JP2000234279A - Dyeing of polyamide-based fibrous structure and dyed material thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for dyeing a polyamide-based fibrous structure excellent in color fastness to washing and level dyeing properties with a reactive dye and to obtain a dyed material thereof. SOLUTION: This method comprises (1) increasing dye liquor temperature conditions from room temperature, suppressing the fixing ratio at a point of time of 40 deg.C to 0-20%, further increasing the dye liquor temperature conditions, suppressing the fixing ratio to 0-30% after the passage of 15 min from the point of time of 40 deg.C and carrying out dyeing, (2) increasing the dye liquor temperature conditions from room temperature and regulating the average fixing ratio for 15 min from the point of time of 40 deg.C to 0.01-1.3%/min and regulating the average fixing ratio for 30 min from the point of time of 40 deg.C to 0.01-2%/min and further (3) regulating the pH to 6-9 when charging the dye into the dye liquor, passing the dye liquor to the acidic side according to the passage of time/increase in temperature and controlling the minimal pH to 2-6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dyeing method which is excellent in wet fastness for washing and in level dyeing for preventing dye spots, etc. when dyeing a polyamide fiber structure with a reactive dye by an exhaustion method. And a dyed product thereof.

[0002]

2. Description of the Related Art Polyamide-based fiber structures are conventionally dyed with a leveling acid dye, a milling acid dye, and a metal complex dye, and are subjected to a fix treatment to improve wet fastness. However, even when dyed in this manner, there are some of which have insufficient wet fastness, and the metal complex salt dye having the highest wet fastness has a dark hue,
There was a problem that clear colors could not be expressed. Furthermore, milling acid dyes and metal complex dyes which are excellent in wet fastness have a high affinity for polyamide, and have a problem that the dye exhaustion rate in the initial stage of dyeing is large, and thus the leveling property is poor.

[0003] Therefore, when dyeing a polyamide-based fiber structure with an acid dye, not only the use of a leveling agent to improve the leveling property, but also the use of a pH sliding agent, etc. In other words, there is a method of dyeing while suppressing the dyeing, that is, a method of setting the pH at the initial stage of the dyeing to an alkali to near neutrality and setting the pH to an acidic side in the latter half of the dyeing to obtain a sufficient exhaustion.
Specifically, for example, a method is known in which the material is slid to an acidic side as the dyeing temperature increases. However, although this method is effective for leveling acid dyes with high water solubility,
Milling acid dyes and metal complex dyes, which have high hydrophobicity and good washing fastness, have a high affinity for polyamide fibers, and therefore have a problem in that the pH dependence of the exhaustion rate is small and the effect is limited. . Therefore, it is difficult to obtain a dyed material having good fastness and excellent levelness, and at present, it is more appropriate to use different dyes according to the intended use.

Furthermore, various modified polyamide-based fiber structures have been developed in response to the demand for functionality, but these tend to have insufficient fastness even by a conventional dyeing method using a milling acid dye or a metal complex dye. And further improvement in the robustness has been desired.

On the other hand, in Japanese Patent Application Laid-Open No. 7-97777,
A method of dyeing a polyamide-based fiber structure in the vicinity of acidity to neutrality using a fiber-reactive reactive dye is disclosed.
It is known that the wet fastness of a dyed product with a reactive dye is good. However, since the migration of the dye is poor, there is a problem that many irregularities such as dye spots are likely to occur, and the leveling property is further inferior to the above-mentioned milling acidic dyes and metal complex dyes.

As a method for dyeing a polyamide with a reactive dye, Japanese Patent Application Laid-Open Nos.
As disclosed in JP-A-209549 and the like, a method has been proposed in which the pH of the dyeing liquor is initially acidic, and finally the pH is shifted from neutral to weakly alkaline. These methods utilize the property that the reaction of the reactive dye proceeds as the pH of the dye liquor increases, and is intended to react after exhausting the dye. However, these methods also have a problem of poor levelness.

As described above, wet fastness and levelness are inconsistent properties, and it has been considered difficult to achieve both.

[0008]

SUMMARY OF THE INVENTION In view of the background of the prior art, an object of the present invention is to provide a method for dyeing a polyamide-based fiber structure excellent in washing fastness and levelness, and a dyed product thereof. is there. The term “leveling property” as used herein particularly refers to preventing dyeing or the like.

