JP2009228188A - Acrylic dyed fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acrylic synthetic fiber improved in blue color-discharge dyeing property, in which blue color discharge dyeing is difficult, without lowering of touch feeling which is caused by fiber shrinkage and hardening. <P>SOLUTION: A method for producing an acrylic dyed fiber includes dyeing an acrylic synthetic fiber containing a mixed polymer composition obtained by mixing 70-99.9 wt.% polymer (A) containing 40-80 wt.% acrylonitrile, 20-60 wt.% halogen-containing monomer which is copolymerizable with acrylonitrile, and 0-5 wt.% sulfonic acid group-containing monomer with (B) 0.1-30 wt.% polymer containing 5-70 wt.% acrylonitrile, 20-94 wt.% another copolymerizable monomer, and 1-40 wt.% sulfonic acid group-containing monomer, wherein total amount of the polymer (A) and the polymer (B) is 100 pts.wt., with a cationic activating agent when dyeing the fiber with a cationic dye for discharge dyeing and then carrying out discharge dyeing treatment of the fiber with a printing paste for discharge dyeing. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an acrylic dyed fiber dyed using a cationic dye for discharging and a cationic activator and a method for producing the same.

Acrylic synthetic fibers have a unique animal hair-like texture, take advantage of their soft feeling and bulkiness, and are widely used in fields such as bore, seal, fleece, and high pile due to their ease of processing. . However, acrylic synthetic fibers have insufficient dischargeability compared to acrylic synthetic fibers, and thus there is a problem that design properties are restricted, and various attempts have been made to improve dischargeability. As a method for improving this dischargeability, an acrylic synthetic fiber containing 0.2 to 5% by weight of acrylic acid, methacrylic acid and alkyl esters thereof has been proposed (Patent Document 1), and discharge to some extent is performed by this method. Although the whiteness after the treatment is improved, the steam heat treatment time required for the discharging process is still long, a problem remains in workability, and the performance is not always sufficient in practice. In addition, a method has been proposed in which a relatively hydrophilic polymer comprising a monomer having a solubility in water at 20 ° C. of 1% or more and a sulfonic acid group-containing monomer is mixed (Patent Document 2). The whiteness after the discharging process is considerably improved, and the steaming time required for the discharging process is shortened. However, even though this method has excellent red and yellow discharge characteristics, there is a problem that the blue color is insufficient, and the remaining blue color is particularly noticeable in medium and light colors dyed at a relatively low dye concentration. Sex is reduced. In addition, a method of mixing a cationic activator with a printing paste for discharging at the time of discharging is proposed (Patent Document 3), but this method improves the blue discharging property, but the fibers shrink and feel when discharging. The problem of becoming harder remains.
JP 2003-183931 A JP 2005-314841 A JP 2000-355886 A

  As mentioned above, conventional acrylic synthetic fibers have insufficient blue dischargeability, and the amount of printing paste for discharge is increased or a cationic activator is added to forcefully blue discharge. When trying to improve the properties, the texture of the fibers shrinking and curing decreased. Accordingly, an object of the present invention is to obtain an acrylic discharge fiber material having a soft texture and at the same time having a good whiteness of the discharge treatment portion, a short steaming time necessary for discharge discharge and excellent workability. It is.

That is, in the present invention, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight, 40 to 80% by weight of acrylonitrile, 20 to 60% by weight of a halogen-containing monomer copolymerizable with acrylonitrile, and sulfonic acid 70 to 99.9 parts by weight of the polymer (A) containing 0 to 5% by weight of the group-containing monomer, 5 to 70% by weight of acrylonitrile, 20 to 94% by weight of other copolymerizable monomers, and the sulfonic acid group-containing monomer 1 100 parts by weight of an acrylic synthetic fiber containing a polymer composition obtained by mixing 0.1 to 30 parts by weight of the polymer (B) containing -40% by weight, 0.001 to 10 parts by weight of a cationic dye for discharging, and Acrylic dyed fibers characterized by containing 0.001 to 10 parts by weight of a cationic activator (Claim 1),
The acrylic system according to claim 1, wherein the amount of the cationic dye for discharging is 0.01 to 6 parts by weight, and the amount of the cationic activator is 0.01 to 6 parts by weight. Regarding dyed fibers (claim 2),
The present invention relates to the acrylic dyed fiber according to claim 1 or 2, wherein the other copolymerizable monomer contained in the polymer (B) is an acrylic ester. Item 3),
In the present invention, the sulfonic acid group-containing monomer contained in the polymer (B) is sodium 2-acrylamido-2-methylpropanesulfonate, according to any one of claims 1 to 3. Acrylic dyed fiber (claim 4),
In the present invention, the sulfonic acid group-containing monomer contained in the polymer (B) is a combination of sodium methallylsulfonate and sodium 2-acrylamido-2-methylpropanesulfonate. (Claim 5) relating to the acrylic dyed fiber according to any one of
The present invention relates to an acrylic dyed fiber according to any one of claims 1 to 5, wherein the cationic activator is a quaternary ammonium compound (claim 6),
The present invention relates to the acrylic dyed fiber according to claim 6, wherein the quaternary ammonium compound is alkyldimethylbenzylammonium chloride (claim 7),
In the present invention, the total amount of the polymer (A) and the polymer (B) is 100 parts by weight, 40 to 80% by weight of acrylonitrile, 20 to 60% by weight of a halogen-containing monomer copolymerizable with acrylonitrile, and sulfonic acid group-containing 70 to 99.9 parts by weight of the polymer (A) containing 0 to 5% by weight of monomer, 5 to 70% by weight of acrylonitrile, 20 to 94% by weight of other copolymerizable monomer and 1 to 40 of sulfonic acid group-containing monomer 100 parts by weight of an acrylic synthetic fiber containing a polymer composition obtained by mixing 0.1 to 30 parts by weight of the polymer (B) containing 5% by weight, 0.001 to 10 parts by weight of a cationic dye for discharging, and a cationic system 0.001 to 10 parts by weight of an activator is obtained by dyeing at 60 to 120 ° C., and relates to a method for producing an acrylic dyed fiber (claim 8),
The present invention relates to a method for producing an acrylic dyed fiber according to claim 8, wherein the temperature during dyeing is 90 to 110 ° C (claim 9),
In the present invention, the other copolymerizable monomer contained in the polymer (B) is an acrylic ester, The method for producing an acrylic dyed fiber according to any one of claims 8 and 9 (Claim 10),
In the present invention, the sulfonic acid group-containing monomer contained in the polymer (B) is sodium 2-acrylamido-2-methylpropanesulfonate, according to any one of claims 8 to 10. A method for producing an acrylic dyed fiber (claim 11),
In the present invention, the sulfonic acid group-containing monomer contained in the polymer (B) is a combination of sodium methallylsulfonate and sodium 2-acrylamido-2-methylpropanesulfonate. The method for producing an acrylic dyed fiber according to any one of Items 10 (Claim 12),
The present invention relates to a method for producing an acrylic dyed fiber according to any one of claims 8 to 12, wherein the cationic activator is a quaternary ammonium compound (claim 13),
The present invention relates to a method for producing an acrylic dyed fiber according to claim 13, wherein the quaternary ammonium compound is alkyldimethylbenzylammonium chloride (claim 14),
The present invention relates to an acrylic discharge fiber material obtained by discharging the acrylic synthetic fiber material containing the acrylic dye fiber according to any one of claims 1 to 7 with a discharge agent (claim 15).

