effect, form total combination and ions binding, finally can make the polyester fiber thing have hydrophobic function.
Describe the reaction structure when adopting " exhaustion method in the bath " below in detail to polyester fiber thing hydrophobic property function.Specifically, after knocking down an amount of polyester fiber thing in the high-pressure type liquid-flow dyeing machine, inject fixed normal-temperature water, afterwards, drop into fixed substituent dihalo compound in triazine class of DISPERSE DYES, possess hydrophilic property and polynary amino-compound, with acetic acid aqueous solution furnishing acid solution after beginning heat up gradually.Such as everyone knows, usually in alkaline solution, organic fiber structure is added man-hour, be subjected to the influence of the electronics transposing property of the substituent dihalo compound in triazine class of possess hydrophilic property, for the temperature band of organic fiber structure at 30 ℃～50 ℃, occur having (-) ion after the transposing reaction for the first time with (H) position of this fiber structure, temperature band at 60 ℃～70 ℃, after transposing reaction for the second time occurring with (H) position of this fiber structure, form the chlorotriazine ring of (-), have with fiber and combine.But,, therefore, can't form a total combination because the polyester fiber structures thing itself does not have (H) position.As everyone knows, can form the chlorotriazine ring of (-) when in acid solution, reaching near 80 ℃, therefore, utilize this electronics transposing property, with (H) halogen position that polynary amino-compound soluble in water had, carry out electronics transposing reaction, then, the chlorotriazine ring of nonionicization is coated on the surface of polyester fiber.Afterwards, though DISPERSE DYES under hot conditions, dye in fiber, ionic because of belonging to nonionic, so, after the coexistence of chlorotriazine ring, form ions binding with polyester fiber, be coated on the fiber surface.According to famous thorough three Mr.s of chemical expert's Beichuan of Japan about research report to the charging property of some materials, wherein polyester fiber is charged in (-) position, but by with the displacement reaction of possess hydrophilic property substituting group dihalo compound in triazine class and polynary amino-compound, the polyester fiber thing that dyeing is come out becomes and has the fiber structure that suppresses the generation of static electricity function.
Among the present invention, as " the xeothermic lasting method " on the second stage, adopt pad, oven dry, high temperature setting method.Here the perfluoroalkyl polyacrylate of the polyester fiber that has formed nonionic chlorotriazine ring by the heat treatment on the phase I and water-soluble or water dispersible and as auxiliary agent from water-based silicon class softener, at least a compound of selecting in water-based melamine urea derivative and the water-based urethane merges use, make them by 60 ℃～190 ℃ heat treatment process on the second stage, form total combination one by one or simultaneously, ions binding, thereby give and improve hydrophobic function, finally can obtain to have the characteristic of easy maintenance, be applicable to the functional polyalkylene ester fiber of life goods, materials and equipments and industry and industry goods, materials and equipments.
The substituent dihalo compound in triazine class of possess hydrophilic property is characterized in that among the present invention, has 2,6--dihalo-4-Y-1, and 3,5-pyrrolotriazine derivatives, the general formula (1) below available represent,
In the formula, X refers to chlorine, the halogen radical of electing in fluorine and the bromine class, Y refer to virtue amino, aryloxy group, aromatic thiohydroxy, alkylamino, alkoxyl, alkylthio group, triazine amino, triazine hydroxyl, the triazine sulfenyl of being replaced by a kind of base of electing in sulfo group, carboxyl, hydroxy and the mercaptan base class at least.And the hydrogen atom in above-mentioned sulfo group, carboxyl, hydroxy and the mercapto also can be replaced by alkalinous metal atom or alkaline earth metal atom.
Represented improvement medicament in above-mentioned general formula (1) about fibrous material, be main material with three halos-S-triazine specifically, it preferably is main material with the tricyanogen chloride, in addition, the acid binding agent of interpolation and tricyanogen chloride isodose is carboxyl again, hydroxy, mercapto, amino, sulfo group, water-soluble or the substituent phenyl amines of possess hydrophilic property such as sulfonic group, phenol, the benzenethiol class, the naphthalene Ammonia, aphthols, amino acids, monomer such as triazines or mixture are condensed into neutral to weakly alkaline compound, or by using sodium bicarbonate, sodium carbonate, NaOH, calcium hydroxide, alkaline matters such as magnesium hydroxide come tricyanogen chloride added in the process of water decomposition and also can obtain.The compound that these compounds are not necessarily pure, so long as in above-claimed cpd, appoint get the compound of two or more materials after reacting with tricyanogen chloride also can, sometimes several unification compounds, during use interim mix the back as the multicomponent class use also can.
