JP2014070295A - Method for dyeing polyarylate fiber and dyed polyarylate fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for dyeing a polyarylate fiber capable of dyeing a polyarylate fiber at a practical dyeing density required for explorations of novel applications thereof, yielding a dyed polyarylate fiber unaccompanied by dyeing irregularities, and yielding a dyed product excellent in terms of dyeing fastness, above all light-resistant fastness; and a dyed polyarylate fiber.SOLUTION: The provided method comprises a dye application step of applying a vat dye or sulfide dye onto a polyarylate fiber, a solvent treatment step of treating the polyarylate fiber with a treatment liquid including a polar solvent, and, following this solvent treatment step, if necessary, a heat treatment step of treating the polyarylate fiber with heat; at least one dyeing operation cycle consisting of the combination of the respective steps is provided.

Description

  The present invention relates to a dyeing method for polyarylate fibers, and more particularly to a dyeing method capable of dyeing polyarylate fibers to a practical dyeing concentration. The present invention also relates to polyarylate fibers dyed by this method.

  The wholly aromatic polyester fiber is also called polyarylate fiber, has high strength and high elastic modulus, and is excellent in heat resistance, flame resistance, chemical resistance, cut resistance, and the like. Patent Document 1 below proposes a high-strength polyarylate fiber having excellent bending fatigue resistance and wear resistance. This polyarylate fiber has almost no hygroscopicity compared to an aramid fiber which is the same high-performance and high-performance fiber, so there is no difference in wet and dry strength, and acid resistance is better than an aramid fiber. Therefore, since this polyarylate fiber has particularly high strength and high elastic modulus, it is used as industrial materials such as ropes, nets, fishing nets and belts, and in particular, heat resistance, flame resistance, chemical resistance, and cut resistance. It is used as various protective work clothes because of its superior properties.

  On the other hand, this polyarylate fiber has a rigid molecular structure and high crystallinity, and a practical dyeing concentration cannot be obtained by the same dyeing method as that for general fibers. The dyeing fastness is not practically sufficient. Therefore, in practice, it is manufactured and used as an original fiber (a fiber made by adding a colorant in the stage before the spinning process). Since such a primary fiber has a limited hue, there is a problem that it cannot sufficiently cope with the abundant hues required for various protective work clothes or new applications of polyarylate fibers.

  Therefore, practical new dyeing methods for polyarylate fibers have been studied. For example, Patent Document 2 below proposes a method in which a fiber structure composed of polyarylate fibers is pretreated with a cationizing agent and then dyed with a dye having an anionic group such as a direct dye.

JP 2004-107826 A JP 2011-111696 A

  By the way, according to the dyeing method of Patent Document 2, dyed materials having various hues can be obtained. Here, in the dyeing method of Patent Document 2, the anion group of the dye interacts with the cation group of the cationizing agent adsorbed on the fiber surface (see Paragraph No. 0015 of Patent Document 2) (paragraph of Patent Document 2). Dyeing). That is, it is considered that the cationizing agent and the anionic dye are fixed on the polyarylate fiber surface in an ionic bond state.

  In such a case, since the hydrophilic group of the anionic dye is blocked, it is considered that the fastness to washing and the fastness to sweat are relatively good (see Table 1 in Examples of Patent Document 2). However, since the dye is not fixed by the original dyeing mechanism, there is a problem that the light fastness is weakened. In addition, even when vat dyes and sulfur dyes with good light fastness are used, hydroquinone type phenolate groups interact with cationizing agents in the reduced state of these dyes (the above-mentioned patent document) 2 paragraph number 0020). In such a state, unlike the original state in which vat dyes and sulfur dyes are in an oxidized state, there is a problem that good light fastness cannot be maintained.

  Further, when a cationizing agent is applied to the woven or knitted fabric by the pad / dry method (see paragraph No. 0017 of Patent Document 2 above), the cationizing agent is applied to the end and the center in the width direction of the woven or knitted fabric. There is a problem in that there is a difference in the amount and uneven dyeing occurs due to variations in the dye density. Furthermore, drying after applying the cationizing agent by the pad-dry method causes a difference in concentration due to migration of the cationizing agent on the surface and inside of the woven or knitted fabric, or on the front and back of the woven or knitted fabric. There is a problem that unevenness occurs.

  In view of the above, the present invention is dyed to a practical dyeing concentration required for new application development of polyarylate fibers, and the dyed polyarylate fibers have uneven dyeing. Furthermore, another object of the present invention is to provide a method for dyeing polyarylate fibers and a dyed polyarylate fiber having good dyeing fastness, in particular, light fastness.

  As a result of diligent research, the present inventors have employed a vat dye or sulfur dye having good light fastness in dyeing polyarylate fibers, and applying these dyes onto polyarylate fibers, It has been found that the above problems can be solved by combining the process of treating the arylate fiber with a polar solvent, and the present invention has been completed.

That is, the dyeing method of the polyarylate fiber according to the present invention, according to the description of claim 1, a dye applying step of applying a vat dye or a sulfur dye to the polyarylate fiber,
A solvent treatment step of treating the polyarylate fiber with a treatment solution containing a polar solvent;
After the solvent treatment step, it has a heat treatment step for heat-treating the polyarylate fiber as necessary, and two dyeing operations shown below,
Dyeing operation 1: Dye application step → Solvent treatment step,
Dyeing operation 2: Dye application step → Solvent treatment step → Heat treatment step
Among them, at least one staining operation is provided once or more.

According to the second aspect of the present invention, in the method for dyeing polyarylate fibers according to the first aspect, the polar solvent has a solubility parameter (δ) value of 18 to 32 (MPa) ^1/2. It is in the range of.

  According to the third aspect of the present invention, in the method for dyeing polyarylate fiber according to the first aspect, the polar solvent is N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethyl. It is at least one selected from the group consisting of acetamide, dimethyl sulfoxide, benzyl alcohol, diethylene glycol, triethylene glycol, sulfuric acid, formic acid, lactic acid, and oxalic acid.

According to the description of claim 4, the method for dyeing polyarylate fiber according to the present invention, the method for dyeing polyarylate fiber according to any one of claims 1 to 3,
A pre-dyeing step performed before the dyeing method or a post-dyeing step performed after,
In the pre-dyeing step or the post-dyeing step, the polyarylate fiber is dyed with a dye other than a vat dye and a sulfur dye.

  According to the description of claim 5, the dyed polyarylate fiber according to the present invention is dyed by the polyarylate fiber dyeing method according to any one of claims 1 to 4. To do.

According to the present invention, in the dyed polyarylate fiber according to claim 5, the lightness (L ^* value) in the L ^* a ^* b ^* color system is 35 or less. It is characterized by.

  According to the present invention, polyarylate fibers can be dyed to a practical dyeing concentration. Moreover, according to the present invention, uneven dyeing does not occur in the dyed polyarylate fiber. Furthermore, since vat dyes or sulfur dyes having good dyeing fastness, particularly light fastness, are used in their original oxidized state, the dyeing fastness of dyed polyarylate fibers, particularly light fastness, is improved. .

  Further, by changing the use concentration and hue of the vat dye or sulfur dye to be used, it is possible to obtain a dyed product having abundant hues from light to dark. In particular, according to the present invention, polyarylate fibers can be dyed in an extremely dark color such as black or navy blue.

Here, as one method for evaluating extremely dark colors such as black and navy blue, L ^* a ^* b was standardized by the International Commission on Illumination (CIE) in 1976 and adopted in JIS Z8729 in Japan. ^* There is lightness (L ^* value) in the color system. This L ^* value is expressed in the range of 100 (white) to 0 (black), and it can be evaluated that the darker the color, the smaller the L ^* value.

For example, in the present invention, an L ^* value of 35 or less can be determined as an extremely dark color. In the present invention, polyarylate fibers can be dyed in an extremely dark color by a dyeing method instead of the original method.

  In addition, as a pre- and post-process of the method for dyeing polyarylate fibers according to the present invention, a pre-dyeing process or a post-dying process using a dye other than a vat dye and a sulfur dye can be performed. By performing these dyeing processes, the dyeing quality and dyeing density of the polyarylate fiber itself are further improved. On the other hand, when the polyarylate fiber is a mixed fiber with other chemical fiber or natural fiber, by performing these dyeing steps, the hue of the polyarylate fiber and the other fiber can be unified, The dyeing quality and dyeing density of the dyed product are further improved.

