CN101821446A - Dyeable crosslinked acrylate fiber, method for producing the same, and dyed crosslinked acrylate fiber obtained by dying the fiber - Google Patents
Dyeable crosslinked acrylate fiber, method for producing the same, and dyed crosslinked acrylate fiber obtained by dying the fiber Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/332—Di- or polyamines
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/338—Organic hydrazines; Hydrazinium compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/70—Material containing nitrile groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/70—Material containing nitrile groups
- D06P3/708—Material containing nitrile groups using reactive dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Abstract
A crosslinked acrylate fiber which is excellent in the property of being evenly and densely dyed, can have high color fastness, and even after dyeing, can have the same properties including moisture-absorbing/releasing properties, antibacterial properties, and deodorizing properties as before dyeing. The dyeable crosslinked acrylate fiber is characterized by being obtained by subjecting an acrylic fiber to a treatment with a hydrazine compound and a treatment with an aminated organic compound having two or more primary amino groups per molecule and then hydrolyzing the fiber.
Description
Technical field
The present invention relates to the cross-linked acrylic acid ester fiber that to dye.More particularly, it relates to the cross-linked acrylic acid ester fiber, wherein during the manufacturing of cross-linked acrylic acid ester fiber by introducing amino with the processing that contains amino organic compound, improving its dyeability thus but do not damage for example moisture absorption/moisture releasing or disappear smelly of performance.
Background technology
Because the cross-linked acrylic acid ester fiber has excellent moisture absorption/moisture releasing performance, exothermicity, disappear smelly performance and anti-microbial property, it is gazed in recent years as multifunctional fibre or high functional fiber.Yet, described fiber have tone from rose pink to brown or have carboxyl and, therefore, though can carry out painted to it with cation dyes, but existing problems aspect tone, for example the water-swellable owing to fiber self causes that its COLOR FASTNESS is poor, is difficult with realistic scale dyeing thus.Therefore, not only only use the fibre structure of described fiber therein but also under situation with the fibre structure of described fiber and other mixed with fibers, its to wherein think the important field of tone for example the application in clothes, living room or the construction material quite be restricted.
For such problem, in patent documentation 1, for blackization contains the carbon black of 0.5-5 weight % in advance in the acrylate fiber as raw fiber, then this raw fiber is carried out the crosslinked importing by hydrazine compound and the importing of the carboxyl by hydrolysis.But this method just is limited to black.Be colored as versicolor raw fiber even use, much more very the industrial color category of dealing with remains impossible fully.
In patent documentation 2, put down in writing for the dyeability of the cross-linked acrylic acid ester fiber being given realistic scale, made it contain the method that in 1 molecule, has hydroxyl and amino stainability compound.In described method, the impregnation process of the aqueous solution by the cross-linked acrylic acid ester fiber being utilized hydroxyl in 1 molecule and amino dyed compound, above-mentioned cross-linked acrylic acid ester fiber is by the processing of the crosslinked introducing of the acrylate fiber being used hydrazine compound and uses the hydrolysis process of the alkaline aqueous solution of slaine to prepare.The fiber of gained shows the dyeability of moistening friction fastness more than 3 grades.
Yet in the method, treatment step significantly increases, and it is inevitable descending in industrial productivity ratio thus.In addition, because by making amino and the carboxyl reaction in the cross-linked acrylic acid ester fiber that to dye in the compound that fiber can be dyeed, so when processing has the cross-linked acrylic acid ester fiber of a large amount of carboxyls, be difficult to give equably (equably) dyeing.In addition, because carboxyl can be dyed the compound sealing, so the possibility that exists the original all moisture absorption/moisture releasing performances of cross-linked acrylic acid ester fiber and the smelly performance that disappears to reduce.
In patent documentation 3, improved colouring method, attempt the raising of the COLOR FASTNESS of cross-linked acrylic acid ester fiber thus.In described method, not partly to form but forms amino part because in the processing of the crosslinked introducing by hydrazine compound, exist wherein crosslinked, so the COLOR FASTNESS of utilizing described amino to dye and get well to reach as the dyeing part of REACTIVE DYES.Yet, because the number of the formed amino of processing by described crosslinked introducing is few, so existing problems aspect level dyeing and deep colour dyeing, on the other hand, wherein have following basic problem: the crosslinked condition that changes the physical property that greatly influences fiber in order to improve dyeability is difficult.
(patent documentation)
1. Japanese Patent Application Publication (JP-A) No.2003-89971
2. Japanese Patent Application Publication (JP-A) No.2003-278079
3. Japanese Patent Application Publication (JP-A) No.2006-70421
Summary of the invention
The present invention is with the problem that solves
That the present invention makes in view of such present situation of the prior art and its objective is the cross-linked acrylic acid ester fiber is provided, it has excellent level dyeing ability and dense colouring power, can present high color fastness and even also can present after the dyeing with dye before identical for example moisture absorption of characteristic/moisture releasing performance, the anti-microbial property or the smelly performance that disappears.
The means of dealing with problems
In order to reach such purpose, the present inventor has excellent chromatic cross-linked acrylic acid ester fiber to manufacturing and furthers investigate, the result, they find, to become the novel cross-linked acrylic acid ester fiber that the amino of the dyeing part of REACTIVE DYES introduces by covalent bond and can be had excellent COLOR FASTNESS in addition equably and with color dyeing, and exothermicity, anti-microbial property or the smelly performance that disappears when for example moisture absorption of the characteristic of cross-linked acrylic acid ester fiber/moisture releasing performance, moisture absorption do not reduce, so finished the present invention.