In the present invention, the substituent dihalo compound in triazine class of possess hydrophilic property refers to, as the following a kind of compound remembered or the mixture of several compounds.
2,6-two chloro-4-(3-aniline sulfonic acid base)-S-triazine
2,6-two chloro-4-(4-aniline sulfonic acid base)-S-triazine
2,6-two chloro-4-(2-aniline sulfonic acid base)-S-triazine
2,6-two chloro-4-(2,5-disulfobenzene amido)-S-triazine
2,6-two chloro-4-(3-5-disulfobenzene amido)-S-triazine
2,6-two chloro-4-(3-carboxyl anilino-)-S-triazine
2,6-two chloro-4-(4-carboxyl anilino-)-S-triazine
2,6-two chloro-4-(2-carboxyl anilino-)-S-triazine
2,6-two chloro-4-(β-carboxy ethyl amino)-S-triazine
2,6-two chloro-4-urea groups-S-triazines
2,6-two chloro-4-sulfo-urea groups-S-triazines
2,6-two chloro-4-(4-carboxyl phenoxy group)-S-triazine
2,6-two chloro-4-(4-carboxyl thiophenyl)-S-triazine
2,6-two chloro-4-hydroxyls-S-triazine Na salt
2,6-two chloro-4-hydroxyls-S-triazine Li salt
2,6-two chloro-4-hydroxyls-S-triazine Mg salt
2,6-two chloro-4-sulphur-S-triazine Na salt
2,6-two chloro-4-(3-sulphur benzene hydroxyl)-S-triazine
2,6-two chloro-4-(3-oxybenzene hydroxyl)-S-triazine
4,4 '-two (4, the different ammonia of 6-two chloro-S-triazine-2-)-stilbenes-2,2-disulfonic acid Na salt
The substituent dihalo triazines of possess hydrophilic property is, also has a lot of effective compounds except above several.The present invention is not limited to the above-mentioned example.Mainly be whether to see that the substituent compound of possess hydrophilic property is with the reactive halogen atom or have the plural reactive base similar to it and be criterion.
In the present invention, for making the chlorotriazine ring nonionicization of the substituent dihalo compound in triazine class of possess hydrophilic property, the polynary amino-compound that is adopted can obtain from cocoon, feather, raw silk, be that a kind of molecular weight is the low molecule below 20000, have the water miscible water decomposition silk that adds, available following method makes.
After earlier putting into cocoon, feather, raw silk etc. in the sink, cleaned approximately 1 hour, dewater with centrifugal dehydrator again after impurity is all removed with normal-temperature water.After dropping into raw material, sodium bicarbonate in the aqueous solution, be warmed up to 100 ℃, this state maintenance after 120 minutes, is separated silk gum and fibroin with centrifugal dehydrator again.The aqueous solution that contains silk gum is put in the ferment decomposer,, in 60 ℃ of temperature, carried out 300 minutes refining with ferment such as alkali protease, cellulases.Also carry out same refining processing for the fibroin of separating.After putting into the aqueous solution that contains silk gum in the vacuum decker, carry out repetitious concentrated processing with materials such as malic acid, citric acids after, filter with screen pack.Afterwards, be sprayed onto in the spray formula dryer that is warmed up to 300 ℃, finally form powder.For in centrifugal dehydrator and filter the back residual fibroin, with carrying out the 3rd, the 4th processing in ferment purifying method and the highly basic, then, for the fibroin that decomposes concentrate process after, adopt and the same method of processing silk gum, finally obtain the powdery fibroin powder.
Undertaken and the molecular weight that adds the water decomposition silk that obtains by above-mentioned processing method, after the evaluation at Japan, Kyoto Prefecture weave machine metal development center, consequently, the molecular weight that low molecule adds water decomposition silk (sericin powder) is 10000, the molecular weight that adds water decomposition silk (fibroin powder) is 1000, all belongs to the water miscible water decomposition silk that adds.The substituent dihalo compound in triazine class of these polynary amino-compounds and possess hydrophilic property, the chlorotriazine ring of formation nonionic is coated on this fiber structure, thereby makes polyester fiber have hydrophobic function in acid bath.
The perfluoroalkyl polyacrylate of indication is in the present invention, have Polyfluoroalkyl (below use R
fCome mark) the complex chemical compound that comprises (methyl) acrylate.So-called (methyl) acrylate refers to, at least a compound of electing from acrylate and methacrylate.Mark about [(methyl) acrylamide] etc. also is same.Have R
f(methyl) acrylate of base refers to R
fThe compound of base for existing in the ethanol residue in (methyl) acrylate.
