JP2009114556A - Dyeable crosslinked acrylate fiber, method for producing the same, and dyed crosslinked acrylate fiber obtained by dying the fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinked acrylate fiber that 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. <P>SOLUTION: The dyeable crosslinked acrylate fiber is 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. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a dyeable cross-linked acrylate fiber. More specifically, by introducing an amino group by treating with an amino group-containing organic compound during the production of the cross-linked acrylate fiber, the dyeability is improved without impairing the performance of moisture absorption and deodorization and deodorization. The present invention relates to a crosslinked acrylate fiber.

Cross-linked acrylate fibers have excellent moisture absorption / release properties, exothermic properties, deodorizing properties, and antibacterial properties, and have been attracting attention in recent years. However, although the fiber has a light pink to brown color or has a carboxyl group, it can be colored with a cationic dye, but due to the water swelling property of the fiber itself, the color fastness to dyeing However, there is a problem in the hue such that it is difficult to dye at a practical level. For this reason, the application to the field where the hue is regarded as important is limited not only in the case of using the fiber alone but also in the mixed fiber structure.

With respect to such a problem, in Patent Document 1, in order to blacken, acrylic fiber that is a raw fiber contains 0.5 to 5% by weight of carbon black in advance, and the raw fiber is crosslinked with a hydrazine compound. And introduction of carboxyl groups by hydrolysis. However, this method is limited to black. Even if raw material fibers colored in various colors are used, industrially it is not possible to deal with a wide variety of colors.

Patent Document 2 describes a method in which a dyeable compound having a hydroxyl group and an amino group is contained in one molecule in order to impart a practical level of dyeability to the crosslinked acrylate fiber. In this method, a crosslinked acrylate fiber obtained by subjecting an acrylic fiber to a crosslinking introduction treatment with a hydrazine compound and hydrolysis with an alkaline metal salt aqueous solution is used in a dyeable compound aqueous solution having a hydroxyl group and an amino group in one molecule. It is impregnated and exhibits a dyeing property of a wet friction fastness of 3 or higher.

However, this method substantially increases the number of processing steps, and industrial productivity cannot be denied. In addition, since it is dyed by reacting the amino group of the dyeable compound with the carboxyl group in the crosslinked acrylate fiber, it should be uniformly applied when treating a crosslinked acrylate fiber having a large amount of carboxyl group. Is difficult. Moreover, when the carboxyl group is blocked by the dyeable compound, the moisture absorption / desorption performance and deodorization performance inherent to the crosslinked acrylate fiber may be lowered.

On the other hand, Patent Document 3 attempts to improve the dyeing fastness of crosslinked acrylate fibers by improving the dyeing method. In this method, there is a portion where an amino group is formed without partial crosslinking during the crosslinking introduction treatment with a hydrazine-based compound, so that the amino group is used as a dyeing seat for reactive dyes. To develop good color fastness. However, since the number of amino groups formed with the crosslinking introduction treatment is small, there are problems in leveling and darkness, and on the other hand, the crosslinking conditions that greatly affect the fiber properties are changed for the purpose of improving dyeability. It has the fundamental problem that it is difficult.
JP 2003-89971 A JP 2003-278079 A JP 2006-70421 A

Under such circumstances, the present inventors have conducted intensive research to obtain a crosslinked acrylate fiber having excellent dyeability, and as a result, a novel crosslinked structure in which an amino group serving as a dyeing seat for reactive dyes is introduced by a covalent bond. Acrylate fiber has been developed, and the fiber can be dyed uniformly and in a dark color without impairing the properties of the cross-linked acrylate fiber such as moisture absorption / release properties, moisture absorption exothermic property, antibacterial property, and deodorant property, and fastness to dyeing The present invention was found to be excellent, and the present invention was completed. The object of the present invention is excellent in levelness and darkness, can express high dyeing fastness, and after dyeing, as in the case before dyeing, characteristics such as moisture absorption and desorption, antibacterial properties, and deodorant properties An object of the present invention is to provide a cross-linked acrylate fiber that can exhibit the above-mentioned properties.