Above-mentioned purpose of the present invention can reach by following means.
[1] the cross-linked acrylic acid ester fiber that can dye, it is characterized in that, be prepared as follows described fiber: acrylic fiber is used the processing of hydrazine compound and is used in the processing that contains amino organic compound that has two or more primary amino radicals in 1 molecule, and processing then is hydrolyzed.
[2] according to the dyeed cross-linked acrylic acid ester fiber of above-mentioned [1], wherein wherein said have containing of two or more primary amino radicals amino organic compound and have three or more amino and have wherein that the zone between the amino is had the structure of the alkylidene keyed jointing of three or more carbon in 1 molecule in 1 molecule.
[3] according to the dyeed cross-linked acrylic acid ester fiber of above-mentioned [1], wherein after processing, use the processing that contains amino organic compound with hydrazine compound.
[4] can the dye manufacture method of cross-linked acrylic acid ester fiber is characterized in that acrylic fiber is used the processing of hydrazine compound and is used in the processing that contains amino organic compound that has two or more primary amino radicals in 1 molecule, and processing then is hydrolyzed.
[5] Ran Se cross-linked acrylic acid ester fiber, it is characterized in that, described fiber is prepared as follows: under acid condition REACTIVE DYES is adsorbed onto according on each the dyeed cross-linked acrylic acid ester fiber among the claim 1-3, then makes the amino reaction in described dyestuff and the described fiber under alkali condition.
Advantage of the present invention
When using of the present invention dyeing during the cross-linked acrylic acid ester fiber, can make all evenly with color dyeing and the cross-linked acrylic acid ester fiber that has durable COLOR FASTNESS in the use of reality, and exothermicity, anti-microbial property or the smelly performance that disappears when for example moisture absorption of characteristic/moisture releasing performance, moisture absorption do not reduce.As a result, although wherein its high and various functions since low dyeing property and cross-linked acrylic acid ester fiber that application and development is restricted be developed to thinking the important field of the tone possibility that becomes now.Of the present invention this can dye, and to require multi-functional or H.D various fields therein be very useful in clothes, living room and the construction material for example to the cross-linked acrylic acid ester fiber.
The specific embodiment
The acrylic fiber that the present invention adopts can be any fiber, as long as it is formed by acrylonitrile (hereinafter, it will be called as " AN ") polymer, and for the AN polymer, can adopt in the copolymer of AN homopolymers and AN and other monomer any.
The copolymerization resultant of AN 40 weight % or more preferably in the AN polymer, more preferably 50 weight % or more, further preferred 80 weight % or more.In the present invention, make the itrile group and the hydrazine compound of the AN polymer that forms the acrylate fiber and contain amino organic compound reaction, thus with cross-linked structure and amino this fiber of introducing.Cross-linked structure and amino physical property and the dyeability that greatly influences fiber respectively, and when AN measures very little, cross-linked structure and amino also tail off inevitably and have the physical property of fiber and the possibility that dyeability becomes not enough, but, be easy to the result who reaches good when the scope of the copolymerization resultant of AN as mentioned above the time.
When the copolymer that adopts AN and other monomer during as the AN polymer, the example of the combined polymerization component beyond the AN comprises and contains sulfonic monomer for example methallylsulfonic acid or p styrene sulfonic acid and their salt, the monomer that contains the carboxylic acid group is for example styrene, vinyl acetate, (methyl) acrylate or (methyl) acrylamide and there are not special restriction in they of (methyl) acrylic acid or itaconic acid and their salt and monomer for example, if it be can with the monomer of AN combined polymerization.
There is not special restriction in the means of the manufacturing acrylic fiber that the present invention is adopted still, and basically, any in known method itself can be used for this manufacturing.Form can be staple fibre, tow (tow), line, braided fabric/textiles, nonwoven fabric etc.Perhaps, also can adopt the intermediate product during the manufacturing step, useless fiber etc.
The advantage that exists is: especially when using the wet type spinning or do/wet type spinning preparation and be not subjected to heat treatment and for example make the heat treated acrylate fiber that has than coarse-texture dry and fine and close or by damp and hot release, or more specifically, when being the acrylic fiber of 30-150% as the water swelling degree of the percentage of the water content of representing based on dried fibres weight wherein, because the dispersibility of fiber in reaction solution, containing permeability that amino organic compound enters fiber etc. uprises, reaction is carried out equably and promptly
Be meant the reaction of itrile group etc. with the hydrazine compound of AN polymer among the present invention with the processing of hydrazine compound.Because such reaction, cross-linked structure is forming between the AN polymer or in this polymer and this cross-linked structure has such effect: promptly the carboxyl of introducing by the hydrolysis process that will mention after a while improves the hydrophily of polymer, can suppress the physical property of fiber when moisture absorption etc. thus and reduce.
The hydrazine compound that the present invention is adopted does not exist special restriction and their example to comprise hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, bromic acid hydrazine (hydrazine bromate) and carbonic acid hydrazine, and the compound that contains a plurality of amino for example ethylenediamine, guanidine sulfate, guanidine hydrochloride, phosphoguanidine and melamine.
Be to instigate the itrile group of AN polymer etc. and contain amino organic compound reaction with the processing that contains amino organic compound among the present invention.As a result, wait that the amino that becomes dyeing part is introduced into.About containing amino organic compound, adopt in 1 molecule, to have containing of two or more primary amino radicals of amino organic compound.This is because need at least one and the amino of the itrile group of AN polymer reaction to become the amino of dyeing part with at least one.This is also because consider and the reactivity of itrile group or REACTIVE DYES, amino primary amino radical preferably.Incidentally, in addition in such processing that contains amino organic compound when the itrile group reaction of the amino of waiting to become dyeing part and AN polymer, cross-linked structure also can be by being formed with the same mode of the processing of hydrazine compound with above mentioned.Can the ratio (rate) of the formation of cross-linked structure be reduced by the control reaction condition.