[0009]

The present invention employs the following means in order to solve the above problems. That is, the method of dyeing a polyamide-based fiber structure of the present invention, when dyeing a polyamide-based fiber structure with a reactive dye,
When the temperature of the dyeing liquor is raised from room temperature, the fixing rate at the time when the temperature reaches 40 ° C. is suppressed to 0 to 20%, and the temperature is continuously raised and the time at 40 ° C. is set to 0 minute. 0 minutes after 15 minutes
The dyeing is characterized in that the dyeing is performed by controlling the temperature of the dyeing solution from room temperature to room temperature when dyeing the polyamide fiber structure with a reactive dye. Starting, the average fixing speed in 15 minutes from the time when the temperature reaches 40 ° C. is 0.01 to 1.3% / minute, and the average fixing speed in 30 minutes from the time when the temperature reaches 40 ° C. is 0.1%. In addition, when dyeing the polyamide-based fiber structure with a reactive dye, the pH at the time of dye injection is set to 6 to 9, and the time elapse and / or Alternatively, slide to the acidic side as the temperature of the dyeing liquor rises.
It is characterized in that it is controlled to 2 to 6. Also,
The dyed product of the present invention is obtained by the method for dyeing a polyamide-based fiber structure.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is directed to the above-mentioned problems, that is, a method for dyeing a polyamide-based fiber structure excellent in washing fastness and levelness. When the fixing rate of the reactive dye in the specific area was controlled to a specific range, the fixing rate was controlled to a specific range, and the pH of the dyeing liquor was controlled, surprisingly, this problem was all at once. It is determined that the problem is solved.

The polyamide-based fiber structure of the present invention is a fiber structure mainly composed of polyamide. In addition, a synthetic polymer such as polyester, acrylic, and polyurethane may be used.
Natural fibers such as wool, silk, and cellulose may be included. The polyamide is a fiber made of a synthetic polymer having an amide bond, such as nylon 4, nylon 6, and nylon 66, and is not particularly limited. Further, the fibrous structure is not particularly limited as long as the structure is made of yarn, woven fabric, knitted fabric, nonwoven fabric, artificial leather, or the like.

In the dyeing method of the present invention, when the polyamide fiber structure is treated under the following conditions, the exhaustion rate of the reactive dye is 1 to 50%, preferably 1.5 to 40%, and more preferably. When a polyamide fiber structure having a high initial exhaustion of a dye of 2 to 30% is used, the effect of the reaction dye is greatly improved in terms of the fastness to the dyeing method using an acid dye. This is a preferred mode in that the leveling effect on dyeing used is high.

Dye: Cibacron Blue FN
-R (manufactured by Ciba Specialty Chemicals Co., Ltd.) or a dye having the same exhaustion property as the dyeing Dyeing conditions Dye concentration 1% owf (based on the weight of the material to be dyed) Dyeing bath pH 5 (acetic acid / sodium acetate buffer system) Ratio 1:40 Temperature 40 ° C. Processing time 5 minutes Even when the method of the present invention is applied to a polyamide fiber having an exhaustion rate of less than 1%, the leveling property is improved, but a remarkable improvement effect is obtained as compared with the conventional method. Difficult to get. On the other hand, if it exceeds 50%, it will be difficult to obtain sufficient levelness even when the method of the present invention is employed.

Here, the exhaustion rate is determined by treating the fiber structure of interest with the above-mentioned dyeing solution for 5 minutes, appropriately diluting the absorbance (Abs.) At the maximum absorption wavelength of the dye in the remaining solution, and spectrophotometrically. It can be easily obtained by the following formula. Y in the formula indicates the exhaustion rate.

Y (%) = 100 × (Abs ₁ −Abs ₂ ) / Abs _{1 In the} formula, Abs ₁ : Abs. Abs ₂ : Abs. The polyamide-based fiber structure preferably employed in the present invention has a difference (M) between the exhaustion rate (X%) and the fixation rate (Y%) obtained by the above treatment within the following formula range. .

1 ≦ M ≦ Y × 2 Here, even when M is less than 1, the leveling property is improved by adopting the present invention, but it is difficult to obtain practically sufficient leveling property. Become. Even in the case of exceeding Y × 2, the leveling property is improved by adopting the present invention, but M is preferably Y × 2 or less as a range where the effect of the present invention appears more remarkably.

The fixation rate in the present invention is a rate of the dye remaining after dyeing the polyamide fiber structure with a reactive dye, washing the dye, and finally leaving the dye, and can be determined by the following equation. The abbreviations in the following formula are as follows. here,
X: (%) = Y × (K / S after washing) / (K / S before washing)
S) The cleaning method mentioned here is performed under the following conditions, but the surfactant is not particularly limited as long as it has a similar cleaning effect. The washing conditions and the soaping treatment preferably applied after the actual dyeing are preferably the same.

Washing liquid Sodium carbonate 2 g / L Gran Up INA-5 (manufactured by Sanyo Chemical Co., Ltd.) 2 g / L Treatment conditions 80 ° C. × 20 minutes Bath ratio 1:70 Further, polyamide fiber structure to which the present invention is preferably adopted The product contains a modified polyamide fiber. Modified polyamide and structural difference, polymer blend, copolymerization, low orientation, low crystallinity, ultra-fine, such as functionality, visual novelty, etc., such as thin fibers that are not uniformly drawn, Polymer-modified fibers such as polymer blends, polymer alloys, and copolymers, and ultrafine polyamides of 0.1 d or less are used. The form containing these modified polyamides is not particularly limited, and mixed fibers with ordinary regular polyamides, mixed weaves, mixed knits, bimetal-type or core-sheath composite yarns, nonwoven fabrics and the like are used.