R
fBase refers to plural hydrogen atom in the perfluoroalkyl and is replaced the base that gets off by fluorine atom.R
fThe carbon element number of base preferably reaches 2-20, wherein 6-16 position the best.In addition, R
fBase constitutes by linear structure or difference, wherein linear structure preferably.If the difference structure, the difference part preferably is present in R
fThe distal portion of base, and carbon number is the short part of 1-4.R
fBase can also contain the halogen atom beyond the fluorine atom, preferably chlorine atom.
R
fThe base end portion be configured with-CF
2CF
3,-CF (CF
3)
2,-CF
2H ,-CFH
2,-CF
2Cl etc., wherein preferably-CF
2CF
3And, at R
fBetween the carbon element in the base and the combination of carbon element, can also insert etheric oxygen atom or thioether sulphur atom.
R
fIf number of fluorine atoms in the base is with [(R
fNumber of fluorine atoms in the base)/(with R
fThe number of hydrogen atoms that contains in the corresponding perfluoroalkyl of the same carbon number of base)] * and 100% form shows, and the 60%th, reasonable, preferably reach 80%.Further describe R
fBase is that most of hydrogen atom of perfluoroalkyl is replaced result's product by fluorine atom.That is to say, preferably endways the position have perfluoroalkyl (below be labeled as R
FBasic) or R
FThe base of base.
R
FThe carbon number of base is reasonable as if reaching 2-20, preferably 6-16.If carbon number does not reach 2, so, can cause the reduction of water proofing property function.Opposite carbon number can cause whole complex to become solid at normal temperatures above 20 and vapor away, and, also be not easy keeping.
R
FConcrete example can enumerate following.In following example, though perhaps can exist same molecular formula, the base that structure is inequality.
C
4F
9-[F (CF
2)
4-, (CF
3)
2CFCF
2-, (CF
3)
3C-etc.], C
5F
11-[F (CF
2)
5-, (CF
3)
3CCF
2-etc.], C
6F
13-[F (CF
2)
6-etc.], C
7F
15-, C
8H
17-, C
9F
19-, C
10F
21-, CI (CF2)
s-(S is 2～16 integer), H (CF
2)
t-(t is 1～16 integer), (CF
3)
2CF (CF
2)
y-(y is 1～14 integer) etc.
If R
fBase is, inserting the base that forms behind etheric oxygen atom or the thioether sulphur atom between the combination of carbon atom and carbon atom, and so, object lesson is as follows.
F (CF
2)
5OCF (CF
3)-, F[CF (CF
3) CF
2O]
rCF (CF
2) CF
2CF
2-, F[CF (CF
3) CF
2O]
zCF (CF
3)-, [CF (CF
3) CF
2O]
u, CF
2CF
2-, F (CF
2CF
2CF
2O)
vCF
2CF
2-, F (CF
2CF
2O)
wCF
2CF
2-(r is 1～6 integer, and z is 1～5 integer, and u is 2～6 integer, and v is 1～6 integer, and w is 1～9 integer) etc.
Have R
f(methyl) acrylate of base is the represented compound that comes out in the chemical formula (2) below preferably.But, R in diagram
fRefer to R
fBase, Q are the organic group of divalent, R
1Refer to hydrogen atom or methyl.
R
f-Q-OCOCR
1＝CH
2………………(2)
As the R in the general formula (2)
fBase, reasonable is the R that does not contain etheric oxygen atom or thioether sulphur atom
fBase, preferably R
FEspecially best is with-(CF
2) (still, f is the integer of 2-20 to F.) the base that shows of form.The reasonable f of being is the integer of 5-17, and preferably f is the integer of 7-13.
Go up the Q of indication for general formula (2), the easiest reaction is-(CH
2) p+q-,-(CH
2)
PCONH (CH2) q-,-(CH
2)
POCONH (CH
2) q-,-(CH
2)
PSO
2NR
2(CH
2) q-,-(CH
2)
PNHCONH (CH
2) q-,-(CH
2)
PCH (OH)-(CH
2) q-etc.But, R
2What represent is hydrogen atom or perfluoroalkyl.Also have, p and q are represented is integer more than 0, and p+q is the integer of 1-22.Have in the middle of these following ,-(CH
2) p+q-,-(CH
2)
PCONH (CH
2) q-,-(CH
2)
PSO
2NR
2(CH
2) q-.And preferably, q once had plural integer and p+q is the situation of 2-6.When particularly p+q is 2-6-(CH
2) p+q-, that is to say that the diformazan base of a fruit is blue and cyclohexane is more suitable.For the R that combines with Q
fThe carbon element atom, fluorine atom in conjunction with aspect its effect be best.