As such instantiation that contains amino organic compound comprise ethylene diamine, diethylenetriamines, trien, tetren, polyvinylamine, polyethylene imine based, 3,3 '-imino group two (propylamine), N-methyl-3,3 '-imino group two (propylamine), N, N '-two (3-aminopropyl) ethylene diamine, N, N '-two (3-aminopropyl)-1,3-(trimethylene diamine), N, N '-two (3-aminopropyl)-1,3-butylene diamine, N, N '-two (3-aminopropyl)-1,4-butylene diamine etc.
In these such containing in the amino organic compound, preferred a kind of be in 1 molecule, have three or more amino and have an amino organic compound that contains of structure that the alkylidene that wherein has three or more carbon is connected to the zone between the amino.Incidentally, as used herein the number of carbon representative between amino directly the number of the carbon of keyed jointing do not comprise carbon number in side chain, the substituting group etc.When in 1 molecule, having two when amino; there is aforesaid possibility: promptly form cross-linked structure and lose the amino of waiting to become dyeing part; and when in 1 molecule, having three or more amino; one or more amino are still residual; even when forming cross-linked structure when the reaction of the itrile group in two amino and the AN polymer; and; because the sterically hindered described amino further possibility with the reaction of the itrile group of AN polymer is low, can more reliably the amino that can become dyeing part be protected thus.
Since have containing of this kind structure amino organic compound have fast reaction speed and react with itrile group can be at short notice, even when treatment temperature is not higher than 100 ℃, so do not need pressurizing vessel and aspect cost, be favourable and be preferred.And, have under the situation that contains amino organic compound of this kind structure, can make the fiber of gained not too painted, this is favourable to dyeing thus.
As having containing of this kind structure of amino organic compound, can give an example 3,3 '-imino group two (propylamine), N-methyl-3,3 '-imino group two (propylamine), N, N '-two (3-aminopropyl) ethylene diamine, N, N '-two (3-aminopropyl)-1,3-(trimethylene diamine), N, N '-two (3-aminopropyl)-1,3-butylene diamine, N, N '-two (3-aminopropyl)-1,4-butylene diamine etc.
In addition, with containing in the processing of amino organic compound, can be by selecting to contain the amount of amino organic compound and the number of the amino in the described compound is easily regulated the dyeing part number.Therefore, can improve level dyeing ability and the ability of dying heavy colour.
In the present invention, acrylic fiber is carried out above-mentioned, and as long as before, can before another kind is handled, carry out in the described processing any after a while with the hydrolysis process of mentioning with hydrazine compound with the processing that contains amino organic compound, perhaps, can carry out two kinds of processing simultaneously.Yet, can obtain following characteristic because depend on processing sequence, so wish after this specific character of approval, to decide processing sequence.
Therefore, at first, under the situation about handling at the same time, though the advantage that exists number of steps to reduce, but be difficult to the unreacted hydrazine compound of recovery and reuse and contain amino organic compound and, in addition, the amino introducing amount and the control of cross-linked structure also become complicated.On the other hand, when carry out individually in the described processing each the time, though number of steps increases the control of structure and the recovery of chemicals/utilize to become easy again.When particularly using the processing of hydrazine compound in the ban, cross-linked structure with contain amino organic compound processing stage existed and the space bit resistive big.Therefore, the above-mentioned amino that forms and wait to become dyeing part hardly by the cross-linked structure that contains amino organic compound can be introduced in the fiber and this is preferred effectively.
With hydrazine compound or contain the physical property of the fiber that the extent of reaction of amino organic compound can be by considering based target and the necessary cross-linked structure of dyeing efficient and amino amount and come to determine suitably.Though and this also can suitably regulate according to reaction condition, must so that become the hydrolysis process of mentioning after a while object functional group for example the residual mode of itrile group react.
To with hydrazine compound or contain amino organic compound handle the aqueous solution that the method for acrylate fiber do not exist special restriction and their example to comprise wherein to prepare this kind compound and with the acrylate fiber be dipped in wherein method and wherein with described solution spraying in or be applied to method on the acrylate fiber.
With the processing of hydrazine compound with after with the processing that contains amino organic compound, also acceptablely be, will handle those residual compounds of back at these and fully remove, use sour processing then.As with the result that handles of acid, can improve the whiteness of fiber and be favourable dyeing.Be used for the example of acid with the processing of acid and comprise for example for example formic acid or acetate of nitric acid, sulfuric acid or hydrochloric acid and organic acid of inorganic acid.
In the present invention, acrylic fiber is used the processing of hydrazine compound and with the processing that contains amino organic compound, then, used the processing of acid if desired, then, processing is hydrolyzed.As the result of hydrolysis process, remain in itrile group wherein not reacting and because the amide groups that a part of itrile group hydrolysis of such processing produces is transformed into carboxyl with the processing of hydrazine compound with in processing that contains amino organic compound or the processing after this carried out with acid.
In the present invention, for cross-linked structure and amino abundant introducing importantly hydrolysis process carrying out with the processing of hydrazine compound with after with the processing that contains amino organic compound.If in the processing that is hydrolyzed with the processing of hydrazine compound with before with the processing that contains amino organic compound, then the result will make hydrazine compound and contain amino organic compound and react in the presence of carboxyl, but, because these compounds and carboxyl form ionic bond easily, so do not carry out with reaction itrile group with target, cross-linked structure and amino introducing become insufficient thus.
