JP4510650B2 - Method for deep color treatment of fiber fabric - Google Patents

Description

  The present invention relates to a deep color treatment method (in-bath treatment method, in-bath treatment method) for improving the color developability of a dyed fiber fabric and enhancing deep colorability and sharpness. More specifically, the present invention relates to a deep color processing method for performing deep color processing by coating a fiber product made of synthetic fiber or wool fiber and dyed in dark color such as black with a resin compound having a low refractive index. More specifically, the present invention relates to a treatment method in which these dyed fabrics are excellent in deep color properties, processing unevenness in the deep color treatment is less likely to occur, and a dyed fiber fabric having higher reproducibility is obtained.

  Conventionally, in the synthetic fiber and the natural fiber, a clear and deep fiber has been studied. In order to improve the deep color property of the fiber fabric, various kinds of modifications such as modification of the fiber surface or modification of the inside of the fiber can be performed. A method has been proposed. Especially in the field where dark colors such as black formal and school uniform determine the product value, it is regarded as a big issue. For example, polyester fibers that are synthetic fibers and wool fibers that are natural fibers have a drawback of lack of dyeability. Insufficient dyeability and darkness have been a major problem.

As measures for improvement, the dyed fiber fabric has a compound having a low refractive index, such as a fluorine-based treatment agent (for example, Patent Document 1 below), a silicone-based treatment agent (for example, Patent Document 2 below), and a urethane-based treatment. There is a method of coating the fiber surface with an agent (for example, Patent Document 3 below). Many of these processing methods are performed by the pad-cure method, but the pad-cure method relies only on the limited partial coating of the fiber surface, and is not necessarily sufficient in terms of the level of deep color and its durability. It ’s hard to say that it ’s at a certain level. Further, there are problems such as adhesion unevenness due to unevenness of aperture due to mangle in the pad method, and occurrence of ending. Further, there is a problem that the level of friction fastness is particularly low in terms of dye fastness.
JP 57-17275 A JP-A-64-45466 JP 57-29682 A

  In addition, in the bath treatment method called the exhaustion method which has been conventionally performed, there is a drawback that it is difficult to stably apply the deep color agent and unevenness is likely to occur. This is because the deep coloring agent is abruptly adsorbed to the fiber, and processing unevenness is likely to occur. Also, when the emulsion is broken, there is a problem of contaminating the can of a processing apparatus such as a fiber fabric or a dyeing machine. is there. On the other hand, a method of stabilizing the emulsion has also been carried out, but in this case, there remains a problem that exhaustion is inferior and deep color level is low.

  Further, although the level of deep color is improved by these means, there has been a problem that, due to the improvement of deep color, there is a tendency that a decrease in deep chromaticity due to dry cleaning or washing, or a decrease in dye fastness is likely to occur.

On the other hand, many methods for improving dyeability by surface modification of fibers have been proposed. There is a method in which fine irregularities are formed on the fiber surface to prevent irregular reflection of light on the fiber surface and aim at deep coloration. For example, in Patent Document 4 below, fine particles having a particle diameter of 0.1 μm or less are 0.5 There are a method in which polyester fibers containing 10% by weight are alkali-treated to form fine irregularities on the fiber surface, and a method in which fine irregularities are formed by plasma etching on the fiber surface (for example, the following patent documents) 5 and 6).
Japanese Patent Publication No.59-24233 JP 59-11709 A Japanese Examined Patent Publication No. 60-37225

Furthermore, there is a method in which a fiber product is previously treated with a compound having a low refractive index and then subjected to low-temperature plasma treatment (for example, Patent Document 7 below). By forming fine irregularities on the fiber surface by these methods, deep coloration is also improved. Especially when a compound having a low refractive index is coated on the surface, the deep color is considerably improved. For example, if the fabrics are rubbed together and the fabrics are entangled during washing, the deep color effect is extremely low, and it is not necessarily at a sufficient level in terms of durability of the deep color. In terms of fastness to dyeing, there was a problem that the level of fastness to friction was particularly low.
JP-A-61-97490

  As described above, the method of imparting a color deepening agent to the surface of the fiber fabric is indispensable for deepening the color of polyester fiber, wool fiber, etc., and a greater deepening effect has been continuously demanded.