As having R
fThe concrete example of (methyl) acrylate of base can be enumerated following several compound.But R
1Represented is hydrogen atom or methyl.
F(CF
2)
5CH
2OCOCR
1＝CH
2、F(CF
2)
6CH
2CH
2OCOCR
1＝CH
2、H(CF
2)
6CH
2OCOCR
1＝CH
2、H(CF
2)
8CH
2OCOCR
1＝CH
2、H(CF
2)
10CH
2OCOCR
1＝CH
2、H(CF
2)
8CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
8CH
2CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
10CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
12CH
2CH
2OCOCR
1＝CH
2、(CF
3)
2CF(CF
2)
4CH
2CH
2OCOCR
1＝CH
2、(CF
3)
2CF(CF
2)
6CH
2CH
2OCOCR
1＝CH
2、(CF
3)
2CF(CF
2)
8CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
8SO
2N(C
3H
7)CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
8(CH
2)
4OCOCR
1＝CH
2、F(CF
2)
8SO
2N(CH
3)CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
8SO
2N(C
2H
5)CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
8CONHCH
2CH
2OCOCR
1＝CH
2、(CF
3)
2CF(CF
2)
5(CH
2)
3OCOCR
1＝CH
2、(CF
3)
2CF(CF
2)
5CH
2CH(OCOCH
3)--OCOCR
1＝CH
2、(CF
3)
2CF(CF
2)
5CH
2CH(OH)CH
2--OCOCR
1＝CH
2、(CF
3)
2CF(CF
2)
7CH
2CH(OH)CH
2--OCOCR
1＝CH
2、F(CF
2)
9CH
2CH
2OCOCR
1＝CH
2、F(CF
2)
9CONHCH
2CH
2OCOCR
1＝CH
2。
Said in the present invention perfluoroalkyl polyacrylate is to contain the two or more R of having
1(methyl) acrylate of base also can.If contain the two or more R of having
1The base (methyl) acrylate the time, preferably contain different carbon number R
1(methyl) acrylate thing of base.Also have, the perfluoroalkyl polyacrylate of indication is in the present invention, contains band R
1Multiple (weight) zoarium beyond the complex of (methyl) acrylate thing of base also can.Talk about its complex, mainly contain following several.Ethene, propylene, butadiene, isoamyl () diene, vinyl chloride, ethylene fluoride, protochloride vinyl, fluoridize olefines such as ethenylidene, chlorobutadiene, the phenylethylene of styrene, α-Jia Jibenyixi, Beta-methyl styrene etc., diacetone acrylamide, N, N-DMAA etc., acrylic amide, polychlorostyrene ether alkene classes such as ether base, vinyl ether, hexamethylene vinyl ether, alkyl halide polyvinyl chloride, virtue ether class, carboxylic acid polyvinyl chlorides such as acetic acid polyvinyl chloride, carboxylic acid aromatics such as acetic acid aryl.
Methyl methacrylate, the butylacrylic acid methyl esters, the cyclohexyl methyl acrylate, the own methyl acrylate of 2-ethyl, the cetyl methyl acrylate, the carbon number 1-26 of classes such as the basic methyl acrylate of 18 (alkane) has a linear structure, or the alkyl acrylate of difference structure perfluoroalkyl, the glycidyl methyl acrylate, the benzyl methyl acrylate, 2-ethoxy second methyl acrylate, 2-hydrogen-oxygen (base)-3-chloropropyl methyl acrylate, polyoxyalkylene list methyl acrylate monomethyl ether, polyoxyalkylene diacrylate methyl esters, the own methyl acrylate of 2-(dimethylamino) ethyl, the methyl acrylate that has the dimethyl silicone polymer base, the methyl acrylate that has the isocyanic acid alkali that is reinforced, the methyl acrylate classes such as methyl acrylate that have the 4th ammonium salt base.
Triallyl cyanurate, N-vinyl carbazole, maleimide, N-perfluor alkane maleimide, maleic anhydride, maleic acid mono alkyl ester, dialkyl maleate etc.
In the present invention, when using the perfluoroalkyl polyacrylate, following compound is, that is to say and have the isocyanic acid alkali that is reinforced more than, and be again the compound that does not have unsaturated combination between repeatability carbon atom and carbon atom, preferably with the structural compounds of the isocyanic acid alkali that was reinforced of itself and usefulness.Afterwards, impel the compound that has two above active hydrogen atoms in polyisocyanates and the molecule to react, then, the best hardening agent that is to use is the structure that the isocyanic acid alkali was strengthened to the compound that therefrom obtains, and carries out catalysis processing with catalyst.