As a more preferred polyamide-based fiber structure, a polyamide-based fiber having a structural difference in the fiber longitudinal direction, polyvinylpyrrolidone, is used in an amount of 3 to 15 to polyamide.
3% by weight or more of 60% by weight or more of at least one copolymer component with respect to the polyamide-based fiber containing the polyamide-based fiber.
What is comprised by the copolyamide fiber etc. copolymerized by less than weight% is used.

These fiber structures are made of nylon 6 or 66.
Compared to a regular polyamide obtained from a homopolymer such as the above and obtained by uniform stretching, blemishes are more likely to occur, but the present invention is a preferable target because the leveling property is greatly improved.

The polyamide-based fiber having a structural difference in the fiber longitudinal direction is a polyamide-based fiber structure having at least one selected from those having a thick and thin morphology and those having a change in crystallinity. Can be. Here, the term “thick and thin form” means that the cross-sectional area changes in the fiber longitudinal direction, and the cross-sectional area ratio of the thick part to the thin part (cross-sectional area ratio of the thick part / cross-sectional area ratio of the detail) is preferably 1 0.2 to 5, more preferably 1.5 to 3 fibers. In addition, the one in which the degree of crystallinity changes in the longitudinal direction of the fiber means that the difference between the high crystallinity part and the low crystallinity part is preferably 0.5% or more, more preferably 1.0% or more. Say.

The term "copolymerized polyamide fiber" refers to a polyamide fiber in which at least one or more copolymer components are copolymerized in an amount of 3% by weight or more and less than 60% by weight with respect to the main component polyamide. It is. Here, the polyamide as the main component refers to the largest component among the two or three or more polyamide components. The polyamide as the main component is preferably nylon 6 or nylon 66 from the viewpoint of robustness. When the amount of the copolymer component is less than 3%, there is a tendency that the difference from the conventional dyeing method is not remarkably exhibited.
In the dyeing method of the present invention, the copolymer component is preferably from 3% to 60%, more preferably from 5% to 50%,
Particularly preferred is a dyeing method useful for 7% or more and 35% or less of copolyamide fibers.

The copolymerization component is not particularly limited as long as it is a different monomer copolymerizable with the main component polyamide. For example, in the case of a polyamide fiber containing nylon 66 as a main component, nylon 4,
Monomers such as nylon 6, nylon 610, nylon 12, nylon 6I (hexamethylenediamine and isophthalic acid), and nylon 6T (hexamethylenediamine and terephthalic acid) are used. Among them, the monomer of nylon 6 (ε-caprolactam) Is preferable because it has excellent yarn-making stability and hardly causes defects in dyeing. For example, nylon 6
In the case of a polyamide-based fiber having as a main component, a monomer such as nylon 4, nylon 66, nylon 610, nylon 12, nylon 6I, or nylon 6T is used as a copolymer component. A condensate composed of a diamine and adipic acid) is preferred because it has excellent spinning stability and hardly causes defects in dyeing.

The reactive dye used in the present invention generally refers to a dye having a reactive group having a covalent bond to a hydroxyl group or an amino group. For example, a monochlorotriazine group (X = Cl, Y = substituent), a monofluorotriazine group (X = F, Y = substituent), a carboxypyridiniotriazine group (X = formula [II]) represented by the formula [I] , Y = substituent),
Formula [III] such as a dichlorotriazine group (X = Y = Cl)
A dye having one or more reactive groups such as a vinylsulfone group and a sulfatoethylsulfone group represented by formula (IV), a fluorochloropyrimidine group and a trichloropyrimidine group represented by formula [IV], and a bromoacrylamide group represented by formula [V]. But,
The present invention is not limited to this, and a reactive group described in, for example, "Explanation Dye Chemistry" (Shishensha) can be employed.

The dye is not particularly limited as long as it has one or more of these reactive groups. For example, the same kind of multifunctional group type reaction having two or more monochlorotriazine groups of the formula [I] in the molecule. It may be a dye or a heteropolyfunctional reactive dye containing a monochlorotriazine group or monofluorotriazine group of the formula [I] and a sulfatoethylsulfone group of the formula [III] in the same molecule. For example, in the formula [I], Y may include the formula [III].

[0026]

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[0027]

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[0028]

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(In the formula [III], Z represents —CH ＝ CH
₂ or —CH ₂ CH ₂ Z ¹ , where Z ¹ is —OS
It represents a leaving group such as O ₃ H, —OCOCH ₃ , —OPO ₃ H ₂ , and —Cl. )

[0030]

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(In the formula [IV], X _{1 to} X ₃ represent Cl or F.)

[0032]

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Although any of the reactive dyes can provide a good dyed fabric by the method of the present invention, the reactive groups of the sulfatoethylsulfone group represented by the formula [III] are protected by a protecting group. In order to obtain a sufficient amount of fixation with a dye having only these reactive groups in the present invention, it is necessary to remove the protective group and activate the reactive group. The deprotection conditions for this type of dye are different for each dye, and the dyeing method of the present invention can be employed if the dye is appropriately selected. However, in general, it is often necessary to add an alkali in order to completely remove these protecting groups,
In such a case, an alkali treatment before and / or during and / or after the dyeing is required to secure sufficient dyeing properties.

