Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/24—Polyamides; Polyurethanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/30—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/24—Polyamides; Polyurethanes
  • D06P3/243—Polyamides; Polyurethanes using vat or sulfur dyes, indigo
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/001—Special chemical aspects of printing textile materials
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/02—After-treatment
  • D06P5/04—After-treatment with organic compounds

Definitions

• the present invention relates to a method for dyeing aramid fibers, and more particularly, to a method for dyeing aramid fibers to a practical dyeing concentration.
• the present invention also relates to an aramid fiber dyed by this method.
• the wholly aromatic polyamide fiber is also referred to as an aramid fiber, has high strength and high elastic modulus, and is excellent in heat resistance, dimensional stability, chemical resistance, etc., and is widely used as industrial fiber.
• This aramid fiber is composed of a para-aramid fiber (polyparaphenylene terephthalamide fiber, etc.) and a para-copolymerized aramid fiber (polyparaphenylene terephthalamide and 3,4'-oxydiphenylene) depending on the position where the amide bond is attached to the aromatic ring.
• copolymer fibers with terephthalamide and meta-aramid fibers (polymetaphenylene isophthalamide fiber or copolymer fibers containing this as a main component).
• Para-aramid fibers are particularly strong and excellent in elastic modulus. They are widely used as protective materials such as bulletproof vests, wear materials such as brake pads, optical fiber reinforcements, and industrial materials such as ropes and nets that require particularly high strength. in use. Para-copolymerized aramid fibers are used for the same applications as para-aramid fibers, but exhibit characteristics in applications that require chemical stability and fatigue resistance. For example, it is widely used for rubber reinforcements, ropes, civil engineering and building applications. On the other hand, meta-aramid fibers are particularly excellent in heat resistance, flame retardancy, chemical resistance, etc., and are widely used as various protective work clothes such as fire fighting clothes.
• aramid fibers have a rigid molecular structure and high crystallinity, and a practical dyeing concentration cannot be obtained with the same dyeing method as general fibers. The fastness is not practically sufficient. Therefore, in actuality, mainly meta-aramid fibers are manufactured and used as original fibers (fibers made by adding a colorant in the stage before the spinning process). Since such an original 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 aramid fibers. Further, in para-aramid fibers and para-copolymerized aramid fibers, fibers having a practical dyeing density such as black and navy blue, including original fibers, have not been produced industrially.
• Patent Document 1 aramid fibers are pretreated with concentrated sulfuric acid, neutralized, and then put into a dyeing bath while maintaining a predetermined moisture content without being dried, and dyed with a disperse dye or a cationic dye.
• a dyeing method has been proposed.
• Patent Document 2 proposes a dyeing method for dyeing under a very high temperature condition of 300 to 400 ° C. using some vat dyes that are stable at high temperatures.
• the dyeing method of the above-mentioned Patent Document 1 can obtain a dyed material with abundant hues.
• the dyeing method of Patent Document 1 has a problem that the dye used is a disperse dye or a cationic dye, and the dyeing fastness, particularly the light fastness is poor.
• the dyeing method of Patent Document 2 uses a vat dye having good light fastness, but the dyeing temperature is very high, and the dyes that can be used for this are limited and abundant. There was a problem that the hue could not be handled sufficiently.
• the dyeing method of Patent Document 2 has a problem that a special apparatus is required and the energy cost is increased. Furthermore, the dyeing method of Patent Document 2 is still insufficient for dyeing para-aramid fibers or para-copolymerized aramid fibers to a practical dye density. On the other hand, when the dyeing method of Patent Document 2 is applied to a meta-aramid fiber, since the treatment is performed at a temperature that greatly exceeds the glass transition point, there has been a problem that the physical properties of the fiber are greatly reduced.
• the present invention is a dyeing method that can be applied to any of para-aramid fibers, para-copolymerized aramid fibers, and meta-aramid fibers. Dyed at a practical dyeing density required for various application developments, and the dyed aramid fiber does not cause uneven dyeing, dimensional changes, or significant deterioration in physical properties. It is an object of the present invention to provide a method for dyeing aramid fibers and a dyed aramid fiber having good fastness, particularly light fastness.
• the present inventors In solving the above-mentioned problems, the present inventors, as a result of diligent research, adopted vat dyes or sulfur dyes with good light fastness to dye aramid fibers, and apply these dyes onto aramid fibers. It has been found that the above problems can be solved by combining the process and the process of treating the aramid fiber with a polar solvent, and the present invention has been completed.
• the method for dyeing aramid fibers according to the present invention includes a dye application step of applying a vat dye or a sulfur dye to the aramid fibers, A solvent treatment step of treating the aramid fiber with a treatment solution containing a polar solvent; After this solvent treatment step, it has a heat treatment step for heat-treating the aramid fiber as necessary, and four dyeing operations shown below, Dyeing operation 1: Dye application step ⁇ Solvent treatment step, Dyeing operation 2: solvent treatment step ⁇ dye application step, Dyeing operation 3: Dye application step ⁇ Solvent treatment step ⁇ Heat treatment step Dyeing operation 4: Solvent treatment step ⁇ heat treatment step ⁇ dye application step, Among them, at least one staining operation is provided once or more.
• the polar solvent has a solubility parameter ( ⁇ ) value of 18 to 32 (MPa) 1/2 . It is in the range.
• the polar solvent is N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide. And at least one selected from the group consisting of dimethyl sulfoxide, benzyl alcohol, diethylene glycol, triethylene glycol, sulfuric acid, formic acid, lactic acid, and oxalic acid.
• the method for dyeing aramid fibers according to the present invention includes the method for dyeing aramid 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 step or the post-dying step, the aramid fiber is dyed with a dye other than a vat dye and a sulfur dye.
• the dyed aramid fiber according to the present invention is characterized by being dyed by the method of dyeing aramid fiber according to any one of claims 1 to 3.
• the lightness (L * value) in the L * a * b * color system is 38 or less.
• the lightness (L * value) in the L * a * b * color system is 30 or less.
• the dyed aramid fiber according to the present invention is characterized by being dyed by the method of dyeing aramid fiber according to claim 4.
• the lightness (L * value) in the L * a * b * color system is 30 or less.
• the present invention can be applied to any of para-aramid fibers, para-copolymerized aramid fibers, and meta-aramid fibers, and these aramid 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 aramid fiber after dyeing. Further, since a vat dye or sulfur dye having good dyeing fastness, particularly light fastness, is used, the dyeing fastness, especially light fastness, of the dyed aramid fiber is improved.
• para-aramid fiber or para-copolymerized aramid fiber which has been considered difficult so far, can be dyed in an extremely dark color such as black or 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.
• CIE International Commission on Illumination
• meta-aramid fibers or para-copolymerized aramid fibers have an L * value of 25 to 27 in an extremely dark color such as black or navy blue. Accordingly, in the present invention, it can be determined that the color is dark when the L * value is 38 or less, and it can be determined that the color is extremely dark when the L * value is 30 or less.
• not only the meta-aramid fibers but also the para-aramid fibers or the para-copolymerized aramid fibers can be dyed in a deep color or an extremely dark color by a dyeing method instead of an original deposition method.
• a pre- and post-process of the method for dyeing aramid fibers according to the present invention a pre-dyeing process or a post-dying process using a dye other than vat dyes and sulfur dyes can be performed.
• the fluff on the surface of the aramid fiber itself is more sufficiently dyed, and the dyeing quality and dyeing density are further improved.
• the aramid fiber is a mixed fiber with other chemical fiber or natural fiber, by performing these dyeing steps, the hue of the aramid fiber and the other fiber can be unified, and the dyed product Dyeing quality and dyeing density are further improved.
• an aramid fiber dyeing method and a dyed aramid fiber having good dyeing fastness, particularly light fastness, abundant hue, and practical dyeing density are obtained. Can be provided. This is effective for the development of new uses for aramid fibers.