  The acrylic dyed fiber of the present invention has a soft texture even after the discharging process, and at the same time the whiteness of the discharged part is good, and the steaming heat treatment time required for discharging is short and the processability is excellent.

  The polymer (A) in the present invention comprises 40 to 80% by weight of acrylonitrile, 20 to 60% by weight of a halogen-containing monomer copolymerizable with acrylonitrile, and 0 to 5% by weight of a sulfonic acid group-containing monomer, but is copolymerized with acrylonitrile. Possible halogen-containing monomers include vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide and the like. Among these, vinyl chloride and vinylidene chloride are preferable, and these may be used alone or in combination. Examples of the sulfonic acid group-containing monomer include allyl sulfonic acid, methallyl sulfonic acid, p-styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, isoprene sulfonic acid, and alkali metal salts thereof.

  In the polymer (A) of the present invention, acrylonitrile is preferably used in an amount of 40 to 80% by weight. However, in order to improve the workability of the fiber, the content of acrylonitrile is preferably 40% by weight or more, and the softening point is In order to obtain sufficient dyeability, the content of acrylonitrile is preferably 80% by weight or less. Further, in the polymer (A) of the present invention, it is preferable to use a halogen-containing monomer in an amount of 20 to 60% by weight. The content of halogen-containing monomer is preferably 60% by weight or less in order to reduce hydrophobicity and obtain sufficient dyeability.

  Furthermore, in the polymer (A) of the present invention, it is preferable to use 0 to 5% by weight of a sulfonic acid-containing monomer, and in order to prevent a decrease in strength without causing voids or sticking to the fiber, The amount is preferably 5% by weight or less.

  The polymer (B) in the present invention comprises 5 to 70% by weight of acrylonitrile, 20 to 94% by weight of other copolymerizable monomers and 1 to 40% by weight of sulfonic acid group-containing monomers.

  In the polymer (B) of the present invention, acrylonitrile is preferably used in an amount of 5 to 70% by weight, but in order to maintain the heat resistance of the fiber, the content of acrylonitrile is preferably 5% by weight or more. In order to suppress the generation of voids in the fiber, the acrylonitrile content is preferably 70% by weight or less.

  In the polymer (B) of the present invention, other copolymerizable monomers include acrylic acid and methacrylic acid and their lower alkyl esters, aminoalkyl esters and glycidyl esters substituted with N or N, N-alkyl, acrylamide and methacrylic acid. Amides and their N or N, N-alkyl-substituted products, carboxyl group-containing vinyl monomers represented by acrylic acid, methacrylic acid, itaconic acid and the like, and anionic vinyl monomers such as sodium, potassium or ammonium salts thereof , Cationic vinyl monomers including quaternized aminoalkyl esters of acrylic acid and methacrylic acid, or vinyl group-containing lower alkyl ethers, vinyl group-containing lower carboxylic acid esters typified by vinyl acetate, vinyl chloride, Vinylidene chloride, vinyl bromide , Vinyl and vinylidene halides such as represented by vinylidene bromide, etc., more styrene are preferred, can be used singly or two or more of these monomers. In the present invention, it is preferable to use 20 to 94% by weight of other copolymerizable monomers. However, in order to obtain sufficient dischargeability, the content of other copolymerizable monomers is 20% by weight or more. The content of other copolymerizable monomers is preferably 94% by weight or less in order to prevent the occurrence of voids and sticking in the fiber. In particular, in terms of dyeability and dischargeability, it is preferable to use an acrylate ester as another copolymerizable monomer. As the acrylate ester, methyl acrylate, ethyl acrylate, butyl acrylate and the like are preferable, and these monomers can be used alone or in admixture of two or more.

  Examples of the sulfonic acid-containing monomer in the polymer (B) include allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and metal salts and amine salts thereof. Preferably, they can be used alone or in combination of two or more. In the polymer (B) of the present invention, it is preferable to use 1 to 40% by weight of the sulfonic acid-containing monomer, and in order to improve dischargeability, the content of the sulfonic acid-containing monomer is preferably 1% by weight or more, The content of the sulfonic acid-containing monomer is preferably 40% by weight or less in order to prevent a decrease in strength without causing voids or sticking in the fiber. Particularly, in terms of compatibility with the polymer (A) of the present invention, the sulfonic acid group-containing monomer contained in the polymer (B) is sodium 2-acrylamido-2-methylpropanesulfonate or sodium methallylsulfonate. And sodium 2-acrylamido-2-methylpropanesulfonate are preferred.

