CN100494556C - Dyeing method for cross linked acrylic fiber and fiber products containing cross linked acrylic fibers dyed by such method - Google Patents
Dyeing method for cross linked acrylic fiber and fiber products containing cross linked acrylic fibers dyed by such method Download PDFInfo
- Publication number
- CN100494556C CN100494556C CNB2005100910224A CN200510091022A CN100494556C CN 100494556 C CN100494556 C CN 100494556C CN B2005100910224 A CNB2005100910224 A CN B2005100910224A CN 200510091022 A CN200510091022 A CN 200510091022A CN 100494556 C CN100494556 C CN 100494556C
- Authority
- CN
- China
- Prior art keywords
- cross linked
- linked acrylic
- acrylic fibers
- fiber
- dyeing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
To provide a method for dyeing a cross-linked acrylate fiber in which dyeing with durability is conventionally considered as impossible with the practical durability using a reactive dye without deteriorating performances such as moisture absorbing and releasing properties or deodorizing properties. The method for dyeing the cross-linked acrylate fiber is characterized as follows. The cross-linked acrylate fiber subjected to a cross-linkage introduction treatment with a hydrazine compound and a hydrolysis treatment with an aqueous solution of an alkaline metal salt is treated with the reactive dye under acidic conditions. The cross-linked acrylate fiber, as necessary, is subsequently treated under alkaline conditions.
Description
Technical field
The fibre that the invention provides a kind of method of implementing to dye and contain the cross linked acrylic fibers that dyes by this method, described method is the cross linked acrylic fibers that can not implement to have durability dyeing to existing, not damaging absorb-discharge humid, using chemically-reactive dyes under the performance such as the smelly property that disappears, implement colouring method with practical durability.
Background technology
Cross linked acrylic fibers has excellent absorb-discharge humid, disappear smelly property, antibiotic property, is gazed in recent years.Known these fiber form and aspect from light peachiness to brown.This acrylic fibers has the carboxyl of performance dry up-take location function, can carry out fiber with cation dyes painted, but fiber self in order to keep water-swellable, colorfastness is poor, thus with it as the dyeing on can not realistic scale.Therefore, still do not use separately in this fiber at the fiber body structure of using with, the application in needs dyeing field also is restricted.
In order to address this problem, in patent documentation 1, at the carbon black that contains 0.5-5 weight % as the raw fiber acrylic fiber that is used for blackization in advance, in this raw fiber, import by produce crosslinked of hydrazine class compound and import the carboxyl that produces by hydrolysis.But this method just is limited to black.On the contrary, be colored as versicolor raw fiber even use, industrial for the kind of different colours can not be thoroughly corresponding means.
In addition, in patent documentation 2, put down in writing, made it contain the method for the stainability compound that in 1 molecule, has hydroxyl and amino for cross linked acrylic fibers being given the dyeability of realistic scale.This method is the cross linked acrylic fibers of being handled, being obtained by the hydrolysis of alkalinous metal saline solution generation by the crosslinked importing that hydrazine class compound produces for implementing in acrylic fiber, with having the method that hydroxyl and amino dyed compound water solution impregnation are handled in 1 molecule, shown the dyeability of moistening friction fastness more than 3 grades.
But treatment process increase in fact in this method can not deny that industrial productivity descends.In addition, amino by can dying compound and the carboxyl reaction in the cross-linked acrylic acid ester fiber and can dying so handle the occasion of the cross linked acrylic fibers with a large amount of carboxyls, be difficult to give dyeing equably.Carboxyl is by being blocked by dying compound, so worry having absorb-discharge humid originally and disappearing smelly performance reduction of cross linked acrylic fibers in addition.
[patent documentation 1] spy opens the 2003-89971 communique
[patent documentation 2] spy opens the 2003-278079 communique
Summary of the invention
The purpose of this invention is to provide can with have excellent absorb-discharge humid, antibiotic property, the cross linked acrylic fibers of the smelly property that disappears is coloured to various colors not damaging under its performance, the colouring method of colorfastness, and the fibre that contains the cross linked acrylic fibers that dyes by this colouring method.The inventor focuses on the dyeing of cross linked acrylic fibers, furthers investigate continuously.It found that colorfastness increases in the occasion with adsorption reaction dyestuff under the acid condition, by handling, further can improve colorfastness then under alkali condition, and then finish the present invention.
That is, the present invention is made of following means.
(1) colouring method of cross linked acrylic fibers, it is characterized in that, acrylic fiber is implemented to handle and pass through by the crosslinked importing of hydrazine class compound the hydrolysis process of alkalinous metal saline solution, obtain cross linked acrylic fibers thus, make this fiber adsorption reaction dyestuff under acid condition.
(2) colouring method of cross linked acrylic fibers, it is characterized in that, acrylic fiber is implemented to handle and pass through by the crosslinked importing of hydrazine class compound the hydrolysis process of alkalinous metal saline solution, obtain cross linked acrylic fibers thus, make this fiber adsorption reaction dyestuff under acid condition, under alkali condition, react afterwards with this dyestuff.
The colouring method of (3) (2) described cross linked acrylic fibers is characterized in that, under alkali condition with the reacted bath of dyestuff pH more than 9.