The above object of the present invention is achieved by the following means. That is,
[1] Obtained by subjecting an acrylic fiber to a hydrolysis treatment after a treatment with a hydrazine compound and a treatment with an amino group-containing organic compound having 1 or more primary amino groups in one molecule. A dyeable cross-linked acrylate fiber characterized by
[2] An amino group-containing organic compound having 1 or more primary amino groups in one molecule is an alkylene group having 3 or more total amino groups in one molecule and having 3 or more carbon atoms between the amino groups. The dyeable cross-linked acrylate fiber according to [1], wherein the dyeable cross-linked acrylate fiber has a structure bonded to each other.
[3] The acrylic fiber is subjected to a treatment with a hydrazine compound and a treatment with an amino group-containing organic compound having 1 or more primary amino groups in one molecule, followed by a hydrolysis treatment. A method for producing a dyeable cross-linked acrylate fiber.
[4] After allowing the reactive dye to be adsorbed to the dyeable cross-linked acrylate fiber according to [1] or [2] under acidic conditions, the dye and the amino group in the fiber are reacted under alkaline conditions. The resulting dyed crosslinked acrylate fiber.

By using the dyeable cross-linked acrylate fiber of the present invention, it is possible to obtain a cross-linked acrylate fiber that is dyed uniformly and darkly and has dyeing fastness that can withstand practical use. This makes it possible to develop cross-linked acrylate fibers, which have advanced and diverse functions, but whose application development has been limited due to low dyeing properties, in fields where hue is important. . Such a dyeable cross-linked acrylate fiber of the present invention is extremely useful in various fields such as clothing, living room, and building materials that are required to be multifunctional or highly functional.

The present invention is described in detail below. The acrylic fiber used in the present invention may be a fiber formed of an acrylonitrile (hereinafter referred to as AN) polymer, and the AN polymer may be an AN homopolymer or AN and other monomers. Any of the copolymers can be employed.

The amount of AN copolymerized in the AN polymer is preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 80% by weight or more. In the present invention, a crosslinked structure and an amino group are introduced into the fiber by reacting the nitrile group of the AN polymer forming the acrylic fiber with the hydrazine compound and the amino group-containing organic compound. The cross-linked structure greatly affects the fiber properties, and the amino group greatly affects the dyeability. If the AN is too small, the cross-linked structure and amino groups must be reduced, and the fiber properties and dyeability may be insufficient. However, it is easy to obtain good results by setting the copolymerization amount of AN within the above range.

When a copolymer of AN and another monomer is employed as the AN polymer, the copolymer components other than AN include sulfonic acid group-containing monomers such as methallylsulfonic acid and p-styrenesulfonic acid, and the like. Its salts, carboxylic acid group-containing monomers such as (meth) acrylic acid and itaconic acid, and salts thereof, monomers such as styrene, vinyl acetate, (meth) acrylic acid ester, (meth) acrylamide, etc. There is no particular limitation as long as it is a polymerizable monomer.

The means for producing the acrylic fiber employed in the present invention is not particularly limited, and basically may be produced by applying a known method as it is. The form may be any form such as short fiber, tow, yarn, knitted fabric, non-woven fabric, etc., and may be used as an intermediate product in the manufacturing process, waste fiber, or the like.

In particular, a relatively coarse structure obtained by wet or dry / wet spinning and not subjected to heat treatment such as dry densification or moist heat relaxation treatment, specifically, percentage of moisture content expressed on the basis of dry fiber weight When an acrylic fiber having a water swelling degree of 30 to 150% is used, the dispersibility of the fiber in the reaction solution and the permeability of the amino group-containing organic compound into the fiber are increased. Has the advantage that it proceeds uniformly and quickly.

The treatment with a hydrazine compound in the present invention refers to reacting a nitrile group of an AN polymer with a hydrazine compound. By this reaction, a crosslinked structure is formed between the AN polymers or in the polymer. The crosslinked structure increases the hydrophilicity of the polymer due to the carboxyl group introduced in the hydrolysis treatment described later, and the fibers are absorbed during moisture absorption. There is an effect of suppressing the deterioration of physical properties.

The hydrazine-based compound employed in the present invention is not particularly limited, and in addition to hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine bromate, hydrazine carbonate, etc., ethylenediamine, guanidine sulfate, guanidine hydrochloride, phosphoric acid, etc. Examples thereof include compounds containing a plurality of amino groups such as guanidine and melamine.