  Therefore, according to the present invention, the polyarylate having no dyeing unevenness in the dyed product, good dyeing fastness, particularly light fastness, rich hue, and practical dyeing density. Fiber dyeing methods and dyed polyarylate fibers can be provided. This is effective for new application development of polyarylate fibers.

  The polyarylate fiber dyed by the dyeing method according to the present invention is generally composed of a polyarylate-based melt anisotropic polymer. As the polyarylate-based melt anisotropic polymer constituting this polyarylate fiber, for example, from the combination of repeating structural units shown in (1) to (11) of Chemical Formula 1 and Chemical Formula 2 in the specification of Patent Document 1 above (See paragraph No. 0007 of Patent Document 1). Examples of the commercially available polyarylate fiber include Vectran (registered trademark) of Kuraray Co., Ltd., which is composed of a copolymer of hydroxybenzoic acid and hydroxynaphthoic acid.

  In the present invention, the polyarylate fiber may have any form, and may be in the state of a fiber such as a filament fiber or a staple fiber, or a filament yarn, a spun yarn, a woven fabric, a knitted fabric, a non-woven fabric, It may be in the state of a fiber structure such as a rope or a net. Moreover, the polyarylate fiber alone may be used, or the mixed state of the polyarylate fiber and other chemical fiber or natural fiber may be used.

  In the present invention, the polyarylate fiber is dyed with a vat dye or a sulfur dye. These vat dyes or sulfur dyes are dyes having good dyeing fastness, and are particularly excellent in light fastness.

  Here, the vat dye is usually used for dyeing cotton and the like, and is originally a dye that is insoluble in water. However, it is reduced by a reducing agent such as sodium dithionite to form butanoic acid or leuco salt. It is adsorbed onto the fiber and then oxidized and dyed onto the fiber again as a water-insoluble dye.

  On the other hand, the sulfur dye is a dye containing a sulfur atom in the molecule and is usually used for dyeing cotton or the like. This sulfur dye is originally a water-insoluble dye, but it is reduced by a reducing agent such as sodium sulfide to become water-soluble and adsorbed to the fiber, and then oxidized to dye the fiber again as a water-insoluble dye. .

  However, in the present invention, the polyarylate fiber is dyed as a water-insoluble dye without reducing the vat dye or sulfur dye. The vat dye or sulfur dye does not have a strong affinity to dye the polyarylate fiber as it is. Further, when the vat dye or sulfur dye is reduced to be water-soluble, the affinity for polyarylate fibers is further reduced.

  However, in the present invention, it is considered that the dyeing property of the vat dye or the sulfur dye on the polyarylate fiber is developed by combining with the solvent treatment with a polar solvent for the polyarylate fiber. Furthermore, if heat treatment is performed as necessary after the solvent treatment, the dyeing property of the vat dye or the sulfur dye to the polyarylate fiber may be further improved. However, at present, the dyeing mechanism of the vat dye or sulfur dye in the present invention on the polyarylate fiber is not clear.

Hereinafter, the method for dyeing polyarylate fibers according to the present invention will be described with reference to each embodiment.
(1) 1st Embodiment The dyeing | staining method which concerns on this 1st Embodiment processes a polyarylate fiber with the dye provision process which provides a vat dye or a sulfur dye to a polyarylate fiber, and the process liquid containing a polar solvent. A solvent treatment step. In the first embodiment, first, a dye application step of applying a vat dye or sulfur dye to the polyarylate fiber in a non-reducing state is performed, and then the polyarylate fiber to which the vat dye or sulfur dye is applied is applied. On the other hand, a solvent treatment step of treating with a treatment liquid containing a polar solvent is performed.

  In the first embodiment, these series of steps are collectively referred to as “staining operation 1”. The dyeing operation 1 (dye application step → solvent treatment step) may be performed only once, or may be repeated a plurality of times if necessary. By repeating this dyeing operation 1 a plurality of times, darker polyarylate fibers can be obtained.

A. Dye provision process The dye used for dyeing | staining of cotton etc. can be used for the vat dye used at this dye provision process normally. In the present invention, it is preferable to use a super fine dye having an average dispersed particle size of several μm or less, preferably 1 μm or less in a state of being dispersed in a staining solution. Among these vat dyes, C.I. I. Vat Yellow 33, C.I. I. Vat Brown 1, C.I. I. Vat Red 1, C.I. I. Vat Violet 9, C.I. I. Vat Blue 4, C.I. I. Vat Blue 6, C.I. I. Vat Blue 20, C.I. I. Vat Green 1, C.I. I. Vat Green 3, C.I. I. Vat Black 8, C.I. I. More preferably, each dye such as Vat Black 25 is used.

  On the other hand, as the sulfur dye used in this dye application step, a dye usually used for dyeing cotton or the like can be used. Among these sulfur dyes, C.I. I. Sulfur Yellow 16, C.I. I. Sulfur Orange 1, C.I. I. Sulfur Red 6, C.I. I. Sulfur Blue 7, C.I. I. Sulfur Blue 15, C.I. I. It is more preferable to use each dye such as Sulfur Black 11.

  At the stage of applying the dye to the polyarylate fiber, the vat dye or the sulfur dye is not in a reduced state and is a water-insoluble dye. Therefore, a dyeing liquid in which a vat dye or a sulfur dye is dispersed in water is used for the dye application to the polyarylate fiber in the dye application step. This dyeing solution contains a vat dye or sulfur dye in a non-reduced dispersion state, and if necessary, a migration inhibitor is used in combination. Any method may be employed for the application of the dyeing liquid, and it may be simple immersing, immersing and squeezing, or applying by spraying or ink jetting.

  The polyarylate fiber to which the dyeing liquid has been applied is then dried if necessary. The polyarylate fiber may be dried at any temperature, but may be usually dried at a temperature of about 80 ° C to 130 ° C. Further, after the polyarylate fiber is dried, heat treatment (treatment different from the heat treatment step described later) may be performed at a higher temperature. Alternatively, the polyarylate fiber to which the dyeing solution is applied may be subjected to a heat treatment that also serves as drying at a temperature of about 130 ° C. to 180 ° C. or higher.

  When this drying temperature is lower than 80 ° C., it takes time to dry the polyarylate fiber. On the other hand, the heat treatment at a temperature higher than 180 ° C. and exceeding the glass transition point of the polyarylate polymer causes a decrease in physical properties. In addition, when processed at an extremely high temperature, the vat dye or sulfur dye may be decomposed, and the hue changes greatly.

  On the other hand, the drying time may be appropriately selected depending on the type and form of the polyarylate fiber and the drying temperature, and is not particularly problematic. Usually, the drying time may be about 30 seconds to 30 minutes. For example, when the polyarylate fiber is a fabric, a drying time of about 1 minute to 10 minutes is preferable when the drying temperature is 105 ° C to 130 ° C.

  At the stage of finishing this drying, the vat dye or sulfur dye is uniformly applied on the polyarylate fiber. However, the polyarylate fiber is not completely dyed with vat dye or sulfur dye. However, at this stage, the vat dyes or sulfur dyes adhere to the polyarylate fibers with a certain degree of affinity even if they do not reach the dyeing. Here, the reason why the vat dye or sulfur dye adheres to the polyarylate fiber is not clear, but these dyes are in a non-reducing water-insoluble state by the physical action such as intermolecular force and the surface of the polyarylate fiber. It is thought that it adheres to.

  Here, when the polyarylate fiber is in the form of a cloth, a series of treatments can be performed while the cloth is running in the longitudinal direction. In this case, the traveling polyarylate fiber fabric is first immersed in a bath filled with a dyeing solution. Subsequently, surplus dyeing liquid is squeezed from the polyarylate fiber fabric by a squeezing means such as mangle. In this way, a polyarylate fiber fabric to which a predetermined amount of dyeing liquid has been uniformly applied is obtained. Next, the polyarylate fiber fabric after squeezing is introduced into a heat treatment apparatus such as a pin tenter while running and dried.

B. Solvent treatment step The polyarylate fiber after the dye application step is put into the subsequent solvent treatment step without washing. In this solvent treatment step, the polyarylate fiber is treated with a polar solvent. In the present invention, a polar solvent is widely interpreted and a substance having a polar functional group in the solvent molecular structure is meant. For example, as aprotic polar solvents among polar solvents, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetophenone, methyl ethyl ketone, N-butylphthalimide, N-isopropylphthalamide And N-methylformanilide. These aprotic polar solvents may be used alone or in combination of two or more, or may be used in combination with a protic polar solvent described below. Among these aprotic polar solvents, N-methylpyrrolidone, N, N, and the like are less likely to cause shrinkage and deterioration of physical properties of polyarylate fibers and are particularly effective for dyeing vat dyes or sulfur dyes. -Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide are preferred.