For polyisocyanates, can enumerate several reasonable polyisocyanates.
4,4 '-methyl diphenylene diisocyanate, 2, aromatic series such as 4 '-methyl diphenylene diisocyanate, toluene di-isocyanate(TDI) isocyanic acid salt, cyclopropane diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, cyclohexane diisocyanate, 1,2-propane diisocyanate, 1,2-butane diisocyanate, trimethyl 1, the own diisocyanate of 6-, isophorone diisocyanate, 4, based on aliphatic isocyanates in order classes such as 4 '-dicyclohexyl methyl hydride diisocyanate, cyclohexene diisocyanate.Also have alicyclic isocyanic acid salt and their isocyanurate sex change body, prepolymer sex change body, dropper sex change body etc.
Can enumerate following several reasonable compound as the catalyst of isocyanic acid alkali.Perfluor alkane ketoxime class, phenol, ethanol class, β-ketene dimer class, lactams.Particularly methyl ethyl ketone oxime, epsilon-caprolactams, phenol, paracresylol, acetylacetonate, diethyl malonate, isopropyl alcohol, t-butanols, maleic acid acid imide etc. are relatively good, are that 120 ℃～180 ℃ compound is relatively good as the dissociation temperature of lactams such as dialkyl ketone oximes, epsilon-caprolactams such as methyl ethyl ketone oxime especially.
The isocyanates of being said in the above with catalyst is, MEICANATE, BP-11, NBP-75, NBP-231 (more than be bright one-tenth chemical industrial company system), WB-730, WB-920, XWB-72-Z56 (more than be, military field pharmaceutical industries corporate system), BI-8 (Japanese carbamate corporate system) etc., adopt the commercial compound also can.
Be coated on chlorotriazine ring on the polyester fiber with the form of nonionicization, form total the combination and ions binding with above-mentioned compound, by this in conjunction with giving hydrophobic function (water system is antifouling) that fiber structure has durability and the function (antifouling) that suppresses dust absorption, thereby reach the purpose of easy maintenance.
In the present invention, for the processing of the hydrophobicity of polyester fiber, adopt as the above-mentioned substituent dihalo compound in triazine class of possess hydrophilic property, polynary amino-compound and have the perfluoroalkyl polyacrylate of water-soluble or water dispersible and water-based silicon class softener, water-based melamine urea derivative and water-based urethane in the supporting use of at least a auxiliary agent selected.Give the easily characteristic of maintenance of this fiber by this processing.Explain the main points briefly, with DISPERSE DYES polyester fiber is dyeed and to add man-hour, in acid bath, electron replacement is carried out at (H) position of substituent dihalo compound in triazine class of possess hydrophilic property and polynary amino-compound, coexist with non-ionic DISPERSE DYES after forming nonionic chlorotriazine ring, impel (+) (-) ion under good equilibrium condition, carry out ions binding with polyester fiber again, thus the purpose that reaches the liningization on this fiber structure and suppress static.Use perfluoroalkyl polyacrylate afterwards and from water-based silicon class softener, water-based melamine urea derivative and water-based urethane, select a kind of at least and usefulness as auxiliary agent with water-soluble or water dispersible.Then, after heat treatment formation nonionicization, form solid figure or netted total the combination and ions binding with the chlorotriazine ring of liningization, and then endowing polyester fiber has the hydrophobic function of durability and reaches the purpose that suppresses dust absorption by anti-static effect, finally makes this fiber structure have the characteristic of easy maintenance.As above-mentioned, processing method among the present invention, be different from for a long time with synthetic resin and carry out process technology compound and lining processing, it be by the hydrophobization processing method of total combination and ions binding formula come to the polyester fiber hydrophobic property and easily maintenance characteristic.
In the present invention; its fibre structure of so-called polyester fiber of hydrophobic property function is; separately or with other mixed with fibers with can, such as, with the blended fiber of natural fabric and regenerated fiber, semisynthetic fibre and nylon fiber, acetate, triacetate, acryloyl group.Specifically be, animal fibers such as spun silk, wool, cashmere, alpaca fibre, mohair, kapok, fiber crops, viscose artificial silk, copper ammonia fibre artificial silk, Lyocell, day silk, cellulose acetate etc. have the cellulose fibre of carboxyl and ethanol hydroxy or are the fiber structure of main component with the regenerated fiber in molecular structure.