In the present invention, the treatment with an amino group-containing organic compound refers to reacting a nitrile group or the like of an AN polymer with an amino group-containing organic compound. As a result, an amino group serving as a dyeing seat is introduced. As the amino group-containing organic compound, one having two or more primary amino groups in one molecule is employed. This requires at least one amino group that reacts with the nitrile group and one amino group that becomes the dyeing seat, and the amino group is a primary amino group from the viewpoint of reactivity with the nitrile group or the reactive dye. It depends on what is desired. In the treatment with the amino group-containing organic compound, a crosslinked structure can be formed in the same manner as in the treatment with the hydrazine-based compound described above, but the rate at which the crosslinked structure is formed can be reduced depending on the reaction conditions.

Specific examples of the amino group-containing organic compound include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyvinylamine, polyethyleneimine, 3,3′-iminobis (propylamine), N-methyl-3,3 ′. -Iminobis (propylamine), N, N'-bis (3-aminopropyl) ethylenediamine, N, N'-bis (3-aminopropyl) -1,3-propylenediamine, N, N'-bis (3- Aminopropyl) -1,3-butylenediamine, N, N′-bis (3-aminopropyl) -1,4-butylenediamine, and the like.

Among such amino group-containing organic compounds, it is more preferable that the number of all amino groups in one molecule is 3 or more, and the amino groups have a structure in which an amino group is bonded with an alkylene group having 3 or more carbon atoms. When the total number of amino groups is 2, as described above, there is a possibility that a cross-linked structure is formed and an amino group to be a dyeing seat may be lost. Even if an amino group reacts with a nitrile group to form a cross-linked structure, one amino group remains, and due to steric restrictions, this amino group is unlikely to react with the nitrile group. A more secure amino group can be secured.

An amino group-containing organic compound having such a structure has a high reaction rate with a nitrile group and can be reacted in a short time even at a treatment temperature of 100 ° C. or less, so that it does not require a pressure vessel and is advantageous in terms of cost. Furthermore, in the case of an amino group-containing organic compound having such a structure, the resulting fiber can be made less colored, which is advantageous for dyeing. The number of carbons referred to here is the number of carbons directly connecting amino groups, and does not include the number of carbons such as branched chains and substituents.

Such amino group-containing organic compounds include 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis (propylamine), N, N′-bis (3-aminopropyl) ethylenediamine, N , N′-bis (3-aminopropyl) -1,3-propylenediamine, N, N′-bis (3-aminopropyl) -1,3-butylenediamine, N, N′-bis (3-aminopropyl) ) -1,4-butylenediamine and the like.

Further, in the treatment with an amino group-containing organic compound, the number of dyeing seats can be easily adjusted by selecting the amount of the amino group-containing organic compound and the number of amino groups of the compound. For this reason, it is possible to improve level dyeing and dark dyeing.

In the present invention, the acrylic fiber is treated with the above-described hydrazine compound and the amino group-containing organic compound, but either treatment may be performed first as long as it is before the hydrolysis treatment described below. You may process simultaneously. However, since there are features as described later depending on the processing order, it is desirable to determine the processing order after recognizing the features.

First, simultaneous processing has the advantage of reducing the number of steps, but it becomes difficult to recover and reuse unreacted hydrazine-based compounds and amino group-containing organic compounds. The control becomes complicated. On the other hand, when each process is performed separately, the number of steps increases, but the recovery and reuse of the drug and the structure control become easy. In particular, when the treatment with the hydrazine-based compound is performed first, a cross-linked structure already exists at the stage of treatment with the amino group-containing organic compound, and the steric restrictions become large. A crosslinked structure is less likely to be formed, and an amino group that becomes a dyeing seat can be efficiently introduced into the fiber, which is preferable.

The degree of reaction of the hydrazine-based compound or amino group-containing organic compound may be set as appropriate in consideration of the amount of cross-linking structure and the amount of amino groups required based on the desired fiber properties and dyeing performance. However, it is necessary to carry out the reaction so that a functional group such as a nitrile group to be subjected to the hydrolysis treatment described later remains.

The method for treating the acrylic fiber with the hydrazine compound or the amino group-containing organic compound is not particularly limited, but an aqueous solution of these compounds is prepared, and the acrylic fiber is immersed in the aqueous solution. A method of spraying or applying the aqueous solution to the system fiber and treating it may be mentioned.