  Here, when using the deep curing agent such as the above-mentioned fluorine-based treatment agent, silicone-based treatment agent, urethane-based treatment agent, etc., when processing by the pad cure method, one of the factors that the color deepening effect is insufficient is In such a treatment method, since the main component of the deep colorant is present only on the surface of the fiber fabric, the interface between the fiber fabric and the processing agent is easy to peel off, or the same compound is applied to the surface of the fiber fabric. This is thought to be due to the fact that it was only partially covered.

  Also, the conventional method called exhaustion in the bath is a treatment in the bath under a limited pH condition, so it is difficult to control the adsorption speed of the deep color agent, and it is difficult to provide it stably. , It has the disadvantage of easily generating unevenness. This is because rapid formulation of the deep colorant to the fiber is likely to occur, and processing prescriptions under conditions where processing irregularities are likely to occur, conversely, processing under stable pH conditions. The prescription does not provide a sufficient deep color effect. Further, when the emulsion is broken, there is a problem of contaminating can bodies such as fiber fabrics and processing apparatuses.

  The present invention improves the problem of conventional deep color processing technology means, the processing stability in deep color processing, especially the stability and durability of the deep color effect at a high level of deep color, to a level where there is no practical problem. An object of the present invention is to provide a finished fiber fabric.

  In the present invention, when a dyed fiber fabric is subjected to deep color processing using a treatment liquid containing a deep color agent, the deep color agent is exhausted by a treatment method in bath (immersion treatment in bath). In the process, the dyed fabric excellent in deep color is only provided by gradually changing with time from the low pH state, that is, the stable state of the emulsion, to the high pH state, that is, the unstable state of the emulsion. In addition, even for thin fabrics that are difficult to obtain a good deep-colored fabric with a general padding method, such as synthetic filament taffeta fabric, there is no processing unevenness and deep color processing with excellent deep color and fastness. The cloth is provided with good reproducibility.

  In addition, exhaustion treatment can easily change the solubility and emulsification of the contained compounds by changing the environmental conditions of the treatment bath. In particular, it can be applied to the fiber fabric. In other words, the conditions that allow the deepest possible amount of the deep colorant to be contained in the treatment bath are used at the beginning of the treatment process, and the conditions change so that the deep colorant is less likely to be present in the treatment bath as late as possible. Let As an example of such a method, in the latter stage of the treatment process, the pH is raised from the initial stage to reduce the solubility or emulsification property of the component containing the deep colorant in the treatment bath, and into the fiber fabric. A method for promoting the transition of Furthermore, if the pH fluctuation is performed slowly, the deep colorant remaining in the treatment liquid can be stably applied to the surface of the fiber fabric, and the fiber fabric can be efficiently and completely covered with the deep colorant. it can.

  When performing deep color processing of a fiber fabric using a treatment liquid containing a deep color agent, the deep color agent is exhausted by a treatment method in a bath (immersion method in a bath). According to the method for deepening the color of the fiber fabric of the present invention, characterized in that the pH is gradually changed with time, the effect of deepening the color can be greatly improved, and processing unevenness in the color deepening is less likely to occur. Thus, a dyed fiber fabric having higher reproducibility and good fastness can be obtained.

That is, in the method for deepening the color of the fiber fabric of the present invention, a dyed fiber fabric after dyeing and processing obtained by dyeing a fiber fabric containing at least one of polyester fiber and wool fiber , Impregnation of the dyed fiber fabric by immersing it in a treatment bath containing a treatment liquid containing a deep color agent, exhausting the deep color agent and performing deep color processing, when increasing the bathochromic and clarity, the pH value of the processing solution in the bathochromic machining start time in the range of 3-5, subsequently, treated by slowly adding an alkali agent progresses bathochromic working fluid p The H value is gradually increased, and the dyed fiber fabric is taken out when the pH value of the treatment liquid is in the range of 6 to 9 .

  The present invention is a treatment method in which a surfactant and / or a solvent is used in combination as a penetrant for improving the penetrability of the deep colorant-containing component in the treatment bath into the fabric and improving the processability.

  As the fiber fabric in the present invention, filaments, spun yarns, woven fabrics, knitted fabrics, non-woven fabrics, etc. made of at least one of synthetic fibers, semi-synthetic fibers, regenerated fibers and natural fibers can be used. Synthetic fibers such as polyester, nylon, acrylic, and aramid fibers, semi-synthetic fibers are cellulose-based semi-synthetic fibers such as acetate (triacetate), and regenerated fibers are cellulose-based regenerated fibers (viscose rayon), cupra Examples of natural fibers such as (copper ammonia rayon) include various fibers such as cotton, wool fibers, silk, and hemp.