• Examples of the aramid fiber dyed by the dyeing method according to the present invention include Twaron (registered trademark) of Teijin Limited and Kevlar (registered trademark) of DuPont Co., Ltd. as para-aramid fibers. As such, there is Technora (registered trademark) of Teijin Limited. On the other hand, there are CONEX (registered trademark) by Teijin Limited and Nomex (registered trademark) by Dupont Co., Ltd. as meta-aramid fibers.
• the form of the aramid fiber may be any form, and may be a fiber state 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, a rope It may be in the state of a fiber structure such as a net.
• any of para-aramid fiber, para-copolymerized aramid fiber, or meta-aramid fiber may be used alone, or a mixed fiber of these may be used. Further, it may be a mixed fiber state of an aramid fiber and other chemical fiber or natural fiber.
• aramid fibers are dyed with vat dyes or sulfur dyes.
• vat dyes or sulfur dyes are dyes having good dyeing fastness, and are particularly excellent in light fastness.
• 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.
• 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.
• a sulfur dye is a dye containing a sulfur atom in a 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. .
• the aramid 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 for dyeing aramid fibers as it is. Further, when the vat dye or sulfur dye is reduced to be water-soluble, the affinity for aramid fibers is further reduced.
• vat dye or sulfur dye dyeing property to the aramid fiber is developed by combining with a solvent treatment with a polar solvent for the aramid fiber. Furthermore, if heat treatment is performed as necessary after the solvent treatment, the dyeing property of vat dyes or sulfur dyes to aramid fibers may be further improved. However, at present, the dyeing mechanism of vat dyes or sulfur dyes on aramid fibers in the present invention is not clear.
• staining method which concerns on this 1st Embodiment is the solvent provision which processes the aramid fiber by the dye provision process which provides a vat dye or a sulfur dye to an aramid fiber, and the process liquid containing a polar solvent. Process.
• the order of these dye application step and solvent treatment step is not particularly limited, but it is preferable to perform the solvent treatment step after the dye application step.
• a dye application step of applying a vat dye or sulfur dye to the aramid fiber in a non-reduced state is performed, and then the aramid fiber to which the vat dye or sulfur dye is applied is applied.
• a solvent treatment step of treating with a treatment solution containing a polar solvent is performed.
• dyeing operation 1 these series of steps are collectively referred to as “dyeing 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 a plurality of times, darker aramid fibers can be obtained.
• A. Dye provision process The dye used for dyeing
• a super fine dye having an average dispersed particle size of several ⁇ m or less, preferably 1 ⁇ m or less in a state of being dispersed in a staining solution.
• 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.
• sulfur dye used in this dye application step a dye usually used for dyeing cotton or the like can be used.
• 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.
• the vat dye or sulfur dye is not in a reduced state and is a dye insoluble in water. 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 aramid fiber in the dye application process.
• 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 used for the application of the dyeing solution, and the dyeing solution may be applied by simple dipping, dipping and squeezing, or spraying or ink jetting.
• the aramid fiber to which the staining solution has been applied is then dried if necessary.
• the aramid fiber may be dried at any temperature, but it may be normally dried at a temperature of about 80 ° C. to 120 ° C. Further, after the aramid fiber is dried, heat treatment (treatment different from the heat treatment step described later) may be performed at a higher temperature. Alternatively, the aramid 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 120 ° C. to 200 ° C. or higher.
• this drying temperature is lower than 80 ° C., it takes time to dry the aramid fiber.
• the treatment temperature is higher than 200 ° C., particularly higher than 280 ° C., the physical properties of the aramid fibers may be greatly reduced.
• heat treatment at a temperature exceeding the glass transition point causes a decrease in physical properties.
• the vat dye or sulfur dye may be decomposed, and the hue changes greatly.
• the drying time may be appropriately selected depending on the type and form of the aramid 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 aramid fiber is a fabric, a drying time of about 1 to 10 minutes is preferable when the drying temperature is 105 ° C.
• vat dye or sulfur dye is uniformly applied on the aramid fiber.
• aramid fibers are not completely dyed with vat dyes or sulfur dyes.
• the vat dyes or sulfur dyes adhere to the aramid fibers with a certain degree of affinity even if they do not reach dyeing.
• the reason why vat dyes or sulfur dyes adhere to aramid fibers is not clear, but these dyes adhere to the surface of aramid fibers by physical action such as intermolecular force in a non-reducing water-insoluble state. It is thought to do.
• the traveling aramid fiber fabric is first immersed in a bath filled with a dyeing solution. Subsequently, surplus dyeing liquid is squeezed from the aramid fiber fabric by a squeezing means such as mangle. In this way, an aramid fiber fabric to which a predetermined amount of dyeing liquid has been uniformly applied is obtained. Next, the aramid fiber fabric after squeezing is introduced into a heat treatment apparatus such as a pin tenter while running and dried.
• a heat treatment apparatus such as a pin tenter
• aprotic polar solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetophenone, methyl ethyl ketone, acetophenone, N-butylphthalimide, N-isopropyl Examples thereof include phthalamide 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.
• N-methylpyrrolidone, N, N— is a solvent that is unlikely to cause shrinkage of the aramid fiber and physical properties and is particularly effective for dyeing vat dyes or sulfur dyes.
• Dimethylformamide, N, N-dimethylacetamide and dimethyl sulfoxide are preferred.
• 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- ⁇ -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) ethano , Alcohols such as 2- (dichlorophenoxy) ethanol, glycols such as ethylene glycol, diethylene glycol,
• 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.
• benzyl alcohol, diethylene glycol, triethylene glycol, sulfuric acid are not particularly susceptible to shrinkage of the aramid fiber and physical properties, and are particularly effective for dyeing vat dyes or sulfur dyes.
• Formic acid, lactic acid and oxalic acid are preferred.
• the solubility parameter ( ⁇ ) can be used as a quantitative index representing the polarity of the polar solvent used in the present invention.
• it is preferable to use a polar solvent having a solubility parameter value in the range of ⁇ 18 to 32 (MPa) 1/2 .
• it is more preferable to use a polar solvent having a solubility parameter value in the range of ⁇ 19 to 28 (MPa) 1/2 .
• the solubility parameter value of the polar solvent is in the above range, and it is considered that the action of the polar solvent on the aramid fiber is caused by being close to the solubility parameter value of the aramid fiber.
• the dyeing property to the aramid fiber of a vat dye or a sulfur dye improves, and the aramid fiber which has a more practical dyeing density can be obtained.
• polar solvents may be used alone as described above, or two or more solvents may be mixed and used.
• concentration of the polar solvent used for the solvent treatment may be appropriately selected depending on the type, shape, and treatment temperature of the aramid fiber to be treated, but it is usually preferable to contain 40% by weight to 100% by weight. More preferably, it is contained in an amount of 50 to 100% by weight.
• 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.
• the sulfuric acid used in the production stage of para-aramid fiber it is necessary to set the concentration to be used more narrowly.
• this solvent treatment step it is preferable to use an aqueous sulfuric acid solution having a concentration of 70% by weight to 90% by weight. Further, it is more preferable to use an aqueous sulfuric acid solution having a concentration of 75% by weight to 85% by weight.
• the aramid fiber is mainly composed of meta-aramid fiber, it is more preferable to use a sulfuric acid aqueous solution concentration of 75 wt% to 80 wt%.
• the staining concentration is within a relatively stable range, and even when the concentration of the polar solvent is slightly changed, 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.
• any solvent compatible with the polar solvent to be used may be used, but water is generally used.
• a certain type of polar solvent for example, N-methylpyrrolidone
• a darker colored product can be obtained by mixing a certain amount of water.
• the concentration of the polar solvent is lower than the above range and the amount of water in the solvent treatment liquid increases, the vat dye or sulfur dye attached to the aramid fiber in the dye application step may fall out in the solvent treatment liquid. It is not preferable.
• the treatment temperature of the polar solvent may be appropriately selected depending on the type, shape and treatment time of the aramid fiber to be treated, but is usually treated at a temperature of 0 ° C. to 70 ° C. Further, the temperature is preferably 10 ° C. to 60 ° C. 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.