After the treatment with the hydrazine-based compound and the treatment with the amino group-containing organic compound, acid treatment may be performed after sufficiently removing these compounds remaining in the treatment. By performing the acid treatment, the whiteness of the fiber can be improved, which is advantageous for dyeing. Examples of the acid used for the acid treatment include mineral acids such as nitric acid, sulfuric acid and hydrochloric acid, and organic acids such as formic acid and acetic acid.

In the present invention, the hydrolysis treatment is performed after the treatment with the hydrazine compound and the treatment with the amino group-containing organic compound. By this hydrolysis treatment, in the treatment with a hydrazine-based compound, the treatment with an amino group-containing organic compound, or the subsequent acid treatment, nitrile groups remaining without reacting or some of the nitrile groups are hydrolyzed by these treatments. The amide group produced in this way is converted to a carboxyl group.

Here, when the hydrolysis treatment is performed before the treatment with the hydrazine compound or the amino group-containing organic compound, the hydrazine compound or the amino group-containing organic compound is reacted in the presence of the carboxyl group. Easily forms an ionic bond with the carboxyl group, so that the reaction with the essential nitrile group does not proceed, and the introduction of the crosslinked structure and amino group becomes insufficient.

The introduction amount of the carboxyl group is such that the group exhibits functions such as moisture absorption / release, moisture absorption exothermicity, and deodorizing property in the crosslinked acrylate fiber, so that the intended function can be sufficiently developed. And can be arbitrarily adjusted depending on the reaction conditions. Generally, it is desirable to introduce 1 to 12 mmol / g, preferably 3 to 10 mmol / g, more preferably 3 to 8 mmol / g of carboxyl groups.

Compounds employed for such hydrolysis treatment include alkaline metal compounds such as alkali metal hydroxides, alkaline earth metal hydroxides and alkali metal carbonates, and compounds capable of acid hydrolysis such as nitric acid, sulfuric acid and hydrochloric acid. Etc. can be used.

Moreover, a reduction process can also be performed after this hydrolysis process. By performing the reduction treatment, the whiteness of the fibers is improved, which is advantageous for dyeing.

The dyeable cross-linked acrylate fiber of the present invention obtained as described above has improved dyeability, as well as hygroscopic, hygroscopic exothermic and deodorant properties like conventional cross-linked acrylate fibers. It is possible to express such functions.

Next, the production method will be described in detail by taking as an example the case where the treatment with the hydrazine-based compound is first performed and the treatment with the amino group-containing organic compound is subsequently performed.

First, the acrylic fiber described above is treated with a hydrazine compound. In this treatment, a crosslinked structure is introduced as described above, and accordingly, the nitrogen content in the fiber increases. For this reason, an increase in nitrogen content is a measure of the amount of cross-linked structure introduced, but in order to obtain good fiber properties, it is desirable to adjust the increase in nitrogen content to 0.1 to 10% by weight. Specific reaction conditions can include conditions for treatment in an aqueous solution having a hydrazine compound concentration of 5 to 60% by weight at 50 to 120 ° C. within 5 hours. Here, the increase in the nitrogen content refers to the difference between the nitrogen content of the acrylic fiber as a raw material and the nitrogen content of the fiber treated with the hydrazine compound.

Next, the fiber that has been treated with the hydrazine compound is washed with water, and then treated with an amino group-containing organic compound. In the treatment, an amino group that becomes a dyeing seat is introduced. Specific reaction conditions include conditions of treatment at 50 to 150 ° C., preferably 80 to 150 ° C. for 30 minutes to 48 hours in an aqueous solution having an amino group-containing organic compound concentration of 1% by weight or more. In particular, when an amino group-containing organic compound having a structure in which amino groups are bonded by an alkylene group having 3 or more carbon atoms is used, the treatment may be performed at 50 to 150 ° C. for 30 minutes to 4 hours. it can. By treating under such conditions, fibers with a high saturation dyeing amount can be obtained, and it becomes possible to exhibit excellent leveling and deep dyeing properties.