The colouring method of each described cross linked acrylic fibers of (4) (1)-(3) is characterized in that acid condition is below pH5.
The colouring method of each described cross linked acrylic fibers of (5) (1)-(4) is characterized in that, chemically-reactive dyes is the dyestuff that reacts with amino.
(6) fibre is characterized in that, contains the cross linked acrylic fibers by each described colouring method dyeing of (1)-(5).
By utilizing colouring method of the present invention can obtain versicolor cross linked acrylic fibers.Thus, can be deployed into owing to the dyeing of existing realistic scale can not be used in the purposes that is restricted, not only can corresponding more and more diversified fashion need, and need not implement special processing to cross linked acrylic fibers, in addition from seeing industrial also very useful with regard to stainable aspect with general dyeing installation.
The specific embodiment
Below the present invention is described in detail.At first, will be among the present invention to ion and-COO
-In conjunction with functional group meter make " carboxyl ", with carboxyl be that pH meter is made " H type " to ion, be that the meter of metal ion is made " slaine type ".For example " COOH " meter is made " H type carboxyl ".
In the colouring method of the present invention, handle and to handle the fiber that obtains by the alkaline metal salt aqueous hydrolysis just passable by the crosslinked importing of hydrazine class compound as the cross linked acrylic fibers of dyeing object so long as by acrylic fiber is implemented.This cross linked acrylic fibers can followingly be made usually.
At first, as the acrylic fiber of the initial feed of cross linked acrylic fibers, so long as by containing more than acrylonitrile (hereinafter referred to as AN) the 40 weight %, more than the preferred 50 weight %, more preferably the fiber that forms of the above AN base polymer of 80 weight % gets final product.As form, can be form arbitrarily such as staple fibre, tow (tow), line, braided fabric, nonwoven fabric, also can be manufacturing process's product, useless fiber etc. midway in addition.The AN base polymer can be any in the copolymer of the independent condensate of AN, AN and other monomers, as the combined polymerization composition beyond the AN, so long as methyl methallyl sulfonic acid, p styrene sulfonic acid etc. contain sulfonic monomer with and the monomer that contains carboxyl such as salt, (methyl) acrylic acid, itaconic acid with and salt, styrene, vinyl acetate, (methyl) acrylate, (methyl) but the monomer of monomers such as acrylamide etc. and AN copolymerization, just there is no particular limitation.This acrylic fiber is handled by the crosslinked importing of hydrazine class compound, and formation is crosslinked on the meaning of not dissolving the earliest in the solvent of acrylic fiber, becomes the cross-linked acrylic acid fibrid, and the result causes the increase of nitrogen content simultaneously.There is no particular limitation as means that crosslinked importing is handled, preferably can adjust to 0.1-10 weight %, the more preferably means of 1-10 weight % by the nitrogen content increase of this processing.As adjusting the means that nitrogen content is 0.1-10 weight %, in the aqueous solution of the concentration 5-60 weight % of industrial preferred hydrazine class compound, handle 5 hours down with interior means for temperature 50-120 ℃ in addition.
As hydrazine class compound used herein, there is no particular limitation, can enumerate hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrobromic acid hydrazine, hydrazine carbonic acid ester etc., contain the compound that ethylenediamine, guanidine sulfate, guanidine hydrochloride, phosphoguanidine, melamine etc. also have a plurality of amino in addition.
The fiber that this process is handled with the crosslinked importing of hydrazine class compound also can be implemented acid treatment after fully removing the hydrazine class compound residual by this processing.Here as the acid of using, can enumerate ore deposit aqueous acids such as nitric acid, sulfuric acid, hydrochloric acid, organic acid etc., there is no particular limitation.As this acid-treated condition, there is no particular limitation, can enumerate down example: probably in the aqueous solution of acid concentration 5-20 weight %, preferred 7-15 weight %, flooded processed fiber 0.5-10 hour down at temperature 50-120 ℃.
Through the fiber handled with the crosslinked importing of hydrazine class compound or further pass through acid-treated fiber next in order to be modified to esters of acrylic acid by the processing that is hydrolyzed of alkalinous metal saline solution.By this processing and acrylic fiber by the crosslinked importing of hydrazine class compound handle irrespectively residual CN base or implement the residual CN base of acid-treated occasion after crosslinked importing is handled, the amide groups that hydrolysis generates with a part of acid treatment is hydrolyzed, and forms carboxyl.The carboxyl of Xing Chenging combines with the metal ion of the alkaline metal salt origin that is used for hydrolysis in addition, so major part is a slaine type carboxyl.As alkaline metal salt used herein, can enumerate alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate etc.There is no particular limitation for the condition of hydrolysis process, and preferred 1-10 weight % on industrial, fibrous physical property more preferably in the aqueous solution of 1-5 weight %, handles 1-10 hour down with interior means for temperature 50-120 ℃.