  The polymer (A) and polymer (B) of the present invention are known compounds as polymerization initiators, such as peroxide compounds, azo compounds, or various redox compounds, emulsion polymerization, suspension polymerization, It can be obtained by a general vinyl polymerization method such as solution polymerization.

  The polymer (A) and polymer (B) of the present invention are dissolved in an organic solvent such as acetone, acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or an inorganic solvent such as zinc chloride, nitric acid, or rhodan salt, and a spinning dope And In this spinning dope, inorganic and / or organic pigments such as titanium oxide or coloring pigments, stabilizers, anti-coloring spinning, stabilizers effective for weather resistance, etc. may be used as long as they do not hinder spinning. Is possible.

  The mixing ratio of the polymer (A) and the polymer (B) of the present invention is such that the polymer (B) is 0.1 to 30 weights with respect to 100 parts by weight of the total amount of the polymer (A) and the polymer (B). In order to obtain sufficient dischargeability, the polymer (B) is preferably 0.1 parts by weight or more, preventing the occurrence of voids and sticking in the fiber, the strength of the fiber, In order to improve the workability, it is preferably 30 parts by weight or less.

  The method for producing an acrylic synthetic fiber of the present invention involves spinning from a nozzle by a conventional wet or dry spinning method, drawing and drying. Moreover, you may perform extending | stretching and heat processing further as needed.

  The acrylic synthetic fiber of the present invention is a synthetic fiber containing less than 80% by weight of acrylonitrile in the fiber.

  The acrylic synthetic fiber of the present invention is a synthetic fiber containing 80% by weight or more of acrylonitrile in the fiber.

  The acrylic dyed fiber of the present invention is obtained by dyeing the above-mentioned acrylic synthetic fiber using a cationic dye for discharging and various dyeing assistants using a conventional dip dyeing method or continuous dyeing method.

  The acrylic synthetic fiber material of the present invention is raw cotton, raw yarn, filament, woven fabric, knitted fabric, woolen fabric, non-woven fabric made of acrylic synthetic fiber or acrylic dyed fiber, and clothing and living materials using these. Means industrial materials.

  The acrylic discharge fiber material of the present invention is obtained by discharging the above-mentioned acrylic synthetic fiber material.

    The present invention is characterized in that a cationic activator is allowed to coexist when an acrylic synthetic fiber containing a polymer (A) and a polymer (B) is dyed with a discharging dye.

  The discharging process referred to in the present invention is a white discharging process or a colored discharging process.

  In the present invention, the white discharging process is an acrylic dyed fiber dyed with a discharging cationic dye, an acrylic synthetic fiber material, zinc-based discharging agent such as stannous chloride or processed tin, zinc formaldehyde sulfoxylate, etc. This is a method in which a printing paste containing discharge is printed and the dye in the printed part is reduced by steaming to decompose it colorlessly to make the dyed part white.

  In the present invention, the color discharge process is performed by adding a tin-based discharging agent such as stannous chloride or processed tin and a reduction-resistant dye to acrylic dyed fibers or acrylic synthetic fiber materials dyed with a cationic dye for discharging. This is a method in which the printing paste for discharging is printed and the dye in the printed part is reduced by steaming and heat treatment to decompose it into a colorless form, and at the same time, the reduction-resistant dye is dyed to develop a new color.

  The cationic dye for discharging according to the present invention is a reductive discharging agent, that is, a cationic dye that can be reduced and decomposed by a tin-based discharging agent such as stannous chloride and processed tin, or a zinc-based discharging agent such as zinc formaldehyde sulfoxylate. For example, a cationic dye having at least one azo group (—N═N—) as a chromophore in the dye structure.

  The printing paste for discharging used in the present invention is conventionally used in ordinary discharging treatments, and is generally a discharging agent, dyeing acid, glue, and in the case of colored discharging, It is a viscous aqueous solution containing a dye dissolving agent according to the purpose. Specifically, as the discharging agent, it is preferable to use a tin discharging agent such as stannous chloride and a zinc discharging agent such as zinc formaldehyde sulfoxylate. The dyeing acid is preferably a non-volatile organic acid, and tartaric acid, malic acid and the like are common. Any paste can be used as long as it is used in general textile printing, for example, carboxymethylcellulose, which is a fiber derivative paste, a processed paste of silac, alginic acid of natural seaweed, polyvinyl alcohol, which is a synthetic paste, etc. Is mentioned. Further, as the color dye, a reduction-resistant cationic dye that is not reductively decomposed by the discharging agent is used, and urea is generally used as a solubilizer for the dye.

  In the case of white discharge processing, the dischargeability as used in the present invention means the whiteness of the discharge processing portion and the sharpness of the outline of the pattern whitened in the dyeing portion. It means the original coloring property of the dye for dyeing (reduction-resistant dye) that is dyed simultaneously with the dye decomposition, and the sharpness of the contour of the pattern dyed in a different color at the dyed portion.

  The cationic activator referred to in the present invention is a quaternary ammonium compound that is usually used as a slow dyeing / leveling agent when an acrylic synthetic fiber is dyed with a cationic dye. There are various types such as an ammonium salt, but alkyldimethylbenzylammonium chloride is particularly preferable.

  Since the polymer (A) in the present invention contains a halogen-containing monomer, it is highly hydrophobic and has poor dischargeability. Therefore, in the prior art, in order to improve the dischargeability, the hydrophilicity is high, like the polymer (B) in the present invention, and the dischargeability containing a sulfonic acid-containing monomer that becomes a dyeing seat with the dye is good. Dischargeability has been improved by mixing polymers. However, when the acrylic dyed fiber containing the polymer (A) and the polymer (B) is subjected to a discharge process, the dye dyed on the polymer (B) can be easily discharged. However, since the dye dyed on the polymer (A) is difficult to discharge, when the discharging property of the entire fiber is evaluated, the discharging property becomes insufficient.