The fiber that has been treated with the amino group-containing organic compound may be subjected to an acid treatment after being washed with water. The acid mentioned above can be employ | adopted as an acid used for an acid treatment. The conditions for the acid treatment are not particularly limited, but the treated fibers are usually immersed in an aqueous solution having an acid concentration of 5 to 20% by weight, preferably 7 to 15% by weight, at 50 to 120 ° C. for 0.5 to 10 hours. An example is given.

The fiber subjected to the above treatment is subjected to a hydrolysis treatment after washing with water. By this treatment, a carboxyl group is formed in the fiber, and the dyeable cross-linked acrylate fiber of the present invention can be obtained. In addition, when a hydrolysis process is performed with the alkaline metal compound mentioned above, since the carboxyl group formed couple | bonds with the metal ion derived from these compounds, most become a metal salt type carboxyl group.

The introduction amount of the carboxyl group may be set in consideration of the function required for the final fiber, but is generally as described above. As specific reaction conditions, in the case of using an alkaline metal compound, conditions for treatment in an aqueous solution of 1 to 10% by weight, more preferably 1 to 5% by weight, at 50 to 120 ° C. within 1 to 10 hours may be mentioned. it can.

A reduction treatment may be performed after the hydrolysis treatment. As the reducing agent to be used, one or a combination of two or more selected from the group consisting of hydrosulfite salt, thiosulfate, sulfite, nitrite, thiourea dioxide, ascorbate, and hydrazine compounds And so on. Examples of the treatment conditions include soaking the treated fiber in an aqueous solution having a drug concentration of 0.5 to 5% by weight at a temperature of 50 ° C. to 120 ° C. for 30 minutes to 5 hours.

The method for dyeing the dyeable cross-linked acrylate fiber of the present invention is not particularly limited, and a dyeing method using a reactive dye that reacts with an amino group can be employed. In particular, when the dyeing method described in Patent Document 3 mentioned in the background section is adopted, the crosslinked acrylate fiber is good without deteriorating the characteristic functions such as hygroscopicity, hygroscopic exothermicity, and deodorizing property. In addition to dyeing fastness, dyed crosslinked acrylate fibers are obtained that have excellent uniformity and darkness that cannot be obtained by applying the dyeing method to conventional crosslinked acrylate fibers. Can be preferred.

Here, the dyeing method described in Patent Document 3 is a method in which a reactive dye is adsorbed to a crosslinked acrylate fiber under acidic conditions, and then the dye and an amino group in the fiber are reacted under alkaline conditions. .

In such a dyeing method, a reactive dye that reacts with an amino group is used. Examples thereof include chlorotriazine dyes such as monochlorotriazine dyes and dichlorotriazine dyes, chloropyrimidine dyes, vinylsulfone dyes, and the like. In addition, dyes having a plurality of the same functional groups, such as dyes having two sulfate ethyl sulfone groups and dyes having two or more monochloro triazine groups, as well as sulfate ethyl sulfone / monochloro triazine dyes, sulfate ethyl sulfone It is also possible to use dyes having a plurality of different functional groups such as / dichlorodichloroazine dyes, sulfate ethyl sulfone / difluoromonochlorotriazine dyes, and the like.

As a procedure for dyeing, first, a reactive dye is adsorbed on a crosslinked acrylate fiber under acidic conditions. The pH of the bath with the reactive dye and acid added is set to 5 or less, and the crosslinked acrylate fiber is immersed in the bath. As the acid for adjusting the pH, an organic acid such as acetic acid, formic acid, lactic acid or tartaric acid, or an aqueous solution of a mineral acid such as nitric acid, sulfuric acid or hydrochloric acid is used. The treatment temperature is usually 60 ° C. or higher.

Next, a covalent bond is chemically generated between the crosslinked acrylate fiber and the dye under alkaline conditions. The crosslinked acrylate fiber in a state where the reactive dye is adsorbed is immersed in water, and the reaction is advanced by adding an alkaline compound so that the bath pH after treatment is finally 9 or more. As the alkaline compound for adjusting the pH, organic acid salts such as alkali metals, carbonates, hydroxides, amine compounds, ammonia and the like are used. The treatment temperature is usually 60 ° C. or higher.