  Among these, polyester fibers and wool fibers, which are fibers that are required to have a deep color effect, are the most important for practical use, and it is more effective to use a fiber fabric containing these fibers. The fiber fabric containing polyester fiber or wool fiber includes natural fibers such as cotton, semi-synthetic fibers such as acetate, regenerated fibers such as rayon, synthetic fibers such as nylon, etc. Examples include those obtained by blending or twisting, knitting, knitting, etc. of at least one of them and polyester fiber or wool fiber.

  In the present invention, a dyed polyester fiber fabric or wool fiber fabric is particularly the center of the object. Here, the dyed polyester fiber fabric refers to one dyed using a dye for polyester, and the dyeing method may be any of dip dyeing, thermosol, and textile printing. These fibers may be subjected to surface change processing such as raising. Further, the dyed wool fiber fabric refers to one dyed using a wool dye, and the dyeing method may be any of dyeing, dip dyeing, and printing. These fibers may be subjected to surface change processing such as raising.

  In the present invention, the dyed fiber fabric must be sufficiently washed. Insufficient washing may reduce fastness, and unfixed dye remaining after washing during deep color processing may break up the emulsion of deep color processing agent and cause processing unevenness. .

  In the present invention, the deep colorant used is a fluorine compound, a silicone compound, an acrylic compound, a urethane compound or the like having a refractive index of 1.50 or less, preferably 1.48 or less. Those blends may also be used. These compounds are usually used as a water-based emulsion by blending a self-emulsified body or an emulsifier. At this time, when a deep colorant containing a compound having a refractive index exceeding 1.50 is used, the refractive index of the fibers constituting the fabric (polyester; 1.725, wool; 1.553) is approached. However, it is not preferable because the deep color effect cannot be obtained.

In the present invention, the fluorine compound means a fluorine compound containing a polyfluoroalkyl group in the chemical structure. A polyfluoroalkyl group (referred to as Rf group) refers to a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. 2-20 are preferable and, as for carbon number of Rf group, 6-16 are especially preferable. The Rf group may have a linear structure or a branched structure, and a linear structure is particularly preferable. In the case of a branched structure, the branched portion is preferably present at the terminal portion of the Rf group and is a short chain having about 1 to 4 carbon atoms. In particular, the Rf group is preferably a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (that is, a perfluoroalkyl group). As the fluorine-based compound, a copolymer obtained by polymerizing the polymer containing the perfluoroalkyl group with another polymerizable monomer that can be polymerized by a known or well-known polymerization method can be used. For example, it may be used in the form of a copolymer with a vinyl compound such as acrylic acid, methacrylic acid, styrene or vinyl chloride, or may be a blend of an acrylic compound, vinyl acetate compound, melamine compound or the like. . These copolymer polymers are commercially available as fluorine-based water repellents, and “Asahi Guard” manufactured by Asahi Glass Co., Ltd. is known.
These fluorine compounds are usually used in the form of a water-soluble emulsion.

  In the present invention, the silicone-based compound generally refers to a compound having a siloxane bond in the chemical structure. Examples include polydimethylsiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, amino-modified silicone, epoxy-modified silicone, alkyl-modified silicone, carboxyl-modified silicone, quaternary ammonium salt-modified silicone, phenol-modified silicone, and fluorine-modified silicone. And various modified silicones such as polyether-modified silicones, silicone surfactants obtained by bonding the above silicone and hydrophilic groups, silicone rubbers, silicone thermoplastic elastomers, and the like.

  In the present invention, it is preferable to use at least one of polydimethylsiloxane, methylhydrogenpolysiloxane, and amino-modified silicone among them because of its easy penetration into the fiber fabric. These silicone compounds are usually used in the form of a water-soluble emulsion.

  In the present invention, an acrylic compound refers to a copolymer obtained by polymerizing a polymer of an acrylic acid monomer and another polymerizable monomer polymerizable with the acrylic acid monomer by a known or well-known polymerization method. Refers to coalescence. Examples of acrylic acid monomers include acrylic acid, methacrylic acid and their derivatives, acrylic acid ester, methacrylic acid ester, N-methylol acrylamide, dimethylaminoethyl methacrylate, and the like. These acrylic compounds are usually used in the form of a water-soluble emulsion.

  In the present invention, the urethane compound is a polyurethane obtained by reacting a urethane prepolymer having an isocyanate group at the terminal with a compound having an amino group, or further reacting a hydrophilic compound, and these urethane compounds. The compound is usually used in the form of a water-soluble emulsion.