  Further, the dischargeability of the polymer (B) is determined by the following: yellow discharge cationic dye (hereinafter referred to as yellow discharge dye), red discharge cationic dye (hereinafter referred to as red discharge dye), blue discharge cationic dye (hereinafter referred to as red discharge dye). However, the dischargeability of the polymer (A) varies depending on the three primary colors of the yellow discharge dye, the red discharge dye, and the blue discharge dye. Aizen Cathilon Discharge Yellow NLH (Hodogaya Chemical Co., Ltd.), red dyeing dyes such as Aizen Cathilon Red CD-FGLH (Hodogaya Chemical Co., Ltd.) and blue dyeing dyes such as Astrazon Blue FGGLD Japan Ltd.), the dischargeability of the blue discharge dye is There is a bad tendency to lay.

  Accordingly, when the acrylic synthetic fiber containing the polymer (A) and the polymer (B) is dyed and discharged with a prescription including a blue discharging dye, the blue discharging dye dyed on the polymer (A). Is not completely discharged, the bluish color remains, and the dischargeability is remarkably deteriorated.

  Therefore, in the present invention, when an acrylic synthetic fiber containing the polymer (A) and the polymer (B) is dyed with a discharge dye including a blue discharge dye, a cationic activator, for example, ASTRAGAL PAN (LANCESS) is used. It was found that the dischargeability is improved by using the product manufactured by Co., Ltd. Although the effect of the cationic activator is not clear, since the cationic activator has a higher dyeing speed than the blue discharging dye, the cationic activator is dyed and sealed first on the dyeing seat of the polymer (A). As a result, the blue discharge dye becomes difficult to be dyed to the polymer (A), and is dyed to the polymer (B) having a high dye exhaustion property and good dischargeability. It is estimated that the dischargeability as a whole of the fiber is improved.

  Similarly to the cationic activator, the yellow discharge dye and the red discharge dye are faster than the blue discharge dye and have a relatively good discharge property. In order to dye the acrylic synthetic fiber containing the coalescence (B) so that the dischargeability is good even when using a blue discharge dye, the dyeing seat of the polymer (A) is blocked. Yellow discharge dye and red discharge dye may be used.

  Therefore, in order to dye the acrylic synthetic fiber containing the polymer (A) and the polymer (B) so as to have good dischargeability using a cationic active agent, a cationic active agent, And it is preferable to use the quantity which can block the dyeing seat of the said polymer (A) for the total quantity of yellow discharge dye and red discharge dye.

  Therefore, by dyeing with a cationic activator, acrylic dyed fibers containing the polymer (A) and the polymer (B) dyed in any hue and from light to dark are discharged. Can be improved.

  In the present invention, the acrylic dyed fiber having good dischargeability is composed of 100 parts by weight of the acrylic synthetic fiber containing the polymer (A) and the polymer (B), and has good dischargeability and is colored more than light color. It is preferable to contain 0.001 part by weight or more of a cationic dye for discharging and 0.001 part by weight of a cationic activator to improve dischargeability, more preferably the polymer ( 100 parts by weight of acrylic synthetic fiber containing A) and the polymer (B), 0.01 part by weight or more of a cationic dye for discharging, and 0.01 part by weight or more of a cationic activator. Is preferred.

  In the present invention, an acrylic dyed fiber having good dischargeability is composed of 100 parts by weight of acrylic synthetic fiber containing the polymer (A) and the polymer (B), and good dischargeability and after dyeing treatment. In order to improve fastness, 10 parts by weight or less of the cationic dye for discharging is used, and the cationic activator blocks not only the dyeing seat of the polymer (A) but also the dyeing seat of the polymer (B). It is preferable to contain 10% by weight or less of a cationic activator so as not to make dyeing impossible, and more preferably an acrylic synthesis containing the polymer (A) and the polymer (B). It is preferable to contain 100 parts by weight of a fiber, 6 parts by weight or less of a cationic dye for discharging, and 6 parts by weight or less of a cationic activator.

  In the present invention, the acrylic dyed fiber having good dischargeability is composed of 100 parts by weight of the acrylic synthetic fiber containing the polymer (A) and the polymer (B), and has good dischargeability and is colored more than light color. In order to improve the dischargeability, 0.001 part by weight or more of the cationic dye for discharging and 0.001 part by weight of the cationic activator in order to improve the dischargeability are dyed at a dyeable temperature of 60 ° C. or more. It is preferable to be obtained, and more preferably, 100 parts by weight of an acrylic synthetic fiber containing the polymer (A) and the polymer (B), 0.01 part by weight or more of a cationic dye for discharging, and a cationic system It is preferable that the activator is obtained by dyeing 0.01 parts by weight or more at 90 ° C. or more.

  In the present invention, an acrylic dyed fiber having good dischargeability is composed of 100 parts by weight of acrylic synthetic fiber containing the polymer (A) and the polymer (B), and good dischargeability and after dyeing treatment. In order to improve fastness, 10 parts by weight or less of the cationic dye for discharging is used, and the cationic activator blocks not only the dyeing seat of the polymer (A) but also the dyeing seat of the polymer (B). It is preferable that the cationic active agent is 10% by weight or less so as not to become undyable and dyed at 120 ° C. or less so that voids are not formed in the fiber after dyeing and color development is not deteriorated. More preferably, 100 parts by weight of the acrylic synthetic fiber containing the polymer (A) and the polymer (B), 6 parts by weight or less of the cationic dye for discharging, and 6 parts by weight or less of the cationic activator. And dye it at 110 ° C or lower It is preferable to be.

Examples Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Prior to the description of the examples, a dyeing method, a discharge processing method, and an evaluation method will be described.
(1) Dyeing method Fibers are set in a dyeing machine (Over Meyer) at a packing density of 0.3 g / ml, and ion-exchanged water is added so that the bath ratio is 1:15. Next, while operating the circulator of the cationic dyeing machine, ultraphosphoric acid (Ultra MT-110: manufactured by Mikajima Chemical Co., Ltd.) becomes 0.3 g / L with respect to ion-exchanged water as a dyeing assistant. Add as follows. In order to improve the dischargeability, when adding a cationic activator, an arbitrary amount of ASTRAGAL PAN (manufactured by LANXESS) is added at this time.