Because carboxyl is to present for example moisture absorption of function/moisture releasing performance, the exothermicity when moisture absorption in the cross-linked acrylic acid ester fiber or the smelly performance that disappears, so can determine suitably that the introducing amount of carboxyl is so that objective function can be presented fully and can it be adjusted to any value according to reaction condition.Yet, usually, preferably with 1-12mmol/g, preferred 3-10mmol/g, more preferably the amount of 3-8mmol/g is introduced carboxyl.
The examples for compounds that adopts in this kind hydrolysis process comprises alkali metal compound for example alkali metal hydroxide, alkaline earth metal hydroxide or alkali carbonate.
Also can after this kind hydrolysis process, reduce processing.As reducing the result who handles, the whiteness of fiber is improved and is favourable to dyeing.The example that is used for the reagent that this kind reduction handles comprises and comprises a kind of chemical substance that is selected from bisulfites, thiosulfate, sulphite, nitrite, thiourea dioxide, ascorbate and hydrazine compound and comprise two or more the chemical substance of therefrom selecting.
In the present invention who as above makes can dye the cross-linked acrylic acid ester fiber, dyeability be improved and, in addition, can with the situation of conventional cross-linked acrylic acid ester fiber under present in the same manner for example moisture absorption of function/moisture releasing performance, when the moisture absorption exothermicity, smelly performance etc. disappears.
Be that example explains manufacture method now by wherein at first using the processing of hydrazine compound, using the situation of the processing that contains amino compound then.
At first, will be applied to the processing of hydrazine compound aforesaid propylene acids fiber and, in described processing, introduce as already mentioned cross-linked structure and, as its result, the amount of nitrogen increases in the fiber.Therefore, wherein the increase of the amount of nitrogen is the index of the amount of the past cross-linked structure of wherein introducing.In order to reach the good physical property of fiber, preferably the increase of the amount of nitrogen is adjusted to the scope of 0.1-10 weight %.The example of special reaction condition for this reason comprises the condition of wherein handling in 5 hours in the aqueous solution that is containing 5-60 weight % hydrazine compound under 50-120 ℃.The above statement of Shi Yonging " increase of the amount of nitrogen " is meant poor as the amount of the nitrogen in the amount of the nitrogen in the acrylate fiber of raw material and the fiber of having handled with hydrazine compound.
Then, will carry out washing and use the processing that contains amino organic compound with the fiber water of the processing of hydrazine compound.In this kind processing, introduce the amino of waiting to become dyeing part.For concrete reaction condition, the concentration that contains amino organic compound under 50-150 ℃, preferred 80-150 ℃ therein of can giving an example wherein is to handle 30 minutes-48 hours condition in the 1 weight % or the higher aqueous solution.Especially when the compound of such structure of alkylidene keyed jointing that adopts zone between the amino to be had three or more carbon when containing amino compound, can under 50-150 ℃, handle 30 minutes-4 hours.As the result who under this condition, handles, can prepare fiber and can present excellent level dyeing ability and dense colouring power now with high saturated dyeing amount.
To having carried out after washing with water, can using the processing of acid with the fiber of the processing that contains amino organic compound.For the acid of the processing that is used for acid, can adopt the acid of giving an example above.Though there is not special restriction in the condition of processing with acid, can generally give an example pending fiber is dipped in acid concentration under 50-120 ℃ is 5-20 weight %, preferred 0.5-10 hour situation in the aqueous solution of 7-15 weight %.
After washing, the fiber water that will carry out above-mentioned processing carries out hydrolysis process.By described processing, carboxyl is introduced described fiber.When using above-mentioned alkali metal compound to be hydrolyzed processing, consequent carboxyl is bonded to derive and plants since then on the metal ion of compound, and its great majority become the carboxyl of slaine type thus.
The introducing amount of carboxyl can by consider that the needed function of final fiber is determined and, usually, with referred to above identical.For concrete reaction condition, using under the situation of alkali metal compound, can give an example wherein and in its concentration is the aqueous solution of 1-10 weight %, preferred 1-5 weight %, to handle 1-10 hour condition under 50-120 ℃.
After such hydrolysis process, can reduce processing.For being used to reduce the reagent of handling, can adopt the material of having mentioned.For treatment conditions, the situation that can generally give an example and wherein pending fiber was dipped under 50-120 ℃ in the aqueous solution that reagent concentration is 0.5-5 weight % 30 minutes-5 hours.
There is not special restriction in colouring method according to the cross-linked acrylic acid ester fiber that dyes of the present invention, and for example, can adopts the colouring method that uses with amino reactive activity dyestuff.During the colouring method especially described in the patent documentation of in adopting " background technology ", mentioning 3, not only have good COLOR FASTNESS but also have the excellent even performance that when described colouring method being applied to conventional cross-linked acrylic acid ester fiber, can not reach and the cross-linked acrylic acid ester fiber of the dyeing of heavy colour performance even can prepare, and for example moisture absorption of the characteristic functions of cross-linked acrylic acid ester fiber/moisture releasing performance, the exothermicity when moisture absorption or the smelly performance that disappears do not reduce.
Incidentally, the colouring method of mentioning in the patent documentation 3 is the method that wherein with cross-linked acrylic acid ester fiber adsorption activity dyestuff, then the amino in described dyestuff and this fiber is reacted under acid condition.