Promote the degree of hydrolysis, promptly the growing amount of carboxyl sees that there is no particular limitation on purpose of the present invention dyes this viewpoint, investigates the required performance of final fiber and sets and get final product.For example, in order to keep hygroscopicity, slaine type carboxyl amount 1-10mmol/g, preferred 3-10mmol/g, further preferred 3-8mmol/g has obtained the result easily, the concentration of the medicament when this can control above-mentioned processing easily and temperature, the combination in processing time.The occasion of the quantity not sufficient 1mmol/g of slaine type carboxyl can not obtain sufficient hygroscopicity, in the occasion that surpasses 10mmol/g, then can not obtain to satisfy the fibrous physical property in the practicality in addition.In addition, in the colouring method of the present invention, in a single day owing to place cross linked acrylic fibers under acid condition, carboxyl becomes the H type, by carrying out ion-exchange treatment after the dyeing, can become slaine type carboxyl as described later.In addition, the fiber CN of this process hydrolysis is residual still not residual can.If the CN base is residual, only otherwise influence dyeability, utilize its reactivity, may give certain function.
In addition, as above-mentioned, the fiber by the alkaline metal salt hydrolysis process has slaine type carboxyl, by implementing acid treatment, also becomes H type carboxyl.There is no particular limitation in the acid of using this moment, can use ore deposit aqueous acids such as nitric acid, sulfuric acid, hydrochloric acid, organic acid etc.
In addition, as cross linked acrylic fibers, as long as can be the processing beyond the acid treatment after the above-mentioned crosslinked importing processing of enforcement, acid treatment, hydrolysis process, the hydrolysis with colouring method dyeing of the present invention with colouring method dyeing of the present invention.
In the above-mentioned cross linked acrylic fibers, when handling, exist a part not to be cross-linked to form amino part, think that the amino of this part forms the dry up-take location of chemically-reactive dyes and is colored with the crosslinked importing of hydrazine class compound.In addition, reduce the occasion of the cross linked acrylic fibers handled after the hydrolysis process, dye on the heavy colour easily, reason is thought also to form amino by reducing the crosslink part of handling importing with hydrazine class compound, for this amino, also become the dry up-take location of chemically-reactive dyes.
Next, the chemically-reactive dyes that uses as the present invention preferably with the chemically-reactive dyes of amino reaction, for example can be enumerated chlorine three azine dyes such as a chlorine three azine dyes, dichloro three azine dyes, chlorine pyrimidine dyestuff, vinyl sulfone dyestuff etc.In addition, the dyestuff etc. that has the dyestuff of 2 sulphate groups ethyl sulfuryls and have a chlorine three azines more than 2 has the dyestuff of a plurality of identical type functional group, further, also can use a sulphate groups ethyl sulfone/chlorine three azineses, sulphate groups ethyl sulfone/dichloro three azineses, sulphate groups ethyl sulfone/difluoro one chlorine three azineses etc. to have dyestuff of a plurality of variety classes functional group etc.
For cross linked acrylic fibers being dyeed, must under acid condition, make chemically-reactive dyes be adsorbed on dye adsorbing process on the cross linked acrylic fibers with this chemically-reactive dyes.As acid condition, make the bath before impregnation of fibers, i.e. the pH of the bath of the state that chemically-reactive dyes and acid is added is preferably below 5, more preferably below 4, further preferably below 3.Usually, carry out under alkalescent-alkali condition with chemically-reactive dyes dyeing, chemically-reactive dyes is difficult to be adsorbed on the cross linked acrylic fibers under this condition.This thinks to have negative electrical charge in the inner a large amount of carboxyl ionization under solutions of weak acidity-alkali condition that exist of cross linked acrylic fibers, on the other hand, because above-mentioned chemically-reactive dyes also has negative electrical charge, so the cause that electricity repels takes place.But along with acidity strengthens, in other words, along with pH reduces, dissociating of the carboxyl in the cross linked acrylic fibers is suppressed, near electroneutral, and adsorption reaction dyestuff and being colored.Therefore, pH is low more, easy more dense dyeing.
In addition, in the above-mentioned dye adsorbing process, also can further and with dyestuff lytic agent, metal block dyeing assistant commonly used such as agent, dispersant, accelerant, retarding agents, dye leveller as required.As the acid of adjusting pH, there is no particular limitation, can enumerate organic acids such as acetic acid, formic acid, lactic acid, tartaric acid, ore deposit aqueous acids such as nitric acid, sulfuric acid, hydrochloric acid.Wherein, see preferred use formic acid from the strong and weak of acid degree with to the viewpoint of the corrosion of dyeing machine.There is no particular limitation for treatment temperature, if more than 60 ℃, the adsorption rate of dyestuff is also fast, we can say industrial to be suitable for.