Next, the bath temperature was raised to 50 ° C. at 5 ° C./min, and the dye weighed according to an arbitrary dye formulation was diluted with hot water and added. Next, the temperature was raised to 70 ° C. at 5 ° C./min. Further, the temperature was raised to 90 ° C. at 2 ° C./min, and held at 90 ° C. for 30 minutes. Thereafter, the temperature was raised to 98 ° C. at 2 ° C./min, and held at 98 ° C. for 60 minutes. Thereafter, it was cooled to 50 ° C. at a rate of 5 ° C./min, washed with water and dried at 50 ° C. for 1 hour to obtain a dyed yarn.
(2) White discharge prescription and discharge evaluation (simple method)
(2-1) White fiber discharge prescription and discharge rate evaluation As a discharge agent, 10% by weight of stannous chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 90% by weight of water were mixed to prepare a discharge agent solution. . 200 ml of this discharging agent solution was set in a pot dyeing machine and heated, and after boiling, 2 g of dyed short fibers were added to perform discharging. 2g of this fiber is fully opened and weighed, put into a sample stage with a measuring surface (bottom) of 40mm in diameter and 20mm in height made of colorless and transparent glass, and a spectrocolorimeter CM-2600d (Konica Minolta Sensing) Was used to measure the hue after the discharge process. In this example / comparative example, if the bluish color remains after discharging, the dischargeability is poor, and the elapsed time until the b value becomes 0 or more after the short fiber is added is the discharging time. It was evaluated that it was excellent in performance.
(3) White discharge prescription and discharge evaluation (pile evaluation method)
(3-1) Preparation of high pile After blending and conditioning the fibers, Kodama Tech Co, Ltd. Opener manufactured by Howa Machine Ltd. A sliver was prepared using a card made by Nagoya. Next, sliver knitting is performed with a high pile weaving machine manufactured by Mayer, and the pile part is cut with a shirring machine manufactured by Iwakura Seiki Co. The adhesive was dried at 130 ° C. for 5 minutes using a Hirano Tecseed tenter. Thereafter, polishing and shearing were performed with a polisher machine and a shearing machine manufactured by Iwakura Seiki Co., Ltd. to complete a high pile having a pile length of 15 mm.
(3-2) High pile white discharge prescription (not including cationic active agent)
Printing paste for discharging is stannous chloride (manufactured by Wako Pure Chemical Industries, Ltd.) 15% by weight, urea (manufactured by Wako Pure Chemical Industries, Ltd.) 5% by weight, Meyprogum NP-25 (manufactured by Sanki Co., Ltd.) ) 11.4 wt% and water 68.6 wt% were mixed. The discharging a printing paste adjusted to Shirushi奈pile surface of the high-pile raw a sign捺量of 200-30Og / m ² using a roller printing machine was carried steamed for 15 minutes on board steamed about 98 ° C. Thereafter, washing and drying were performed. Next, in order to improve pile disturbance and texture of the high pile original fabric, polishing treatment and shearing treatment were performed, and the high pile fabric was adjusted to the form of the final product to obtain a discharge high pile.
(3-3) High pile white discharge formulation (including cationic active agent)
Printing paste for discharging is 1.5% by weight of ASTRAGAL PAN (manufactured by LANXESS), 15% by weight of stannous chloride (manufactured by Wako Pure Chemical Industries, Ltd.), urea (manufactured by Wako Pure Chemical Industries, Ltd.) It was prepared by mixing 5.0% by weight, 11.4% by weight of Meyprogum NP-25 (manufactured by Sanki Co., Ltd.) and 67.1% by weight of water. The adjusted printing paste for printing is printed on the pile surface of the high-pile raw fabric at a printing amount of 200 to 300 g / m ² using a roller printing machine, and steaming heat treatment is carried out in a steamer at about 98 ° C. for 15 minutes. Thereafter, washing and drying were performed. Next, in order to improve pile disturbance and texture of the high pile original fabric, polishing treatment and shearing treatment were performed, and the high pile fabric was adjusted to the form of the final product to obtain a discharge high pile.
(3-4) Evaluation of dischargeability of discharge high pile The dischargeability of discharge high pile obtained as described in (3-2) and (3-3) above was evaluated by the following method.

  The dischargeability is determined by arranging the hair so that the part of the discharge high pile surface that covers the surface of the pile covers the pile surface, and placing a colorless and transparent glass plate thereon, the spectrocolorimeter CM-2600d (Konica Minolta Sensing Co., Ltd.) Company) was used to measure the hue after the discharge process. In this example / comparative example, those with a bluish color remaining in the discharge part were regarded as defective discharge characteristics, and those having a b value of 0 or more after the discharge process were evaluated as having excellent discharge characteristics. The evaluation criteria are as follows.

[○] The b value of the discharge part is 0 or more (no blueness in the discharge part), and the discharge property is good
[×] The b value of the discharge portion is less than 0 (the discharge portion has a bluish color), and the discharge property is poor (3-5) Evaluation of discharging high pile texture The feeling of discharging high pile was performed by sensory evaluation. The evaluation criteria are as follows.
[○] Soft and smooth texture [△] Texture with a slight roughness [×] Texture with a large roughness (Production Example 1)
In a pressure-resistant polymerization reactor having an internal volume of 20 L, 12000 g of ion-exchanged water, 54 g of sodium lauryl sulfate, 25.8 g of sodium sulfite, 13.2 g of sodium hydrogen sulfite, 0.06 g of iron sulfate, 294 g of acrylonitrile (hereinafter abbreviated as AN), vinyl chloride. (Hereafter abbreviated as VC)
3150 g was charged and replaced with nitrogen. The internal temperature of the polymerization machine was adjusted to 50 ° C., and 2.1 g of ammonium persulfate was added as an initiator to initiate polymerization. On the way, polymerization was performed in 5 hours and 10 minutes while adding 2526 g of AN, 30 g of sodium styrenesulfonate (hereinafter abbreviated as 3S), and 13.8 g of ammonium persulfate. Then, unreacted VC was collect | recovered, latex was discharged | paid out from the superposition | polymerization machine, salting out, heat processing, filtration, water washing, dehydration, and drying were performed, and the polymer 1 was obtained.