In such colouring method, use and amino reactive activity dyestuff.The example of REACTIVE DYES comprises chlorotriazine dyestuff for example a chlorotriazine dyestuff or a dichloro triazine dye, chlorine pyrimidine dyestuff and vinyl sulfone dyestuff.The dyestuff that can also use the dyestuff with a plurality of identical type functional group for example to have the dyestuff of 2 sulfato ethyl sulfuryls or have the dyestuff of two or more chlorotriazine bases and have a plurality of different functional groups is sulfato ethyl sulfone/chlorotriazine dyestuff, sulfato ethyl sulfone/dichlorotriazine class dyestuff or sulfato ethyl sulfone/difluoro one chlorotriazine dyestuff for example.
Dyeing process be, at first, under acid condition with the cross-linked acrylic acid ester fiber adsorption activity dyestuff that dyes of the present invention.More specifically, making the pH of the bath under the state that adds REACTIVE DYES and acid is 5 or lower, then the cross-linked acrylic acid ester fiber that dyes of the present invention is dipped in wherein.About being used to regulate the acid of pH, can use for example for example nitric acid, sulfuric acid or aqueous solution of hydrochloric acid of acetate, formic acid, lactic acid or tartaric acid and inorganic acid of organic acid.Usually, make treatment temperature at 60 ℃ or higher.
Then, under alkali condition, chemically form covalent bond between the amino in dyestuff and the present invention can dye the cross-linked acrylic acid ester fiber.More specifically, the cross-linked acrylic acid ester fiber that dyes of the present invention that is adsorbed with the state of REACTIVE DYES is dipped in the water, last to wherein adding alkali compounds to continue reaction, making the pH that bathes in this processing back is 9 or higher.The example that is used to regulate the alkali compounds of pH comprises alkali-metal acylate, carbonate or hydroxide etc., amines and ammonia.Usually, the temperature that is used to handle is 60 ℃ or higher.
After dyeing by such colouring method, equilibrium ion in the fiber becomes by the state that replaces from the ion of above-mentioned alkali compounds and can utilize further ion-exchange and be transformed into the carboxyl of required slaine type and/or the carboxyl of H type, thus can for example moisture absorption of regulatory function/moisture releasing performance, the exothermicity when moisture absorption or the smelly performance that disappears.
Embodiment
Hereinafter, will be specifically described the present invention, but the present invention is not limited to following embodiment with the following examples.Unless stipulate that in addition the term that uses among the embodiment " part " and " percentage " are by weight.
(1) carboxyl amount [mmol/g]
After 200ml water being added in about 1g sample, add 1 mol aqueous hydrochloric acid solution so that pH be 2 and wash sample with water, dehydration and dry.After it is by intensive drying, and smart its about 0.2g of title (A[g]) and use the sodium hydrate aqueous solution of 0.1 mol to determine titration curve according to conventional methods.Determine the consumption (B[ml]) of the sodium hydrate aqueous solution that consumed by carboxyl by this titration curve and by calculate the amount (mmol/g) of carboxyl with following formula.
Carboxyl amount [mmol/g]=0.1B/A
(2) saturated hydroscopicity (%)
With air drier 105 ℃ to about 5.0g sample drying 16 hours, measure its weight (C[g]).In the insulating box of 20 ℃ of temperature and 65% relative humidity, place after this sample 24 hours, measure such moisture absorption the weight (D[g]) of sample.By the result of last planar survey, by calculate saturated hydroscopicity (%) with following formula.
Saturated hydroscopicity [%]=(D-C)/C} * 100
(3) saturated dyeing amount [% owf]
With REACTIVE DYES Sumifix Supra Blue BRF (making) by Sumitomo Chemical (0.60g) and formic acid to add in the water pH with preparation 120ml to be 2.0 dye bath.The sample (0.60g) that changes carboxyl wherein into the H type is dipped in the described dye bath and carries out the processing 5 hours of dyestuff absorption under 60 ℃.Use U-1100 spectrophotometer (making) to measure to handle by Hitachi the back by the staining solution for preparing from the dye bath filtered sample absorption spectrum and utilize spectrophotometric analysis the amount of residual dye is quantitative by the absorption under the peak wavelength of 610nm.By the result who measures, by calculate saturated dyeing amount (% owf) with following formula.
Saturated dyeing amount [% owf]={ (amount [g] of the dyestuff of the amount of the dyestuff of interpolation [g]-residual)/example weight [g] } * 100
Because when the so for a long time saturable dye amount of quantitative change that is included in the amino in the sample also becomes greatly, so it can be as the index of amino amount in the sample.
(4) color fastness to perspiration
With REACTIVE DYES Sumifix Black ENS150 (making) by Sumitomo Chemical (0.49g) and formic acid to add in the water pH with preparation 120ml to be 2.0 dye bath.The sample (7.00g) that changes carboxyl wherein into the H type is dipped in the described dye bath and carries out the processing 5 hours of dyestuff absorption under 60 ℃.After washing the sample of gained with water, it is dipped in the 210ml water and temperature increase to 60 ℃., so that being 11, pH then flooded 1 hour down to wherein adding sodium carbonate at 60 ℃.Then, wash with water successively, soap, the sample that washes with water and dewater and dye with preparation.The sample of preparation is like this carried out using alkaline artificial perspiration's test and using the sample that becomes before fade ash card (gray scale for colorchange and fading) and the test relatively according to JIS L 0848, judge COLOR FASTNESS thus.When color fastness to perspiration at 3 grades or when above, it is the ability practicality.
(5) colour fastness to rubbing
To by with the judgement of above-mentioned color fastness to perspiration in the sample that dyes of identical mode carry out using the test of friction test type II and using staining ash card (grayscale for staining) to judge that friction is with the painted degree of byssus according to JIS L 0849.When colour fastness to rubbing at 3 grades or when above, it is the ability practicality.