• the dyeing concentration is within a relatively stable range, and even when the temperature of the polar solvent fluctuates slightly, the dyeing concentration hardly changes. Therefore, stable industrial production is possible when the temperature of the polar solvent is in the above-described range.
• the temperature of the polar solvent is higher than the above range, the physical properties of the aramid fiber may be deteriorated or extremely contracted.
• 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 aramid fiber.
• the treatment time for the solvent treatment is appropriately selected depending on the concentration and temperature of the polar solvent, and the treatment time is usually 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. As described above, when the processing time for 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.
• the processing time of the solvent treatment is controlled within a predetermined range. Therefore, it is preferable that the aramid fiber treated with the polar solvent is washed quickly. Moreover, when processing with a sulfuric acid, it is preferable to neutralize and wash rapidly.
• the aramid fibers may be washed with water or hot water, but reduction washing may be performed to remove undyed vat dyes or sulfur dyes attached to the surface of the aramid fibers. .
• the solvent treatment can be performed while running in the longitudinal direction.
• the traveling aramid fiber fabric is first immersed in a bath filled with a treatment liquid containing a polar solvent. Subsequently, the surplus treatment liquid is squeezed from the aramid fiber fabric by squeezing means such as mangle. Next, the aramid fiber fabric after squeezing is introduced into a continuous washing machine while running and is washed, neutralized or reduced and washed.
• 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.
• 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.
• concentration of an aramid fiber can be improved by repeating the above-mentioned dyeing
• staining method which concerns on this 2nd Embodiment is the solvent provision which processes the aramid fiber by the dye provision process which provides a vat dye or a sulfur dye to an aramid fiber, and the process liquid containing a polar solvent. And a heat treatment step of heat treating the aramid fiber after the solvent treatment step.
• staining operation 3 these series of steps are collectively referred to as “staining operation 3”.
• the dyeing operation 3 (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 a plurality of times, darker aramid fibers can be obtained.
• 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 aramid fiber after the solvent treatment is introduced into the subsequent heat treatment step without being washed, neutralized or reduced and washed.
• This heat treatment may be a dry heat treatment or a wet heat treatment, but is usually preferably a dry heat treatment.
• This heat treatment is preferably performed at a temperature of 50 ° C. or higher and 200 ° C. or lower.
• the aramid fiber is treated in a state where a polar solvent is applied. Therefore, when the temperature is higher than 200 ° C., the physical properties of the aramid fiber may be deteriorated, which is not preferable.
• the vat dye or sulfur dye may be decomposed, and the hue changes greatly.
• the heat treatment time may be appropriately selected in relation to the type and form of aramid fibers, the type of vat dye or sulfur dye used, and is not particularly problematic, but usually 30 seconds to 30 minutes. It is done in about time. 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 is slightly changed, and the dyeing is performed at a practical dyeing density. be able to.
• the aramid fiber fabric after the above-mentioned solvent treatment step may be introduced into a continuous heat treatment apparatus while being run and heat-treated.
• 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.
• the action when these solvent treatment and heat treatment are combined is not clear, but by treating the aramid fiber with the polar solvent having the above-mentioned concentration and heat-treating at the above-mentioned temperature, a rigid molecule is obtained. It is conceivable that the intermolecular bonds of the aramid fibers having a structure and high crystallinity are further loosened than when the solvent treatment alone, 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 the heat treatment. Thus, the vat dye or sulfur dye dyed on the aramid fiber in the solvent treatment step is considered to be more strongly dyed into the fine voids of the aramid fiber by the heat treatment step after the solvent treatment step.
• the aramid fiber after the heat treatment step is washed to remove the remaining polar solvent.
• washing with water or hot water may be performed, but reduction washing may be performed in order to remove undyed vat dye or sulfur dye attached to the surface of the aramid fiber.
• 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.
• concentration of an aramid fiber can be improved by repeating the above-mentioned dyeing
• an aramid fiber and a vat dye are used before the dyeing operation 1 or the dyeing operation 3 described in the first embodiment or the second embodiment. It has a pre-dyeing step of dyeing with dyes other than sulfur dyes.
• the dyeing operation 1 or the dyeing operation 3 performed after the pre-dyeing step may be performed only once, or may be repeated a plurality of times as necessary.
• a darker aramid fiber can be obtained by repeating this dyeing operation 1 or dyeing operation 3 a plurality of times.
• a pre-dyeing step is performed on unstained aramid fibers.
• 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 aramid fibers themselves are dyed, a carrier or the like may be used in combination as in the conventional dyeing method for aramid fibers. On the other hand, when the aramid 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.
• the dye used can be any dye that has an affinity for the aramid fiber.
• a disperse dye a cationic dye, an acid dye, or the like
• a dye selected from the viewpoint of dyeability and dyeing fastness for aramid fibers it is preferable to use a dye selected from the viewpoint of dyeability and dyeing fastness for aramid fibers.
• an appropriate dye may be used for the other fibers.
• the other fiber is a polyester fiber, a disperse dye is used.
• the other fiber is cotton or rayon fiber, reactive dye or direct dye is used.
• the aramid fiber When the aramid fiber itself is dyed, the aramid fiber is put into a dyeing solution containing the dye, the temperature of the dyeing solution is increased to the dyeing temperature, and the dyeing temperature is maintained for a predetermined time.
• the dyeing temperature is adjusted depending on the kind and form of aramid fibers, the kind of dye used, and the dyeing concentration, but it may usually be a temperature of 80 ° C. to 150 ° C. Further, the temperature is preferably from 100 ° C. to 140 ° C., more preferably from 120 ° C. to 135 ° C. In the case of dyeing at a temperature exceeding 100 ° C., a high-temperature high-pressure dyeing machine is used.
• 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.
• the dyeing time is 10 minutes to 90 minutes. Within the range is preferable.
• the bath ratio for dyeing is not particularly limited, and may be in the range of 1: 5 to 1: 100, for example.
• the aramid fiber after dyeing is washed by a normal method. Further, reduction cleaning may be performed in the same manner as in the conventional dyeing process with disperse dyes.
• the following dyeing operation is subsequently performed on the aramid fibers subjected to the above pre-dying process.
• 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.
• solvent treatment step in the third embodiment performs the same operation as the solvent treatment step in the first embodiment or the second embodiment.
• a heat treatment step may be performed as necessary.
• operation similar to the heat treatment process in the said 2nd Embodiment is performed.
• the following effects can be achieved by performing the pre-staining step.
• the aramid fiber itself for example, by performing a pre-dyeing step with a disperse dye, a cationic dye or an acid dye, the fluff on the surface of the aramid fiber itself is more fully dyed, and the dyeing quality and dyeing density are further increased. improves.
• the aramid fiber is a mixed fiber with other chemical fiber or natural fiber
• the hue of the aramid fiber and the other fiber is obtained by performing a pre-dyeing step with a dye capable of dyeing these other fibers.
• the dyeing quality and dyeing density of the dyed product are further improved.
• an aramid fiber is treated with a vat dye and sulfide. It has a post-dyeing step of dyeing with a dye other than the dye.
• the dyeing operation 1 or the dyeing operation 3 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 aramid fibers can be obtained.
• 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.
• solvent treatment step in the fourth embodiment performs the same operation as the solvent treatment step in the first embodiment or the second embodiment.
• 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.
• 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.
• the aramid 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 3 unlike the pre-dying step of the third embodiment.
• the dyeing dye after performing a series of dyeing operation 1 or dyeing operation 3 and passing through a post-dyeing step, the dyeing dye has a practical dyeing density and has a fastness to dyeing. A dyed aramid fiber having good light fastness can be obtained.
• the following effects can be achieved by performing the post-dyeing step.