Next, 1400 g of acetone, 930 g of water, AN
150 g, 540 g of methyl acrylate (hereinafter abbreviated as MA), 300 g of 2-acrylamido-2-methylpropane sulfonic acid soda (hereinafter abbreviated as SAM), and 10 g of methallyl sulfonic acid soda (hereinafter abbreviated as MX). The nitrogen was replaced. The temperature inside the polymerization machine was adjusted to 55 ° C., and 5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as an initiator to initiate polymerization. On the way, polymerization was performed for 16 hours while adding 10 g of 2,2′-azobis (2,4-dimethylvaleronitrile), and then the temperature was raised to 70 ° C. and polymerization was performed for 6 hours to obtain a polymer 2 solution having a polymer concentration of 30% by weight. Got. Acetone is added so that the polymer 1 is 30% by weight, and the polymer 2 solution is added to the dissolved polymer 1 solution so that the weight ratio of the polymer is polymer 1: polymer 2 = 96: 4. The mixture thus obtained was used as a spinning dope. The obtained spinning dope was discharged through a 0.08 mmφ, 8500 hole die into an aqueous 30 wt% acetone solution at 25 ° C. and further stretched 2.0 times in an aqueous 20 wt% acetone solution at 25 ° C. and then 60 times. Washed with water at ℃. Subsequently, it was dried at 130 ° C., further stretched 1.8 times at 125 ° C., and further subjected to relaxation heat treatment at 145 ° C. to obtain a 3 dtex acrylic synthetic fiber. Subsequently, the obtained acrylic synthetic fiber was crimped and cut into 44 mm.

(Production Example 2)
2100 g of acetone, 230 g of water, 150 g of AN, 830 g of MA, and 20 g of SAM were charged into a pressure-resistant polymerization reactor having an internal volume of 5 L and polymerized in the same manner as the polymer 2 of Production Example 1 to obtain a solution of polymer 3. A solution of polymer 3 is added to a solution of polymer 1 in which acetone is added and dissolved so that the polymer 1 obtained in Production Example 1 is 30% by weight, and the weight ratio of the polymer is polymer 1: polymer 3 = 90. : The mixture obtained so as to have a ratio of 10 was used as a spinning dope. The obtained spinning solution was spun using the same method as in Production Example 1 to obtain an acrylic synthetic fiber.

(Production Example 3)
1750 g of acetone, 580 g of water, 500 g of AN, 400 g of MA, and 100 g of SAM were charged into a pressure-resistant polymerization reactor having an internal volume of 5 L, and polymerized in the same manner as Polymer 2 in Production Example 1 to obtain a solution of Polymer 4. Acetone was added so that the polymer 1 obtained in Production Example 1 would be 30% by weight, and the solution of polymer 4 was added to the dissolved solution of polymer 1 so that the polymer weight ratio was polymer 1: polymer 4 =
A mixture of 90:10 ratio was used as a spinning dope. The obtained spinning solution was spun using the same method as in Production Example 1 to obtain an acrylic synthetic fiber.

(Production Example 4)
Acetone was added so that the polymer 1 obtained in Production Example 1 was 30% by weight, and the dissolved polymer 1 solution was used as the spinning dope. The obtained spinning solution was spun using the same method as in Production Example 1 to obtain an acrylic synthetic fiber.

製造例１〜３で得られた、アクリル系合成繊維の組成を表１に示す。

Table 1 shows the compositions of the acrylic synthetic fibers obtained in Production Examples 1 to 3.

(Production Example 5)
The acrylic synthetic fiber obtained in Production Example 1 was dyed by the method described in “(1) Dyeing method” above using the following cationic activator and discharging cationic dye.
Cationic activator:
ASTRAGAL PAN (manufactured by LANXESS) ... 3.0% omf
Cationic dye for discharging:
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.5% omf
(Production Example 6)
The acrylic synthetic fiber obtained in Production Example 1 was dyed by the method described in “(1) Dyeing method” above using the following cationic activator and discharging cationic dye.
Cationic activator:
ASTRAGAL PAN (manufactured by LANXESS) ... 5.0% omf
Cationic dye for discharging:
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.5% omf
(Production Example 7)
The acrylic synthetic fiber obtained in Production Example 1 was dyed by the method described in "(1) Dyeing method" above using the following cationic dye for discharging.
Cationic dye for discharging:
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.5% omf
(Production Examples 8 to 10)
The acrylic synthetic fibers obtained in Production Examples 1 to 3 were dyed in a gray color by the method described in the above “(1) Dyeing method” using a cationic activator and a discharging cationic dye.
Cationic activator:
ASTRAGAL PAN (manufactured by LANXESS) ... 3.0% omf
Cationic dye for discharging:
Aizen Cathilon Discharge Yellow NLH
(Hodogaya Chemical Co., Ltd.) ... 0.45% omf
Aizen Cathilon Red CD-FGLH (Hodogaya Chemical Co., Ltd.)
... 0.19% omf
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.11% omf
Dyeing of the acrylic synthetic fibers of Production Example 1, Production Example 2 and Production Example 3 under the above conditions is designated Production Example 8, Production Example 9 and Production Example 10, respectively.

(Production Examples 11 to 13)
The acrylic synthetic fibers obtained in Production Examples 1 to 3 were dyed in a gray color by the method described in the above “(1) Dyeing method” using a cationic dye for discharging.
Cationic dye for discharging:
Aizen Cathilon Discharge Yellow NLH
(Hodogaya Chemical Co., Ltd.) ... 0.45% omf
Aizen Cathilon Red CD-FGLH (Hodogaya Chemical Co., Ltd.)
... 0.19% omf
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.11% omf
Dyeing of the acrylic synthetic fibers of Production Example 1, Production Example 2 and Production Example 3 under the above conditions is referred to as Production Example 11, Production Example 12 and Production Example 13, respectively.