In the present invention, be meant with the hydrophobicity processing method of above-mentioned medicament polyester fiber, adopt in the heat treatment on the phase I " exhaustion method in the bath ", both used the high-pressure type liquid-flow dyeing machine, the process that in 30 ℃～140 ℃ temperature range, heats up gradually.30 times that the water yield in the dyeing machine are transferred to polyester fiber weight with after interior, drops into the DISPERSE DYES of this fibre weight 0.1-5%.Calculate by medicament purity 100%, drop into the polynary amino-compound of substituent dihalo compound in triazine class of 0.1-10% (o.w.f) possess hydrophilic property and 0.01-10% (o.w.f).Acidic materials such as the acetic acid of input 0.1-10% (o.w.s), glacial acetic acid, malic acid, citric acid are transferred to 3.5～6.5 to the pH value.After transferring liquid to finish, with 2 ℃/minute speed, the heat treatment process process that in 30 ℃～140 ℃ temperature range, heats up gradually.Keep lowering the temperature after 30 minutes～60 minutes in 100 ℃～140 ℃ scope, then, the same method when taking to use disperse dyeing is usually carried out hot water wash, washing, setting processing, dries processing at last.
For making polyester fiber have hydrophobic function, the heat treatment on the second stage be adopt that " xeothermic lasting method " pads, oven dry, high stable shape handle.Dryer can adopt rotary drum dryer, stretching dryer, shrink dryer etc. according to the situations such as fabric, braiding and nonwoven fabric of polyester fiber.Earlier this fiber structure is carried out substantial oven dry in 60 ℃～120 ℃ temperature and handle, then, in 140 ℃～190 ℃ temperature, carry out high stable shape and handle.Pad under the prerequisite of trough inner water temperature in attention, this fiber structure be soaked in perfluoroalkyl polyacrylate with water-soluble or water dispersible with as auxiliary agent from water-based silicon class softener, in the mixed liquor of at least a material of selecting in water-based melamine urea derivative and the water-based urethane, its use amount separately is, perfluoroalkyl polyacrylate with water-soluble or water dispersible is the 0.1-10% (o.m.f) of this fiber structure, as auxiliary agent from water-based silicon class softener, at least a material of selecting in water-based melamine urea derivative and the water-based urethane is the 0.1-10% of this fiber structure.For these mixtures better are penetrated in the fiber, can add polynary ethanol class material.After making the abundant absorbent solution of this polyester fiber, soak one by one and roll or two soak two and roll or repeatedly pad and make the water absorption rate of this fiber reach 20%～200%, the multiple-effect fruit is good more more to pad number of times sometimes.Then, as the heat treatment first time, the substantial oven dry of carrying out in the scope of 60 ℃～120 ℃ of xeothermic temperature several minutes to 60 minutes is handled.As the heat treatment second time, in the scope of 140 ℃～190 ℃ of temperature, the high temperature setting of carrying out 30 seconds to 30 minutes is handled.
In the present invention, as long as have the processing technology in following two stages and processing sequence also passable.The one, as the heat treatment on the phase I, adopt " exhaustion method in the bath " to carry out little by little hyperthermic treatment.The 2nd, as the heat treatment on the second stage, adopt that " xeothermic lasting method " pads, the dry heat treatment of oven dry, high temperature setting.
Embodiment 1
In the high pressure liquid stream dyeing machine, drop into water 216kg, 2,6-two chloro-4-(3-thio phenyl amido)-S-triazine 10% aqueous solution 3.8kg, acetic acid 400cc, add water decomposition silk 360g, pasty state DISPERSE DYES 920g after, the flat fabric 18kg that puts into 100% polyester fiber carries out black-dyeing processing.At normal temperatures machine run after 5 minutes, is risen to 135 ℃ to dye liquor temperature with 2 ℃/minute speed,, then, carry out 85 ℃ of hot water wash, washings, formalize, pad, dry processing this state maintenance draining after 30 minutes.Afterwards, with having the perfluoroalkyl polyacrylate 7kg of water-soluble or water dispersible and isocyanates 500g and the water that is reinforced, be in harmonious proportion out to pad and use mixed solution 100L.After making the water absorption rate of this fiber structure reach 70% with roll, in 110 ℃, dry.The heat treatment that the high temperature setting of then carrying out in 170 ℃ tiling dryer 30 seconds is handled on the second stage of back is all over.Evaluation result for this fiber structure that processes is in this way represented with table 1.
Comparative example 1
Adopt polyester fiber structures thing similarly to Example 1, then, only with having the perfluoroalkyl polyacrylate 7kg of water-soluble or water dispersible and the isocyanates 500g that is reinforced, carry out heat treatment process similarly to Example 1, its result represents with table 1.