  In the present invention, only one type of deep coloring agent may be used, or two or more types having different contents may be used. When two or more types are used, the respective deep coloring agents may be mixed and added simultaneously, or may be divided into two or more times and optionally added in a separate bath.

  In the present invention, the penetrant used is a specific surfactant, and may be an anionic, cationic, nonionic, amphoteric active agent or a blend thereof. Among them, a nonionic active agent is preferable. And an anionic activator.

  In the present invention, the nonionic penetrant is preferably a nonionic surfactant made of polyoxyalkylene monoalkyl ether or polyoxyalkylene monoalkenyl ether. The alkyl group and alkenyl group each have 4 to 26 carbon atoms. Preferably there is. In addition, each of the alkyl group and alkenyl group may have a linear structure or a branched structure, and the alcohol may be any of primary, secondary, and tertiary. Specific examples of the alkyl group and alkenyl group include octyl group, decyl group, dodecyl group, 2-ethylhexyl group, tetradecyl group, hexadecyl group, octadecyl group and oleyl group. Examples of the anionic penetrant include alkyl sulfate ester, sulfosuccinate ester, ether sulfate of polyoxyalkylene nonionic activator, and the like.

  In the present invention, the solvent used as the penetrant is not particularly limited as an organic solvent that can be dissolved in water in an aqueous medium as long as the solubility in 100 g of water is 10 g or more. One or more selected from monohydric alcohols such as alcohol, ethyl alcohol and isopropyl alcohol, adducts thereof with alkylene oxide, and saturated polyhydric alcohols such as ethylene glycol and propylene glycol are preferred.

  In the present invention, the deep-coloring agent or the concomitant agent is added to the treatment bath as it is or diluted to an appropriate concentration. The active ingredient amount of the deep color processing agent used is preferably 0.05 to 10% by weight, more preferably 0.1 to 4% by weight, based on the fiber. When the amount of the deep color processing agent is too large, not only is the waste of the processing waste, but also the obtained deep color property is lowered, the frictional fastness is lowered, and the texture is changed. Further, if it is 0.05% by weight or less, sufficient deep colorability cannot be obtained.

  In the penetrant used in the present invention, the amount of penetrant used is 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the treated cloth. When the penetrant concentration is high, the permeability of the treatment bath to the fiber is improved but the foaming property is increased, and further, the emulsion of the deep color agent is stabilized, and the adsorption amount of the deep color agent to the fiber is reduced. Therefore, sufficient deep color cannot be obtained. Further, when the penetrant concentration is low, sufficient penetrability cannot be obtained, and processing unevenness is likely to occur.

  In the present invention, another additive may be used in combination in the treatment bath and in the deep colorant solution to further enhance the deep color effect, or to improve processability and stabilize the process (deep color properties). Improvers, crosslinkers, fastness enhancers, antifoaming agents, chelating agents, leveling agents, stabilizers, inorganic salts, etc.).

  In this invention, a deep color processing agent is processed at 20-100 degreeC, Preferably, it is 30-80 degreeC. If the treatment temperature is too low, the amount of the deep color processing agent adsorbed on the fiber is small, and a sufficient deep color effect cannot be obtained, and the difference in water temperature between summer and winter may result in a difference in deep color. Conceivable. Also, if the temperature is too high, the dye will cry out of the fiber, reducing its fastness, and the emulsion of the deep colorant will be fragile. It can no longer be obtained.

  In the present invention, the addition of the alkaline agent for pH slide to the treatment bath may be started at any stage from immediately after the start of the processing until after reaching the predetermined temperature, but the most preferable is the addition after reaching the predetermined temperature. Yes, it is good to add in portions over a period of 10 to 60 minutes.

  In the present invention, the fiber fabric is treated with the above-mentioned treatment agent. The fiber fabric is placed in an apparatus such as a liquid dyeing machine, and is processed at a predetermined temperature and time in the apparatus. A deep colorant, a surfactant as a penetrating agent, and a solvent may be used in combination in the treatment bath.

  In the present invention, in order to more efficiently apply the color deepening agent, the apparatus for treating the fiber fabric is a facility for circulating the liquid, a facility for circulating the fiber fabric, or the like, like a liquid dyeing machine. It is preferable to have both. Here, the alkaline agent for the pH slide may be introduced by injecting the medium into the fabric processing apparatus using a chemical liquid automatic injection apparatus called a dosing apparatus or a similar apparatus, or using a metering pump. In order to circulate the fiber fabric, the fiber fabric may be rotated by flowing the liquid in a container filled with the fiber fabric such as a liquid dyeing machine.