• the aramid fiber itself for example, by performing a post-dyeing step with a disperse dye, a cationic dye or an acid dye, the fluff on the surface of the aramid fiber itself is more fully dyed, and the dyeing quality and dyeing density are further increased. improves.
• the aramid fiber is a mixed fiber with other chemical fiber or natural fiber
• the hue between the aramid fiber and the other fiber is performed by performing a post-dyeing step with a dye capable of dyeing these other fibers. The dyeing quality and dyeing density of the dyed product are further improved.
• Example 1 N-methyl-2-pyrrolidone was used as a polar solvent, and a fabric made of aramid fibers (hereinafter referred to as “aramid fabric”) was dyed based on the second embodiment described above.
• aramid fabric a fabric made of aramid fibers
• para-based aramid fabric a twill woven fabric having a basis weight of 244 g / m 2
• para-copolymerization A twill woven fabric with a basis weight of 244 g / m 2 (hereinafter referred to as “para-copolymerized aramid fabric”) using 20-count double yarn of 100% by weight of aramid fiber for warp and weft, and 40-count double of 100% by weight of meta-aramid fiber.
• a twill fabric (hereinafter referred to as “meta-aramid fabric”) having a basis weight of 200 g / m 2 and using warp and weft yarns was used. These aramid fabrics were used after being desizing and scouring by a usual method.
• Dye application process was performed by a continuous method, and a vat dye was applied to each aramid fabric by pad-niping a dye solution containing the vat dye using a test mangle device.
• the pickup rates at this time were 61% by weight of para-aramid fabric, 58% by weight of para-copolymerized aramid fabric, and 67% by weight of meta-aramid fabric, respectively.
• vat dye 50 g / L of vat dye was dispersed in a non-reduced state, and Tamanori SA-25 (Arakawa Chemical Industries, Ltd .; hereinafter referred to as “Tamanori”) was used in combination as a migration inhibitor.
• the dye used was Mikethren Blue BC super-fine (Dyster Japan Co., Ltd. vat dye, CI Vat Blue 6).
• each aramid fabric after the dyeing solution was applied was dried at 105 ° C. for 5 minutes, and the vat dye was adhered to the fiber surface of each aramid fabric.
• Each aramid fabric after drying was put into the subsequent solvent treatment step (N-methyl-2-pyrrolidone treatment step) without washing or reducing washing.
• N-methyl-2-pyrrolidone treatment process As a polar solvent, N-methyl-2-pyrrolidone was used and treated as an aqueous solution having a concentration of 60% by weight.
• a test mangle device was used for applying the treatment liquid, and each aramid fabric after the dye application step was subjected to solvent treatment by a continuous method.
• the treatment temperature at this time was 20 ° C.
• the aramid fabric was immersed in the treatment solution for 1 second and immediately squeezed with mangle.
• the pickup rates at this time were 59% by weight of para-aramid fabric, 59% by weight of para-copolymerized aramid fabric, and 62% by weight of meta-aramid fabric, respectively.
• Heat treatment step A test baking box apparatus was used for the heat treatment, and each aramid fabric after the solvent treatment was subjected to a dry heat treatment at 105 ° C. for 5 minutes to attach the vat dye to each aramid fabric.
• Each aramid fabric after the heat treatment was dried after removing residual N-methyl-2-pyrrolidone by washing with water and washing with hot water.
• Comparative Example 1 In contrast to Example 1 described above, Comparative Example 1 was used in which each aramid fabric was subjected only to the dye application step and not subjected to the solvent treatment step and the heat treatment step. Specifically, dye application was performed under the same conditions as in Example 1 above, and reduction cleaning was performed on each aramid fabric after application of vat dye. This reduction cleaning was performed under the same conditions as in Example 1, and then washed with hot water and water and dried to obtain each aramid fabric of Comparative Example 1.
• Example 1 The dyed aramid fabrics of Example 1 and Comparative Example 1 dyed as described above were evaluated as follows.
• Total K / S value The surface dyeing concentration of each dyed aramid fabric was expressed as a total K / S value. The larger the total K / S value, the deeper the aramid fabric is dyed.
• the total K / S 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.
• K represents an extinction coefficient
• 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 formula for each aramid fabric.
• Lightness (L * value) The degree of dark color of each dyed aramid 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 aramid fabrics.
• 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 aramid fibers, was evaluated. The light fastness of an aramid fiber was evaluated as follows, since it was difficult to evaluate the yellowish browning of the fiber itself in addition to the dye discoloration caused by light irradiation. Each aramid fabric was irradiated with a blue scale grade 4 and the change was graded with a gray scale for fading. 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 grade 3-4. The evaluation results are shown in Table 1.
• each of the aramid fabrics has a practical dyeing density (total K / S value) and lightness (L * value). Have good light fastness. Furthermore, although not shown in Table 1, in the dyed aramid fabrics of Example 1, the properties of practical high-performance fibers are maintained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was. On the other hand, in Comparative Example 1, each of the aramid fabrics is inferior in dyeing density, lightness, and light fastness compared to Example 1, and in particular, the dyeing concentration, lightness, and light fastness of the meta-aramid fabric are insufficient. It was something.
• Example 2 N-methyl-2-pyrrolidone was used as a polar solvent, and an aramid fabric was dyed based on the second embodiment described above.
• a twill woven fabric having a basis weight of 160 g / m 2 (hereinafter referred to as “mixed spinning”) using 40-count double yarns in which 95% by weight of a meta-aramid fiber and 5% by weight of a para-copolymerized aramid fiber are used for warp and weft.
• Aramid fabric was used. This blended aramid fabric was used after being desizing and scouring by a usual method.
• Example 1 Dye provision process With respect to the above Example 1, the same operation as in Example 1 was performed except that the dye used was changed to the following sulfur dye. The pickup rate at this time was 80% by weight. In the dyeing solution, 50 g / L of a sulfur dye was dispersed in a non-reducing state, and tamanori was used in combination as a migration inhibitor.
• the sulfur dye used was Asathio Blue RC200 (sulfur dyes manufactured by Asahi Chemical Industry Co., Ltd., CI Sulfur Blue 7).
• Example 2 Drying was performed in the same manner as in Example 1 above, and the blended aramid fabric after the dyeing solution was applied was dried at 105 ° C. for 5 minutes, and the sulfur dye was adhered to the fiber surface of the blended aramid fabric.
• the dried blended aramid fabric was put into the subsequent solvent treatment step (N-methyl-2-pyrrolidone treatment step) without washing or reducing washing.
• Example 2 Solvent treatment process (N-methyl-2-pyrrolidone treatment process)
• Example 2 the same N-methyl-2-pyrrolidone as in Example 1 was used as the polar solvent, but the concentration was 100% by weight.
• a test mangle device was used for applying the treatment liquid, and the mixed aramid fabric after the dye application step was subjected to solvent treatment by a continuous method. The processing temperature at this time was 50 degreeC.
• the blended aramid fabric was dipped in the treatment solution for 1 second and immediately squeezed with mangle. The pickup rate at this time was 88% by weight.
• Heat treatment step Heat treatment is performed in the same manner as in Example 1 above, and using a test baking box apparatus, the mixed aramid fabric after the solvent treatment is subjected to a dry heat treatment at 105 ° C. for 5 minutes to attach the sulfur dye to the mixed aramid fabric. did.
• the heat-treated blended aramid fabric was prepared by removing the remaining N-methyl-2-pyrrolidone by washing with hot water and water, drying, and dyeing the blended aramid fabric of Example 2 in navy blue having a practical dyeing density. Obtained.
• Example 2 the blended aramid fabric was subjected only to the dye application step, and the solvent treatment step and the heat treatment step were not used as Comparative Example 2. Specifically, the dye application step was performed under the same conditions as in Example 2, and the blended aramid fabric after the sulfur dye was applied was washed with hot water, washed with water, dried, and dyed navy blue. A blend of aramid fabrics was obtained.
• Example 2 The dyed blended aramid 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.
• Example 2 a blended aramid fabric having a practical dyeing density (total K / S value) and lightness (L * value) could be obtained. Moreover, the blended aramid fabric of Example 2 has good light fastness. Further, although not shown in Table 2, in the dyed blended aramid fabric of Example 2, the properties of a practical high-performance fiber are maintained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was. On the other hand, in Comparative Example 2, the dyeing density and lightness are considerably inferior to those of Example 2, and the light fastness is low, so that practical dyeings are not obtained.
• Example 3 N-methyl-2-pyrrolidone was used as a polar solvent, and an aramid fabric was dyed based on the second embodiment described above.