In addition, after dyeing by such a dyeing method, the counter ion of the carboxyl group in the fiber is replaced with an ion derived from the alkaline compound. However, by performing ion exchange, the desired metal salt-type carboxyl group and / or Alternatively, it can be converted into an H-type carboxyl group, whereby functions such as moisture absorption and desorption, moisture absorption exothermicity, and deodorization can be adjusted.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In addition, unless otherwise indicated, the part and percentage in an Example are shown on a weight basis.

(1) Amount of carboxyl group [mmol / g]
After adding 200 ml of water to about 1 g of the sample, 1 mol / l hydrochloric acid aqueous solution was added to adjust the pH to 2, and the sample was washed with water, dehydrated and dried. Next, after sufficiently drying, about 0.2 g was precisely weighed (A [g]), and a titration curve was obtained with a 0.1 mol / l aqueous sodium hydroxide solution according to a conventional method. The consumption amount (B [ml]) of sodium hydroxide aqueous solution consumed by carboxyl groups was determined from the titration curve, and the carboxyl group amount (mmol / g) was calculated by the following formula.
Amount of carboxyl group [mmol / g] = 0.1 B / A

(2) Saturated moisture absorption [%]
About 5.0 g of the sample is dried with a hot air dryer at 105 ° C. for 16 hours, and the weight is measured (C [g]). The sample is then placed in a constant temperature bath at 20 ° C. and 65% RH for 24 hours. The weight of the sample thus absorbed is measured (D [g]). From the above measurement results, calculation was performed according to the following equation.
Saturated moisture absorption [%] = {(D−C) / C} × 100

(3) Saturated dyeing amount [% owf]
Reactive dye Sumifix Supra Blue BRF (manufactured by Sumitomo Chemical Co., Ltd.) 0.60 g and formic acid were added to water to prepare a dye bath having a pH of 2.0 and 120 ml. In the dye bath, 0.60 g of a sample in which the carboxyl group was H-shaped was immersed, and dye adsorption treatment was performed at 60 ° C. for 5 hours. The absorption spectrum of the dyeing solution obtained by filtering the sample from the dyed bath after the treatment was measured using U-1100 Spectrophotometer (manufactured by Hitachi, Ltd.), and the amount of residual dye was determined from the absorbance at the peak wavelength of 610 nm by the absorptiometry. Was quantified. The saturated dyeing amount was calculated from the measurement result by the following formula.
Saturated dyeing amount [% owf] = (input dye amount [g] −residual dye amount [g]) / sample weight [g] × 100
Since the amount of saturated dyeing increases as the amount of amino groups contained in the sample increases, it becomes an index of the amino group content.

(4) Sweat Dye Fastness Reactive Dye Sumifix Black ENS150 (manufactured by Sumitomo Chemical Co., Ltd.) 0.49 g and formic acid were added to water to prepare a dye bath having a pH of 2.0 and 120 ml. In the dye bath, 7.00 g of a sample in which the carboxyl group was H-shaped was immersed, and dye adsorption treatment was performed at 60 ° C. for 5 hours. The obtained sample was washed with water, then immersed in 210 ml of water, and heated to 60 ° C. Next, sodium carbonate was added to adjust the pH to 11, and immersed for 1 hour at 60 ° C. Thereafter, washing with water, soaping, washing with water, and dehydration were sequentially performed to prepare a stained sample. The prepared sample was tested in accordance with JIS-L-0848 using an alkaline artificial sweat, and compared with the sample before the test using a gray scale for color fading, the dyeing fastness was determined. If the sweat dyeing fastness is 3rd grade or higher, it can withstand practical use.

(5) Fastness to wet friction dyeing A sample dyed in the same manner as the above-described determination of fastness to sweat dyeing is tested according to JIS-L-0849 using a friction tester type II, and a gray scale for contamination. Was used to determine the degree of coloring of the white cotton fabric for friction. The wet friction dyeing fastness can withstand practical use as long as it is grade 3 or higher.