  Among polar solvents, protic polar solvents include sulfuric acids, formic acid, lactic acid, maleic acid, oxalic acid and other protic acids, 1-propanol, 1-octanol, benzyl alcohol, DL-β-ethylphenethyl alcohol, 2- Ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2- Methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamic alcohol, p-anisyl alcohol, benzhydrol, 2- (4-chlorophenoxy) ethanol, 2- (4-chlorophenoxyethoxy) ethanol , Alcohols such as 2- (dichlorophenoxy) ethanol, ethylene glycol, diethylene glycol, triethylene glycol, glycols such as PEG200, PEG400, PEG600, propylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, propylene glycol monophenyl Examples include monoethers or monoesters of glycols such as phenyl ether, dipropylene glycol monophenyl ether, cellosolve, n-butyl cellosolve, and hydroxyethyl acrylate. These protic polar solvents may be used alone or in combination of two or more, or may be used in combination with the aprotic polar solvent described above. Among these protic polar solvents, polyarylate fibers are less susceptible to shrinkage and physical properties, and particularly effective for dyeing vat dyes or sulfur dyes include benzyl alcohol, diethylene glycol, triethylene glycol, Sulfuric acid, formic acid, lactic acid and oxalic acid are preferred.

Further, the solubility parameter (δ) can be used as a quantitative index representing the polarity of the polar solvent used in the present invention. In the present invention, it is preferable to use a polar solvent having a solubility parameter value in the range of δ = 18 to 32 (MPa) ^1/2 . Here, for example, the solubility parameter value of the polyarylate fiber is assumed to be δ = 19 (MPa) ^1/2 (for example, the value (cal / cm ³ ) described in JP-A-2003-89920) ^{1 / 2} is converted into units). Therefore, the solubility parameter value of the polar solvent is in the above range, and when the solubility parameter value of the polyarylate fiber is close to or slightly larger, the action of the polar solvent on the polyarylate fiber is considered to occur. By this, the dyeing property to the polyarylate fiber of a vat dye or a sulfur dye improves, and the aramid fiber which has a more practical dyeing density can be obtained.

  These polar solvents may be used alone as described above, or two or more solvents may be mixed and used. The concentration of the polar solvent used for the solvent treatment may be appropriately selected depending on the shape of the polyarylate fiber to be treated and the treatment temperature, but it is usually preferably 40 to 100% by weight, and 50 More preferably, it is contained in an amount of 100% by weight. However, oxalic acid is usually a solid having crystal water and its solubility is small. Therefore, oxalic acid is preferably used as an aqueous solution of about 10% by weight.

  On the other hand, it is necessary to set the use concentration of sulfuric acid to be narrower. In this solvent treatment step, it is preferable to use an aqueous sulfuric acid solution having a concentration of 90% by weight or more.

  When the concentration of the polar solvent is in the above range, the staining concentration is within a relatively stable range, and even when the concentration of the polar solvent varies slightly, the staining concentration hardly changes greatly. Therefore, stable industrial production is possible when the concentration of the polar solvent is in the above-described range.

  Here, as the diluent for the polar solvent, any solvent compatible with the polar solvent to be used may be used, but water is generally used. In the case of a certain type of polar solvent such as N-methylpyrrolidone, a darker dyed product can be obtained by mixing a certain amount of water. On the other hand, when the concentration of the polar solvent is lower than the above range and the amount of water in the solvent treatment liquid is increased, the vat dye or sulfur dye attached to the polyarylate fiber in the dye application step may be dropped into the solvent treatment liquid. There is not preferable. In such a case, it is possible to prevent the dye from dropping off by adding a water-soluble salt.

  The treatment temperature of the polar solvent may be appropriately selected depending on the shape of the polyarylate fiber to be treated and the treatment time, but is usually treated at a temperature of 0 ° C to 70 ° C. Moreover, it is preferable that it is the temperature of 10 to 60 degreeC. However, when sulfuric acid is used, the temperature of the sulfuric acid aqueous solution may be 0 ° C. or higher and 50 ° C. or lower, and more preferably 0 ° C. or higher and 30 ° C. or lower.

  When the temperature of the polar solvent is in the above-mentioned range, the dyeing concentration is within a relatively stable range, and even when the temperature of the polar solvent is slightly changed, the dyeing concentration hardly changes. Therefore, stable industrial production is possible when the temperature of the polar solvent is in the above-described range. On the other hand, when the temperature of the polar solvent is higher than the above range, the physical properties of the polyarylate fiber may be lowered or extreme shrinkage may occur. In addition, the dyeing density may change greatly due to slight fluctuations in the temperature of the polar solvent. This is presumably because the high-temperature polar solvent causes a large change in the molecular structure of the polyarylate fiber.

  The treatment time for the solvent treatment is appropriately selected depending on the concentration and temperature of the polar solvent, and is usually treated in a time of about 0.1 seconds to 30 minutes. Furthermore, the treatment time for the solvent treatment is preferably about 1 second to 5 minutes. Even if the processing time of the solvent treatment is about 1 second, the effect of the solvent treatment is maintained. Thus, when the processing time of the solvent treatment is about 1 second to 30 minutes, the dyeing density hardly changes even when the processing time is slightly changed, and the dyeing is performed at a practical dyeing density. can do.

  Thus, it is preferable that the processing time of the solvent treatment is controlled within a predetermined range. Therefore, it is preferable that the polyarylate fiber treated with the polar solvent is quickly washed. Moreover, when processing with a sulfuric acid, it is preferable to neutralize and wash rapidly. Here, the polyarylate fibers may be washed with water or hot water, but reduction washing is performed to remove undyed vat dyes or sulfur dyes adhering to the surface of the polyarylate fibers. Also good.

  Here, when the polyarylate fiber is in the form of a cloth, the solvent treatment can be performed while running in the longitudinal direction. In this case, the traveling polyarylate fiber fabric is first immersed in a bath filled with a treatment liquid containing a polar solvent. Subsequently, surplus treatment liquid is squeezed from the polyarylate fiber fabric by a squeezing means such as mangle. Next, the polyarylate fiber fabric after squeezing is introduced into a continuous washing machine while running and is washed, neutralized or reduced and washed. When these series of processes are performed continuously, the time from immersion to washing, neutralization washing or reduction washing can be stably controlled. Thereby, the processing time of the immersion treatment can be maintained at a preferable timing, and uniform solvent treatment can be performed.

  Although the action of these solvent treatments is not clear, by treating the polyarylate fibers with the polar solvent having the above-mentioned concentration, the intermolecular bonds of the polyarylate fibers having a rigid molecular structure and high crystallinity are partially obtained. It is considered that a lot of fine voids are generated. On the other hand, it is also conceivable that these polar solvents act on the dye molecules. Thus, it is considered that the vat dye or sulfur dye adhered to the fiber surface in the dye application step is strongly dyed in the fine voids of the polyarylate fiber by the solvent treatment step.

  In the first embodiment, as described above, a vat dye or a sulfur dye having particularly good light fastness is used. In this way, through a series of dyeing operations 1 (dye application step → solvent treatment step), a polyarylate fiber having a practical dyeing density and good dyeing fastness, particularly light fastness. A dyed product can be obtained. In particular, the dyeing method according to the present invention is a unique dyeing method that does not exist in the conventional dyeing method, and does not use the technique of adsorption by reduction, which is the original dyeing mechanism of vat dyes or sulfur dyes.

Moreover, the dyeing | staining density | concentration of a polyarylate fiber can be improved by repeating the above-mentioned dyeing | staining operation 1 (dye provision process-> solvent processing process) in multiple times. That is, a deeper color polyarylate fiber can be obtained by performing the second dyeing operation 1 again on the polyarylate fiber dyed by one dyeing operation 1 by the above-described method. Furthermore, the dyeing density can be further improved by repeating the same dyeing operation 1 again. Thus, the dyeing fastness of the dyed product dyed in dark color can maintain a good state.
(2) 2nd Embodiment The dyeing | staining method which concerns on this 2nd Embodiment processes a polyarylate fiber by the dye provision process which provides a vat dye or a sulfur dye to a polyarylate fiber, and the process liquid containing a polar solvent. A solvent treatment step, and a heat treatment step for heat-treating the polyarylate fiber after the solvent treatment step. In the second embodiment, these series of steps are collectively referred to as “staining operation 2”. The dyeing operation 2 (dye application step → solvent treatment step → heat treatment step) may be performed only once, or may be repeated a plurality of times if necessary. By repeating this dyeing operation 2 a plurality of times, darker polyarylate fibers can be obtained.