• the same dyeing operation as in Example 1 was repeated a plurality of times for each dyed aramid fabric obtained in Example 1 above.
• the above-mentioned Example 1 was dyed once, and the dyeing operation combining the dye application step, the solvent treatment step and the heat treatment step was repeated for a total of 3 times, a total of 5 times and a total of 7 times of the dyeing operation. went. However, reduction cleaning was performed only after the final staining operation.
• Example 3 Each dyed aramid fabric of Example 3 dyed as described above was evaluated in the same manner as in Example 1.
• 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.
• Example 3 the dyeing concentration (total K / S value) is greatly improved as the number of dyeing operations increases, compared to Example 1 in which the dyeing operation is performed once.
• the lightness (L * value) was reduced to about 30 or less, and each aramid fabric of extremely dark color could be obtained.
• each of these extremely dark aramid fabrics has good light fastness.
• the properties of practical high-performance fibers are maintained without causing dyeing unevenness, dimensional changes, or significant deterioration in physical properties.
• Example 4 N-methyl-2-pyrrolidone was used as a polar solvent, and an aramid fabric was dyed based on the second embodiment described above.
• the same aramid fabric as in Example 1 above was subjected to a dyeing operation with a vat dye a plurality of times in the same manner as in Example 3.
• the vat dye used was Indanthren Brilliant Pink R (Dyster Japan Co., Ltd. vat dye, CI Vat Red 1).
• the same dyeing operation was performed once as a result of the dyeing operation combining the dye application step, the solvent treatment step, and the heat treatment step as in Example 1 above, and the same dyeing operation was repeated twice in total. A total of three staining operations were performed. However, reduction cleaning was performed only after the final staining operation.
• Example 4 Each dyed aramid fabric of Example 4 dyed as described above was evaluated in the same manner as in Example 1.
• Table 4 shows the evaluation results of the total K / S value for evaluating the staining density, the lightness (L * value) for evaluating the degree of dark color, and the light fastness.
• each aramid fabric As can be seen from Table 4, in each aramid fabric, as the number of dyeing operations is increased, the dyeing density (total K / S value) is greatly improved as compared to one dyeing operation, and dark aramid fabrics can be obtained. did it. However, the lightness (L * value) is greater than 38 due to the fact that 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. On the other hand, as shown in Table 4, each aramid fabric has good light fastness. Furthermore, although not shown in Table 4, the dyed aramid fabrics of Example 4 maintain the properties of practical high-performance fibers without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was.
• Example 5 N-methyl-2-pyrrolidone was used as a polar solvent, and an aramid fabric was dyed based on the above-described fourth embodiment (dyeing with vat dyes ⁇ post-dyeing with disperse dyes). In Example 5, a post-dyeing step with a disperse dye was then performed on each aramid fabric dyed with the vat dye obtained in Example 1 above.
• Post-dyeing step with disperse dye Dyeing is carried out by a dip dyeing method with disperse dye, and each aramid after dyeing vat dye obtained in Example 1 above using a high-temperature high-pressure dyeing tester mini color (manufactured by Tecsum Giken Co., Ltd.) The fabric was dyed without reducing washing.
• As the staining solution Dianix Blue FBL-E (Disperse dye manufactured by Dystar Japan Co., Ltd., CI Disperse Blue 56) 5% owf was used, and a pH 5 acetic acid / sodium acetate buffer was used in combination.
• the dyeing was performed at a high temperature and high pressure dyeing at a bath ratio of 1: 100 at 135 ° C. for 60 minutes.
• Each aramid fabric after dyeing was subjected to reduction cleaning in the same manner as dyeing with disperse dyes for ordinary polyester fibers.
• the reduction cleaning is performed under the condition of 1 g / L of sodium dithionite and 1 g / L of sodium hydroxide as a reducing agent at 80 ° C. for 1 minute, followed by hot water washing, water washing and drying.
• Each aramid fabric of Example 5 dyed in navy blue was obtained.
• each aramid fabric was only dyed with a disperse dye as Comparative Example 3. Specifically, only the disperse dye dyeing step similar to the above Example 5 was performed without performing any dyeing operation of the dye applying step, the solvent treatment step and the heat treatment step according to the present invention. Similarly, each of the aramid fabrics of Comparative Example 3 dyed in navy blue was obtained by performing reduction washing, hot water washing, water washing and drying.
• Comparative Example 4 >> Moreover, what carried out only the solvent processing process, the heat processing process, and the disperse dye dyeing process to each aramid fabric with respect to the said Example 5 was made into the comparative example 4. Specifically, after performing only the solvent treatment step and the heat treatment step without performing the dye application step for applying the vat dye, the same disperse dye dyeing step as in Example 5 is performed, and then the same as in Example 5. Each of the aramid fabrics of Comparative Example 4 was subjected to reduction washing, hot water washing, water washing and drying to obtain a navy blue dyeing.
• Example 5 The dyed aramid fabrics of Example 5, Comparative Example 3 and Comparative Example 4 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.
• Example 5 the dyeing density (total K / S value) is greatly improved in Example 5 dyed with disperse dyes as compared with Example 1 dyed with vat dyes alone, and the lightness. (L * value) was reduced to 30 or less, and each aramid fabric of extremely dark color could be obtained. As shown in Table 5, each of the extremely dark aramid fabrics has a light fastness that is even better than that of Example 1. Further, in each aramid fabric of Example 5, the fluff on the fabric surface was dyed in a very dark color with both the vat dye and the disperse dye, and the surface quality of the fabric was further improved. Further, although not shown in Table 5, in each dyed aramid fabric of Example 5, the properties of practical high-performance fibers are maintained without causing dyeing unevenness, dimensional change, or significant deterioration in physical properties. Was.
• Comparative Example 3 all the aramid fabrics are inferior in dyeing density and brightness as compared with Example 5. Further, each of these aramid fabrics was dyed only with a disperse dye, and the light fastness was insufficient as compared with Example 5 and Example 1. In Comparative Example 4, the dyeing density and lightness with the disperse dye are improved as compared with Comparative Example 3 due to the effect of the solvent treatment. However, each aramid fabric of Comparative Example 4 is inferior in dyeing density and lightness as compared with Example 5. In addition, each aramid fabric of Comparative Example 4 was dyed only with a disperse dye, and the light fastness was insufficient as compared with Example 5.
• Example 6 sulfuric acid was used as a polar solvent, and an aramid fabric was dyed based on the first embodiment described above. In this Example 6, the same blended aramid fabric as in Example 2 was used. This blended aramid fabric was used after being desizing and scouring by a usual method.
• Example 6 Dye application step In this Example 6, the same vat dye “Mikethren Blue BC super-fine” as in Example 1 or the same vat dye “Indanthren Brilliant Pink R” as in Example 4 was used. The operation in the dye application step was performed in the same manner as in Example 1. The pickup rate at this time was 80% by weight.
• the drying was performed in the same manner as in Example 1 above, and the blended aramid fabric after the dyeing solution was applied was dried at 105 ° C. for 5 minutes, and the vat dye was adhered to the fiber surface of the blended aramid fabric.
• the dried blended aramid fabric was put into the subsequent solvent treatment step (sulfuric acid treatment step) without washing or reducing washing.
• Solvent treatment process (sulfuric acid treatment process) The sulfuric acid treatment was carried out by a continuous method, and the mixed aramid fabric after the dye application step was subjected to sulfuric acid treatment using a test mangle device.
• concentration of the sulfuric acid aqueous solution used was 77% by weight, and the treatment temperature was 20 ° C. After dipping, the solution was squeezed with mangles to obtain a pick-up rate of 156% by weight, quickly washed with water, neutralized with an aqueous sodium carbonate solution and washed with water.
• the immersion time with the sulfuric acid aqueous solution was 30 seconds.
• the blended aramid fabric after the solvent treatment step was thoroughly washed with water and then dried.
• Comparative Example 5 For Example 6, the mixed aramid fabric was subjected to only the dye application step and was not subjected to sulfuric acid treatment, and Comparative Example 5 was obtained. Specifically, the dye application step was performed under the same conditions as in Example 1 above, and reduction washing was performed on the blended aramid fabric after application of the vat dye. This reduction washing was performed under the same conditions as in Example 1, and then washed with hot water and water and dried to obtain a blended aramid fabric of Comparative Example 5.
• Example 6 The dyed mixed aramid fabrics of Example 6 and Comparative Example 5 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.