  In the present invention, an acid is used to adjust the initial pH to 3 to 5 when the fiber fabric is treated with the above-described treatment agent, and as the acid, an organic acid such as formic acid, acetic acid, maleic acid or the like is used. preferable. When the deep color treatment is performed under conditions where the initial pH exceeds 5, it is not preferable because unevenness of the deep color agent tends to occur and the quality is poor.

  In the present invention, as the alkali agent for raising the pH when the fiber fabric is treated with the treatment agent, inorganic alkali agents such as sodium carbonate, sodium phosphate, caustic soda and ammonia, and organic amines such as alkylamine and alkanolamine are used. Although it can be used, it is preferable to use organic amines such as alkylamines and alkanolamines, and more preferred are diethanolamine and triethanolamine. The reason for this is that the increase in pH is not rapid but linear, which contributes to the stabilization of processing. When an alkaline agent whose pH is rapidly increased is used, or when an alkaline agent is added at once and the pH is rapidly increased, unevenness occurs in exhaustion of the deep colorant to the fiber fabric, resulting in poor quality. The final product is obtained. In addition, when the final pH value of the treatment liquid is 6 or less, the adsorption amount of the color deepening agent to the fiber is lowered, and a sufficient deep color effect cannot be obtained. Further, when the final pH value exceeds 9, a deep color effect can be obtained, but an adsorption unevenness of the color deepening agent occurs, resulting in processing unevenness, and a deep color effect with good quality cannot be obtained. In addition, the pH change rate for increasing the pH when treating with the treatment agent is preferably 0.5 / min or less, more preferably 0.3 / min or less. When the pH change rate exceeds 0.5 / min, uneven adsorption tends to occur and deep unevenness occurs. Further, when the pH change rate is 0.05 / min or less, there is no problem in the deep color property, but the processing time becomes long and a problem is left in the processing cost.

  In the present invention, after the deep color treatment, the deep color treatment is performed by drying and heat treatment in order to form a uniform film on the fiber surface. Drying conditions are preferably 80 to 130 ° C., and heat treatment conditions are preferably 120 to 200 ° C. × 30 seconds to 3 minutes.

  EXAMPLES Next, although an Example demonstrates this invention further, this invention is not limited at all by these Examples.

In addition, the measurement in an Example and a comparative example was performed with the following method.

<Measurement of deepening effect>
The L * value described in JIS Z 8729 (color display method—L *, a *, b * color system and L *, u *, v * color system) was determined as a value representing deep color. A smaller L * value indicates a greater deep color effect. The colorimeter was measured by using SZ-Σ80 manufactured by Nippon Denshoku Industries Co., Ltd. The light source was D65 and the viewing angle was 2 °. In addition, the absolute value of the difference between the L * values before and after the treatment is ΔL *.

<Penetration>
The penetration of the deep color treatment liquid into the processed fabric was judged visually.

<Processing unevenness>
The sample was judged visually.

<Ending (hue difference at the center of the process)
Samples of each processing work were sampled and measured with a colorimeter (L *, a *, b *), and the absolute value of the variation was evaluated as ΔE * by the following equation. Larger ΔE * value indicates greater ending
ΔE * = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2

<Friction fastness>
Evaluation was carried out according to JIS L-0849 type II method (Gakushin shape method).

<Dry cleaning (DC) treatment>
In accordance with JIS L-1095 (2), dry cleaning with charge soap was performed, and this process was repeated three times to evaluate durability after the dry cleaning process.

[Example 1]
83 decitex (75 denier)-36 filament polyester yarn, S, Z twist 2500 T / m strong twist yarn on the front of warp, S twist 800 T / m twist on the back of warp, S, Z twist on weft Using a back satin satin georgette woven with a warp density of 220 / 吋 and a weft density of 87 / 吋 using a strong twisted yarn of 2500 T / m, heat at 180 ° C. The woven fabric having a weight per unit area of 180 g / m ² subjected to alkali weight reduction processing (alkali weight loss rate 20%) was obtained. Using this woven fabric, dyeing and reduction washing were performed with a liquid dyeing machine under the following conditions.