From this viewpoint, in the present invention, simplicity,
Monochlorotriazine group, monofluorotriazine group, carboxypyridiniotriazine group, excellent in reproducibility,
Dichlorotriazine group, fluorochloropyrimidine group,
It is preferable to use a reactive dye having at least one selected from a trichloropyrimidine group and a bromoacrylamide group. Further, more preferably a reactive dye having one or more of a bromoacrylamide group, a monochlorotriazine group, a monofluorotriazine group, a carboxypyridiniotriazine group, and a fluorochloropyrimidine group,
Sufficient dyeing property can be secured, and the washing fastness can be further improved. As long as it has one or more of these reactive groups, the other reactive groups may be of a different functional group type, for example, from a vinyl sulfone group or a sulfatoethyl sulfone group.

Examples of the dye having these reactive groups include Sumix dye (manufactured by Sumitomo Chemical Co., Ltd.) and Sumi dye.
fix Supra dye (Sumitomo Chemical Co., Ltd.), Rem
azol dye (manufactured by Dystar Co., Ltd.), Celmazo
1 dye (manufactured by Mitsui BASF Dye Co., Ltd.), Levafix
Dye (manufactured by Dystar Co., Ltd.), Procion dye (manufactured by Mitsui BASF Dye Co., Ltd.), Cibacron dye (manufactured by Ciba Specialty Chemicals Co., Ltd.), Basile
n dye (Mitsui BASF Dye Co., Ltd.), Drimare
ne dye (manufactured by Clariant Co., Ltd.), Drymalan
Dyes (manufactured by Clariant Co., Ltd.), Realan dyes (manufactured by Dystar Co., Ltd.), Lanasol dyes (manufactured by Ciba Specialty Chemicals Co., Ltd.), Kayacion dyes (manufactured by Nippon Kayaku Co., Ltd.), Mikacation dyes (Nippon Kayaku ( And Kayaceron React dyes (manufactured by Nippon Kayaku Co., Ltd.).

Among them, Sumix Supra dyes (manufactured by Sumitomo Chemical Co., Ltd.) having a monochlorotriazine group and a vinyl sulfone group (or a reactive group forming a vinyl sulfone group), a monochlorotriazine group, a monofluorotriazine group or a monofluorotriazine group Cibacron dye having fluorotriazine group and vinyl sulfone group (or reactive group forming vinyl sulfone group) (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lanasol dye having bromoacrylamide group (manufactured by Ciba Specialty Chemicals Co., Ltd.), monochloro Procion dye having a triazine group (Mitsui BASF Dye Co., Ltd.)
Kayacio having a monochlorotriazine group
n dye (manufactured by Nippon Kayaku Co., Ltd.), Kayaceron React dye having carboxypyridiniotriazine group (manufactured by Nippon Kayaku Co., Ltd.), monochlorotriazine group or monochlorotriazine group and vinyl sulfone group (or vinyl sulfone group) Basi with reactive group to form)
len dye (manufactured by Mitsui BASF), Drimalan F dye having a fluorochloropyrimidine group (manufactured by Clariant), Drimarene K and R dye having a fluorochloropyrimidine group (manufactured by Clariant), fluorochloropyrimidine Dye (manufactured by Dystar Co., Ltd.) having a group and a vinylsulfone group (or a reactive group forming a vinylsulfone group), Levafix EA or EN dye having a fluorochloropyrimidine group or a monofluorotriazine group (Dystar) And Remazol RU-N and SN dyes having a monochlorotriazine group and a vinylsulfone group (or a reactive group forming a vinylsulfone group) (manufactured by Dystar Co., Ltd.) can be preferably used.

In the present invention, when dyeing a polyamide-based fiber structure with a reactive dye, not particularly the exhaustion rate,
The present invention is characterized by focusing on the sticking rate defined in the present invention. That is, even if attention is paid to the exhaustion rate and the exhaustion rate as in the conventional dyeing method, it is not possible to obtain sufficient levelness when dyeing with a reactive dye. Even if the exhaustion rate is the same, the fixation rate referred to here depends on the type of dye and the dyeing conditions. Therefore, the fixation rate cannot be directly determined from the exhaustion rate. It is difficult to obtain levelness. Conversely, even if the exhaustion rate is high, a dye excellent in leveling property can be provided within the fixing rate range of the present invention.