(6) Dark dyeing The dark dyeing property of the sample dyed in the same manner as in the determination of the fastness to sweat dyeing was visually evaluated in the following three stages. If it is ◎ or ○, it can withstand practical use.
A: Dense color and excellent dyeing quality B: Slight defects in the acceptable range for the product exist X: Dyeing is insufficient and there are serious defects that cannot be shipped as a product

(7) Leveling property The dyeing spots of the sample dyed in the same manner as in the above-described determination of the fastness to sweat dyeing were visually evaluated in the following three stages. If it is ◎ or ○, it can withstand practical use.
◎: Homogeneous and excellent dyeing quality ○: There are slight defects that are acceptable as a product ×: Dyeing is uneven and there are serious defects that cannot be shipped as a product

(Production of acrylic fiber A)
A spinning stock solution in which 10 parts of an acrylonitrile polymer (90% intrinsic viscosity [η]: 1.2 in dimethylformamide at 30 ° C.) consisting of 90% acrylonitrile and 10% methyl acrylate was dissolved in 90 parts of a 48% rhodium soda aqueous solution was prepared by a conventional method. Then, spinning, washing, drawing, drying, wet heat treatment and the like were performed to obtain 0.9 dtex acrylic fiber A.

(Production of acrylic fiber B)
A spinning stock solution in which 10 parts of an acrylonitrile polymer (intrinsic viscosity [η]: 1.2 in 30 ° C. dimethylformamide) consisting of 90% acrylonitrile and 10% vinyl acetate was dissolved in 90 parts of a 48% aqueous rhodium soda solution according to a conventional method. Spinning, washing with water, stretching, drying, wet heat treatment, and the like were performed to obtain 0.9 dtex acrylic fiber B.

Example 1
The acrylic fiber A was treated with a mixed aqueous solution of 15% hydrazine hydrate and 3% 3,3′-iminobis (propylamine) at 110 ° C. for 3 hours and washed with water. Then, it was treated with 8% nitric acid at 100 ° C. for 1 hour and washed with water. Subsequently, it was treated with a 5% aqueous sodium hydroxide solution at 90 ° C. for 2 hours, washed with water, dehydrated and dried to obtain the dyeable cross-linked acrylate fiber of Example 1. The fibers were evaluated for carboxyl group amount, saturated moisture absorption, saturated dyeing amount, fastness to sweat dyeing, fastness to wet friction dyeing, deep dyeability, and levelness. The results are shown in Table 1.

(Example 2)
Acrylic fiber A was treated with hydrazine hydrate 15% aqueous solution at 110 ° C. for 3 hours, washed with water, then treated with 3,3′-iminobis (propylamine) 3% aqueous solution at 110 ° C. for 3 hours, Washed with water. Then, it was treated with 8% nitric acid at 100 ° C. for 1 hour and washed with water. Subsequently, a 5% aqueous sodium hydroxide solution was treated at 90 ° C. for 2 hours, washed with water, dehydrated, and dried to obtain a dyeable cross-linked acrylate fiber of Example 2. The evaluation results are shown in Table 1.

(Example 3)
Acrylic fiber A was treated with hydrazine hydrate 15% aqueous solution at 110 ° C. for 3 hours, washed with water, then treated with 3,3′-iminobis (propylamine) 6% aqueous solution at 110 ° C. for 3 hours, Washed with water. Then, it was treated with 8% nitric acid at 100 ° C. for 1 hour and washed with water. Subsequently, a 5% aqueous sodium hydroxide solution was treated at 90 ° C. for 2 hours, washed with water, dehydrated, and dried to obtain a dyeable cross-linked acrylate fiber of Example 3. The evaluation results are shown in Table 1.

Example 4
The acrylic fiber A was treated with 3,3′-iminobis (propylamine) 3% aqueous solution at 110 ° C. for 3 hours, washed with water, then treated with hydrazine hydrate 15% aqueous solution at 110 ° C. for 3 hours, Washed with water. Then, it was treated with 8% nitric acid at 100 ° C. for 1 hour and washed with water. Subsequently, a 5% aqueous sodium hydroxide solution was treated at 90 ° C. for 2 hours, washed with water, dehydrated, and dried to obtain a dyeable cross-linked acrylate fiber of Example 4. The evaluation results are shown in Table 1.

(Example 5)
The dyeable cross-linked acrylate fiber of Example 5 in the same manner as in Example 2, except that 3,3'-iminobis (propylamine) is changed to N-methyl-3,3'-iminobis (propylamine). Got. The evaluation results are shown in Table 1.

(Example 6)
A dyeable cross-linked acrylate fiber of Example 6 was obtained in the same manner as in Example 2, except that 3,3′-iminobis (propylamine) was changed to triethylenetetramine. The evaluation results are shown in Table 1.