A. Dye provision process The dye provision process in this 2nd Embodiment performs operation similar to the dye provision process in the said 1st Embodiment.

B. Solvent Treatment Step The solvent treatment step in the second embodiment performs the same operation as the solvent treatment step in the first embodiment. However, in the second embodiment, the polyarylate fiber after the solvent treatment is introduced into the subsequent heat treatment step without being washed, neutralized or reduced and washed.

C. Heat treatment step In the polyarylate fiber after the solvent treatment step described above, the vat dye or sulfur dye is already dyed. Here, it is considered that by performing the heat treatment, the dyeing of the vat dye or the sulfur dye on the polyarylate fiber further proceeds and the dyed product becomes more robust. However, when sulfuric acid is used as the polar solvent, the fiber strength is greatly reduced, so that heat treatment cannot be performed.

  This heat treatment may be a dry heat treatment or a wet heat treatment, but usually a dry heat treatment is preferred. This heat treatment is preferably performed at a temperature of 50 ° C. or higher and 180 ° C. or lower. In the heat treatment step, since the polyarylate fiber is treated in a state where a polar solvent is applied, when the temperature is higher than 180 ° C., the physical properties of the polyarylate fiber may be deteriorated, which is not preferable. In addition, when processed at an extremely high temperature, the vat dye or sulfur dye may be decomposed, and the hue changes greatly.

  On the other hand, the treatment time of the heat treatment may be appropriately selected depending on the type and form of the polyarylate fiber, the type of vat dye or sulfur dye used, and is not particularly problematic, but usually 30 seconds to 30 seconds. It takes about a minute. Furthermore, the heat treatment time is preferably about 30 seconds to 5 minutes. Even if the heat treatment time is about 30 seconds, the effect of the heat treatment is maintained. As described above, when the heat treatment time is about 30 seconds to 30 minutes, the dyeing density hardly changes even when the treatment time slightly varies, and the dyeing is performed at a practical dyeing density. be able to.

  Here, when the polyarylate fiber is in the form of a cloth, the polyarylate fiber cloth after the solvent treatment step described above may be introduced into a continuous heat treatment apparatus while being run and heat-treated. When a series of treatments from the solvent treatment step to the heat treatment step are performed continuously, the treatment time from the solvent immersion to the heat treatment can be controlled stably, and the treatment times of the solvent treatment and the heat treatment are preferred timing. And uniform solvent treatment and heat treatment can be performed.

  Here, the action when combining these solvent treatment and heat treatment is not clear, but by treating the polyarylate fiber with the polar solvent having the above-mentioned concentration and heat-treating at the above-mentioned temperature, it becomes rigid. It is conceivable that the intermolecular bonds of the polyarylate fibers having a molecular structure and high crystallinity are further loosened than when the solvent treatment alone is performed, and more fine voids are generated. On the other hand, it is also conceivable that the action of the polar solvent on the dye molecule is increased by heat treatment. Thus, the vat dye or sulfur dye dyed on the polyarylate fiber in the solvent treatment step is considered to be more strongly dyed into the fine voids of the polyarylate fiber by the heat treatment step after the solvent treatment step. .

  Next, the polyarylate fiber after the heat treatment step is washed to remove the remaining polar solvent. As this washing, washing with water or hot water may be performed, but reduction washing may be performed to remove undyed vat dye or sulfur dye attached to the surface of the polyarylate fiber.

  In the second embodiment, as described above, a vat dye or sulfur dye having particularly good light fastness is used. In this way, by passing through a series of dyeing operations 2 (dye application step → solvent treatment step → heat treatment step), a polychrome having a practical dyeing density and having good dyeing fastness, particularly light fastness. A dye of arylate fiber can be obtained. In particular, the dyeing method according to the present invention is a unique dyeing method that does not exist in the conventional dyeing method, and does not use the technique of adsorption by reduction, which is the original dyeing mechanism of vat dyes or sulfur dyes.

Moreover, the dyeing | staining density | concentration of a polyarylate fiber can be improved by repeating the above-mentioned dyeing | staining operation 2 (dye provision process-> solvent processing process-> heat processing process) in multiple times. That is, a deeper color polyarylate fiber can be obtained by performing the second dyeing operation 2 again on the polyarylate fiber dyed by one dyeing operation 2 by the above-described method. Furthermore, the dyeing density can be further improved by repeating the same dyeing operation 2 again. Thus, the dyeing fastness of the dyed product dyed in dark color can maintain a good state.
(3) Third Embodiment In the dyeing method according to the third embodiment, a polyarylate fiber is used as a vat dye before the dyeing operation 1 or the dyeing operation 2 described in the first embodiment or the second embodiment. And a pre-dyeing step of dyeing with dyes other than sulfur dyes. Note that the staining operation 1 or the staining operation 2 performed after the pre-staining step may be performed only once, or may be repeated a plurality of times as necessary. By repeating this dyeing operation 1 or dyeing operation 2 a plurality of times, darker polyarylate fibers can be obtained.

D1. Pre-dyeing step In the dyeing method according to the third embodiment, first, a pre-dyeing step is performed on unstained polyarylate fibers. In this pre-dyeing step, a dyeing liquid containing dyes other than vat dyes and sulfur dyes is used. The dyeing method in the pre-dying step may be any method, but dyeing mainly by dip dyeing is performed. The prescription of the dyeing solution used in the pre-dying step may be the same as the usual dyeing method for the dye used. Therefore, when the polyarylate fiber itself is dyed, a carrier or the like may be used in combination. On the other hand, when the polyarylate fiber is a mixed fiber with other chemical fibers or natural fibers and these other fibers are dyed, a normal dyeing method for the other fibers may be performed.

  When the polyarylate fiber itself is dyed in this pre-dying step, the dye used can be any dye that has an affinity for the polyarylate fiber. For example, it is preferable to use disperse dyes. On the other hand, when the polyarylate fiber is a mixed fiber with other chemical fiber or natural fiber, and dyeing these other fibers, an appropriate dye may be used for the other fibers. For example, when the other fiber is a normal polyester fiber (polyethylene terephthalate fiber), a disperse dye is used. When the other fiber is cotton or rayon fiber, reactive dye or direct dye is used.

  When the polyarylate fiber itself is dyed, the polyarylate fiber is put into a dye-containing dyeing solution, the temperature of the dyeing solution is increased to the dyeing temperature, and this dyeing temperature is maintained for a predetermined time. . Although this dyeing | staining temperature is adjusted with the form of a polyarylate fiber, the kind of dye to be used, and dyeing | staining density | concentration, it should just be a temperature of 80 to 150 degreeC normally. Moreover, it is preferable that it is a temperature of 100 to 140 degreeC, and it is more preferable that it is a temperature of 120 to 135 degreeC. In the case of dyeing at a temperature exceeding 100 ° C., a high-temperature high-pressure dyeing machine is used.

  When dyeing polyarylate fibers themselves, a sufficient dyeing density cannot be obtained if the dyeing temperature is lower than 80 ° C., while it is generally used when the dyeing temperature is higher than 150 ° C. Compared to the high-temperature and high-pressure dyeing machine, a special specification device is required, and the energy cost is also increased.

  On the other hand, the dyeing time after the temperature rise may be appropriately selected in relation to the type of dye, the dyeing temperature, and the dyeing device. For example, at a dyeing temperature of 135 ° C. using a disperse dye, the dyeing time is 10 minutes to 90 minutes. Within the range is preferable. The dyeing bath ratio is not particularly limited, and may be in the range of 1: 5 to 1: 100, for example. The polyarylate fiber after dyeing is washed by an ordinary method. Further, reduction cleaning may be performed in the same manner as in the conventional dyeing process with disperse dyes.

  In the third embodiment, the following dyeing operation is subsequently performed on the polyarylate fibers subjected to the above pre-dying process.

A. Dye provision process The dye provision process in this 3rd Embodiment performs operation similar to the dye provision process in the said 1st Embodiment or the said 2nd Embodiment.

B. Solvent Treatment Step The solvent treatment step in the third embodiment performs the same operation as the solvent treatment step in the first embodiment or the second embodiment.

C. Heat Treatment Step In the third embodiment, a heat treatment step may be performed as necessary. In addition, when performing a heat treatment process in 3rd Embodiment, operation similar to the heat treatment process in the said 2nd Embodiment is performed.