Specifically, as the temperature conditions of the dyeing liquor, the temperature was raised from room temperature, and when the temperature reached 40 ° C., the fixation rate was 0%.
-20%, preferably 0-15%, more preferably 1
-10%, the temperature was further increased, and the fixing rate after 15 minutes when the time at 40 ° C. was set to 0 minute was 0-30%,
Preferably, the dyeing is suppressed to 5 to 30%. Further, the dyeing is preferably carried out with the fixation rate after 30 minutes when the time point at 40 ° C. is set to 0 minutes being suppressed to 1 to 50%, more preferably 5 to 50%. If the fixation rate exceeds 20% when the temperature rises to 40 ° C., or exceeds 30% after 15 minutes when the time at 40 ° C. is set to 0 minute, unevenness such as dye spots or the like may occur. More likely to occur. Similarly, not so much after 15 minutes,
Even if it exceeds 50% after 30 minutes, the frequency of occurrence of unevenness such as spots is high. In addition, when the time at 40 ° C. is set to 0 minute, 3
When the fixation rate after 0 minutes is less than 1%, a very long dyeing time is required to obtain a sufficient fixation amount, which causes a problem of cost increase or a sufficient fixation amount cannot be obtained. Sometimes there are problems. Here, the charging temperature of the dye is not particularly limited, and the dyeing can be performed at room temperature to about 40 ° C.

The sticking rate mentioned here can be determined as follows according to the above-mentioned measuring method. Here, the absorbance (Abs) is appropriately diluted and measured.

X ₀ (%) = (KS ₂ / KS ₁ ) × Y _Xt (%) = (KS ₃ / KS ₂ ) × X _{0 In the} formula, X ₀ : final fixation rate after completion of dyeing (%) X _t: fixed rate after dyeing start t minutes (%) Y: the final exhaustion rate after staining completion (%) KS _1: after staining, washing prior to K / S values KS _2: after staining, K after cleaning / S value KS ₃ : K / S value after washing the fabric t minutes after the start of dyeing Y (%) = 100 × (Abs ₁ −Abs ₂ ) / Abs _{1 In the} formula, Abs ₁ : dye solution before dyeing Abs. Abs ₂ : Abs. Of the stain after staining. In the present invention, when dyeing a polyamide-based fiber structure with a reactive dye, the temperature of the dyeing solution after dye introduction is 40 ° C.
The average fixing rate for 15 minutes from the time when the temperature reached
It is controlled at 1 to 1.3% / min, preferably 0.05 to 1.0% / min, and the average fixing speed for 30 minutes from the time when the temperature reaches 40 ° C is 0.01 to 2% / min. , Preferably 0.0
5 to 1.5% / min, more preferably 0.1 to 1.2%
/ Minute at a controlled rate. If the average fixation rate for 15 minutes from the time when the temperature reaches 40 ° C. is less than 0.01%, a very long dyeing time is required to obtain a sufficient fixation amount, which may cause a problem of cost increase. However, there is a problem that a sufficient amount of fixation may not be obtained. Further, when the average fixing speed for 30 minutes after the temperature reaches 40 ° C. exceeds 2% / min, unevenness such as spots tends to occur.

The method of such fixing control is not particularly limited, but the exhaustion fixing speed differs under the same conditions depending on the fabric and the dye used. Therefore, it is necessary to collect data such as the exhaustion rate and the fixing rate during the dyeing time. There is. Therefore, it is necessary to perform a preliminary check with a laboratory dyeing machine, change various staining conditions so as to fall within the scope of the present invention, adjust the fixation rate, and set an optimal staining method. As a control method, for example, a method of adding an acid or an alkali while constantly monitoring the dyeing liquor during dyeing, or a method of controlling the temperature, a method of adding the dye in the first step without adding all the dyes, and the like may be used. However, from the viewpoint of simplicity, a method is preferred in which the pH of the dyeing liquor is initially set at around neutrality by initially charging all the dyes, and then gradually slid to acidic to control. According to these methods, the fixation of the reactive dye proceeds sufficiently even under acidic conditions, and the larger the dye exhaustion amount, the larger the amount of fixation. Since it does not have the same affinity as gold dyes, it is easy to control the rate of exhaustion fixation by controlling pH and temperature, and leveling properties can be greatly improved. Further, it was also found that it is difficult to improve the levelness by transfer dyeing because fixation proceeds sequentially after exhaustion, and that the effect of improvement by slow dyeing is high. Accordingly, the polyamide-based fiber structure of the present invention is dyed with a reactive dye, and the pH of the dyeing liquor is gradually slid from near neutral to acidic at the start to achieve both leveling property by slow dyeing and wet fastness. Can be.

In the present invention, a reactive dye is used to improve wet fastness, and in order to compensate for the uneven dyeing, the pH of the dye bath at the start of dyeing is neutralized, and the time and / or
Alternatively, the pH of the dye bath is shifted to the acidic side as the temperature rises. The method of shifting is not particularly limited, and for example, a method of adding acetic acid, formic acid or the like during dyeing, a method of previously adding a pH sliding agent that shifts to an acidic side, and the like can be used. In terms of simplicity and reproducibility,
A method of adding a pH sliding agent is preferred. Such pH
The sliding agent is not particularly limited as long as it is a compound that generates an acid depending on temperature and / or time, and for example, ammonium sulfate or the like can be used. Other commercially available products (for example, Meisan PC, PM, LM, etc. (manufactured by Meisei Chemical Co., Ltd.)) can also be used.
In the method of adding acid during the dyeing, there is often a problem in reproducibility. Therefore, a method of adding a pH sliding agent in advance and sliding the pH is preferable.