(Example 7)
In Example 2, after treatment with an aqueous sodium hydroxide solution and washing with water, further treatment with an aqueous 1% thiourea dioxide solution at 90 ° C. for 2 hours, washing with water, dehydration, and drying were carried out. A dyeable cross-linked acrylate fiber was obtained. The evaluation results are shown in Table 1.

(Example 8)
A dyeable cross-linked acrylate fiber of Example 8 was obtained in the same manner as in Example 2 except that the acrylic fiber A was changed to the acrylic fiber B. The evaluation results are shown in Table 1.

Example 9
In Example 8, after treatment with an aqueous sodium hydroxide solution and washing with water, further treatment with an aqueous 1% thiourea dioxide solution at 90 ° C. for 2 hours, washing with water, dehydration and drying were performed. A dyeable cross-linked acrylate fiber was obtained. The evaluation results are shown in Table 1.

(Comparative Example 1)
The acrylic fiber A was treated with a 15% aqueous solution of hydrazine hydrate at 110 ° C. for 3 hours and washed with water. Then, it was treated with 8% nitric acid at 100 ° C. for 1 hour and washed with water. Subsequently, a 5% aqueous sodium hydroxide solution was treated at 90 ° C. for 2 hours, washed with water, dehydrated and dried to obtain a crosslinked acrylate fiber of Comparative Example 1. The evaluation results are shown in Table 1.

(Comparative Example 2)
A crosslinked acrylate fiber of Comparative Example 2 was obtained in the same manner as in Example 2, except that 3,3′-iminobis (propylamine) was changed to n-butylamine. The evaluation results are shown in Table 1.

(Comparative Example 3)
The acrylic fiber A was treated with a hydrazine hydrate 15% aqueous solution at 110 ° C. for 3 hours and washed with water. Then, it was treated with 8% nitric acid at 100 ° C. for 1 hour and washed with water. Subsequently, it was treated with a 5% aqueous sodium hydroxide solution at 90 ° C. for 2 hours and washed with water. Further, a 3% aqueous solution of 3,3′-iminobis (propylamine) was treated at 110 ° C. for 3 hours, washed with water, dehydrated and dried to obtain a crosslinked acrylate fiber of Comparative Example 3. The evaluation results are shown in Table 1.

In each of Examples 1 to 9, dyeable cross-linked acrylate fibers showing good characteristics were obtained. When Examples 1, 2, and 4 are compared, it can be seen that when the treatment with the amino group-containing organic compound is performed after the treatment with the hydrazine-based compound, fibers having more excellent dyeing characteristics can be obtained. Further, when Examples 2, 5, and 6 are compared, the amino group-containing organic compound having a structure in which the total number of amino groups in one molecule is 3 or more and the amino groups are bonded by an alkylene group having 3 or more carbon atoms. It is understood that the amount of saturated dyeing is increased when amino acid is employed, and amino groups are more efficiently introduced.

Since Comparative Examples 1 and 2 are not treated with an amino group-containing organic compound having two or more primary amino groups in one molecule, Comparative Example 3 is treated with an amino group-containing organic compound after hydrolysis. Therefore, the saturated dyeing amount was low, and the deep dyeing property and the level dyeing property were inferior.

Claims (4)

The acrylic fiber is obtained by subjecting an acrylic fiber to a treatment with a hydrazine compound and a treatment with an amino group-containing organic compound having 1 or more primary amino groups in one molecule, followed by a hydrolysis treatment. Dyeable cross-linked acrylate fiber. An amino group-containing organic compound having two or more primary amino groups in one molecule is bonded to each other by an alkylene group having three or more amino groups as the total number of amino groups in one molecule and having three or more carbon atoms. The dyeable cross-linked acrylate fiber according to claim 1, which has a structure. Dyeing characterized by subjecting acrylic fiber to treatment with hydrazine compound and treatment with amino group-containing organic compound having 1 or more primary amino groups in one molecule, followed by hydrolysis treatment For producing a water-soluble crosslinked acrylate fiber. The dyed crosslinked acrylate fiber according to claim 1 or 2 is adsorbed with a reactive dye under acidic conditions, and then dyed by reacting the dye with an amino group in the fiber under alkaline conditions. Cross-linked acrylate fiber.