As described above, make the cross linked acrylic fibers of chemically-reactive dyes absorption on realistic scale, have colorfastness, can use cross linked acrylic fibers as dyeing.In addition, the cross linked acrylic fibers that obtains is a purpose to improve moisture pick-up properties etc., wants to make carboxyl in this fiber become the occasion of slaine type, the situation that exists chemically-reactive dyes to break away from by ion-exchange.Avoid the occasion of such phenomenon and the occasion that further needs excellent colorfastness in hope, effectively way is: after above-mentioned dye adsorbing process, make under alkali condition and chemical covalent bond takes place between cross linked acrylic fibers and dyestuff carry out immobilization and handle.This immobilization is handled and can be carried out under alkali condition, and the bath pH after wishing to handle is more than 9.The above-mentioned chemically-reactive dyes that is adsorbed on the cross linked acrylic fibers by dye adsorbing process forms covalent bond owing to handle activation by depickling under alkali condition with cross linked acrylic fibers, so under the such weak basic condition of the bath pH less than after the processing 9, preferentially carry out the electricity repulsion with the carboxyl in the aforementioned cross linked acrylic fibers, the chemically-reactive dyes stripping is in water before forming covalent bond, there is the unsettled situation of the form and aspect that are colored thing after dyeing, not preferred in the practicality.
In order to make the bath pH after immobilization is handled carry out the immobilization processing more than 9, preferably in the alkali compounds of the amount more than 9, carry out the immobilization processing at the bath pH that adds after handling.Here, as alkali compounds, there is no particular limitation, can adopt acylate, carbonate, hydroxide and amines, the ammonia etc. of alkali metal and alkaline-earth metal.As reaction temperature, can at room temperature carry out, can suitably adopt more than 60 ℃ in order to improve reaction speed.In addition, in this immobilization is handled, also can also use with the various medicaments such as dyeing assistant such as pollutant, sticking agent that prevent that generally are used for by chemically-reactive dyes dyeing.
As described above, immobilization under alkali condition is handled because be to carry out after the dye adsorbing process under the acid condition, can be after dye adsorbing process, but be not must be after horse back.For example, the situation that can exist has: after dye adsorbing process, washing is carried out the immobilization processing after being colored thing under alkali condition, or be colored thing be cross linked acrylic fibers and other raw materials constitute fibre the time at the dyeing process of his raw material of the laggard Xingqi of dye adsorbing process, under alkali condition, carry out immobilization processing etc. then.
In addition, the carboxyl in the cross linked acrylic fibers after immobilization is handled also can become desired slaine type carboxyl or H type carboxyl by further ion-exchange according to desired function.For example, in the occasion of giving the ammonia deodorizing function, slaine type carboxyl can be changed into H type carboxyl by adding acid.In addition, in the occasion of giving the pH pooling feature, can adjust the ratio of slaine type carboxyl and H type carboxyl by adjusting pH with acid or alkali.In addition, different with the occasion of only carrying out dye adsorbing process, chemically-reactive dyes is owing to form covalent bond with cross linked acrylic fibers, so the disengaging of the dyestuff when being not easy to cause ion-exchange.
The thing that is colored that dyes through above-mentioned processing is implemented washing, is soaped and fixedly processing of carrying out in order to improve moistening colorfastness as required and the finishing agent processing of carrying out in order to improve quality etc. become goods.Here, as the dyeing object of colouring method of the present invention, can enumerate line, yarn (also comprising the lap yarn), filament, fabric, volume thing, nonwoven fabric, paper shape thing, tablet, duplexer, cotton fibres such as (comprising spherical and block).These dyeing objects can be the article that only are made of cross linked acrylic fibers, also can be and with the article of other raw materials formations.As can and other raw materials of usefulness, can use natural fabrics such as cotton, fiber crops, thin,tough silk, wool, goats hair, semisynthetic fibres such as regenerated fiber, cellulose acetate fibre, Promix such as artificial silk, cuprammonium, リ ヨ セ Le, regenerated protein, synthetic fiber such as nylon, fragrant acid amides, polyester, acrylic acid, polyethylene, polypropylene, polyvinyl alcohol, polyvinyl chloride, polyurethane etc., further, also can adopt inorfils such as glass fibre, carbon fiber, alumina fibre etc. according to purposes.Also the other materials of usefulness is not limited to fiber in addition, also can be materials such as resin, particle.
Dyeing to as and if with the occasion of the fibre of cross linked acrylic fibers and other materials formation, can be by implementing colouring method of the present invention respectively and being applicable to that the method for other materials dyes.For example, also use the words of cotton fibre as other materials, can adopt following method: at first, after implementing colouring method of the present invention cross linked acrylic fibers in the fibre being dyeed, implement as required to soap, implement cotton common colouring method then to the cotton fiber dyeing in the fibre, soap, fix and handle.
Particularly cotton fiber dyeing is also used the occasion of chemically-reactive dyes, under alkali condition, carry out the fixing of dye processing and can implement the dyeing process separately of cross linked acrylic fibers and cotton fiber respectively, also can implement immobilization simultaneously and handle two fibers.Promptly, the following method of preferred employing: after at first under acid condition, making chemically-reactive dyes be adsorbed on the cross-linked acrylic acid ester fiber, washing, after making chemically-reactive dyes be adsorbed on the cotton fiber with cotton common colouring method then, these two carries out the fixing of dye processing to cross linked acrylic fibers and cotton fiber simultaneously under alkali condition, soaps, washes, drying etc.
On the other hand, the occasion of cotton fiber formerly dyes, preferably after in the dyestuff absorption process of the cross linked acrylic fibers that carries out under the acid condition dyestuff not break away from dyestuff from cotton fiber such, implement in each dyeing process of each fiber the immobilization under alkali condition and handle.