(Production Example 14)
The acrylic synthetic fiber obtained in Production Example 4 was dyed in a gray color by using the cationic dye for discharging and the method described in “(1) Dyeing method” above.
Cationic dye for discharging:
Aizen Cathilon Discharge Yellow NLH
(Hodogaya Chemical Co., Ltd.) ... 0.45% omf
Aizen Cathilon Red CD-FGLH (Hodogaya Chemical Co., Ltd.)
... 0.19% omf
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.11% omf
A product obtained by dyeing the acrylic synthetic fiber of Production Example 4 under the above conditions is referred to as Production Example 14.

(Production Example 15)
The acrylic synthetic fiber obtained in Production Example 4 was dyed gray using the cationic activator and the discharging dye cationic dye by the method described in “(1) Dyeing method” above.
Cationic activator:
ASTRAGAL PAN (manufactured by LANXESS) ... 1.0% omf
Cationic dye for discharging:
Aizen Cathilon Discharge Yellow NLH
(Hodogaya Chemical Co., Ltd.) ... 0.45% omf
Aizen Cathilon Red CD-FGLH (Hodogaya Chemical Co., Ltd.)
... 0.19% omf
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.11% omf
A product obtained by dyeing the acrylic synthetic fiber of Production Example 4 under the above conditions is referred to as Production Example 15.

(Production Example 16)
The acrylic synthetic fiber obtained in Production Example 4 was dyed gray using the cationic activator and the discharging dye cationic dye by the method described in “(1) Dyeing method” above.
Cationic activator:
ASTRAGAL PAN (manufactured by LANXESS) ... 3.0% omf
Cationic dye for discharging:
Aizen Cathilon Discharge Yellow NLH
(Hodogaya Chemical Co., Ltd.) ... 0.45% omf
Aizen Cathilon Red CD-FGLH (Hodogaya Chemical Co., Ltd.)
... 0.19% omf
Astrazon Blue FGGL (manufactured by Dystar Japan Ltd.)
... 0.11% omf
A product obtained by dyeing the acrylic synthetic fiber of Production Example 4 under the above conditions is referred to as Production Example 16.

(Production Examples 17 to 23)
The acrylic dyed fibers dyed in Production Examples 8 to 13 and 15 were processed into a high pile by the method described in (3-1) Preparation of high pile. Production Example 8, Production Example 9, Production Example 10, Production Example 11, Production Example 12, Production Example 13, and Production Example 15 using high-pile using the acrylic dyed fibers were produced in Production Example 17, Production Example 18, and Production Example, respectively. 19, Production Example 20, Production Example 21, Production Example 22, and Production Example 23.

(Examples 1-5)
The discharge speed of the acrylic dyed fibers obtained in Production Examples 5, 6, and 8 to 10 was evaluated by the method described in the above “(2) White discharge prescription and discharge evaluation (simple method)”. The results are shown in Table 2. By using a cationic activator at the time of dyeing, the dischargeability was improved and the discharge time was 30 minutes or less. If the discharge time is 30 minutes or less, after actually processing into a high pile, a discharge process is performed by the discharge method of “(3-2) High pile white discharge prescription (not including cationic active agent)” described above. However, it can be determined that it is a level that can be discharged into white without any problem.

(Comparative Examples 1-4)
The discharge speed of the acrylic dyed fibers obtained in Production Examples 7 and 11 to 13 was evaluated by the method described in “(2) White discharge prescription and dischargeability evaluation (simple method)”. The results are shown in Table 2. If the cationic activity was not used during dyeing, the discharging property was poor and the discharging time was 40 minutes or more. When the discharge time exceeds 30 minutes, it is difficult to discharge the white color under the general discharge processing conditions after actually processing into a high pile.

(Comparative Example 5)
The discharge speed of the acrylic dyed fibers obtained in Production Example 14 was evaluated by the method described in “(2) White discharge prescription and dischargeability evaluation (simple method)”. Since the acrylic dyed fiber obtained in Production Example 14 does not contain the polymer (B) indicated in the claims, the discharging dye cationic dye is dyed on the polymer 1 having poor discharging property and discharged. The property became poor and the discharge time was 40 minutes or more. When the discharge time exceeds 30 minutes, it is difficult to discharge the white color under the general discharge processing conditions after actually processing into a high pile.

(Comparative Example 6)
The discharge speed of the acrylic dyed fibers obtained in Production Example 15 was evaluated by the method described in “(2) White discharge prescription and discharge evaluation (simple method)”. Since the acrylic dyed fiber obtained in Production Example 15 does not contain the polymer (B) shown in the claims, the cationic dye for discharging is the above-mentioned polymer 1 having poor dischargeability together with the cationic activator. The dischargeability was poor, and the discharge time was 40 minutes or longer. When the discharge time exceeds 30 minutes, it is difficult to discharge the white color under the general discharge processing conditions after actually processing into a high pile.

(Comparative Example 7)
When the acrylic synthetic fiber obtained in Production Example 4 is dyed by the method shown in Production Example 16, the cationic synthetic fiber obtained in Production Example 4 does not contain the polymer (B) indicated in the claims, In addition, since the cationic active agent has a higher dyeing speed than the cationic dye for discharging, and exists in excess, the cationic active agent blocks the portion where the dye contained in the polymer 1 is bonded first. Consequently, the cationic dye for discharging was not dyed on the acrylic synthetic fiber and could not be dyed.