  In the third embodiment, as described above, by performing a series of dyeing operations 1 or 2 after performing the pre-dyeing step, the dyeing dye has a practical dyeing density and has a fast dyeing strength. A dyed polyarylate fiber having good light fastness can be obtained.

Furthermore, in the third embodiment, the following effects can be achieved by performing the pre-staining step. First, for the polyarylate fiber itself, for example, by performing a pre-dyeing step with a disperse dye, the dyeing quality and dyeing density of the aramid fiber itself are further improved. On the other hand, when the polyarylate fiber is a mixed fiber with other chemical fiber or natural fiber, by performing a pre-dyeing step with a dye capable of dyeing these other fibers, the polyarylate fiber and the other fiber The hue of the dye can be unified, and the dyeing quality and dyeing density of the dyed product are further improved.
(4) Fourth Embodiment In the dyeing method according to the fourth embodiment, after the dyeing operation 1 or the dyeing operation 2 described in the first embodiment or the second embodiment, a polyarylate fiber is used as a vat dye and It has a post-dyeing step of dyeing with dyes other than sulfur dyes. The dyeing operation 1 or the dyeing operation 2 performed before the post-dyeing step may be performed only once, or may be repeated a plurality of times as necessary. By repeating this dyeing operation a plurality of times, darker polyarylate fibers can be obtained.

A. Dye provision process The dye provision process in this 4th Embodiment performs operation similar to the dye provision process in the said 1st Embodiment or the said 2nd Embodiment.

B. Solvent Treatment Step The solvent treatment step in the fourth embodiment performs the same operation as the solvent treatment step in the first embodiment or the second embodiment.

C. Heat treatment step In the fourth embodiment, a heat treatment step may be performed if necessary. In addition, when performing a heat treatment process in 4th Embodiment, operation similar to the heat treatment process in the said 2nd Embodiment is performed.

D2. Post-dyeing step The post-dyeing step in the fourth embodiment performs the same operation as the pre-dyeing step described in the third embodiment. However, the polyarylate fiber dyed in the post-dyeing step is already dyed with the vat dye or the sulfur dye by the dyeing operation 1 or the dyeing operation 2 unlike the pre-dyeing step of the third embodiment.

  In the fourth embodiment, as described above, after performing a series of dyeing operation 1 or dyeing operation 2, a post-dyeing step is performed, thereby having a practical dyeing density and dyeing fastness. A dyed polyarylate fiber having good light fastness can be obtained.

  Furthermore, in the fourth embodiment, the following effects can be achieved by performing the post-dyeing step. First, for the polyarylate fiber itself, for example, by performing a post-dyeing step with a disperse dye, the dyeing quality and the dyeing density of the polyarylate fiber itself are further improved. On the other hand, when the polyarylate fiber is a mixed fiber with other chemical fiber or natural fiber, by performing a post-dyeing step with a dye capable of dyeing these other fibers, the polyarylate fiber and the other fiber The hue of the dye can be unified, and the dyeing quality and dyeing density of the dyed product are further improved.

  Hereinafter, based on each said embodiment, the following each Example and the dyeing | staining of the comparative example were performed with respect to the polyarylate fiber.

In Example 1, benzyl alcohol was used as a polar solvent, and a double-face knitted fabric (hereinafter referred to as “polyarylate knitted fabric”) having a basis weight of 632 g / m ^{2 made} of polyarylate fibers was dyed based on the first embodiment described above. This polyarylate knitted fabric was used after scouring by a usual method. In Example 1, the polyarylate knitted fabric was subjected to a dyeing operation combining the dye application step and the solvent treatment step described below, and was performed once. Further, the same dyeing operation was repeated on the polyarylate knitted fabric subjected to this one dyeing operation, and the dyeing operation was carried out twice in total and three times in total. In Example 1, reductive cleaning is not performed.

A. Dye provision process Dye provision was performed by a continuous method, and using a test mangle device, a vat dye was imparted to a polyarylate knitted fabric by pad-niping a dye solution containing the vat dye. The pickup rate at this time was 58% by weight. In the dyeing solution, 50 g / L of vat dye: Mikethren Blue BC super-fine (Dystar Japan Co., Ltd. vat dye, CI Vat Blue 6: hereinafter referred to as “Blue BC”) in a non-reducing state As a migration inhibitor, GERMADYE AM-X (manufactured by RAON CHEMICAL) 10 g / L was used in combination.

  For drying, a test baking box apparatus was used, and the polyarylate knitted fabric after the dyeing solution was applied was dried at 130 ° C. for 2 minutes to adhere the vat dye to the fiber surface of the polyarylate knitted fabric. The dried polyarylate knitted fabric was directly put into the subsequent solvent treatment step (benzyl alcohol treatment step) without washing or reducing washing.

B. Solvent treatment process (benzyl alcohol treatment process)
In Example 1, benzyl alcohol (99.5% product) was used as a polar solvent without dilution. A test mangle device was used for applying the treatment liquid, and the polyarylate knitted fabric after the dye application step was subjected to solvent treatment by a continuous method. The treatment temperature at this time was 30 ° C. In the treatment, the polyarylate knitted fabric was dipped in the treatment liquid for 1 second and immediately squeezed with mangle. The pickup rate at this time was 61% by weight. The polyarylate knitted fabric after the solvent treatment step is washed with hot water, washed with water and dried to obtain the polyarylate knitted fabric of Example 1 (one dyeing operation) dyed in blue having a practical dyeing concentration. It was.

  Next, the above-described dyeing operation was repeated a plurality of times for the polyarylate knitted fabric after one dyeing operation. More specifically, the polyarylate knitted fabric of Example 1 was further dyed a total of 2 times and 3 times in total by repeating the dyeing operation in which the dye application step and the solvent treatment step were combined, and further dyed dark blue. (2 and 3 staining operations) were obtained.

  In contrast to Example 1, the polyarylate knitted fabric was subjected to only the dye application step and not subjected to the solvent treatment step as Comparative Example 1. Specifically, the dye application was performed only once under the same conditions as in Example 1, and the polyarylate knitted fabric after application of the vat dye was washed with hot water, washed with water, and dried. Knitted fabric was obtained.

  The dyed polyarylate knitted fabrics of Example 1 and Comparative Example 1 dyed as described above were evaluated as follows.

Staining density (total K / S value):
The surface dyeing density of the dyed polyarylate knitted fabric was expressed as a total K / S value. The larger the total K / S value, the deeper the polyarylate knitted fabric is dyed. The total K / S value is a value obtained by totaling 16 K / S values of 16 wavelengths measured at 20 nm intervals in a measurement range of wavelengths from 400 nm to 700 nm. The K / S value is obtained from the reflectance R at each wavelength by the following Kubelka-Munk equation. Here, K represents an extinction coefficient, and S represents a light scattering coefficient.

K / S = (1-R) ² / 2R
The value of reflectance R at each wavelength was measured using a spectrophotometer UV-3100 (manufactured by Shimadzu Corporation) equipped with an integrating sphere. Table 1 shows the total K / S value calculated by the above equation for the polyarylate knitted fabric.

Lightness (L ^* value):
The degree of dark color of the dyed polyarylate knitted fabric was evaluated by the lightness (L ^* value) in the L ^* a ^* b ^* color system described above. The L ^* value is expressed in the range of 100 (white) to 0 (black), and the darker the color, the lower the L ^* value. The L ^* value was measured using a color difference meter CR-200 (manufactured by Minolta Camera Co., Ltd.). Table 1 shows L ^* values of the obtained polyarylate knitted fabric.

Color fastness:
In addition to the dyeing density (total K / S value) and lightness (L ^* value), dyeing fastness was confirmed as a basic evaluation item of the dyed product. In particular, light fastness (JIS L0842), which is a problem in dyeing fastness of polyarylate knitted fabric, was evaluated. The light fastness of the polyarylate knitted fabric was evaluated in the following manner because it was difficult to evaluate the yellowish browning of the fiber itself in addition to the dye discoloration caused by light irradiation. The polyarylate knitted fabric was subjected to blue scale quaternary irradiation, and the change was graded with a gray scale for color change. In addition, in addition to the five grades from the first grade (bad) to the fifth grade (good), the grade evaluation was also performed in the middle of each grade. For example, the evaluation between grade 3 and grade 4 was 3-4 grade. The evaluation results are shown in Table 1.