<Dyeing conditions>
Dianix Tuxedo Black F conc liquid
(Disperse dye, manufactured by Dystar) 15% (owf)
Disper N-700 (manufactured by Meisei Chemical Co., Ltd., dispersion leveling agent) 0.5 g / L
Acetic acid (90%) 0.3 g / L
Bath ratio 1:20
Dyeing temperature / time 130 ° C x 45 minutes

<Reduction cleaning conditions>
Caustic soda (48 ° Be) 2g / L
Hydrosulfite 2g / L
Rakkor ISF (made by Meisei Chemical Co., Ltd., soaping agent) 1g / L
Bath ratio 1:20
Treatment temperature / time 80 ° C. × 20 minutes After that, polyester back satin satin georgette fabric (L * value 13.47) dyed black after drying with water was obtained.

  This dyed fabric 4 fabric (200 m) was put into a high-pressure liquid flow dyeing machine (manufactured by Nisaka Seisakusho) equipped with an automatic chemical addition device (bath ratio 1:20) and then heated to 40 ° C. (2 ° C./min) First, acetic acid (90% product) was added to a concentration of 0.25 g / L and circulated for 5 minutes, then 8% (ow F.) Was added and circulated for 5 minutes. The bath pH before addition of acetic acid was 6.97, and the bath pH after addition of the deep colorant was 4.19.

(Deep coloring agent composition)
Asahi Guard AG-8095 45 parts (Fluorine-based water repellent, refractive index 1.42 manufactured by Asahi Glass Co., Ltd.)
15 parts of Torre Silicone SM8702 (Amino-modified dimethylpolysiloxane manufactured by Toray Dow Co., Ltd., refractive index 1.48)
Penetration agent (polyoxyethylene alkyl ether (carbon number of alkyl group = 10 to 13)) 5 parts Solvent (dipropylene glycol) 4 parts Water 31 parts ――――――――――――――――― ―――――――――――――――――――
100 copies

  Subsequently, while keeping the temperature at 40 ° C., diethanolamine is dividedly added over 20 minutes with an automatic chemical solution addition device (dosing machine) so as to have a concentration of 0.5 g / L. The bath pH at the end of the addition was 7.13. Then, it was washed with water, dehydrated and dried (110 ° C. × 2 minutes) and heat-treated (170 ° C. × 1 minute) by a conventional method.

  As a result of measuring the above-mentioned deepening effect on the treated sample, the L * value was 10.10, and the difference ΔL * with respect to the L * value of the dyed fabric was 3.37, and the deepening effect was very high. High processing was possible. Further, ΔE * between them was within 0.13, and the uniformity was excellent and there was no unevenness. Further, the fastness to friction (dry / humidity) was 4/4 + grade, and the L * value after three dry cleanings was 10.28, indicating durability.

[Comparative Example 1]
Using the same dyed fabric 4 as in Example 1, acetic acid was not added, pH slide treatment was not carried out, 8% (owf) of a deep color treatment agent according to the above formulation was added, and 40 ° C. It was treated for 30 minutes, washed with water, dehydrated and dried (110 ° C. × 3 minutes) in the same manner as in Example 1, and then heat-treated (170 ° C. × 1 minute). The initial pH of the treatment bath was 6.94, and the pH at the end was 7.14.

  As a result of measuring the above-mentioned deepening effect on the treated sample, the L * value was 11.34, the difference ΔL * with respect to the L * value of the dyed fabric was 2.13, and the standard deepening It was an effect. Further, ΔE * between them was 0.23 and the uniformity was good, but a lot of processing unevenness was observed. Further, the fastness to friction (dry / humidity) was excellent at 4/4 grade, and the L * value after 3 times of dry cleaning was 11.67, and a certain degree of durability was recognized.

[Comparative Example 2]
Acetic acid (90% product) was added to a concentration of 0.25 g / L using the same dyed fabric 4 as in Example 1 and circulated for 5 minutes. 8% (o.w.) deep color treatment was added and treated at 40 ° C. for 25 minutes, washed with water, dehydrated and dried (110 ° C. × 3 minutes) in the same manner as in Example 1, and heat treated (170 ° C. × 1 minute) ) The initial pH of the treatment bath was 6.94, the pH after addition of acetic acid was 4.19, and the pH at the end was 4.01.