• Example 6 a blended aramid fabric having a practical dyeing density (total K / S value) and lightness (L * value) in the vat dye “Blue BC” can be obtained. It was. On the other hand, the vat dye “Pink R” of Example 6 is a prescription for dyeing bright red as in Example 4 above, and the lightness (L * value) does not show a very small value. However, a blended aramid fabric having a practical dyeing density (total K / S value) is also obtained with the vat dye “Pink R”. Moreover, all the blended aramid fabrics of Example 6 have good light fastness.
• Example 7 sulfuric acid was used as a polar solvent, and an aramid fabric was dyed based on the first embodiment described above.
• the blended aramid fabrics dyed with the vat dye “Mikethren Blue BC super-fine” were compared with the above Example 6 and The same staining operation was repeated several times.
• the above Example 6 was used as one dyeing operation, and the dyeing operation combined with the dye application step and the solvent treatment step (sulfuric acid treatment step) was repeated three times in total, five times in total, and seven times in total. The operation was performed. However, reduction cleaning was performed only after the final staining operation.
• Example 7 The dyed blended aramid fabric of Example 7 dyed as described above was evaluated in the same manner as in Example 1 above.
• Table 7 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.
• Example 7 the staining density (total K / S value) is greatly improved and the lightness (L * ) is increased as the number of staining operations is increased in comparison with Example 6 in which one staining operation is performed . (Value) was reduced to 25 or less, and an extremely dark colored mixed aramid fabric could be obtained. As shown in Table 7, these extremely dark blended aramid fabrics have good light fastness. Furthermore, although not shown in Table 7, in the dyed blended aramid fabric of Example 7, the properties of practical high-performance fibers are maintained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was.
• Example 8 sulfuric acid was used as a polar solvent, and an aramid fabric was dyed based on the first embodiment described above. In Example 8, the same blended aramid fabric as in Example 6 was dyed with a sulfur dye. This blended aramid fabric was used after desizing and scouring in the same manner as in Example 6 above.
• Example 6 Drying was carried out in the same manner as in Example 6 above, and the blended aramid fabric after the dyeing solution was applied was dried at 105 ° C. for 5 minutes to adhere the sulfur dye to the fiber surface of the blended aramid fabric.
• the dried blended aramid fabric was put into the subsequent solvent treatment step (sulfuric acid treatment step) without washing or reducing washing.
• Example 8 Solvent treatment process (sulfuric acid treatment process)
• sulfuric acid treatment was performed on the blended aramid fabric after the dye application step in the same manner as in Example 6.
• the concentration of the sulfuric acid aqueous solution used was 77% by weight, the treatment temperature was 20 ° C., and the immersion time was 30 seconds.
• the pick-up rate at this time was 156% by weight, and was washed with water, neutralized and washed in the same manner as in Example 6 and dried to obtain a blended aramid fabric of Example 8 having a practical dyeing concentration.
• Comparative Example 6 was made by performing only the dye application step on the blended aramid fabric and not performing the sulfuric acid treatment. Specifically, the dye application step was performed under the same conditions as in Example 8 above, and the blended aramid fabric after the sulfurized dye was applied was washed with water and dried to obtain a blended aramid fabric of Comparative Example 6.
• Example 8 The dyed blended aramid fabrics of Example 8 and Comparative Example 6 dyed as described above were evaluated in the same manner as in Example 1 above. However, the brightness (L * value) is not measured. Table 8 shows the evaluation results of the total K / S value for evaluating the dyeing density and the light fastness.
• Example 8 a blended aramid fabric having a practical dyeing density (total K / S value) could be obtained. Moreover, all the blended aramid fabrics of Example 8 have good light fastness. Further, although not shown in Table 8, the dyed blended aramid fabric of Example 8 maintains the properties of practical high-performance fibers without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was. On the other hand, in Comparative Example 6, both the dyeing density and the light fastness are inferior compared to Example 8, and a practical dyed product cannot be obtained.
• Example 9 sulfuric acid was used as a polar solvent, and an aramid fabric was dyed based on the first embodiment described above.
• an aramid fiber mainly composed of para aramid fibers a twill weave having a basis weight of 144 g / m 2 (hereinafter referred to as “para System single yarn aramid fabric). This para-single yarn aramid fabric was used after being desizing and scouring by a usual method.
• Example 9 the operating conditions and dyes used in the dye application step and solvent treatment step (sulfuric acid treatment step) were the same as in Example 6 above. At this time, the pickup rate in the dye application step was 61% by weight, and the pickup rate in the solvent treatment step was 126% by weight. After the dyeing operation with the vat dye as described above, reduction washing was performed in the same manner as in Example 1 to obtain a para single yarn aramid fabric of Example 9 having a practical dyeing concentration.
• Comparative Example 7 >> In contrast to Example 9, the para single yarn aramid fabric was subjected to only the dye application step and was not subjected to sulfuric acid treatment, and Comparative Example 7 was obtained. Specifically, the dye application step was performed under the same conditions as in Example 9 above, and reduction washing was performed under the same conditions as in Example 1 on the para single yarn aramid fabric after application of vat dye. Thereafter, washing with hot water, washing with water and drying were performed to obtain a para single yarn aramid fabric of Comparative Example 7.
• Example 9 The dyed para single yarn aramid fabrics of Example 9 and Comparative Example 7 dyed as described above were evaluated in the same manner as in Example 1 above. However, the brightness (L * value) is not measured. Table 9 shows the evaluation results of the total K / S value for evaluating the dyeing density and the light fastness.
• Example 9 a para single yarn aramid fabric having a practical dyeing density (total K / S value) could be obtained. Moreover, all the para type
• Example 10 sulfuric acid was used as a polar solvent, and an aramid fabric was dyed based on the first embodiment described above.
• Example 10 among the dyed para single yarn aramid fabrics obtained in Example 9, the para single yarn aramid fabrics dyed with the vat dye “Mikethren Blue BC super-fine” were used.
• the same dyeing operation as in Example 9 was repeated several times. Specifically, the above Example 9 was used as a single dyeing operation, and the dyeing operation combined with the dye application step and the solvent treatment step (sulfuric acid treatment step) was repeated three times in total, five times in total, and seven times in total. The operation was performed. However, reduction cleaning was performed only after the final staining operation.
• Example 10 The dyed para single yarn aramid fabric of Example 10 dyed as described above was evaluated in the same manner as in Example 1 above. However, the brightness (L * value) is not measured. Table 10 shows the total K / S value for evaluating the dyeing concentration and the evaluation results of light fastness.
• Example 10 As can be seen from Table 10, in Example 10, as the number of dyeing operations increases, the dyeing density (total K / S value) is greatly improved as compared to Example 9 in which one dyeing operation is performed. A woven fabric could be obtained. These extremely dark para single yarn aramid fabrics, as shown in Table 10, have good light fastness. Further, although not shown in Table 10, in the dyed para single yarn aramid fabric of Example 10, practical high-performance fibers without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. The nature was maintained.
• Example 11 sulfuric acid was used as a polar solvent, and an aramid fabric was dyed based on the above-described fourth embodiment. In Example 11, the same blended aramid fabric as in Example 6 was used. This blended aramid fabric was used after being desizing and scouring by a usual method.
• Example 11 Dye-applying step In Example 11, the above-mentioned dye was used except that 60 g / L of Mikethren Grey M super-fine (Dyster Japan Co., Ltd. vat dye, CI Vat Black 8) was used. The same operation as in Example 1 was performed. The pickup rate at this time was 80% by weight.
• the drying was performed in the same manner as in Example 1 above, and the blended aramid fabric after the dyeing solution was applied was dried at 105 ° C. for 5 minutes, and the vat dye was adhered to the fiber surface of the blended aramid fabric.
• the dried blended aramid fabric was put into the subsequent solvent treatment step (sulfuric acid treatment step) without washing or reducing washing.
• Post-dyeing process with disperse dye Dyeing is carried out by a dip dyeing method with disperse dye, and high-temperature high-pressure dyeing tester mini color (manufactured by Tecsum Giken Co., Ltd.) is used to dry the blended aramid fabric after sulfuric acid treatment as described above. Stained. Kaylon Polyester Navy Blue NB-E (Nippon Kayaku Co., Ltd. disperse dye, CI No. unknown) 10% owf was used as the staining solution, and a pH 5 acetic acid / sodium acetate buffer was used in combination.