表１から分かるように、実施例１においては、各ポリアリレート編物のいずれにおいても、実用的な染色濃度（トータルＫ／Ｓ値）、明度（Ｌ^*値）及び良好な耐光堅牢度を有している。また、染色操作の回数が増すにつれ染色濃度（トータルＫ／Ｓ値）が大きく向上し、更に濃色のポリアリレート編物を得ることができた。特に、各ポリアリレート編物の明度（Ｌ^*値）は３５以下であり、いずれも極濃色であった。

As can be seen from Table 1, in Example 1, each of the polyarylate knitted fabrics has a practical dyeing density (total K / S value), lightness (L ^* value), and good light fastness. ing. Further, as the number of dyeing operations increased, the dyeing density (total K / S value) was greatly improved, and a dark-colored polyarylate knitted fabric could be obtained. In particular, the lightness (L ^* value) of each polyarylate knitted fabric was 35 or less, and all were extremely dark colors.

  Further, although not shown in Table 1, in each dyed polyarylate knitted fabric of Example 1, practical high-performance fiber properties can be obtained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was maintained. On the other hand, in Comparative Example 1, compared with Example 1, the dyeing density, lightness, and light fastness of the polyarylate knitted fabric were insufficient.

  In Example 2, benzyl alcohol was used as a polar solvent in the same manner as in Example 1, and a polyarylate knitted fabric was dyed with a vat dye different from Example 1 based on the first embodiment described above. This polyarylate knitted fabric was used after scouring by a usual method.

A. Dye application process In Example 2, the dye used was changed to vat dye: Indanthren Brilliant Pink R (Dystar Japan Co., Ltd. vat dye, CI Vat Red 1: hereinafter referred to as “Pink R”) Except for the above, the same operation as in Example 1 was performed. The pickup rate at this time was 58% by weight.

  In the drying, the polyarylate knitted fabric after dyeing liquid application was dried at 130 ° C. for 2 minutes in the same process as in Example 1 above, and the vat dye was adhered to the fiber surface of the polyarylate knitted fabric. The dried polyarylate knitted fabric was directly put into the subsequent solvent treatment step (benzyl alcohol treatment step) without washing or reducing washing.

B. Solvent treatment process (benzyl alcohol treatment process)
In Example 2, the operating conditions of the solvent treatment step with benzyl alcohol were the same as in Example 1 above. At this time, the pickup rate in the solvent treatment step was 61% by weight. The polyarylate knitted fabric after this solvent treatment step is washed with hot water, washed with water and dried to obtain the polyarylate knitted fabric of Example 2 dyed in red having a practical dyeing density (one dyeing operation). It was.

  Next, the above-described dyeing operation was repeated a plurality of times for the polyarylate knitted fabric after one dyeing operation. More specifically, the polyarylate knitted fabric of Example 2 was further dyed a total of 2 times and 3 times in total by repeating the dyeing operation in which the dye application step and the solvent treatment step were combined, and further dyed dark red. (2 and 3 staining operations) were obtained.

  In contrast to Example 2, the polyarylate knitted fabric was subjected to only the dye application step and not subjected to the solvent treatment step as Comparative Example 2. Specifically, the dye application was performed only once under the same conditions as in Example 2, and the polyarylate knitted fabric after application of the vat dye was washed with hot water, washed with water, and dried. Knitted fabric was obtained.

The dyed polyarylate knitted fabrics of Example 2 and Comparative Example 2 dyed as described above were evaluated in the same manner as in Example 1 above. Table 2 shows the total K / S value for evaluating the dyeing density, the lightness (L ^* value) for evaluating the degree of dark color, and the light fastness evaluation results.

表２から分かるように、実施例２においては、各ポリアリレート編物のいずれにおいても、実用的な染色濃度（トータルＫ／Ｓ値）、明度（Ｌ^*値）及び良好な耐光堅牢度を有している。また、染色操作の回数が増すにつれ染色濃度（トータルＫ／Ｓ値）が大きく向上し、更に濃色のポリアリレート編物を得ることができた。

As can be seen from Table 2, in Example 2, each of the polyarylate knitted fabrics has a practical dyeing density (total K / S value), lightness (L ^* value), and good light fastness. ing. Further, as the number of dyeing operations increased, the dyeing density (total K / S value) was greatly improved, and a dark-colored polyarylate knitted fabric could be obtained.

On the other hand, the lightness (L ^* value) is larger than 35 because the dye used is “Pink R”. This is because Example 2 is a prescription for dyeing bright red, and is not a prescription intended for dark navy blue or black.

  Although not shown in Table 2, in each dyed polyarylate knitted fabric of Example 2, the properties of practical high-performance fibers can be obtained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was maintained. On the other hand, in Comparative Example 2, the dyeing density, lightness, and light fastness of the polyarylate knitted fabric were insufficient as compared with Example 2.

  Example 3 uses three types of polar solvents, N-methyl-2-pyrrolidone, DL-lactic acid and oxalic acid, respectively. Based on the second embodiment described above, a polyarylate knitted fabric similar to that of Example 1 above is used. Stained. This polyarylate knitted fabric was used after scouring by a usual method.

A. Dye provision process In Example 3, the same operation as Example 1 was performed using vat dye: Blue BC as in Example 1 above. The pickup rate at this time was 58% by weight. For drying, the same operation as in Example 1 was performed. The dried polyarylate knitted fabric was put into each subsequent solvent treatment step as it was without washing or reducing washing.

B. Solvent treatment step In Example 3, N-methyl-2-pyrrolidone (98% product) was diluted with water and used as a 60 wt% aqueous solution. DL-lactic acid (90% product) was used without dilution. Oxalic acid (dihydrate) was dissolved in water and used as a 10 wt% aqueous solution. A test mangle device was used for applying the treatment liquid, and the polyarylate knitted fabric after the dye application step was subjected to solvent treatment by a continuous method. The treatment temperature at this time was 30 ° C. for all. In the treatment, the polyarylate knitted fabric was dipped in the treatment liquid for 1 second and immediately squeezed with mangle. The pick-up rates of the polar solvents at this time were 72% by weight of an N-methyl-2-pyrrolidone aqueous solution, 81% by weight of DL-lactic acid, and 75% by weight of an oxalic acid aqueous solution, respectively.

C. Heat treatment process Using a test baking box apparatus for heat treatment, the polyarylate knitted fabric after each solvent treatment (with each solvent applied) is subjected to a dry heat treatment at 130 ° C. for 2 minutes to convert the vat dye into the polyarylate knitted fabric. I was dyed. The polyarylate knitted fabric after this heat treatment step is washed with hot water, washed with water and dried to obtain each polyarylate knitted fabric of Example 3 dyed in blue having a practical dyeing density (one dyeing operation). It was.

  Next, the above-described dyeing operation was repeated a plurality of times for the polyarylate knitted fabric after one dyeing operation. Specifically, the dyeing operation combining the dye application step, the solvent treatment step, and the heat treatment step was repeated for a total of two times and a total of three times of the dyeing operation, and further dyed in deep blue. Each polyarylate knitted fabric (dyeing operations 2 and 3 times) was obtained.

  In contrast to Example 3, the polyarylate knitted fabric was subjected to only the dye application step and not subjected to the solvent treatment step and the heat treatment step as Comparative Example 3. Specifically, the dye application was performed only once under the same conditions as in Example 1, and the polyarylate knitted fabric after application of the vat dye was washed with hot water, washed with water, and dried. Knitted fabric was obtained.

The dyed polyarylate knitted fabrics of Example 3 and Comparative Example 3 dyed as described above were evaluated in the same manner as in Example 1 above. Table 3 shows the evaluation results of the total K / S value for evaluating the dyeing density, the lightness (L ^* value) for evaluating the degree of dark color, and the light fastness.

表３から分かるように、実施例３においては、各ポリアリレート編物のいずれにおいても、実用的な染色濃度（トータルＫ／Ｓ値）、明度（Ｌ^*値）及び良好な耐光堅牢度を有している。また、染色操作の回数が増すにつれ染色濃度（トータルＫ／Ｓ値）が大きく向上し、更に濃色のポリアリレート編物を得ることができた。

As can be seen from Table 3, in Example 3, each of the polyarylate knitted fabrics has a practical dyeing density (total K / S value), lightness (L ^* value), and good light fastness. ing. Further, as the number of dyeing operations increased, the dyeing density (total K / S value) was greatly improved, and a dark-colored polyarylate knitted fabric could be obtained.

  Furthermore, although not shown in Table 3, in the dyed polyarylate knitted fabric of Example 3, the properties of practical high-performance fibers can be obtained without causing dyeing unevenness, dimensional change, or significant deterioration in physical properties. Was maintained. On the other hand, in Comparative Example 3, compared with Example 3, the dyeing density, lightness, and light fastness of the polyarylate knitted fabric were insufficient.