(6) dense colouring power
To by with the judgement of above-mentioned color fastness to perspiration in the sample that dyes of identical mode estimate dense colouring powers (with the dyeability of heavy colour) by naked eyes according to following three grades.When the result was " ◎ " or " zero ", it was the ability practicality.
◎: dark and dyeing the grade excellence
Zero: exist in the tiny flaw in the scope of allowing as product
*: major defect insufficient and that existence is not allowed as product dyes
(7) level dyeing ability
By naked eyes according to following three grades of evaluations with and the judgement of above-mentioned color fastness to perspiration in the dye speck of the sample that dyes of the same method.When the result is " ◎ " or " zero ", then be can anti-practicality ability.
◎: dyeing be homogeneous (evenly) and dyeing grade excellence
Zero: exist in the tiny flaw in the scope of allowing as product
*: the major defect that dyeing heterogeneity (evenly) and existence are not allowed as product
(preparation of acrylic fiber A)
The acrylonitrile polymer (inherent viscosity in 30 ℃ the dimethyl formamide [η] is 1.2) (10 parts) that will comprise 90% acrylonitrile and 10% methyl acrylate is dissolved in 90 parts of 48% aqueous solution of sodium sulfocyanate, according to conventional methods the spinning solution of gained is carried out washing, extension, drying, humid heat treatment of spinning, water etc., to obtain the acrylic fiber A of 0.9dtex.
(preparation of acrylic fiber B)
The acrylonitrile polymer (inherent viscosity in 30 ℃ the dimethyl formamide [η] is 1.2) (10 parts) that will comprise 90% acrylonitrile and 10% vinyl acetate is dissolved in 90 parts of 48% aqueous solution of sodium sulfocyanate, according to conventional methods the spinning solution of gained is carried out washing, extension, drying, humid heat treatment of spinning, water etc., to obtain the acrylic fiber B of 0.9dtex.
(embodiment 1)
With containing 15% hydrazine hydrate and 3% 3, the mixed aqueous solution of 3 '-imino group two (propylamine) was handled 3 hours and was washed with water acrylic fiber A under 110 ℃.It was handled 1 hour and washed with water under 100 ℃ with 8% nitric acid then.Then, it was handled 2 hours under 90 ℃ with 5% aqueous solution of NaOH, then water washs, dewaters and be dry and obtain the dyeed cross-linked acrylic acid ester fiber of embodiment 1.To described estimation of fibres carboxyl amount, saturated hydroscopicity, saturated dyeing amount, color fastness to perspiration, colour fastness to rubbing, dense colouring power and level dyeing ability.The results are shown in table 1.
(embodiment 2)
15% aqueous solution with hydrazine hydrate was handled 3 hours acrylic fiber A under 110 ℃, washed with water, and with 3,3% aqueous solution of 3 '-imino group two (propylamine) was handled 3 hours and washed with water down at 110 ℃.It was handled 1 hour and washed with water under 100 ℃ with 8% nitric acid then.Then, under 90 ℃, it was handled 2 hours, then carry out the washing, dehydration of water and dry and obtain the dyeed cross-linked acrylic acid ester fiber of embodiment 2 with 5% aqueous solution of NaOH.Its evaluation result is shown in table 1.
(embodiment 3)
15% aqueous solution with hydrazine hydrate was handled 3 hours acrylic fiber A under 110 ℃, washed with water, and with 3,6% aqueous solution of 3 '-imino group two (propylamine) was handled 3 hours and washed with water down at 110 ℃.It was handled 1 hour and washed with water under 100 ℃ with 8% nitric acid then.Then, under 90 ℃, it was handled 2 hours, then carry out the washing, dehydration of water and dry and obtain the dyeed cross-linked acrylic acid ester fiber of embodiment 3 with 5% aqueous solution of NaOH.Its evaluation result is shown in table 1.
(embodiment 4)
With 3,3% aqueous solution of 3 '-imino group two (propylamine) was handled 3 hours acrylic fiber A under 110 ℃, washed with water, handled 3 hours and washed with water down at 110 ℃ with 15% aqueous solution of hydrazine hydrate.It was handled 1 hour and washed with water under 100 ℃ with 8% nitric acid then.Then, under 90 ℃, it was handled 2 hours, then carry out the washing, dehydration of water and dry and obtain the dyeed cross-linked acrylic acid ester fiber of embodiment 4 with 5% aqueous solution of NaOH.Its evaluation result is shown in table 1.
(embodiment 5)
Carry out with embodiment 2 in identical method, except with 3,3 '-imino group two (propylamine) changes over N-methyl-3,3 '-imino group two (propylamine) is to obtain the dyeed cross-linked acrylic acid ester fiber of embodiment 5.Its evaluation result is shown in table 1.
(embodiment 6)
Carry out with embodiment 2 in identical method, except with 3,3 '-imino group two (propylamine) changes over trien, to obtain the dyeed cross-linked acrylic acid ester fiber of embodiment 6.Its evaluation result is shown in table 1.
(embodiment 7)
In embodiment 2, after washing with the processing of the aqueous solution of NaOH and water, further with 1% aqueous solution of thiourea dioxide under 90 ℃ to this fiber treatment 2 hours and carry out washing, dehydration and dry and dyeed cross-linked acrylic acid ester fiber acquisition embodiment 7 of water.Its evaluation result is shown in table 1.
(embodiment 8)
Carry out with embodiment 2 in identical method, except acrylic fiber A is changed over acrylic fiber B, to obtain the dyeed cross-linked acrylic acid ester fiber of embodiment 8.Its evaluation result is shown in table 1.