Also use the occasion of the fibre of acrylic fiber in addition as other raw materials, can adopt following method: at first use cation dyes to implement the common colouring method of acrylic fiber, after the dyeing of the acrylic fiber in the fibre, implement as required to soap, implement colouring method of the present invention then, cross linked acrylic fibers in the fibre is dyeed, soap, fix and handle.In addition, if when carrying out the dyeing of cross linked acrylic fibers earlier, cross linked acrylic fibers is polluted by cation dyes during the dyeing of the acrylic fiber that carries out afterwards, because the Color that can not obtain to expect, so preferably at first acrylic fiber is dyeed.
As other raw materials, and with the occasion of acrylic fibers peacekeeping cotton fiber, promptly, the occasion of the fibre that is made of acrylic fiber, cotton fiber, this three of cross linked acrylic fibers, the combination of dyeing order that can be by above-mentioned cotton fiber/cross linked acrylic fibers and acrylic fiber/cross linked acrylic fibers be dyeed.
Other raw materials are occasions of wool, the following method of preferred employing: the common colouring method of at first implementing wool, to behind woolen dyed in the fibre, implement as required to soap, implement colouring method of the present invention then, to the dyeing of the cross linked acrylic fibers in the fibre, soap, fix and handle.In addition,,, can implement dyeing process separately respectively, handle but preferably two fibers are carried out immobilization simultaneously with also the occasion with cotton fiber is same for the fixing of dye processing under alkali condition.
In addition, using chemically-reactive dyes that wool and cross linked acrylic fibers are dyed homochromy occasion, also is one of method for optimizing in same bathtub dyeing.But, for wool and cross linked acrylic fibers because the adsorption rate of dyestuff has very big difference, so wool heavy colour, the such uneven dyeing of cross linked acrylic fibers light color may take place.Therefore, preferably take in the dyeing bathtub, to add measure of retarding agents and dye leveller etc. or the like, regulate the adsorption rate of dyestuff.
In addition, in the colouring method of the present invention, do not need special dyeing installation, can use according to the general dyeing installation that is colored thing.This is favourable one side from industrial seeing.
Above-described the present invention is following colouring method: acrylic fiber is implemented to handle and hydrolysis process by the alkalinous metal saline solution obtains cross linked acrylic fibers by the crosslinked importing of hydrazine class compound, this cross linked acrylic fibers is handled with chemically-reactive dyes under acid condition, according to circumstances, under alkali condition, handle then, can dye shades of colour not damaging under its performance to cross linked acrylic fibers with excellent absorb-discharge humid, antibiotic property, deodorization, colorfastness might as well, it is of the utmost importance for its meaning.
[embodiment]
Followingly the present invention is specifically described, but the present invention is not limited to following embodiment according to embodiment.The not special explanation of " part " among the embodiment and " percentage " is represented with weight basis in addition.
(1) slaine type carboxyl amount (mmol/g)
The smart about 1g of cross linked acrylic fibers that claims (Xg) intensive drying, behind the water that wherein adds 200ml, add the 1mol/l aqueous hydrochloric acid solution while heating to 50 ℃,, obtain titration curve with the sodium hydrate aqueous solution of 0.1mol/l according to well-established law then to pH2.Obtain the consumption figure (Yml) of the sodium hydrate aqueous solution that carboxyl consumes from this titration curve, calculate carboxyl amount (mmol/g) according to following formula then.
(carboxyl amount)=0.1Y/X
In addition, in above-mentioned carboxyl quantitative determination operation, need not adjust pH2, obtain titration curve equally, calculate H type carboxyl amount (mmol/g) by adding the 1mol/l aqueous hydrochloric acid solution.Calculate slaine type carboxyl amount from these results by following formula.
(slaine type carboxyl amount)=(carboxyl amount)-(H type carboxyl amount)
(2) saturated hydroscopicity (%)
With air drier at 105 ℃ to dry 16 hours of the about 5.0g of sample, gravimetry (W1g).Under 20 ℃ of temperature, sample is put into the insulating box 24 hours of 65%RH then.Like this, measure the weight of the sample of moisture absorption.(W2g)。From above measurement result, calculate according to following formula.
(saturated hydroscopicity %)=(W2-W1)/W1} * 100
(3) light-fast dyeings fastness (level)
According to the standard of JIS-L-0842 (the 3rd exposure method), blackboard (black panel) thermometer is set at 63 ± 3 ℃, test, judge to become the degree of fading.Determinator uses ス ガ testing machine (strain) system Standard UV Long Life Fade Mater.If the light-fast dyeings fastness more than 3 grades, then be can anti-practicality fastness.
(4) sweat colorfastness (level)
According to the JIS-L-0848 benchmark, use alkaline synthetic perspiration to test, use to become and fade relatively with the sample before gray scale and the test, judge the degree that change is faded.If the sweat colorfastness more than 3 grades, then be can anti-practicality fastness.
(5) moistening friction colorfastness
According to the JIS-L-0849 benchmark, test by frictional testing machine II shape, use to pollute and judge the friction painted degree of byssus with gray scale.If moistening friction colorfastness more than 3 grades, then be can anti-practicality fastness.