  Example 4 uses each of three types of polar solvents, N-methyl-2-pyrrolidone, DL-lactic acid and oxalic acid, as in Example 3 above, and a polyarylate knitted fabric based on the second embodiment described above. It dye | stained with the vat dye different from the said Example 3. This polyarylate knitted fabric was used after scouring by a usual method.

A. Dye provision process In Example 4, except having changed the dye to be used into vat dye: Pink R, operation similar to the said Example 3 was performed. The pickup rate at this time was 58% by weight.

  In the drying, the polyarylate knitted fabric after dyeing liquid application was dried at 130 ° C. for 2 minutes in the same process as in Example 1 above, and the vat dye was adhered to the fiber surface of the polyarylate knitted fabric. The dried polyarylate knitted fabric was put into each subsequent solvent treatment step as it was without washing or reducing washing.

B. Solvent treatment step In Example 4, the operating conditions of the solvent treatment step with each polar solvent were the same as in Example 3 above. The pick-up rates of the polar solvents at this time were 72% by weight of an N-methyl-2-pyrrolidone aqueous solution, 81% by weight of DL-lactic acid, and 75% by weight of an oxalic acid aqueous solution, respectively.

C. Heat treatment step In Example 4, the operating conditions of the heat treatment step were the same as in Example 3 above, and vat dye was dyed on the polyarylate knitted fabric. The polyarylate knitted fabric after this heat treatment step is washed with hot water, washed with water and dried to obtain each polyarylate knitted fabric of Example 4 dyed in red having a practical dyeing density (one dyeing operation). It was.

  Next, the above-described dyeing operation was repeated a plurality of times for the polyarylate knitted fabric after one dyeing operation. Specifically, the dyeing operation combining the dye application step, the solvent treatment step and the heat treatment step was repeated to perform the dyeing operation a total of 2 times and a total of 3 times, and further dyed dark red of Example 4 Each polyarylate knitted fabric (dyeing operations 2 and 3 times) was obtained.

  In contrast to Example 4, the polyarylate knitted fabric was subjected to only the dye application step and not subjected to the solvent treatment step and the heat treatment step as Comparative Example 4. Specifically, the dye application was performed only once under the same conditions as in Example 2, and the polyarylate knitted fabric after application of the vat dye was washed with hot water, washed with water, and dried. Knitted fabric was obtained.

The dyed polyarylate knitted fabrics of Example 4 and Comparative Example 4 dyed as described above were evaluated in the same manner as in Example 1 above. Table 3 shows the evaluation results of the total K / S value for evaluating the dyeing density, the lightness (L ^* value) for evaluating the degree of dark color, and the light fastness.

表４から分かるように、実施例４においては、各ポリアリレート編物のいずれにおいても、実用的な染色濃度（トータルＫ／Ｓ値）、明度（Ｌ^*値）及び良好な耐光堅牢度を有している。また、染色操作の回数が増すにつれ染色濃度（トータルＫ／Ｓ値）が大きく向上し、更に濃色のポリアリレート編物を得ることができた。

As can be seen from Table 4, in Example 4, each of the polyarylate knitted fabrics has a practical dyeing density (total K / S value), lightness (L ^* value), and good light fastness. ing. Further, as the number of dyeing operations increased, the dyeing density (total K / S value) was greatly improved, and a dark-colored polyarylate knitted fabric could be obtained.

On the other hand, the lightness (L ^* value) is larger than 35 because the dye used is “Pink R”. This is because Example 4 is a prescription for dyeing vivid red and is not a prescription intended for dark navy blue or black.

  Moreover, although not shown in Table 4, in each dyed polyarylate knitted fabric of Example 4, the properties of practical high-performance fibers can be obtained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was maintained. On the other hand, in Comparative Example 4, the dyeing density, lightness and light fastness of the polyarylate knitted fabric were insufficient as compared with Example 4.

  Example 5 uses four types of polar solvents, benzyl alcohol, N-methyl-2-pyrrolidone, DL-lactic acid, and oxalic acid, respectively, and the third embodiment described above (pre-dyeing with disperse dyes → by vat dyes). Polyarylate knitted fabric was dyed on the basis of dyeing). In Example 5, a pre-dying step was first performed with a disperse dye on a polyarylate knitted fabric. Next, the same dyeing operation as in Example 1 or Example 3 was performed on the polyarylate knitted fabric after the pre-staining step using each polar solvent.

D1. Pre-dyeing step with disperse dye Unstained polyarylate knitted fabric was scoured by a conventional method, and dyed with disperse dye. The dyeing was performed by the dip dyeing method, and the polyarylate knitted fabric was dyed using a high-temperature and high-pressure dyeing tester mini color (manufactured by Tecsum Giken Co., Ltd.). As a staining solution, Diax Blue ER 150% (Disperse dye manufactured by Dystar Japan Co., Ltd., CI Disperse Blue 56: hereinafter referred to as “Blue ER”) 5.0% owf is used, and the pH is 5 Staining was performed using acetic acid / sodium acetate buffer.

  Dyeing was performed at a bath ratio of 1:20, and high-temperature high-pressure dyeing was performed at 135 ° C. for 60 minutes. The polyarylate knitted fabric after dyeing was subjected to reduction cleaning in the same manner as dyeing with disperse dyes for ordinary polyester fibers. In the reduction cleaning, sodium dithionite 5 g / L as a reducing agent and sodium hydroxide 5 g / L were used in combination at 80 ° C. for 1 minute, and this reduction cleaning was repeated twice. Thereafter, washing with hot water, washing with water and drying were performed to obtain a polyarylate knitted fabric pre-dyed with a disperse dye.

  Next, the dyeing operation using benzyl alcohol as a polar solvent was performed only once on the polyarylate knitted fabric that had been pre-dyed with a disperse dye in the same manner as in Example 1 above. Similarly, for the polyarylate knitted fabric that was pre-dyed with a disperse dye, three kinds of polar solvents, N-methyl-2-pyrrolidone, DL-lactic acid, and oxalic acid were used in the same manner as in Example 3 above. The staining operation used was performed only once. Thus, each polyarylate knitted fabric of Example 5 dye | stained by extremely dark blue was obtained.

  A comparative example 5 was prepared by subjecting the polyarylate knitted fabric only to pre-dying with a disperse dye and not performing the same dyeing operation as in Example 1 or Example 3 to Example 5 above. Moreover, after pre-dying a disperse dye to a polyarylate knitted fabric, only the dye provision process similar to the said Example 1 was performed, and the solvent processing process and the heat processing process were not performed, and it was set as the comparative example 6.

The dyed polyarylate knitted fabrics of Example 5, Comparative Example 5 and Comparative Example 6 dyed as described above were evaluated in the same manner as in Example 1 above. Table 5 shows the evaluation results of the total K / S value for evaluating the dyeing density, the lightness (L ^* value) for evaluating the degree of dark color, and the light fastness.

表５から分かるように、建染染料のみで染色された上記実施例１（表１参照）又は上記実施例３（表３参照）に比べ、分散染料による前染色がなされた実施例５においては、いずれも、染色濃度（トータルＫ／Ｓ値）が大きく向上し、また明度（Ｌ^*値）が３５以下と小さくなり、極濃色のポリアリレート編物を得ることができた。この極濃色のポリアリレート編物は、表５に示すように、非常に良好な耐光堅牢度を有している。

As can be seen from Table 5, compared to Example 1 (see Table 1) or Example 3 (see Table 3) dyed with vat dye alone, Example 5 was pre-dyed with a disperse dye. In both cases, the dyeing density (total K / S value) was greatly improved, and the lightness (L ^* value) was reduced to 35 or less, and an extremely dark polyarylate knitted fabric could be obtained. As shown in Table 5, this extremely dark polyarylate knitted fabric has a very good light fastness.

  Moreover, in the polyarylate knitted fabric of Example 5, the surface quality of the knitted fabric was further improved. Further, although not shown in Table 5, the dyed polyarylate knitted fabric of Example 5 maintains the properties of a practical high-performance fiber without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was. On the other hand, in Comparative Example 5 and Comparative Example 6, the dye density, lightness, and light fastness of the polyarylate knitted fabric were insufficient as compared with Example 5.

  In Example 6, N-methyl-2-pyrrolidone or DL-lactic acid was used as a polar solvent, respectively, and a polyarylate knitted fabric was dyed with a sulfur dye based on the second embodiment described above. This polyarylate knitted fabric was used after scouring by a usual method.