In the present invention, the pH at the time of dye introduction, that is, at the start of dyeing, is adjusted to 6 to 9, preferably 6 to 8, more preferably 7 to 8, and the pH is adjusted to the most acidic side of the liquor. The slide is adjusted to a pH of 2 to 6, preferably 3 to 5.5. If the pH at the beginning of dyeing is less than 6, sufficient levelness cannot be obtained, and the most acidic pH
Is more than 6, it is not possible to obtain a sufficient amount of fixation, especially in dark colors. Conversely, when the pH at the start of staining exceeds 9, in order to obtain a sufficient amount of fixation, an acid is added later to adjust the pH.
Must be greatly reduced, which is not preferable in terms of reproducibility. On the other hand, if the pH at the most acidic side is less than 2, excessive dyeing may cause problems such as deterioration in fastness and strength, which is not preferable. The setting of the pH is affected by the target fiber structure and the dye used, and the higher the combination of the dye exhaustion rate, the higher the initial pH. Further, the lower the final dye fixation rate, the lower the pH on the most acidic side is preferable. In order to attain a sufficient leveling property and fixing property at the same time, the difference between the lowest pH point and the highest pH point during dyeing is preferably 0.5 to 7, more preferably 1 to 5, particularly preferably 1.5 to 5. It is better to control to ~ 4.

In the present invention, by controlling the temperature together with the pH slide, the leveling property is more effectively improved. The pH slide can finally obtain a sufficient fixation while suppressing the rapid exhaustion in the early stage of dyeing, and the temperature control can suppress the speed. In the present invention, the heating rate is preferably 0.1 ° C./min to 3 ° C./min.
Min, more preferably from 0.5 ° C / min to 2 ° C, particularly preferably from 0.5 ° C / min to 1.5 ° C / min, and preferably from 80 to 120 ° C. However, if the heating rate is reduced, the dyeing time becomes longer, which leads to an increase in cost.
It is preferable that the temperature is raised to 80 ° C. to 120 ° C. at a temperature raising rate higher than the above temperature raising rate, and that the dyeing treatment is performed at that temperature for 10 to 80 minutes. If the rate of temperature rise is less than 0.1 ° C./min, the dyeing time will be long and there will be a problem in terms of cost. If it exceeds 3 ° C./min, the leveling properties will be poor. Further, when the temperature is 50 ° C. or higher, the temperature can be raised at a speed higher than the initial temperature rising speed in order to shorten the dyeing time. The temperature for raising the heating rate is 50 ° C to 80 ° C
Is preferred. Even if the speed is increased below 50 ° C., the effect of improving the leveling property is small, and if the speed is increased after exceeding 80 ° C., the cost reduction effect is small. The time at which the rate of temperature rise is increased is determined by the exhaustion rate of the dye.
%, Preferably 20-80%, more preferably 40-80%
It is preferable to increase the heating rate at the time of 80%.

In the present invention, it is preferable to further add a leveling agent to the dyeing liquor. As such a leveling agent, a conventionally known fiber affinity leveling agent and / or dye affinity leveling agent can be used. For example, various substances such as anionic surfactants, cationic surfactants, nonionic surfactants, surfactants such as amphoteric surfactants, and inorganic salts such as sodium sulfate may be used. In the staining method of the present invention,
Surfactants having an affinity for dyes are preferred, surfactants containing tertiary and / or quaternized nitrogen atoms in the molecular structure are particularly preferred, and amphoteric surfactants containing anionic groups are more preferred. It is preferably used. A dyed product using such a leveling agent is preferable in terms of improvement in fastness of the dyed product and leveling property. In addition to the amphoteric surfactant, an anionic surfactant, a nonionic surfactant, a cationic surfactant, an inorganic salt and the like can be used in combination. As such amphoteric surfactants, amino acid type, betaine type and the like can be used, and in the present invention, amino acid type and / or analog type thereof, that is, surface active agent such as carboxylic acid of alkylamine and / or half ester compound thereof, etc. Activators are more preferably used. For example, a maleic acid or phthalic acid half ester compound of an alkoxy fatty acid amine can be used.

Further, additives such as an antifoaming agent, a light fastness improver and a wet fastness improver may be added to the dyeing liquor, or various fastness improvers and functional chemicals may be post-processed after dyeing. it can.

In the present invention, after dyeing with a reactive dye, it is possible to perform a fix treatment using tannic acid or the like as in the case of dyeing with an acid dye, but in order to further improve the fastness, It is preferable to perform a soaping process for removing unfixed dyes.