[making of the weaving silk A of cross linked acrylic fibers]
10 parts of AN class condensates that will be made of acrylonitrile (AN) 90%, vinyl acetate 10% (30 ℃ inherent viscosity [η]=1.2 in dimethyl formamide) are dissolved in 90 parts of 48% the sodium thiocyanate water solutions, obtain the stoste that spins, after spinning, extend (full extension ratio: 10 times) according to well-established law, dry under the atmosphere of dry bulb/wet bulb=120 ℃/60 ℃, humid heat treatment obtains the raw fiber of one-dimensional fibrousness 0.9dtex.The crosslinked importing that this raw fiber carried out 98 ℃ * 5 hours is handled washing in 20% aqueous solution of hydrazine hydrate.The increase of the nitrogen content by this processing is 5%.Then, in 3% the aqueous solution of nitric acid, carry out 90 ℃ * 2 hours acid treatment.Then in 3% aqueous solution of NaOH, carry out 90 ℃ * 2 hours hydrolysis process, use the ion-exchange water washing.The cross linked acrylic fibers that obtains through above-mentioned processing is the carboxyl with 5.5mmol/g, and saturated hydroscopicity is 45%.This cross linked acrylic fibers is immersed in the 1N aqueous hydrochloric acid solution 30 minutes, changes carboxyl into the H type, washing, drying is made the braided wire (braided wire A) of metric count 1/52, the evaluation of dyeing with dry product.
[making of the braided wire B of cross linked acrylic fibers]
In making above-mentioned braided wire A, use the carboxyl that will make as the ratio blending of the cross linked acrylic fibers of H type and acrylic fibers commonly used with 30:70, make the braided wire (braided wire B) of metric count 1/52.
[making of the braided wire C of cross linked acrylic fibers]
In making above-mentioned braided wire A, use the carboxyl that will make as the ratio blending of the cross linked acrylic fibers of H type and kapok with 30:70, make the braided wire (braided wire C) of metric count 1/52.
[making of the braided wire D of cross linked acrylic fibers]
In making above-mentioned braided wire A, use the carboxyl that will make as the ratio blending of the cross linked acrylic fibers of H type and wool with 50:50, make the braided wire (braided wire D) of metric count 1/52.
[embodiment 1]
Chemically-reactive dyes Sumifix Supra Blue BRF (Sumitomo Chemical system) 0.03g and 90% aqueous formic acid are added in the water, make the dye bath of 100ml, pH2.4.A is immersed in the dye bath with the 3g braided wire, keeps at 60 ℃ and carries out dye adsorbing process in 30 minutes.Then, soap, wash, drying, the braided wire that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.Dye heavy colour as the resulting braided wire of table 1, colorfastness also can tolerate practicality.Do not show high value for saturated hydroscopicity, this thinks that carboxyl is transformed into that the state of H type causes.
[embodiment 2]
Chemically-reactive dyes Sumifix Supra Blue BRF (Sumitomo Chemical system) 0.03g and 90% aqueous formic acid are added in the water, make the dye bath of 100ml, pH2.4.A is immersed in the dye bath with the 3g braided wire, keeps at 60 ℃ and carries out dye adsorbing process in 30 minutes.Behind the braided wire that washing obtains, be immersed in the water of 100ml, be warmed up to 60 ℃.Then, add sodium carbonate, carried out the immobilization processing in 30 minutes by keeping.Dye bath pH after the processing is 10.0.Then soap, wash, drying, the braided wire that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.Dye heavy colour as the resulting braided wire of table 1, colorfastness is than embodiment 1 height.Saturated in addition hydroscopicity is identical with original cross linked acrylic fibers, and this thinks that carboxyl is not a dry up-take location, and immobilization is transformed into the cause of Na type carboxyl under alkali condition when handling.
[embodiment 3]
Chemically-reactive dyes Sumifix Supra Yellow 3RF (Sumitomo Chemical system) 0.03g and acetic acid are added in the water, make the dye bath of 60ml, pH2.8.A is immersed in the dye bath with the 3g braided wire, keeps at 60 ℃ and carries out dye adsorbing process in 30 minutes.Behind the braided wire that washing obtains, be immersed in the water of 60ml, be warmed up to 60 ℃.Then, add sodium carbonate, carried out the immobilization processing in 30 minutes by keeping.Dye bath pH after the processing is 9.0.Then soap, wash, drying, the braided wire that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.Dye light color as the resulting braided wire of table 1, have good colorfastness.Saturated in addition hydroscopicity is identical with original cross linked acrylic fibers.
[embodiment 4]
Chemically-reactive dyes Sumifix Black ENS 150% (Sumitomo Chemical system) 0.21g and 90% aqueous formic acid are added in the water, make the dye bath of 180ml, pH2.4.A is immersed in the dye bath with the 3g braided wire, keeps at 60 ℃ and carries out dye adsorbing process in 30 minutes.Behind the braided wire that washing obtains, be immersed in the water of 180ml, be warmed up to 60 ℃.Then, add sodium carbonate, carried out the immobilization processing in 30 minutes by keeping.Dye bath pH after the processing is 8.2.Then soap, wash, drying, the braided wire that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.Become the yellow black of band point as the resulting braided wire of table 1, have good colorfastness.