A. Dye provision process In Example 6, the dye used is sulfur dye: Asathio Blue RC200 (Asahi Chemical Industry Co., Ltd. sulfur dye, CI Sulfur Blue 7: hereinafter referred to as “Blue RC200”), Asathiosol Bordeaux S-3B (Sulfurized dye manufactured by Asahi Chemical Industry Co., Ltd., CI Sulfur Red 6: hereinafter referred to as “Bord. S-3B”) or Asathiosol Indigo Green S-BG (sulfurized dye manufactured by Asahi Chemical Industry Co., Ltd., CI Sulfur) (Blue 15: hereinafter referred to as “Green S-BG”). The pickup rate at this time was 56% by weight.

  In the drying, the polyarylate knitted fabric after the dyeing solution was applied in the same process as in Example 1 above was dried at 130 ° C. for 2 minutes to adhere the sulfur dye to the fiber surface of the polyarylate knitted fabric. The dried polyarylate knitted fabric was put into each subsequent solvent treatment step as it was without washing or reducing washing.

B. Solvent treatment step In Example 6, the operating conditions of the solvent treatment step with the polar solvent N-methyl-2-pyrrolidone or DL-lactic acid were the same as in Example 3 above. The pick-up rates of the polar solvents at this time were 72% by weight of an N-methyl-2-pyrrolidone aqueous solution and 81% by weight of DL-lactic acid, respectively.

C. Heat treatment step In Example 6, the operating conditions of the heat treatment step were the same as in Example 3 above, and the sulfur dye was dyed on the polyarylate knitted fabric. The polyarylate knitted fabric after this heat treatment step was washed with hot water, washed with water and dried to obtain each dyed polyarylate knitted fabric of Example 6 having a practical dyeing density (only once dyeing operation). .

  In contrast to Example 6, the polyarylate knitted fabric was subjected to only the dye application step and not subjected to the solvent treatment step and the heat treatment step as Comparative Example 7. Specifically, the dye application was performed only once under the same conditions as in Example 6, and the polyarylate knitted fabric after the sulfur dye was applied was washed with hot water, washed with water and dried, and the polyarylate knitted fabric of Comparative Example 7 was dried. Got.

The dyed polyarylate knitted fabrics of Example 6 and Comparative Example 7 dyed as described above were evaluated in the same manner as in Example 1 above. Table 6 shows the evaluation results of the total K / S value for evaluating the dyeing density, the lightness (L ^* value) for evaluating the degree of dark color, and the light fastness.

表６から分かるように、硫化染料を使用した場合にも、各ポリアリレート編物は実用的な染色濃度（トータルＫ／Ｓ値）、明度（Ｌ^*値）及び良好な耐光堅牢度を有している。更に、表６には示していないが、実施例６の染色された各ポリアリレート編物においては、染色ムラや寸法変化、或いは、物性低下が大きく生じることなく、実用的な高性能繊維の性質を維持していた。一方、比較例７においては、実施例６に比べポリアリレート編物の染色濃度、明度及び耐光堅牢度が不十分なものであった。

As can be seen from Table 6, each polyarylate knitted fabric has a practical dyeing density (total K / S value), lightness (L ^* value), and good light fastness even when sulfur dyes are used. Yes. Further, although not shown in Table 6, in each dyed polyarylate knitted fabric of Example 6, the properties of practical high-performance fibers can be obtained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was maintained. On the other hand, in Comparative Example 7, the dyeing density, brightness, and light fastness of the polyarylate knitted fabric were insufficient as compared with Example 6.

  As in Examples 1 to 6 described above, according to the present invention, polyarylate fibers can be dyed to a practical dyeing concentration. Further, according to the present invention, dyeing unevenness, dimensional change, or deterioration of physical properties does not occur greatly in the dyed polyarylate fiber. Further, since a vat dye or sulfur dye having good dyeing fastness, particularly light fastness, is used, the dyeing fastness, particularly light fastness, of the dyed polyarylate fiber is improved.

Further, by changing the use concentration and hue of the vat dye or sulfur dye to be used, it is possible to obtain a dyed product having a rich hue from light to dark. In particular, according to the present invention, it is possible to dye polyarylate fiber, which has been difficult until now, to an extremely dark color such as black or navy blue (for example, L ^* value is 35 or less).

  In addition, as a pre- and post-process of the dyeing method of the polyarylate fiber according to the present invention, by performing a pre-dyeing step with a dye other than the vat dye and the sulfur dye, the dyeing quality of the polyarylate fiber itself is improved, and further the dyeing concentration Will improve. On the other hand, when the polyarylate fiber is a mixed fiber with other chemical fiber or natural fiber, by performing these dyeing steps, the hue of the polyarylate fiber and the other fiber can be unified, The dyeing quality and dyeing density of the dyed product are further improved.

  Therefore, according to the present invention, the polyarylate having no dyeing unevenness in the dyed product, good dyeing fastness, particularly light fastness, rich hue, and practical dyeing density. Fiber dyeing methods and dyed polyarylate fibers can be provided. This is effective for new application development of polyarylate fibers.

In implementing the present invention, not only the above-described embodiments but also the following various modifications may be mentioned.
(1) In each of the above examples, the polyarylate fiber is dried after the dye solution containing a vat dye or sulfur dye is applied to the polyarylate fiber, but the present invention is not limited thereto, and the dye solution is applied. Later, the polyarylate fiber may be put into the solvent treatment step without drying.
(2) In each of the above examples, the polyarylate fiber to which the vat dye or sulfur dye was added in the dye application step was added to the subsequent solvent treatment step without washing. However, the vat dye or sulfur dye after the dye application step adheres to the polyarylate fiber with a certain degree of affinity. Therefore, the polyarylate fiber after the dye application step may be washed and then introduced into the solvent treatment step.
(3) In each of the above embodiments, the reduction cleaning is not performed after the dyeing operation. However, the reduction cleaning may be performed if necessary, and the prescription of the reduction cleaning is not limited to the alkaline system, but is an acidic system. You may make it perform the reduction | restoration washing by the reduction | restoration prescription of this.
(4) In Examples 3 to 6 above, DL-lactic acid mixed with optical isomers was used as the polar solvent. However, the present invention is not limited to this, and D-lactic acid or L-lactic acid should be used. May be.
(5) In Example 5 described above, no carrier or thickening agent is used for dyeing the disperse dye. In the present invention, pre-dying or post-dying is merely auxiliary dyeing, and it is not necessary to use a carrier or the like. Also good.
(6) In Example 5, the disperse dye was dyed as a pre-dyeing step before the dyeing operation with the vat dye based on the third embodiment, but the present invention is not limited to this. The disperse dye may be dyed as a post-dyeing step after the dyeing operation with the vat dye based on the form.
(7) In each of the above embodiments, the polyarylate knitted fabric is dyed. However, the invention is not limited to this, and it may be a woven fabric, a nonwoven fabric, or the like, or may be a yarn, cotton, or the like. .

Claims (6)

A dye application step of applying a vat dye or sulfur dye to the polyarylate fiber;
A solvent treatment step of treating the polyarylate fiber with a treatment solution containing a polar solvent;
After the solvent treatment step, it has a heat treatment step for heat-treating the polyarylate fiber as necessary, and two dyeing operations shown below,
Dyeing operation 1: Dye application step → Solvent treatment step,
Dyeing operation 2: Dye application step → Solvent treatment step → Heat treatment step
A method for dyeing polyarylate fibers, comprising at least one dyeing operation among them. The method for dyeing polyarylate fibers according to claim 1, wherein the polar solvent has a solubility parameter (δ) in the range of 18 to 32 (MPa) ^1/2 .   The polar solvent is selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, benzyl alcohol, diethylene glycol, triethylene glycol, sulfuric acid, formic acid, lactic acid, and oxalic acid. The method for dyeing polyarylate fibers according to claim 1, wherein at least one kind is used. A method for dyeing polyarylate fibers according to any one of claims 1 to 3,
A pre-dyeing step performed before the dyeing method or a post-dyeing step performed after,
In the pre-dying process or the post-dying process, the polyarylate fiber is dyed with a dye other than a vat dye and a sulfur dye.   A dyed polyarylate fiber characterized by being dyed by the method for dyeing polyarylate fiber according to any one of claims 1 to 4. 6. The dyed polyarylate fiber according to claim 5, wherein the lightness (L ^* value) in the L ^* a ^* b ^* color system is 35 or less.