Table 1
During LO=RH40%, the generation (V) of friction proof voltage
Residual proof voltage (V) after LI=friction proof voltage finishes
The half life=the necessary time (second) when the LO value arrival of friction end back partly subtracts
Embodiment 2
Water with 270kg, 2,6-two chloro-4-hydroxyls-S-triazine Na salt 10% aqueous solution 3.6kg, acetic acid 100cc, Powdered DISPERSE DYES 540g, adding water decomposition silk 360g stirs in indoor temperature, be purpose to dye navy then, the above-mentioned mixed liquor that mixes up is put in the high-pressure type liquid-flow dyeing machine, behind the Yang Liubu 17kg of input 100%, be penetrated in the polyester fiber fully for making above-mentioned mixed liquor, machine run is 10 minutes at normal temperatures, afterwards, be warmed up to 90 ℃ gradually, drop into behind the 18cc acetic acid this moment this temperature was kept 10 minutes with 3 ℃/minute speed.Kept after temperature is raised to 130 ℃ 30 minutes, and then carried out draining, hot water wash, washing, setting, stoving process, at last with pad, the method for oven dry, high temperature setting, carry out processing method similarly to Example 1, its result represents with table 2.
Comparative example 2
Adopt polyester fiber structures thing similarly to Example 2, then, only with having the perfluoroalkyl polyacrylate 7kg of water-soluble or water dispersible and the isocyanates 500g that is reinforced, carry out heat treatment process similarly to Example 1, its result represents with table 2.
Table 2
Embodiment 3
Water with 252kg, 2,6-two chloro-4-(4-thio phenyl amido)-S-triazine 10% aqueous solution 2.4kg, acetic acid 50cc, pasty state DISPERSE DYES 1780g, add water decomposition silk 250g and in indoor temperature, stir, with the above-mentioned mixed liquor that mixes up in the high-pressure type liquid-flow dyeing machine, to the processing of dyeing of polyester fiber 65%, cotton 35% T/C, 2/2 twill woven.Afterwards, be warmed up to 90 ℃ gradually, drop into behind the 50cc acetic acid this moment this temperature was kept 10 minutes with 2 ℃/minute speed.After being raised to 120 ℃, temperature kept 20 minutes, then carry out draining, hot water wash, washing, setting, stoving process, carry out cotton dyeing with reactive dye again, at last with pad, the method for oven dry, high temperature setting, carry out processing method similarly to Example 1, its result represents with table 3.
Comparative example 3
Adopt T/C cloth similarly to Example 3, carry out the processing method same with comparative example 2, its result represents with table 3.
Table 3
The Spray determination method is a kind of assay method of the U.S., it be cloth be converted into after the fixed angle, drip towards cloth from last, then, measure the wet situation of cloth, 50 refer to half wet condition.
Oil Drop assay method Oil Repellency Test (AATCC test Method 118) is 1 grade～8 grades different hydrocarbon (oil) of carbon number, after dripping to cloth top, have or not minute surface reflection (the wet or not wet degree of observation) above the observation cloth, number of levels is big more big more with regard to the instruction card surface tension, that is to say that the number of levels of experimental result is big more just to illustrate that the hydrophobicity of cloth, grease proofness are good more.
Washing methods AATCC 135 (2) is (A) (ii) 20 times (III)
140 ℃ of flatiron JISL 1096 method H-1
From embodiment shown in the table 11 and comparative example 1, can know in the present invention, improved significantly in the water system washing, for the hydrophobic durability (water system is antifouling) of friction, fully shown the superiority of the technology of the present invention.In addition, nonionic phenomenon by substituent dihalo compound in triazine class of possess hydrophilic property and polynary amino-compound, suppressed the generation of static, prevented the adsorption phenomena (antifouling) of dust, finally reach the purpose of giving easy maintenance function for the polyester fiber thing, obtained good effect.
Claims (8)
1. the method for endowing polyester fiber with hydrophobic function during with disperse dyeing, it is characterized in that: the heat treatment as the phase I is soaked in the polyester fiber thing in the coexistence solution of the substituent dihalo compound in triazine class of possess hydrophilic property and polynary amino-compound and dye liquor, adopts " exhaustion method in the bath " this polyester fiber thing to be carried out 30 ℃～140 ℃ intensification heat treatment; Then, adopt " xeothermic lasting method " in 60 ℃～190 ℃ temperature, to heat-treat as the heat treatment of second stage.