(embodiment 9)
In embodiment 8, after washing with the processing of the aqueous solution of NaOH and water, further with 1% aqueous solution of thiourea dioxide under 90 ℃ to this fiber treatment 2 hours and carry out washing, dehydration and dry and dyeed cross-linked acrylic acid ester fiber acquisition embodiment 9 of water.Its evaluation result is shown in table 1.
(comparative example 1)
15% aqueous solution with hydrazine hydrate was handled 3 hours and was washed with water acrylic fiber A under 110 ℃.It was handled 1 hour and washed with water under 100 ℃ with 8% nitric acid then.Then, under 90 ℃, it was handled 2 hours, then carry out the washing, dehydration of water and dry and obtain the cross-linked acrylic acid ester fiber of comparative example 1 with 5% aqueous solution of NaOH.Its evaluation result is shown in table 1.
(comparative example 2)
Carry out with embodiment 2 in identical method, except with 3,3 '-imino group two (propylamine) changes over n-butylamine and obtains the cross-linked acrylic acid ester fiber of comparative example 2.Its evaluation result is shown in table 1.
(comparative example 3)
15% aqueous solution with hydrazine hydrate was handled 3 hours and was washed with water acrylic fiber A under 110 ℃.It was handled 1 hour and washed with water under 100 ℃ with 8% nitric acid then.Then, it was handled 2 hours and washed with water under 90 ℃ with 5% aqueous solution of NaOH.And then with 3,3% aqueous solution of 3 '-imino group two (propylamine) was handled 3 hours it under 110 ℃, then carried out the washing, dehydration of water and dry and obtain the cross-linked acrylic acid ester fiber of comparative example 3.Its evaluation result is shown in table 1.
As can be seen from Table 1, in whole embodiment 1-9, can prepare the dyeed cross-linked acrylic acid ester fiber that shows superperformance.When embodiment 1,2 and 4 compares each other, find to prepare fiber with better dyeing property using after the processing with hydrazine compound under the situation of the processing that contains amino organic compound.When embodiment 2,5 and 6 compares each other, discovery adopt in 1 molecule, have three or more amino and further have under the situation that contains amino organic compound in the wherein zone between the amino and the structure of alkylidene keyed jointing with three or more carbon, saturated dyeing amount and dense colouring power height, what hence one can see that is, have containing of this kind structure of amino organic compound if adopt, then amino is more effectively introduced.
In comparative example 1 and 2, be not used in the processing that contains amino organic compound that has two or more primary amino radicals in 1 molecule, in comparative example 3, after hydrolysis process, use the processing that contains amino organic compound.Therefore, in any in them, low and dense colouring power of saturated dyeing amount and level dyeing ability are all poor.
Industrial applicability
The cross-linked acrylic acid ester fiber that dyes of the present invention can be equably and is colored and has in actual use durable color fastness with heavy colour, keeps simultaneously for example moisture absorption of the peculiar characteristic of cross-linked acrylic acid ester fiber/moisture releasing performance, the exothermicity when moisture absorption, anti-microbial property or deodorization. Therefore, the cross-linked acrylic acid ester fiber that dyes of the present invention can be widely used for requiring therein multi-functional or H.D various field for example clothes, living room and construction material.
Claims (5)
1. cross-linked acrylic acid ester fiber that can dye, it is characterized in that, be prepared as follows described fiber: acrylic fiber is used the processing of hydrazine compound and is used in the processing that contains amino organic compound that has two or more primary amino radicals in 1 molecule, and processing then is hydrolyzed.
2. according to the dyeed cross-linked acrylic acid ester fiber of claim 1, wherein said in 1 molecule, have containing of two or more primary amino radicals amino organic compound in 1 molecule, have three or more amino and have wherein that the zone between the amino is had the structure of the alkylidene keyed jointing of three or more carbon.
3. according to the dyeed cross-linked acrylic acid ester fiber of claim 1, wherein after processing, use the processing that contains amino organic compound with hydrazine compound.
4. can the dye manufacture method of cross-linked acrylic acid ester fiber is characterized in that acrylic fiber is used the processing of hydrazine compound and is used in the processing that contains amino organic compound that has two or more primary amino radicals in 1 molecule, and processing then is hydrolyzed.