• Dyeing was performed at a high temperature and high pressure dyeing at a bath ratio of 1: 100 at 130 ° C. for 60 minutes.
• the blended aramid fabric after dyeing was subjected to reduction cleaning in the same manner as dyeing with disperse dyes for ordinary polyester fibers.
• the reduction washing was performed under the same conditions as in the post-dyeing step of Example 5 above, followed by washing with hot water and water and drying to obtain a blended aramid fabric of Example 11 dyed in extremely dark black. .
• Comparative Example 8 was obtained by performing only the dyeing process with the disperse dye on the unstained blended aramid fabric with respect to Example 11 described above. In Comparative Example 8, the conditions in the dyeing step with the disperse dye were the same as in Example 11 above.
• Comparative Example 9 was obtained by performing only the solvent treatment step (sulfuric acid treatment step) and the dyeing step with the disperse dye with respect to Example 11 described above. That is, in Comparative Example 9, a blended aramid fabric subjected to sulfuric acid treatment was dyed only with a disperse dye. In Comparative Example 9, the conditions for sulfuric acid treatment and dyeing with a disperse dye were the same as in Example 11 above.
• Example 11 The dyed blended aramid fabrics of Example 11, Comparative Example 8, and Comparative Example 9 dyed as described above were evaluated in the same manner as in Example 1 above. However, the brightness (L * value) is not measured. Table 11 shows the evaluation results of the total K / S value for evaluating the dyeing density and the light fastness.
• Example 11 the dyeing density (total K / S value) was greatly improved, and an extremely dark colored mixed aramid fabric could be obtained. Moreover, the blended aramid fabric of Example 11 has good light fastness. Further, in the blended aramid fabric of Example 11, the fluff on the fabric surface was dyed in an extremely dark color with both the vat dye and the disperse dye, and the surface quality of the fabric was further improved. Furthermore, although not shown in Table 11, in the dyed blended aramid fabric of Example 11, the properties of a practical high-performance fiber are maintained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was.
• Comparative Example 8 the dyeing density is inferior to that in Example 11, and the light fastness is remarkably inferior, so that a practical dyed product cannot be obtained.
• Comparative Example 9 a sufficient dyeing density is obtained, but since the dyeing is carried out only with a disperse dye, the light fastness is remarkably inferior, and a practical dyed product cannot be obtained.
• Example 12 In Example 12, benzyl alcohol was used as a polar solvent, and an aramid fabric was dyed based on the first embodiment described above. In Example 12, the same para-aramid fabric as in Example 1 was used. This para-aramid fabric was used after desizing and scouring by a usual method.
• Example 12 Dye provision process
• the following vat dye was provided by the same operation as Example 1 described above.
• the pickup rate at this time was 58% by weight.
• 50 g / L of the same vat dye “Mikethren Grey M super-fine” as in Example 11 is dispersed in a non-reducing state, and GERMADYE AM-X (manufactured by RAON CHEMICAL) is used as a migration inhibitor. 10 g / L was used in combination.
• Drying was performed by drying the para-aramid fabric after the dyeing solution was applied in the same process as in Example 1 above at 110 ° C. for 2 minutes to attach the vat dye to the fiber surface of the para-aramid fabric.
• the para-aramid fabric after drying was put into the subsequent solvent treatment step (benzyl alcohol treatment step) without washing or reducing washing.
• Example 12 Solvent treatment process (benzyl alcohol treatment process)
• benzyl alcohol 99.5% product
• Example 12 Solvent treatment process
• benzyl alcohol 99.5% product
• the treatment temperature at this time was 20 ° C.
• the para-aramid 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.
• Example 12 the heat treatment after the solvent treatment was not performed, and the para-aramid fabric after the solvent treatment step was washed with hot water and water to remove residual benzyl alcohol, and then subjected to reduction washing. This reduction cleaning was performed in the same manner as in Example 1 above. Thereafter, washing with hot water, washing with water and drying were performed to obtain a para-aramid fabric of Example 12 dyed in black having a practical dyeing concentration.
• Example 12 The dyed para-aramid fabric of Example 12 dyed as described above was evaluated in the same manner as in Example 1 above.
• Table 12 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.
• Example 12 the para-aramid fabric has a practical dyeing density (total K / S value) and lightness (L * value), and good light fastness. have. Further, although not shown in Table 12, in the dyed para-aramid fabric of Example 12, the properties of practical high-performance fibers can be obtained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was maintained.
• Example 13 In Example 13, benzyl alcohol was used as a polar solvent, and an aramid fabric was dyed based on the first embodiment described above. In Example 13, the same dyeing operation as in Example 12 was repeated a plurality of times on the dyed para-aramid fabric obtained in Example 12 above. Specifically, the above Example 12 was used as one dyeing operation, and the dyeing operation in which the dye application step and the solvent treatment step were further combined was repeated for a total of two times, a total of three times, and a total of four times of dyeing operations. However, reduction cleaning was performed only after the final staining operation.
• Example 13 The dyed para-aramid fabric of Example 13 dyed as described above was evaluated in the same manner as in Example 1 above.
• Table 13 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.
• Example 13 in Para-aramid fabric, in Example 13, as the number of dyeing operations increased, the dyeing density (total K / S value) greatly improved compared to Example 12 in which the dyeing operation was performed once. Further, the lightness (L * value) was reduced to 30 or less, and an extremely dark para-aramid fabric could be obtained. As shown in Table 13, this extremely dark para-aramid fabric has good light fastness. Further, although not shown in Table 13, in the dyed para-aramid fabric of Example 13, the properties of practical high-performance fibers can be obtained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. Was maintained.
• Example 14 >> In Example 14, four types of polar solvents, triethylene glycol, formic acid, DL-lactic acid and oxalic acid were used as polar solvents, respectively, and aramid fabrics were dyed based on the second embodiment described above. In Example 14, the same para-aramid fabric as in Example 1 was used. This para-aramid fabric was used after desizing and scouring by a usual method.
• Example 14 Dye application step In Example 14, the same operation as in Example 12 was carried out using the vat dye “Mikethren Gray M super-fine” in the same manner as in Example 12. The pickup rate at this time was 58% by weight. For drying, the same operation as in Example 12 was performed. The para-aramid fabric after drying was directly put into each subsequent solvent treatment step without washing or reducing washing.
• Example 14 Solvent treatment step In Example 14, triethylene glycol (95% product), formic acid (98% product) and DL-lactic acid (85% product) were all used without dilution. On the other hand, oxalic acid (dihydrate) was dissolved in water and used as a 10 wt% aqueous solution. For the application of the treatment liquid, a test mangle device was used, and the para-aramid fabric after the dye application step was subjected to solvent treatment by a continuous method. The treatment temperature at this time was 20 ° C. for all. In the treatment, the para-aramid 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 75% by weight of triethylene glycol, 71% by weight of formic acid, 81% by weight of DL-lactic acid, and 75% by weight of an oxalic acid aqueous solution, respectively.
• Heat treatment step A test baking box apparatus was used for the heat treatment, and the vat dye was attached to the para-aramid fabric by subjecting the para-aramid fabric after each solvent treatment to a dry heat treatment at 110 ° C. for 2 minutes.
• the para-aramid fabric after the heat treatment was dried after removing polar solvents remaining by hot water washing and water washing.
• Example 14 The dyed para-aramid fabric of Example 14 dyed as described above was evaluated in the same manner as in Example 1.
• Table 14 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.
• Example 14 the para-aramid fabric has a practical dyeing density (total K / S value) and lightness (L * value) in any of the four polar solvents. In addition, it has good light fastness. Furthermore, although not shown in Table 14, in the dyed para-aramid fabric of Example 14, the properties of practical high-performance fibers can be obtained without causing dyeing unevenness, dimensional change, or significant deterioration in physical properties. Was maintained.
• Example 15 In Example 15, five polar solvents, benzyl alcohol, triethylene glycol, formic acid, DL-lactic acid, and oxalic acid were used as polar solvents, respectively.
• the aramid fabric was dyed on the basis of dyeing with a dye.