The soaping treatment in the present invention means a washing treatment for removing unfixed dyes or dyes which are dyed with a weak bonding force and are easily detached after dyeing. This is different from the fix treatment in which the dye dyed in is enclosed in the fiber. Such a soaping treatment is preferably performed at pH 6 to 13, more preferably at pH 8 to 12, particularly preferably at pH 10 to 12.
In this case, the unfixed dye can be removed more and the fastness is improved. When the pH is lower than 6, the wet fastness is reduced, and when the pH is higher than 13, discoloration occurs, which is not preferable. It is preferable to appropriately add a conventionally known surfactant or the like to the cleaning solution adjusted by the above pH in order to improve the cleaning effect. The surfactant is not particularly limited, and for example, an anionic surfactant, a nonionic surfactant, or a combination thereof can be used.

The dyed product of the present invention is a dyed product of a polyamide fiber structure dyed by the dyeing method of the present invention, and is a dyed product having good fastness and excellent levelness with no uneven dyeing. is there. Accordingly, it can be suitably used in various fields requiring robustness such as clothing and sports.

[0050]

The present invention will be described in detail with reference to the following examples.

In the Examples and Comparative Examples, the following fabric I was used, the average fixing speed under each dyeing condition was measured, and the washing fastness of the obtained dyed fabric and the dyeing unevenness of the entire fabric were visually evaluated (視). : A counter-level, ：: A counter-level, Δ: B counter-level, ×: C counter-level).
The washing fastness was determined according to JIS L-0844 A-2 method, and contamination was determined with 9 fibers.

The used fabric and the method of measuring the exhaustion rate and the fixation rate are shown below. Table 1 shows the exhaustion rate and the fixation rate of the fabrics I and II under the following exhaustion rate measurement conditions.

Fabric I: 110 denier 24 of nylon 6
1. filament, cross-sectional area difference (cross-sectional area difference between thick part and detail)
Plain woven fabric composed of multifilaments No. 1 Fabric II: 110-denier 24-filament regular yarn of nylon 6 (initial exhaustion rate measurement) Dyeing conditions Cibacron Blue FN-R 1% owf (manufactured by Ciba Specialty Chemicals Co., Ltd.) Dyeing solution pH 5 (Acetic acid / sodium acetate buffer) Bath ratio 1:20 Dye temperature 40 ° C Washing condition Gran-up INA-5 (manufactured by Sanyo Chemical Co., Ltd.) 2g / L Sodium carbonate 2g / L Washing liquid temperature 80 ° C Bath ratio 1:70 Processing time 20 minutes (Measurement method) Exhaust rate measurement: Spectrophotometer U-3400 (manufactured by Hitachi, Ltd.) used Y (%): Exhaust rate Y (%) = (Abs ₁ −Abs ₂ ) / Abs ₁ × 100 where Abs ₁ : Abs. Abs ₂ : Abs. Fixing rate measurement: using a spectrophotometer CM-3700d (manufactured by Minolta Co., Ltd.) X (%): Fixing rate X (%) = (KS ₂ / KS ₁ ) × Y In the formula, KS ₁ : K before washing / S KS ₂ : K / S after washing

[0054]

[Table 1]

Example 1 Dyeing and post-treatment were carried out under the following conditions, and the evaluation results are shown in Table 2 and FIGS. (Dyeing conditions) Monofluorotriazine + vinyl sulfone type reactive dye Cibacron Blue FN-R 1% owf (manufactured by Ciba Specialty Chemicals Co., Ltd.) Albegal B 2% owf (manufactured by Ciba Specialty Chemicals Co., Ltd.) pH 6.4 Minimum pH of the dye liquor 4.2 Maysan PC (manufactured by Meisei Chemical Co., Ltd.) 1 g / L + acetic acid bath ratio 1:20 Temperature of dye liquor Room temperature → 1 ° C./min Heating → 90 ° C. for 40 minutes Treatment (Post-treatment conditions) Gran-up INA-5 (manufactured by Sanyo Chemical Co., Ltd.) 2 g / L sodium carbonate 2 g / L Treatment temperature 80 ° C. Treatment time 20 minutes Example 2 The temperature rising rate was as described in Example 1 The same staining and post-treatment were performed, and the evaluation results are shown in Table 2 and FIG. 2 (b).

Dyeing liquid temperature condition: room temperature → 0.5 ° C./min heating →
60 ° C. → 1 ° C./min temperature rise → treatment at 90 ° C. for 40 minutes Example 3 Dyeing pH was set to the following conditions, dyeing and post-treatment were performed as in Example 2, and the evaluation results are shown in Table 2 and FIG. 2 (c). Indicated.

Dyeing liquor pH 7.6 at the time of dye introduction The minimum pH of the liquor 5.1 Meisan PC (manufactured by Meisei Chemical Co., Ltd.) 1 g / L Comparative Example 1 The pH of the dyeing was as follows, and Dyeing and post-treatment were performed in the same manner as in Example 1, and the evaluation results are shown in Table 2 and FIG. 1 (d).

PH 3.9: acetic acid / sodium acetate buffer Comparative Example 2 The pH of the dyeing was set as follows, and thereafter the dyeing and post-treatment were performed in the same manner as in Example 1, and the evaluation results were shown in Table 2 and FIG. It was shown to.