5. Ran Se cross-linked acrylic acid ester fiber, it is characterized in that, described fiber is prepared as follows: under acid condition REACTIVE DYES is adsorbed onto according on each the dyeed cross-linked acrylic acid ester fiber among the claim 1-3, then makes the amino reaction in described dyestuff and the described fiber under alkali condition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007285630A JP5056358B2 (en) | 2007-11-02 | 2007-11-02 | Dyeable cross-linked acrylate fiber, method for producing the same, and dyed cross-linked acrylate fiber obtained by dyeing the fiber |
| JP2007-285630 | 2007-11-02 | ||
| PCT/JP2008/001835 WO2009057235A1 (en) | 2007-11-02 | 2008-07-09 | Dyeable crosslinked acrylate fiber, process for producing the same, and dyed crosslinked acrylate fiber obtained by dyeing the fiber |
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| Publication Number | Publication Date |
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| CN101821446A true CN101821446A (en) | 2010-09-01 |
| CN101821446B CN101821446B (en) | 2013-09-11 |
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| CN200880110676.9A Expired - Fee Related CN101821446B (en) | 2007-11-02 | 2008-07-09 | Dyeable crosslinked acrylate fiber, method for producing the same, and dyed crosslinked acrylate fiber obtained by dying the fiber |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP5056358B2 (en) |
| KR (1) | KR101414364B1 (en) |
| CN (1) | CN101821446B (en) |
| ES (1) | ES2380028B2 (en) |
| TW (1) | TWI435969B (en) |
| WO (1) | WO2009057235A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266473A (en) * | 2013-06-24 | 2013-08-28 | 河南省科学院化学研究所有限公司 | Phosphonium salt modified acrylic fibre antibacterial material and preparation method thereof |
| CN105274836A (en) * | 2014-05-29 | 2016-01-27 | 日本爱克兰工业株式会社 | Good-dispersity crosslinking acrylate fiber |
| CN111826764A (en) * | 2020-07-28 | 2020-10-27 | 吴忠德悦纺织科技有限公司 | Preparation method of modified multi-component composite yarn |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4487083B2 (en) * | 2008-09-10 | 2010-06-23 | 日本エクスラン工業株式会社 | Cross-linked acrylate fiber and method for producing the same |
| JP5590341B2 (en) * | 2009-07-22 | 2014-09-17 | 日本エクスラン工業株式会社 | Acid dye-dyeable hygroscopic fiber and method for producing the same |
| JP5765570B2 (en) * | 2010-09-08 | 2015-08-19 | 日本エクスラン工業株式会社 | Thermal insulation fiber |
| KR101156368B1 (en) * | 2010-11-25 | 2012-06-13 | 숭실대학교산학협력단 | Method for manufacturing conductive acrylic fibers having high heat resistant property |
| CN105246513B (en) * | 2013-05-24 | 2017-07-04 | 日本爱克兰工业株式会社 | Functional particle and the resin containing it |
| TWI645086B (en) * | 2013-09-20 | 2018-12-21 | 日本Ｅｘｌａｎ工業股份有限公司 | Crosslinking acrylate based fiber and fiber structure comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6375041A (en) * | 1986-09-13 | 1988-04-05 | ミハイル ペトロヴイツチ ズベレフ | Production of anion exchange fiber |
| JP4674429B2 (en) * | 2001-09-18 | 2011-04-20 | 日本エクスラン工業株式会社 | Black high moisture absorbing / releasing fiber |
| JP3959738B2 (en) * | 2002-03-22 | 2007-08-15 | 日本エクスラン工業株式会社 | Reactive dye-dyeable cross-linked acrylate fiber and fiber structure and process for producing them |
| FR2866904A1 (en) * | 2004-02-26 | 2005-09-02 | Marti Juan Batlle | PROCESS FOR PRODUCING RETICULATED POLYACRYLATE FIBERS |
| JP4696724B2 (en) * | 2004-08-03 | 2011-06-08 | 日本エクスラン工業株式会社 | Method for dyeing cross-linked acrylate fibers and fiber products containing cross-linked acrylate fibers dyed by the dyeing method |
| CN100494556C (en) * | 2004-08-03 | 2009-06-03 | 日本爱克兰工业株式会社 | Dyeing method for cross linked acrylic fiber and fiber products containing cross linked acrylic fibers dyed by such method |
| WO2006027910A1 (en) * | 2004-09-07 | 2006-03-16 | Japan Exlan Company Limited | Slowly moisture-absorbing and -releasing crosslinked acrylic fiber |
| JP4487083B2 (en) * | 2008-09-10 | 2010-06-23 | 日本エクスラン工業株式会社 | Cross-linked acrylate fiber and method for producing the same |
| JP5590341B2 (en) * | 2009-07-22 | 2014-09-17 | 日本エクスラン工業株式会社 | Acid dye-dyeable hygroscopic fiber and method for producing the same |
-
2007
- 2007-11-02 JP JP2007285630A patent/JP5056358B2/en active Active
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2008
- 2008-07-09 CN CN200880110676.9A patent/CN101821446B/en not_active Expired - Fee Related
- 2008-07-09 WO PCT/JP2008/001835 patent/WO2009057235A1/en active Application Filing
- 2008-07-09 ES ES201090019A patent/ES2380028B2/en not_active Expired - Fee Related
- 2008-07-09 KR KR1020107009527A patent/KR101414364B1/en active IP Right Grant
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266473A (en) * | 2013-06-24 | 2013-08-28 | 河南省科学院化学研究所有限公司 | Phosphonium salt modified acrylic fibre antibacterial material and preparation method thereof |
| CN103266473B (en) * | 2013-06-24 | 2015-08-05 | 河南省科学院化学研究所有限公司 | Quaternary alkylphosphonium salt modified acrylic fibre anti-biotic material and preparation method thereof |
| CN105274836A (en) * | 2014-05-29 | 2016-01-27 | 日本爱克兰工业株式会社 | Good-dispersity crosslinking acrylate fiber |
| CN105274836B (en) * | 2014-05-29 | 2021-03-16 | 日本爱克兰工业株式会社 | Cross-linked acrylic ester fiber with good dispersibility |
| CN111826764A (en) * | 2020-07-28 | 2020-10-27 | 吴忠德悦纺织科技有限公司 | Preparation method of modified multi-component composite yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5056358B2 (en) | 2012-10-24 |
| ES2380028A1 (en) | 2012-05-08 |
| TWI435969B (en) | 2014-05-01 |
| TW200928045A (en) | 2009-07-01 |
| ES2380028B2 (en) | 2012-12-20 |
| KR101414364B1 (en) | 2014-07-01 |
| KR20100083156A (en) | 2010-07-21 |
| CN101821446B (en) | 2013-09-11 |
| WO2009057235A1 (en) | 2009-05-07 |
| JP2009114556A (en) | 2009-05-28 |
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