  As a result of measuring the above-mentioned deepening effect on the treated sample, the L * value is 12.41, the difference ΔL * with respect to the L * value of the dyed fabric is 1.06, and the deepening effect is as follows. The result was inferior. Further, ΔE * between them was 0.18, the uniformity was good, and there was no processing unevenness. Further, the fastness to friction (dry / humidity) was as good as 4/4 grade, and the L * value after 12.3 dry cleaning was 12.73, and some durability was recognized.

[Comparative Example 3]
Using the same dyed fabric 5 as in Example 1, it was immersed in an 8% by weight treatment solution of the deep color treatment agent according to the above formulation by the padding method, and squeezed to a pick-up amount of 70% by mangle, After drying at 110 ° C. for 3 minutes, heat treatment was performed at 170 ° C. for 1 minute. The pH of the padding treatment bath was 6.88.

As a result of measuring the deepening effect on the sample after the treatment, the L * value was 12.02, and the difference ΔL * with respect to the L * value of the dyed fabric was 1.45. Further, the hue difference between the processing reaction start and the processing reaction end was 0.84 in terms of ΔE * value, which showed poor uniformity and ending, and slight processing unevenness was also observed. Further, the fastness to friction (dry / wet) was inferior to grade 3/2, and further, the L * value after dry cleaning 3 times was 13.03, and the durability was judged to be low.
The above results are summarized in Table 1.

[Example 2]
A wool fiber fabric (wool surge fabric) with a warp density of 77 yarns / 吋 and a weft density of 69 yarns / 吋 with a 2/2 oblique structure using wool yarn of No. 48 twin yarn (wool surge fabric) is pretreated by a conventional method ( Scouring and drying) to obtain a woven fabric having a weight per unit area of 280 g / m ² . This woven fabric was dyed and chromed by the 1-bath 2-stage method under the following conditions.

<Dyeing conditions>
(First stage)
Sunchrome Black P2B
(Sumika Chemtex Co., Ltd., mordant dye) 6% (owf)
Chromers W (manufactured by Meisei Chemical Co., Ltd., friction fastness improver) 3% (owf)
Acetic acid (90%) 2% (o.w.)
Anhydrous mirabilite 5% (o.w.)
Formic acid (80%) 2% (owf)
Bath ratio 1:30
Dyeing temperature / time 97 ℃ × 60min

(Second stage: chroming; after dyeing under the above conditions, continue cooling to 80 ° C. and add the following formulation)
Potassium dichromate 2% (owf)
Chromers W (manufactured by Meisei Chemical Co., Ltd., friction fastness improver) 1% (owf)
1:30
Processing temperature / time 97 ℃ × 30min

Thereafter, a wool fiber fabric (wool surge fabric, L * value 14.11) was obtained by washing with hot water, washing with water, drying and dyeing black.
Next, using this dyed wool fiber fabric, deep color processing was performed under the following conditions.
After 100 g of dyed wool fiber fabric was put into a dyeing machine having an internal volume of 300 ml (bath ratio 1:20), the temperature was raised to 40 ° C. (2 ° C./min). After adding and circulating for 5 minutes so that it might become a density | concentration of 25 g / L, 8% (owf) of the deep color processing agent adjusted with the following composition was added, and it circulated for 5 minutes. The pH before addition of acetic acid was 7.10, and the pH after addition of the deep colorant was 4.22.

(Deep coloring agent composition)
Asahi Guard AG-8095 45 parts (Fluorine-based water repellent, refractive index 1.42 manufactured by Asahi Glass Co., Ltd.)
15 parts of Torre Silicone SM8702 (Amino-modified dimethylpolysiloxane manufactured by Toray Dow Co., Ltd., refractive index 1.48)
Penetration agent (polyoxyethylene alkyl ether (carbon number of alkyl group = 10 to 13)) 5 parts Solvent (dipropylene glycol) 4 parts Water 31 parts ――――――――――――――――― ―――――――――――――――――――
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  Subsequently, while keeping the temperature at 40 ° C., diethanolamine is added over 20 minutes with an automatic chemical solution addition apparatus (dosing machine) to a concentration of 0.5 g / L. The pH at the end of the addition was 7.34. Then, it was washed with water, dehydrated and dried (100 ° C. × 3 minutes) and heat-treated (160 ° C. × 1 minute) by a conventional method.

  As a result of measuring the above-mentioned deepening effect on the treated sample, the L * value was 11.70, and the difference ΔL * with respect to the L * value of the dyed fabric was 2.41, and the deepening effect was good. Was able to be processed. Further, no processing unevenness was observed. Further, the L * value after dry cleaning 3 times was 11.82, and durability was recognized.