• the pre-dying process was first performed with the disperse dye with respect to the para aramid fabric similar to the said Example 1.
• the dyeing was carried out at a high bath temperature ratio of 1:20 at a temperature of 135 ° C. for 60 minutes.
• the para-aramid fabric after dyeing was subjected to reduction washing in the same manner as dyeing with disperse dyes for ordinary polyester fibers.
• sodium dithionite 5 g / L as a reducing agent and sodium hydroxide 5 g / L were used in combination for 1 minute at 80 ° C.
• the reduction cleaning was repeated twice. Thereafter, washing with hot water, washing with water and drying were performed to obtain a para-aramid woven fabric pre-dyed with a disperse dye.
• the para-aramid fabric that has been pre-stained is polarized with benzyl alcohol, triethylene glycol, formic acid, DL-lactic acid, or oxalic acid in the same manner as in Example 12 or Example 14, respectively.
• the para-aramid fabric of Example 15 dyed to an extremely dark black was obtained by performing a dyeing operation used as a solvent and reduction washing.
• Example 15 The dyed para-aramid fabric of Example 15 dyed as described above was evaluated in the same manner as in Example 1 above.
• Table 15 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.
• Example 15 in which pre-dyeing with a disperse dye was made in comparison with Example 12 (see Table 12) or Example 14 (see Table 14) dyed only with vat dyes.
• the dyeing density total K / S value
• the lightness L * value
• this extremely dark para-aramid fabric has very good light fastness.
• the fluff on the fabric surface was dyed in an extremely dark color with both the vat dye and the disperse dye, and the surface quality of the fabric was further improved.
• the properties of practical high-performance fibers can be obtained without causing uneven dyeing, dimensional changes, or significant deterioration in physical properties. was maintained.
• Example 16 DL-lactic acid was used as a polar solvent, and an aramid fabric was dyed based on the above-described third embodiment (pre-dying with a cationic dye ⁇ dying with a vat dye).
• a pre-dyeing process was performed with a cationic dye on the same para-aramid fabric as in Example 1 above.
• the para-aramid fabric after this pre-dying step was dyed with vat dye and DL-lactic acid as in Example 14 above.
• Pre-dyeing step with cationic dye The undyed para-aramid fabric was desized and scoured in the usual manner, and dyed with a cationic dye. Dyeing was performed by the dip dyeing method, and para-aramid fabrics were dyed using a high-temperature high-pressure dyeing tester mini color (manufactured by Tecsum Giken Co., Ltd.) For the staining solution, Kayacryl Navy RP-ED (cationic dye manufactured by Nippon Kayaku Co., Ltd., CI No. unknown) 5.0% owf was used in combination with sodium nitrate 25 g / L and a commercially available carrier. A pH 5 acetic acid / sodium acetate buffer was used.
• the dyeing was carried out at a high bath temperature ratio of 1:20 at a temperature of 135 ° C. for 60 minutes.
• the para-aramid fabric after dyeing was washed with hot water and washed with water and dried to obtain a para-aramid fabric pre-dyed with a cationic dye.
• Example 12 the pre-dyed para-aramid fabric was dyed in the same manner as in Example 12 using the same vat dye “Mikethren Blue BC super-fine” 50 g / L as in Example 1 above.
• An application step was performed.
• the pickup rate at this time was 58% by weight.
• the para-aramid fabric after the dye application step was subjected to a solvent treatment step using DL-lactic acid as a polar solvent, a heat treatment step and a reduction washing in the same manner as in Example 14 to obtain an extremely dark color.
• a para-aramid fabric of Example 16 dyed in navy blue was obtained.
• Comparative Example 10 a para-aramid fabric which was only dyed with a cationic dye was used as Comparative Example 10. Specifically, the dyeing step, the solvent treatment step, and the heat treatment step according to the present invention were all performed without performing any dyeing operation, and the same dyeing step with the cationic dye as in Example 16 was performed.
• the para-aramid fabric of Comparative Example 10 dyed in navy blue was obtained by carrying out reduction washing, hot water washing, and water washing in the same manner as above.
• Example 16 The dyed para-aramid fabrics of Example 16 and Comparative Example 10 dyed as described above were evaluated in the same manner as in Example 1 above.
• Table 16 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.
• Example 16 dyed with a cationic dye and a vat dye, the dyeing density (total K / S value) was higher than that of Comparative Example 10 dyed with only a cationic dye, and the brightness was also high. (L * value) decreased to 30 or less, and an extremely dark para-aramid fabric could be obtained.
• the light fastness of Comparative Example 10 dyed with only the cationic dye is remarkably weak, whereas in Example 16 dyed with the vat dye in addition to the cationic dye, a large improvement in light fastness is observed. .
• the fluff on the fabric surface was dyed in a very dark color with both the cationic dye and the vat dye, and the surface quality of the fabric was further improved.
• Table 16 in the dyed para-aramid fabric of Example 16, the properties of practical high-performance fibers can be obtained without causing dyeing unevenness, dimensional change, or significant deterioration in physical properties. was maintained.
• the present invention can be applied to any of para-aramid fibers, para-copolymerized aramid fibers, and meta-aramid fibers.
• the fiber 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 aramid fiber after dyeing. Further, since a vat dye or sulfur dye having good dyeing fastness, particularly light fastness, is used, the dyeing fastness, especially light fastness, of the dyed aramid fiber is improved.
• para-aramid fiber or para-copolymerized aramid fiber which has been considered difficult so far, can be dyed in an extremely dark color such as black or navy blue (for example, L * value is 30 or less). it can.
• a pre- and post-process of the method for dyeing aramid fibers according to the present invention by performing a pre-dyeing step or a post-dyeing step with dyes other than vat dyes and sulfur dyes, fluff on the surface of the aramid fibers themselves is sufficiently dyed. The dyeing quality is improved and the dyeing density is further improved.
• the aramid fiber is a mixed fiber with other chemical fiber or natural fiber, by performing these dyeing steps, the hue of the aramid fiber and the other fiber can be unified, and the dyed product Dyeing quality and dyeing density are further improved.
• a method for dyeing aramid fibers and a dyed aramid fiber having good dyeing fastness, particularly light fastness, abundant hue, and practical dyeing density can be provided. This is effective for the development of new uses for aramid fibers.
• the solvent treatment process is performed after the dye application process, but the present invention is not limited to this, and the dye application process may be performed after the solvent treatment process.
• the aramid fabric is dried after the dye solution containing a vat dye or sulfur dye is applied to the aramid fabric, but the present invention is not limited to this. You may make it throw in a solvent treatment process, without drying a textile fabric.
• a lot of navy blue or black is used except for some vivid hues. However, these embodiments show that dark colors or extremely dark colors can be dyed. .
• the aramid fibers to which the vat dye or sulfur dye was added in the dye application step were put into the solvent treatment step that continued without washing.
• the vat dye or sulfur dye after the dye application step adheres to the aramid fiber with a certain degree of affinity. Therefore, the aramid fiber after the dye application step may be washed and then introduced into the solvent treatment step.
• Example 14 and 15 DL-lactic acid mixed with optical isomers was used as the polar solvent.
• the present invention is not limited to this, and D-lactic acid or L-lactic acid should be used. May be.
• Example 11 and Example 15 no carrier or deep dyeing agent is used for dyeing the disperse dye.
• pre-dying or post-dying is merely auxiliary dyeing, and it is not necessary to use a carrier or the like.
• various carriers used in normal aramid dyeing may be used in combination, and the dye may be further colored.
• the aramid fabric is dyed.
• the present invention is not limited to this, and may be a knitted fabric, a non-woven fabric or the like, or may be a yarn, cotton or the like.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Coloring (AREA)

Priority Applications (8)

Applications Claiming Priority (4)

Publications (1)

Family

ID=46931364

Family Applications (1)

Country Status (9)

Cited By (5)

Families Citing this family (8)

Citations (8)

Family Cites Families (9)

• 2012
  • 2012-03-29 WO PCT/JP2012/058390 patent/WO2012133662A1/ja active Application Filing
  • 2012-03-29 US US14/007,819 patent/US20140020190A1/en not_active Abandoned
  • 2012-03-29 CN CN201280016988.XA patent/CN103459710B/zh active Active
  • 2012-03-29 JP JP2013507727A patent/JP5938396B2/ja active Active
  • 2012-03-29 EP EP12763059.8A patent/EP2692942A4/en not_active Withdrawn
  • 2012-03-29 KR KR1020137028615A patent/KR20140037833A/ko active IP Right Grant
  • 2012-03-29 MX MX2013011267A patent/MX2013011267A/es unknown
  • 2012-03-29 BR BR112013025123A patent/BR112013025123A2/pt not_active IP Right Cessation
  • 2012-03-29 CA CA2830147A patent/CA2830147A1/en not_active Abandoned

Patent Citations (8)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events