2. according to the method for the described endowing polyester fiber with hydrophobic function of claim 1, it is characterized in that: contain in the substituent dihalo compound in triazine class of described possess hydrophilic property in the general formula (1) represented 2,6-dihalo-4-Y-1,3,5-pyrrolotriazine derivatives;
In the formula, X refers to chlorine, the halogen radical of electing in fluorine and the bromine class, Y refers to virtue amino, aryloxy group, aromatic thiohydroxy, alkylamino, alkoxyl, alkylthio group, triazine amino, triazine hydroxyl, the triazine sulfenyl of being replaced by a kind of base of electing in sulfo group, carboxyl, hydroxy and the mercaptan base class at least, or triazine ammonia stilbene amino.
3. according to the method for the described endowing polyester fiber with hydrophobic function of claim 2, it is characterized in that; Described sulfo group, carboxyl, hydroxy, and the hydrogen atom in the mercapto also can be replaced by alkali metal atom or alkaline earth metal atom.
4. according to the method for the described endowing polyester fiber with hydrophobic function of claim 1, it is characterized in that: described " exhaustion method in the bath " is in bath raio is dye liquor below 1: 30, weight in described polyester fiber structures thing is 100%, the substituent dihalo compound in triazine class of possess hydrophilic property of the DISPERSE DYES of input 0.1%～5% and 0.1%～10% 100% weight concentration and 0.01%～10% polynary amino-compound, after in this coexistence solution, soaking this polyester fiber, intensification heat treatment as the phase I, after gradually bath temperature being risen to 30 ℃～140 ℃ with 40～60 fens clock times, in 100 ℃～140 ℃ temperature, be incubated 10～60 minutes.
5. according to the method for the described endowing polyester fiber with hydrophobic function of claim 1, it is characterized in that: in the intensification heat treatment of second stage, weight in described polyester fiber structures thing is 100%, use amount with perfluoroalkyl polyacrylate of water-soluble or water dispersible is 0.1%～10%, and the use amount of at least a auxiliary agent of selecting from water-based silicon class softener, water-based melamine urea derivative and water-based urethane is 0.1%～10%.
6. according to the method for the described endowing polyester fiber with hydrophobic function of claim 1, it is characterized in that: have hydrophobicity for making the polyester fiber thing, this fibre object is soaked in the coexistence solution of at least a auxiliary agent of selecting in perfluoroalkyl polyacrylate with water-soluble or water dispersible and water-based silicon class softener, water-based melamine urea derivative and the water-based urethane as the heat treatment of second stage, then, adopt that " xeothermic lasting method " dries, high-temperature process in 60 ℃～190 ℃ temperature.
7. according to the method for claim 1,5,6 described endowing polyester fiber with hydrophobic function, it is characterized in that: in the above the molecule of perfluoroalkyl polyacrylate, water-based silicon class softener, water-based melamine urea derivative and water-based urethane of water-soluble or water dispersible of the heat treatment of second stage, preferably contain water-soluble sub stituents such as sulfo group, carboxyl, hydroxy.
8. according to the method for claim 1,4,6, described endowing polyester fiber with hydrophobic function, it is characterized in that: in the described solution, add at least a material in acetic acid, malic acid, glacial acetic acid and the citric acid, the pH value is blended into 3.5～6.5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605616A (en) * | 2012-03-16 | 2012-07-25 | 李民旭 | Method of enabling fiber structures to be continuously durable and hydrophobic |
| CN103088629A (en) * | 2012-12-18 | 2013-05-08 | 华南理工大学 | Method for carrying out super-hydrophobic modification on PET fabric surface |
| CN105026637A (en) * | 2012-07-17 | 2015-11-04 | 菱衣商业有限公司 | Method for imparting permanent long-lasting water repellency to textile structure |
| CN117364330A (en) * | 2023-10-10 | 2024-01-09 | 诸暨市维纳斯针纺有限公司 | Anti-pilling environment-friendly fabric |
-
2008
- 2008-12-29 CN CN200810208040A patent/CN101768861A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605616A (en) * | 2012-03-16 | 2012-07-25 | 李民旭 | Method of enabling fiber structures to be continuously durable and hydrophobic |
| CN105026637A (en) * | 2012-07-17 | 2015-11-04 | 菱衣商业有限公司 | Method for imparting permanent long-lasting water repellency to textile structure |
| CN103088629A (en) * | 2012-12-18 | 2013-05-08 | 华南理工大学 | Method for carrying out super-hydrophobic modification on PET fabric surface |
| CN103088629B (en) * | 2012-12-18 | 2015-06-03 | 华南理工大学 | Method for carrying out super-hydrophobic modification on PET fabric surface |
| CN117364330A (en) * | 2023-10-10 | 2024-01-09 | 诸暨市维纳斯针纺有限公司 | Anti-pilling environment-friendly fabric |
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