[Comparative Example 4]
Using the same dyed wool fiber fabric as in Example 2, no acetic acid was added, and no pH slide treatment was performed, and 8% (owf) of a deep color treatment agent according to the above formulation was added and treated for 30 minutes. In the same manner as in Example 1, it was washed with water, dehydrated, dried (100 ° C. × 3 minutes), and heat-treated (160 ° C. × 1 minute). The initial pH of the treatment bath was 6.78 and the pH at the end was 7.10.

  As a result of measuring the above-mentioned deepening effect on the treated sample, the L * value was 11.70, and the difference ΔL * with respect to the L * value of the dyed fabric was 2.41, indicating a good deepening effect. Met. However, processing unevenness was recognized. Further, the L * value after dry cleaning 3 times was 11.97, and a certain degree of durability was recognized.

[Comparative Example 5]
Using the same dyed wool fiber fabric as in Example 2, acetic acid (90% product) was added to a concentration of 0.25 g / L and circulated for 5 minutes. 8% (owf) of the color deepening treatment agent according to No. 5 was added, treated at 40 ° C. for 25 minutes, washed with water, dehydrated and dried (100 ° C. × 3 minutes) as in Example 2, and heat treated (160 ° C. × 1 minute). The initial pH of the treatment bath was 6.78, the pH after addition of acetic acid was 4.21, and the pH at the end was 4.56.

  As a result of measuring the above-mentioned deepening effect on the treated sample, the L * value was 12.10, the difference ΔL * with respect to the L * value of the dyed fabric was 2.01, and the deepening effect was The result was inferior. Further, the L * value after dry cleaning 3 times was 12.35, and some durability was recognized.

[Comparative Example 6]
Using the same dyed wool fiber fabric as in Example 2, it was immersed in an 8% by weight treatment solution of the deep color treatment agent according to the above formulation by a padding method, and squeezed to a pick-up amount of 60% by mangle, After drying at 100 ° C. for 3 minutes, heat treatment was performed at 160 ° C. for 1 minute. The pH of the padding bath was 7.02.

As a result of measuring the above deepening effect on the treated sample, the L * value was 13.00, and the difference ΔL * with respect to the L * value of the dyed fabric was 1.11. In addition, some processing unevenness was observed. Further, the L * value after three dry cleanings was 13.20, which was judged to be durable, but the deep color level was judged to be low.
The results are summarized in Table 2.

  From the experimental results of Tables 1 and 2, by using the deep color treatment method of the present invention, the deep color processed cloth not only has excellent deep color but also has no processing unevenness and excellent deep color and fastness. Can be manufactured.

Claims (6)

The dyed fiber fabric after the dyeing process is immersed in a treatment bath containing a treatment liquid containing a deep colorant, and the deep colorant is exhausted to perform deep color processing, thereby performing the dyeing. In the deepening treatment method for improving the color developability of the fiber fabric and enhancing the deep colorability and sharpness, the fiber fabric containing at least one of polyester fiber and wool fiber is subjected to a dyeing treatment as the dyed fiber fabric. And the pH of the treatment liquid at the start of the deep color processing is in the range of 3 to 5, and then the alkali agent is gradually added along with the progress of the deep color processing. gradually increasing the p H value of the liquid, deep color process method of a fiber fabric, characterized in that the pH value of the treatment liquid removing said dyed fiber fabric at the range of 6-9. The method for deepening a fiber fabric according to claim 1, wherein a metering pump or a chemical liquid automatic addition and injection device is used as means for adding an alkaline agent to the treatment liquid . The deep colorant is composed of an aqueous emulsion containing at least one compound selected from the group consisting of a fluorine compound having a refractive index of 1.50 or less, a silicone compound, an acrylic compound, and a urethane compound. The method for deepening a color of a textile fabric according to claim 1 or 2, wherein: The active ingredient amount of the deep color agent to be exhausted by the dyed fiber fabric is 0.05 to 10% by weight with respect to the dyed fiber fabric. The deepening method of the textile fabric as described in any one of Claims 1-3. The method for deep coloration of a fiber fabric according to any one of claims 1 to 4, wherein the temperature of the treatment bath is in the range of 20 ° C to 100 ° C. The depth of the fiber fabric according to any one of claims 1 to 5, wherein after the dyed fiber fabric is taken out from the treatment liquid, a dry heat treatment at 100 ° C or higher is further performed on the dyed fiber fabric. Coloring method.