（実施例６〜８）
製造例１７〜１９で作成したハイパイルを、上記「（（３−２）ハイパイルの白色抜染処方（カチオン系活性剤を含まない）」記載の方法で抜染処理し、「（３−４）抜染ハイパイルの抜染性評価」に記載した方法で抜染性を評価し、さらに、上記「（３−５）抜染ハイパイル風合評価」に記載した方法で抜染ハイパイルの風合いを評価した。その結果を表３に示す。染色の際にカチオン系活性を用いる事で、ハイパイル加工品の抜染性も良好で、かつ、抜染後の風合いも良好であった。

(Examples 6 to 8)
The high piles produced in Production Examples 17 to 19 were subjected to discharge treatment by the method described in the above “((3-2) High pile white discharge formulation (not including cationic active agent)”, and “(3-4) Discharge high pile. The dischargeability was evaluated by the method described in “Evaluation of dischargeability”, and the texture of discharge highpile was evaluated by the method described in “(3-5) Evaluation of discharge highpile texture.” The results are shown in Table 3. By using the cationic activity at the time of dyeing, the discharge property of the high pile processed product was good and the texture after discharging was also good.

(Comparative Examples 8-11)
The high piles produced in Production Examples 20 to 23 were discharged by the method described in the above “((3-2) High pile white discharge prescription (not including cationic active agent)”, and “(3-4) Discharge high pile of The dischargeability was evaluated by the method described in “Evaluation of dischargeability”, and the texture of the high pile after discharge was evaluated by the method described in “(3-5) Evaluation of discharge highpile texture.” The results are shown in Table 3. Although the texture after discharging was good, a cationic activator was not used at the time of dyeing, so the discharging high pile discharging property remained blue and the discharging property was poor.

(Comparative Examples 12-14)
The high piles produced in Production Examples 20 to 22 were discharged by the method described in the above “((3-3) High pile white discharge formulation (including cationic active agent)”, and “(3-4) discharge high pile The dischargeability was evaluated by the method described in “Evaluation of dischargeability”, and the texture of discharge highpile was further evaluated by the method described in “(3-5) Evaluation of discharge highpile texture.” Table 3 shows the results. When using a printing paste for discharging that contains cationic activity, the high-pile processed product has good discharging properties, but the texture after the discharging process shrinks the tip of the hair to which the printing paste for discharging has adhered. Since the end of the hair did not stretch in the refinishing process after the treatment, the texture was very rough.

Claims (15)

  The total amount of the polymer (A) and the polymer (B) is 100 parts by weight, 40 to 80% by weight of acrylonitrile, 20 to 60% by weight of a halogen-containing monomer copolymerizable with acrylonitrile, and 0 to 5 monomers of a sulfonic acid group-containing monomer 70 to 99.9 parts by weight of the polymer (A) containing 5% by weight contains 5 to 70% by weight of acrylonitrile, 20 to 94% by weight of other copolymerizable monomers, and 1 to 40% by weight of a sulfonic acid group-containing monomer. 100 parts by weight of an acrylic synthetic fiber containing a polymer composition in which 0.1 to 30 parts by weight of the polymer (B) to be mixed, 0.001 to 10 parts by weight of a cationic dye for discharging, and a cationic activator An acrylic dyed fiber characterized by containing 001 to 10 parts by weight.   The acrylic dyed fiber according to claim 1, wherein the amount of the cationic dye for discharging is 0.01 to 6 parts by weight and the amount of the cationic activator is 0.01 to 6 parts by weight.   The acrylic dyed fiber according to claim 1 or 2, wherein the other copolymerizable monomer contained in the polymer (B) is an acrylate ester.   The acrylic dyed fiber according to any one of claims 1 to 3, wherein the sulfonic acid group-containing monomer contained in the polymer (B) is sodium 2-acrylamido-2-methylpropanesulfonate. .   The sulfonic acid group-containing monomer contained in the polymer (B) uses sodium methallylsulfonate and sodium 2-acrylamido-2-methylpropanesulfonate together. The acrylic dyed fiber described.   The acrylic dyed fiber according to any one of claims 1 to 5, wherein the cationic activator is a quaternary ammonium compound.   The acrylic dyed fiber according to claim 6, wherein the quaternary ammonium compound is alkyldimethylbenzylammonium chloride.   The total amount of the polymer (A) and the polymer (B) is 100 parts by weight, 40 to 80% by weight of acrylonitrile, 20 to 60% by weight of a halogen-containing monomer copolymerizable with acrylonitrile, and 0 to 5 monomers of a sulfonic acid group-containing monomer 70 to 99.9 parts by weight of the polymer (A) containing 5% by weight contains 5 to 70% by weight of acrylonitrile, 20 to 94% by weight of other copolymerizable monomers, and 1 to 40% by weight of a sulfonic acid group-containing monomer. 100 parts by weight of an acrylic synthetic fiber containing a polymer composition in which 0.1 to 30 parts by weight of the polymer (B) to be mixed, 0.001 to 10 parts by weight of a cationic dye for discharging, and a cationic activator A method for producing an acrylic dyed fiber, which is obtained by dyeing 001 to 10 parts by weight at 60 to 120 ° C.   The method for producing an acrylic dyed fiber according to claim 8, wherein the temperature during dyeing is 90 to 110 ° C.   The method for producing an acrylic dyed fiber according to claim 8 or 9, wherein the other copolymerizable monomer contained in the polymer (B) is an acrylate ester.   The acrylic dyed fiber according to any one of claims 8 to 10, wherein the sulfonic acid group-containing monomer contained in the polymer (B) is sodium 2-acrylamido-2-methylpropanesulfonate. Manufacturing method.   11. The sulfonic acid group-containing monomer contained in the polymer (B) uses sodium methallyl sulfonate and sodium 2-acrylamido-2-methylpropane sulfonate together. A method for producing the acrylic dyed fiber according to claim 1.   The method for producing an acrylic dyed fiber according to any one of claims 8 to 12, wherein the cationic activator is a quaternary ammonium compound.   The method for producing an acrylic dyed fiber according to claim 13, wherein the quaternary ammonium compound is alkyldimethylbenzylammonium chloride.   An acrylic discharging fiber material obtained by discharging the acrylic synthetic fiber material containing the acrylic dyeing fiber according to any one of claims 1 to 7 with a discharging agent.