[embodiment 5]
Cation dyes Nichilon Black G 200% (day one-tenth system of changing into) 0.05g and acetic acid are added in the water, make the dye bath of 100ml, pH4.0.B is immersed in this dye bath with the 3g braided wire, boil 30 minutes after, the washing, the acrylic fiber among the braided wire B is dyeed.The braided wire that obtains is impregnated in the following dye bath, promptly, add chemically-reactive dyes Sumifix BlackENS 150% (Sumitomo Chemical system) 0.13g and 90% aqueous formic acid to make 100ml, pH2.8 in the water dye bath, keep at 60 ℃ and carried out dye adsorbing process in 30 minutes.Behind the braided wire that washing obtains, be immersed in the water of 100ml, be warmed up to 60 ℃.Then, add sodium carbonate, carried out the immobilization processing in 30 minutes by keeping.Dye bath pH after the processing is 10.9.Then soap, wash, drying, the braided wire that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.As the resulting braided wire of table 1 is black, and the acrylic fibers peacekeeping cross linked acrylic fibers in the braided wire has been dyed black respectively as can be known.
[embodiment 6]
Chemically-reactive dyes Sumifix Black ENS 150% (Sumitomo Chemical system) 0.13g and 90% aqueous formic acid are added in the water, make the dye bath of 100ml, pH2.8.C is immersed in the dye bath with the 3g braided wire, keeps at 60 ℃ and the cross linked acrylic fibers among the braided wire C is carried out dye adsorbing process in 30 minutes.Be impregnated into again by chemically-reactive dyes Sumifix Black ENS 150% (Sumitomo Chemical system) 0.14g is added in the dye bath of making 100ml in the water behind the braided wire that washing obtains, be warmed up to 80 ℃.Then, add anhydrous sodium sulfate, carry out dye adsorbing process by keeping 30 minutes Temperature on Cotton Fiber.Then the dye bath temperature is reduced to 60 ℃, adds ammonium carbonate, carry out the immobilization processing by keeping 30 minutes temperature.Dye bath pH after the processing is 10.9.Then soap, wash, drying, the braided wire C that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.Dye black as the resulting braided wire of table 1, have good colorfastness.
[embodiment 7]
Chemically-reactive dyes Lanaset Blue (CIBA system) 0.015g and acetic acid are added in the water, make the dye bath of 100ml, pH3.5.D is immersed in the dye bath with the 3g braided wire, keeps at 98 ℃ and the wool among the braided wire D is carried out dye adsorbing process in 30 minutes.Soaping is impregnated into by chemically-reactive dyes Sumifix Supra Blue BRF (Sumitomo Chemical system) 0.015g and 90% aqueous formic acid are added in the dye bath of making 100ml, pH2.7 in the water behind the braided wire that obtains again, and is warmed up to 80 ℃, washing.Be impregnated into then in the water of 60 ℃ of 100ml, add sodium carbonate, carry out the immobilization processing by keeping 15 minutes temperature.Dye bath pH after the processing is 10.4.Then soap, wash, drying, the braided wire D that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.Dye blueness as the resulting braided wire of table 1, have good colorfastness.
[comparative example 1]
In embodiment 1, add except replacing aqueous formic acid the sodium carbonate, implement dye adsorbing process equally.Dye bath pH is 8.0, and dyestuff does not adsorb, and can not dye.
[comparative example 2]
ACID DYES Telon Blue GW (ダ イ ス -system) 0.03g and 90% aqueous formic acid are added in the water, make the dye bath of 60ml, pH2.2.The braided wire A of 3g is impregnated in the dye bath, is heated to 60 ℃,, carry out dye adsorbing process by keeping 30 minutes.Then, soap, the dyestuff stripping can not be dyeed.
[comparative example 3]
In comparative example 2, do not soap, wash, drying, the braided wire that obtains dyeing.The evaluation result of the braided wire that obtains is as shown in table 1.Though the braided wire that obtains as shown in table 1 is colored in appearance, the colorfastness of sweat is had only 1 grade, not the braided wire in the tolerance practicality.
Table 1
Claims (6)
1. the colouring method of cross linked acrylic fibers, it is characterized in that, acrylic fiber is implemented to handle and pass through by the crosslinked importing of hydrazine class compound the hydrolysis process of alkalinous metal saline solution, obtain cross linked acrylic fibers thus, make this fiber adsorption reaction dyestuff under acid condition.
2. the colouring method of cross linked acrylic fibers, it is characterized in that, acrylic fiber is implemented to handle and pass through by the crosslinked importing of hydrazine class compound the hydrolysis process of alkalinous metal saline solution, obtain cross linked acrylic fibers thus, make this fiber adsorption reaction dyestuff under acid condition, under alkali condition, react afterwards with this dyestuff.
3. the colouring method of the described cross linked acrylic fibers of claim 2 is characterized in that, under alkali condition with the reacted bath of dyestuff pH more than 9.