PH 5.1: acetic acid / sodium acetate buffer Comparative Example 3 The pH of the dyeing was set as follows, and the dyeing and post-treatment were carried out in the same manner as in Example 1, and the evaluation results were shown in Table 2 and FIG. It was shown to.

Dyeing liquor pH 4 at the time of dye introduction Maximum pH of the dying liquor 6.3 (adjusted with Kaya Slide 509 (manufactured by Nippon Kayaku Co., Ltd.) 1 g / L and acetic acid) Note that FIG. 1 and FIG. Are Example 1 and Comparative Example 1
3 is a graph showing the fixation rates of Examples 1 to 3;
3 is a graph showing a fixation ratio of No. 3; The abscissa in the figure shows the lapse of the staining time, and the time when the staining solution reached 40 ° C. is shown as 0 minute. The vertical axis shows the change in the fixation rate over the course of the dyeing time, and the net rectangles at 15 minutes and 30 minutes indicate the range of the present invention.

[0061]

[Table 2]

From these results, it was found that in Examples 1 to 3, the leveling property was improved and compatibility with the washing fastness was able to be measured as compared with Comparative Examples 1 to 3.

[0063]

According to the present invention, a polyamide fiber structure having good washing fastness and excellent levelness can be provided.

[Brief description of the drawings]

FIG. 1 is a graph showing the fixation ratio of Example 1 and Comparative Examples 1 to 3,

FIG. 2 is a graph showing sticking rates of Examples 1 to 3.

Claims (10)

[Claims] When a polyamide fiber structure is dyed with a reactive dye, the temperature condition of the dyeing liquor is increased from room temperature to a fixing rate of 0 to 20% when the temperature reaches 40 ° C. A method for dyeing a polyamide-based fiber structure, wherein the dyeing is further suppressed to 0 to 30% after 15 minutes when the temperature at 40 ° C. is set to 0 minute by continuing the temperature increase and dyeing. . 2. The method according to claim 1, wherein the dyeing is suppressed so that the fixing rate after 30 minutes is 1 to 50% when the temperature is further increased and the time at 40 ° C. is set to 0 minute. Item 6. A method for dyeing a polyamide fiber structure according to Item 1. 3. In the case of dyeing a polyamide-based fiber structure with a reactive dye, the temperature condition of the dyeing liquor is started from room temperature, and the average fixing speed in 15 minutes from the time when the temperature reaches 40 ° C. is 0. 0.01 to 1.3% / min, and the average fixing speed in 30 minutes from the time when the temperature reached 40 ° C. is 0.01 to 1.3%.
A method for dyeing a polyamide-based fiber structure, wherein the rate is 2% / minute. 4. When dyeing a polyamide-based fiber structure with a reactive dye, the pH at the time of dye injection is adjusted to 6 to 9, and the dye is slid to the acidic side with the lapse of time and / or the temperature of the dye liquor rises. PH 2-6 when most acidic
A method for dyeing a polyamide-based fiber structure, characterized in that: 5. The dyeing method according to claim 4, wherein the difference between the pH at the time of adding the dye and the pH at the most acidic side of the dye liquor is controlled in the range of 0.5 to 7. For dyeing polyamide-based fiber structures. 6. The process according to claim 1, wherein a polyamide fiber structure having an exhaustion rate of the reactive dye of 1 to 50% when treated under the following conditions is used. A method for dyeing a polyamide-based fiber structure. Dye: Cibacron Blue FN-R (manufactured by Ciba Specialty Chemicals Co., Ltd.) or a dye having the same exhaustion property Dyeing conditions Dye concentration 1% owf (based on weight of dyed material) Dye bath pH 5 (acetic acid / acetic acid) Sodium buffer system) Bath ratio 1:40 Dye bath temperature 40 ° C Processing time 5 minutes 7. The difference between the exhaustion rate (X%) and the fixation rate (Y%) of the reactive dye when treated under the following conditions (M: M = XY).
The method for dyeing a polyamide-based fiber structure according to any one of claims 1 to 6, wherein a polyamide-based fiber structure having a range of the following formula is used. 1 ≦ M ≦ Y × 2 Dye: Cibacron Blue FN-R (manufactured by Ciba Specialty Chemicals Co., Ltd.) or a dye having an exhaustion property equivalent thereto Dyeing conditions Dye concentration 1% owf (based on weight of dyed material) Dyeing Bath pH 5 (acetic acid / sodium acetate buffer system) Bath ratio 1:40 Dye bath temperature 40 ° C Treatment time 5 minutes 8. The method according to claim 1, wherein said reactive dye has at least one of a bromoacrylamide group, a monochlorotriazine group, a monofluorotriazine group, a carboxypyridiniotriazine group and a fluorochloropyrimidine group. The method for dyeing a polyamide fiber structure according to any one of the above. 9. A method for dyeing a polyamide-based fiber structure according to claim 1, wherein a soaping treatment is carried out with a washing solution having a pH of 6 to 13 after the dyeing. 10. A dyed article obtained by the method for dyeing a polyamide fiber structure according to any one of claims 1 to 9.