4. the colouring method of each described cross linked acrylic fibers of claim 1-3 is characterized in that, acid condition is below the pH5.
5. the colouring method of each described cross linked acrylic fibers of claim 1-4 is characterized in that, chemically-reactive dyes is the dyestuff that reacts with amino.
6. fibre is characterized in that, contains the cross linked acrylic fibers by each described colouring method dyeing of claim 1-5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004226690 | 2004-08-03 | ||
| JP2004226690 | 2004-08-03 | ||
| JP2005187653 | 2005-06-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1734008A CN1734008A (en) | 2006-02-15 |
| CN100494556C true CN100494556C (en) | 2009-06-03 |
Family
ID=36076602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100910224A Active CN100494556C (en) | 2004-08-03 | 2005-08-03 | Dyeing method for cross linked acrylic fiber and fiber products containing cross linked acrylic fibers dyed by such method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100494556C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5056358B2 (en) * | 2007-11-02 | 2012-10-24 | 日本エクスラン工業株式会社 | Dyeable cross-linked acrylate fiber, method for producing the same, and dyed cross-linked acrylate fiber obtained by dyeing the fiber |
| WO2010029664A1 (en) * | 2008-09-10 | 2010-03-18 | 日本エクスラン工業株式会社 | Crosslinked acrylate-based fibers and the production thereof |
| CN102575415B (en) * | 2009-07-22 | 2014-02-19 | 日本爱克兰工业株式会社 | Moisture-absorbing fiber dyeable with acid dyes and method for producing same |
| WO2013069659A1 (en) * | 2011-11-10 | 2013-05-16 | 日本エクスラン工業株式会社 | Moisture-absorbing deodorizing fibers, method for producing fibers, and fiber structure comprising fibers |
| JP6228511B2 (en) * | 2014-05-29 | 2017-11-08 | 日本エクスラン工業株式会社 | Cross-linked acrylate fiber with good dispersibility |
| TWI735447B (en) * | 2015-08-06 | 2021-08-11 | 日商日本Ｅｘｌａｎ工業股份有限公司 | Anti-virus material, and anti-viral material-containing anti-virus product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003183978A (en) * | 2001-09-26 | 2003-07-03 | Mizuno Corp | Moisture absorbing and releasing fiber, method for producing the same and fiber product using the same |
-
2005
- 2005-08-03 CN CNB2005100910224A patent/CN100494556C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003183978A (en) * | 2001-09-26 | 2003-07-03 | Mizuno Corp | Moisture absorbing and releasing fiber, method for producing the same and fiber product using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1734008A (en) | 2006-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100494556C (en) | Dyeing method for cross linked acrylic fiber and fiber products containing cross linked acrylic fibers dyed by such method | |
| CN105556026B (en) | Crosslink propylene acid esters series fiber and the fiber structure containing the fiber | |
| CN103541213B (en) | Wash the dyeing and finishing technology of bright and beautiful snow pear suede cotton like fabric | |
| US6497732B1 (en) | Fiber-reactive polymeric dyes | |
| TWI435969B (en) | Dyeable crosslinked acrylate-based fibers, the preparation method thereof, and dyed crosslinked acrylate-based fibers obtained by dyeing said fibers | |
| CA1097864A (en) | Hygroscopic fibres and filaments of synthetic polymers | |
| KR101250048B1 (en) | Method for dyeing of crosslinked acrylate fibers, and fiber products containing the crosslinked acrylate fibers dyed thereby | |
| CN106958052B (en) | A kind of preparation method of graphene-anti-static polyacrylonitrile fibre | |
| CN111058316A (en) | Alkaline pad dyeing method for chinlon 56 and cellulose fiber blended fabric | |
| CN111335048A (en) | Pad dyeing method for chinlon 56 and protein fiber blended fabric | |
| CN110230212B (en) | Polyester textile dyeing method | |
| TWI739033B (en) | Moisture-absorptive acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber | |
| CN111041585A (en) | Water-repellent polyester functional master batch and preparation method thereof | |
| JP3959738B2 (en) | Reactive dye-dyeable cross-linked acrylate fiber and fiber structure and process for producing them | |
| GB2285009A (en) | Porous acrylonitrile fibres | |
| CN109580705B (en) | Moisture-releasing and cooling fiber and fiber structure containing the same | |
| CN110938990B (en) | Flame-retardant acrylic fiber and preparation method thereof | |
| CN110080010B (en) | Preparation method of colored cellulose fibers | |
| CN112323168A (en) | Photochromic fiber and preparation method thereof | |
| JP4338574B2 (en) | Colored moisture absorbing / releasing exothermic fiber and method for producing the same | |
| CN111826977A (en) | Acid printing method for chinlon 56 and protein fiber blended fabric | |
| WO2010101182A1 (en) | Moisture absorbing fiber dyeable with cationic dye, and method for producing same | |
| JP7276703B2 (en) | Dyeing method for fiber structure containing acrylonitrile/crosslinked acrylate system | |
| CN116676795B (en) | Dyeing process of polyester-cotton blended fabric | |
| WO1998053127A1 (en) | Polymer additive for fiber dye enhancement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |