JP5273923B2 - Method for dyeing cellulose / synthetic polyamide composite fiber product and fiber product thereof - Google Patents

Description

  The present invention relates to a method for dyeing a composite fiber product such as a fabric made of cellulose fiber and synthetic polyamide fiber, and a fiber product obtained thereby.

  When a composite material composed of cellulose fibers and synthetic polyamide fibers is dyed with reactive dyes and acid dyes, there is a problem that the reactive dyes used for dyeing the cellulose fibers also stain the synthetic polyamide fibers. . The degree of dyeing of the reactive dye on the synthetic polyamide fiber varies depending on the dye. That is, the ratio of the reactive dye dyed to the cellulose fiber and the ratio of dyeing to the synthetic polyamide fiber (distribution rate) vary depending on the reactive dye used. Further, in the dyeing of reactive dyes on synthetic polyamide fibers, not only will there be a difference depending on the dye used, but also the degree will vary depending on the mixing ratio of the materials and the dyeing environment.

  As mentioned above, dyeing of reactive dyes on synthetic polyamide fibers is an inhibiting factor, so dyeing cellulose fiber / synthetic polyamide fiber composite materials into a single color (same color) using reactive dyes and acid dyes It is extremely difficult. In order to solve this problem, the following proposals have been made in the prior art.

  Patent Document 1 (Japanese Patent Laid-Open No. 14-069864, “Dyeing method of mixed fibers of cellulose fibers and polyamide fibers”) uses both reactive dyes represented by a specific general formula (chemical structure). It is disclosed to dye the fibers to an approximate color.

  That is, in this method, by using a specific reactive dye having a limited chemical structure, the dyeing distribution ratio of the reactive dye to the cellulose fiber and the synthetic polyamide fiber is made uniform so as to enable the same color dyeing.

  Patent Document 2 (Japanese Patent No. 2995992, “Inkjet Textile Printing Method”) describes dyeing of a cellulose fiber / polyamide fiber composite material. It is disclosed that ink droplets are made small by operation and printed.

  In other words, in ink jet printing, drop the ink droplets in order from the slow reactive dye or reduce the ink droplet volume of the slow reactive dye to reduce the change in the dyeing property due to the reaction speed of the reactive dye and dye the same color. It is what.

  Further, in Patent Document 3 (Japanese Patent Laid-Open No. 7-150477, “Modification Method and Dyeing Method of Modified Fiber Material”), an agent having an amino group is applied to a fabric and then dyed with an anionic dye. It is disclosed.

  That is, the composite fiber is pre-treated with a cationic agent and then dyed with an anionic dye. By adsorbing the dye ionically to the cationized fiber surface regardless of the fiber product, a good condition is obtained. It is said that a level dyeing having a fastness to use can be obtained.

  Further, Patent Document 4 (JP-A-12-273771, “Dyeing aid for polyamide / cellulose composite fiber, dyeing method and fiber product”) gives an anionic chemical to contaminate polyamide with dye. Is disclosed.

  That is, in order to prevent the anionic dye (reactive dye, direct dye, etc.) for dyeing the cellulose material from contaminating the polyamide fiber, a specific antifouling agent is added by pretreatment or dyeing. It is supposed to do.

  However, each of the above conventional techniques has the following problems.

  Since Patent Document 1 is a method of reducing the difference in the distribution ratio of dyes by using a reactive dye having a specific chemical structure, in order to use a reactive dye limited in chemical structure. There is a problem that the hue is limited.

  The method of Patent Document 2 is a method in which droplets are deposited in order from a reactive dye having a slower reactivity by ink jet printing, or the ink volume is reduced as a dye having a slower reaction. Therefore, in order to reduce the difference in distribution rate, It ’s just a simple adjustment. Therefore, since the original chemical factor is not fundamentally improved, the effect is small.

  Patent Document 3 is a method in which reactive dyes are ionically adsorbed by pretreatment with a cationic agent, such as a decrease in fastness such as wetting, friction, and light resistance, and a problem of poor whitening contamination in printing. Cause the negative effects. That is, since the reactive dye is only adsorbed on the formed cationic drug, the binding of the dye is weak, and it is easily affected by the cationic substance itself. For this reason, there is a strong concern about a decrease in fastness. In the printing process, since the white field that should not be colored is also cationized, if the unfixed dye that has fallen off is anionic during soaping, the dye naturally contaminates the white field ionicly. it is conceivable that.

  Patent Document 4 is a method for preventing the dyeing (contamination) of reactive dyes on polyamide fibers by using a specific antifouling agent. The effect is weak and limited. If the anti-staining effect is extremely high, the dyeing of acidic dyes that must be dyed on the synthetic polyamide is also inhibited. For this reason, it is necessary to limit the anti-contamination effect. As a result, the anti-contamination effect cannot be expected for dark colors.

As described above, with the conventional technology, the effect of reducing the difference in the distribution ratio of reactive dyes between polyamide fiber and cellulose fiber is weak, there is a concern that the hue and density are limited, fastness may be reduced, and printing There were concerns about contamination of the product against white spots.
Japanese Patent Laid-Open No. 14-069864 Japanese Patent No. 2995992 JP-A-7-150477 Japanese Patent Laid-Open No. 12-237771

  The present invention has been made in view of the above, and in dyeing a composite fiber product composed of cellulose fibers and synthetic polyamide fibers using reactive dyes and acidic dyes, problems due to dyeing or contamination of reactive dyes on synthetic polyamides. An object of the present invention is to provide a dyeing method for dyeing cellulose fibers and synthetic polyamide fibers as much as possible, and a fiber product dyed thereby.

The method for dyeing cellulose / synthetic polyamide composite fiber products of the present invention uses two or more reactive dyes and two or more acid dyes mixed together to dye composite fiber products made of cellulose fibers and synthetic polyamide fibers. In order to solve the above-described problem, a dye having an inorganic / organic value of 4.0 to 6.0 is used as a reactive dye, and an inorganic / organic value of 1 is used as an acidic dye. A value obtained by subtracting the inorganic / organic value of the acidic dye from the inorganic / organic value of the reactive dye as the reactive dye and acidic dye having the same hue is 1.0 . Acid dye group comprising two or more acid dyes, using a reactive dye and an acid dye that are 5 or more , and from the minimum inorganic / organic value of the reactive dye group comprising the two or more reactive dyes The maximum inorganic / organic value of By using a reactive dye and an acid dye having a subtracted value of 1 or more, the cellulose fiber and the synthetic polyamide fiber are dyed as much as possible.

  In the dyeing method of the present invention, an ink jet method can be used for dyeing using a reactive dye and an acid dye.

  The cellulose / synthetic polyamide composite fiber product of the present invention is obtained by the dyeing method of the present invention described above.

  According to the present invention, by using an acid dye having a lower inorganic / organic value than the reactive dye in the same hue, the acidic dye is preferentially dyed on the synthetic polyamide fiber over the reactive dye, In order to suppress the dyeing to the synthetic polyamide, the reactive dye and the acid dye can be dyed on the cellulose fiber and the synthetic polyamide fiber at a certain ratio with good reproducibility. In addition, even in the case of intermediate colors mixed with three primary color inks (Yellow / Magenta / Cyan ink), the extreme dyeing of reactive dyes on synthetic polyamide fibers is suppressed, and the color cracks between the two fibers are extremely different. The same color dyeing can be easily performed without generating the color.

  Therefore, the obtained printed matter has good color matching properties, no contamination and bleeding due to soaping, and good wet fastness.

  In particular, when a reactive dye having an inorganic / organic value of 4.0 to 6.0 is used, dyeing to a synthetic polyamide is effectively prevented, such as soaping contamination, bleeding, poor wet fastness, etc. There is no problem.

  In addition, when two or more dyes are mixed to dye an intermediate color such as gray or brown, the minimum value of the inorganic / organic value of the reactive dye group consisting of two or more reactive dyes is used. When a dye having a value obtained by subtracting the maximum value of the inorganic / organic value of the acid dye group consisting of acid dyes is 1 or more, the three primary colors are dyed in a well-balanced manner, and no color breakage occurs.

  The present invention is characterized in that, in dyeing a composite material composed of cellulose fibers and synthetic polyamide fibers, the affinity of reactive dyes and acid dyes for polyamide fibers is determined on the basis of the inorganic / organic values as described above. To do.

  More specifically, in the selection of the reactive dye of the same hue and the acidic dye to be used, the inorganic / organic value of the acidic dye is determined from the inorganic / organic value of the reactive dye (hereinafter also referred to as the reactive dye IOB value). Hereinafter, a dye having a value obtained by subtracting an acid dye IOB value) of 1.5 or more is used. Thereby, the dyeing of the reactive dye to the synthetic polyamide fiber can be suppressed to a low concentration.

That is,
(Reactive dye IOB value) − (Acid dye IOB value) ≧ 1.5
In this case, since the acid dye is preferentially dyed on the synthetic polyamide fiber, the dyeing of the reactive dye on the synthetic polyamide fiber is limited to a level that is not problematic in practice. In order to further improve the effect of the present invention, this value is more preferably 1.8 or more.

on the other hand,
(Reactive dye IOB value)-(Acid dye IOB value) <1.5
The reaction used to dye the cellulose fiber when the affinity of the reactive dye and acid dye to the synthetic polyamide fiber is similar, or the IOB value of the reactive dye is lower than the IOB value of the acidic dye Since the dye is dyed on the synthetic polyamide fiber, the cellulose fiber is not sufficiently dyed. On the contrary, the synthetic polyamide fiber is dyed darkly, making it difficult to dye both fibers in the same color.

  The “inorganic / organic value (IOB value)” referred to in the present invention is a numerical value calculated based on the method described in Norihiko Kuroki and “Dyeing Theory Chemistry”, pages 66 to 70, published by Tsuji Shoten. That is, using Table 3.3 “Numerical values of inorganic group”, the numerical values can be obtained according to “Calculation Example”. The organic value is 20 for one carbon atom, the inorganic value is 100 for one hydroxyl group, and organic values such as other substituents and inorganic values are appropriately determined based on these values. .

  In addition, “dye as much as possible” means that the difference in hue, saturation, and brightness is as small as possible when comparing cellulose fibers and synthetic polyamide fibers, and color vision is preferably normal. Therefore, it is assumed that the difference is small to the extent that an observer having a standard attention level visually determines the same color.

  If the IOB value is too low for the reactive dye group to be used, dyeing to the synthetic polyamide fiber is likely to occur. Conversely, if it is too high, it remains on the dyed fabric due to its strong affinity for water. When non-fixed dye is easily cryed out by water, soaping contamination, bleeding, and poor wet fastness are likely to occur. In order to suppress these problems, it is desirable to use a reactive dye having an inorganic / organic value of 4.0 to 6.0.

  In addition, when dyes of two or more hues are used to dye them in a mixed color, the reactive dyes and acid dyes of all hues used are used to prevent the reactive dyes from being attached to the polyamide fibers in a more balanced manner. The difference between the inorganic / organic values of the reactive dye group and the acidic dye group (subtract the maximum inorganic / organic value of the acidic dye group from the minimum inorganic / organic value of the reactive dye group) It is preferable to select a dye having a value of 1 or more.

  Although it is a premise of the present invention that the colors of the reactive dye and the acid dye are selected so that the cellulose fiber and the synthetic polyamide fiber are dyed as much as possible, the dyes of the same color are not necessarily used and are mixed. A dye that is as much as possible when dyeing may be selected. Here, the “same color dye” is, for example, a combination of a red reactive dye and a red acidic dye, and “a dye that becomes as much as possible when mixed and dyed” is, for example, an orange reactive dye. And a combination of yellow and red acid dyes.

  In addition, the use of two or more dyes mixed includes both the case where the dyes are mixed in advance and the case where the dyes are mixed (colored) on the fabric.

  Although the dyeing | staining method of this invention can be performed according to the conventional method except selection of the above-mentioned dye, when a preferable embodiment is given, it is as follows.

  First, it is preferable to apply a neutral to weakly alkaline aqueous dispersion containing a fibrin-reactive compound to a cloth or a color paste containing a dye in advance.

  As described in JP-A No. 2002-161486, the fibrin-reactive compound is an agent that promotes the reaction between the reactive dye and the cellulose fiber, and specifically includes a pyridine-based compound, a pyrazine-based compound, and a quinoline-based compound. It can be selected from alicyclic or aromatic compounds having one or two ring nitrogens, amino acid compounds, and the like such as compounds, piperidine compounds, piperazine compounds and the like. Preferred examples include pyridine-based compounds such as picolinic acid, nicotinic acid, isonicotinic acid, dinicotinic acid, dipicolinic acid and the like, and pyridinecarboxylic acid amide-based compounds such as nicotinic acid amide and picolinic acid amide. And methylpyridine compounds such as pyridinemethanol, α-picoline and β-picoline, and aminopyridine compounds such as pyridylamine and dimethylpyridineamine. These fibrin-reactive compounds are preferably present in the treatment liquid in an amount of 0.3 to 5.0% by weight.

  Usually, dyeing of cellulose fibers with reactive dyes is performed in an alkaline manner, and dyeing of synthetic polyamide fibers with acidic dyes is performed in a neutral to acidic manner. In contrast, in the present invention, when dyeing cellulose fibers and synthetic polyamide fibers at the same time, it is preferable to set the pH to neutral to weak alkali and dye. In this case, by adding the above-mentioned fiber reactive compound to the fabric or color paste, the reactive dye is more likely to be dyed on the cellulose fiber even if it is neutral to weakly alkaline.

  Therefore, since the dyeing of the reactive dye to the cellulose fiber is promoted by adding the fiber reactive compound to the cloth or the like, the dark dyeing is possible even if the color is dark or the cellulose mixture ratio is high. Is possible.

  In addition, in the acidic dye group to be used, by using an inorganic / organic value of 1.0 to 4.0 having higher affinity for the synthetic polyamide fiber than the reactive dye group. It becomes easy to be dyed on the synthetic polyamide fiber before the reactive dye group, and the same color can be obtained more efficiently.

  In particular, for the basic three primary colors mainly used for blending colors such as brown and gray, the minimum value of the inorganic / organic value of the reactive dye group is changed to the inorganic / organic value of the acidic dye group. By using the one with the maximum value minus 1 or more, the three primary colors are well-balanced, making it easier to be dyed on the synthetic polyamide before the reactive dye group, and obtaining the same color more efficiently. it can.

  The object to be dyed of the present invention may be a fiber product made of cellulose fiber and synthetic polyamide fiber, and the form of the fiber product here is not limited, and yarn, fabric (woven fabric, nonwoven fabric, knitted fabric) In addition to materials such as, all products after sewing are included.

  Examples of the cellulose fiber of the present invention include cotton, hemp, and regenerated cellulose. Examples of the regenerated cellulose include viscose rayon, copper ammonia rayon, and purified cellulose.

  Examples of methods for applying reactive dyes and acid dyes to fabrics include dip dyeing, pad dyeing, and printing, but are more applicable to printing methods than dip dyeing, pad dyeing, and the like for dyeing yarn or the entire fabric. It is effective. This is because the textile printing method is more preferable in that not only the entire fabric can be dyed into a single hue without color breakage, but also various hue expressions can be made without being limited by the hue.

  Furthermore, examples of the method for applying the dye to the fabric by textile printing include an ink jet method, screen printing, rotary printing, and the like, and it is preferable to use the ink jet method because a variety of patterns can be easily expressed in detail.

  As for the type of the ink jet method, for example, a continuous method such as a charge modulation method, a charge jet method, a micro dot method and an ink mist method, an on-demand method such as a piezo conversion method and an electrostatic suction method can be adopted. In particular, the piezo method is preferable because it is excellent in stability of ink discharge amount and continuous discharge property, and can be manufactured at a relatively low cost.

  When the dye is applied to the fabric by the inkjet method, it is preferable to include a step of forming an ink receiving layer on the fabric before the applying step. The ink receiving layer thus formed instantaneously receives the reactive dye ink and acidic dye ink ejected from the nozzle and holds them appropriately, so that ink bleeding can be prevented.

  Next, steaming at 150 ° C. or higher is preferably performed in order to promote the dyeing of the fiber to the reactive dye cellulose. By performing steam heat treatment at 150 ° C. or higher, the effect of imparting an aqueous dispersion of neutral to weak alkali containing the above-mentioned fibrin-reactive compound appears remarkably.

  After steaming, washing is performed to remove undyed dye. As a cleaning method, a cleaning agent, a white spot anti-staining agent, or the like is appropriately selected and used, and the treatment is usually performed at 40 ° C to 60 ° C. By using the reactive dye and acid dye selected according to the present invention, even if there are some variations in conditions such as temperature and time in the fixing process and washing process, the influence on the color pattern from these conditions is minimal. It is possible to obtain a printed matter with limited color reproducibility and excellent color reproducibility. For printed textiles that have been washed, in order to improve wet fastness, chlorine fastness, light fastness, etc., polyamine-based, polycation-based fixing agent, tannin or synthetic tannin-based fixing agent as post-treatment as necessary UV absorbers, antioxidants, and the like can be used.

  EXAMPLES Hereinafter, although the Example of this invention is given with a comparative example and this invention is demonstrated in more detail, this invention is not limited by a following example. In the examples and comparative examples, “%” represents “% by weight”.

  In the following examples and comparative examples, reactive dyes and acid dyes shown in the following Table 1 were used. The table shows the C.I.No., hue, and inorganic / organic values of the dye.

[Examples 1 and 2, Reference Examples 1 to 4 , Comparative Examples 1 to 3]
In the Examples , Reference Examples and Comparative Examples, the following types and amounts of dyes were added to the printing pastes prepared according to the following formulations to prepare color pastes.
Fine gum HE-S 6% (CMC paste manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Sodium acetate 2%
Niacin 1%
Urea 10%
Reactive dye x%
Acid dye y%
Water remaining%

  The prepared color paste was printed on a cloth using a 1200 mesh screen by screen printing, and two designs of width 30 mm × length 100 mm were printed at intervals of 2 mm in the width direction.

  As the test cloth, a 6 nylon / cotton composite plain weave was used. The composition of the fabric was 100% warp 6 nylon / 100% weft cotton. That is, a plain weave with a blend ratio of 6 nylon 50% and cotton 50% was used. The printed fabric was dried at 100 ° C. for 2 minutes, and then steamed by heating steam at 160 ° C. for 20 minutes. The steamed dough was thoroughly washed with running water, and then washed with hot water at 40 ° C. for 10 minutes using 50 times the amount of water relative to the fabric weight. Furthermore, it was treated at 40 ° C. for 10 minutes in a fix bath containing Dimafix ESB (manufactured by Meisei Chemical Industry Co., Ltd., an anionic fix agent) at a rate of 2 g / L, washed with water and dried. The obtained dyed fabric was evaluated according to the following criteria.

(Evaluation of same color)
The same color was judged visually by using 10 dyeing testers as judges. The warp and weft have no hue difference and have the same color, 3 points, the warp and weft have a slight difference in hue, the same color is slightly better, the warp and weft have a hue difference, and the same color is inferior The thing was evaluated as 1 point, and the same color was determined as follows from the total score of 10 judges.
26 to 30 points Excellent 21 to 25 points Good 16 to 20 points Somewhat bad 0 to 15 points Bad

(Evaluation of bleeding)
It was measured how many mm the gap provided as a width of 2 mm between the two printed symbols was, and bleeding was evaluated as follows. In addition, the numerical value of the unit less than 0.1 mm was rounded off.
1.6 mm to 2.0 mm Excellent 1.1 mm to 1.5 mm Good 0 mm to 1.0 mm Bad

(Evaluation of wet fastness)
A sweat (alkali) fastness test was conducted according to JIS L0848, and graded according to a gray scale for contamination.

[ Reference Example 1]
Reactive Red 24 (inorganic / organic 5.1) 1.0%
Acid Red 138 (Inorganic / organic 3.2) 0.75%
(Reactive dye IOB value) − (Acid dye IOB value) = 1.9 (≧ 1.5)
(Reactive dye IOB value) Within 4-6

[Comparative Example 1]
Reactive Red 22 (inorganic / organic 4.3) 1.0%
Acid Red 138 (Inorganic / organic 3.2) 0.75%
(Reactive dye IOB value)-(Acid dye IOB value) = 1.1 (<1.5)
(Reactive dye IOB value) Within 4-6

[ Reference Example 2]
Reactive Red 226 (Inorganic / organic value 7.8) 1.0%
Acid Red 138 (Inorganic / organic 3.2) 0.75%
(Reactive dye IOB value) − (Acid dye IOB value) = 4.6 (≧ 1.5)
(Reactive dye IOB value) 4 to 6 out of range

Table 2 shows the evaluation results of Reference Examples 1 and 2 and Comparative Example 1.

[ Reference Example 3]
Reactive Blue 19 (inorganic / organic value 4.2) 1.0%
Acid Blue 138 (Inorganic / organic 2.6) 0.75%
(Reactive dye IOB value) − (Acid dye IOB value) = 1.6 (≧ 1.5)
(Reactive dye IOB value) Within 4-6

[Comparative Example 2]
Reactive Blue 19 (inorganic / organic value 4.2) 1.0%
Acid Blue 185 (inorganic / organic value 4.5) 0.75%
(Reactive dye IOB value)-(Acid dye IOB value) =-0.3 (<1.5)
(Reactive dye IOB value) Within 4-6

[ Reference Example 4]
Reactive Blue 176 (inorganic / organic 8.2) 1.0%
Acid Blue 138 (inorganic / organic 2.6) 0.75%
(Reactive dye IOB value) − (Acid dye IOB value) = 5.6 (≧ 1.5)
(Reactive dye IOB value) 4 to 6 out of range

Table 3 shows the evaluation results of Reference Examples 3 and 4 and Comparative Example 2.

[Example 1 ]
Reactive Yellow 13 (inorganic / organic value 5.6) 2.0%
Acid Yellow 127 (inorganic / organic 2.5) 1.5%
Reactive Red 24 (inorganic / organic 5.1) 1.0%
Acid Red 138 (Inorganic / organic value 3.2) 0.75%
(Reactive dye IOB value in yellow phase)-(Acid dye IOB value in yellow phase) = 3.1 (≧ 1.5)
(Reactive dye IOB value in red phase)-(Acid dye IOB value in red phase) = 1.9 (≧ 1.5)
Reactive dye group IOB value within 4-6 range, Acid dye group IOB value within 1-4 range (Reactive dye group minimum IOB value)-(Maximum IOB value of acid dye group) = 1.9 (≥1.0 )

[Comparative Example 3]
Reactive Yellow 2 (inorganic / organic 4.7) 2.0%
Acid Yellow 19 (Inorganic / organic value 3.8) 1.5%
Reactive Red 24 (inorganic / organic 5.1) 1.0%
Acid Red 265 (Inorganic / organic 4.1) 0.75%
(Reactive dye IOB value in yellow phase) − (Acid dye IOB value in yellow phase) = 0.9 (<1.5)
(Reactive dye IOB value in the red phase) − (Acid dye IOB value in the red phase) = 1.0 (<1.5)
Reactive dye group IOB value within 4-6 range, Acid dye group IOB value within 1-4 range (Reactive dye group minimum IOB value)-(Maximum IOB value of acid dye group) = 0.6 (<1.0 )

[Example 2 ]
Reactive Yellow 13 (inorganic / organic value 5.6) 2.0%
Acid Yellow 127 (inorganic / organic 2.5) 1.5%
Reactive Red 226 (Inorganic / organic value 7.8) 1.0%
Acid Red 138 (Inorganic / organic value 3.2) 0.75%
(Reactive dye IOB value in yellow phase)-(Acid dye IOB value in yellow phase) = 3.1 (≧ 1.5)
(Reactive dye IOB value in the red phase)-(Acid dye IOB value in the red phase) = 4.6 (≧ 1.5)
Reactive dye group IOB value outside the range of 4-6, acidic dye group IOB value within 1-4 range (minimum IOB value of reactive dye group)-(maximum IOB value of acidic dye group) = 2.4 (≧ 1.0 )

Table 4 shows the evaluation results of Examples 1 and 2 and Comparative Example 3.

[ Reference Example 5 , Comparative Example 4]
The following reference examples and comparative examples were carried out by the inkjet printing method.

As a fabric used for the test, a 6 nylon / cotton composite plain weave was used as described above. The composition of the fabric was 100% warp 6 nylon / 100% weft cotton. That is, a plain weave with a blend ratio of 6 nylon 50% and cotton 50% was used. Further, prior to inkjet printing, the following treatment liquid was applied to this fabric by the Dip / Nip method (pickup rate 100%) and dried at 100 ° C. for 2 minutes.
Fine gum HE-L 4% (CMC paste made by Daiichi Kogyo Seiyaku Co., Ltd.)
Sodium acetate 2%
Niacin 1%
Urea 10%
Water remaining%

Using the above-mentioned pre-treated cloth, inks in which reactive dyes and acid dyes are mixed in Yellow, Red, and Blue, which will be described later, are applied in amounts of 10 g / m ² , 20 g / m ² , 30 g / m ² , 40 g / m in an inkjet method. Each matrix pattern of m ² was given. The matrix pattern was 50 mm square, and each ink was arranged in a line from the left side in the width direction in the order of application amounts of 10 g / m ² , 20 g / m ² , 30 g / m ² , and 40 g / m ² with a gap of 2 mm. The fabric to which the ink was applied was air-dried and then steamed with 160 ° C. heating steam for 20 minutes. The steamed dough was thoroughly washed with running water, and then washed with hot water at 40 ° C. for 10 minutes using 50 times the amount of water relative to the fabric weight. Furthermore, it was treated at 40 ° C. for 10 minutes in a fix bath containing Dimafix ESB (manufactured by Meisei Chemical Industry Co., Ltd., an anionic fix agent) at a rate of 2 g / L, washed with water and dried.

The ink jet printing apparatus used was an on-demand serial scanning ink jet printing apparatus, and the application conditions were a nozzle diameter of 100 μm, a driving voltage of 100 V, a frequency of 5000 Hz, and a resolution of 360 dpi. Evaluation was performed according to the same criteria as the above-mentioned Examples , Reference Examples, and Comparative Examples. For evaluation of bleeding, a gap between ink application amounts of 30 g / m ² and 40 g / m ² was measured.

[ Reference Example 5 ]
<Ink A>
Reactive Yellow 13 (inorganic / organic value 5.6) 6.0%
Acid Yellow 127 (inorganic / organic 2.5) 4.5%
Diethylene glycol dimethyl ether 1.5%
Remaining pure water (Reactive dye IOB value)-(Acid dye IOB value) = 3.1 (≧ 1.5)
<Ink B>
Reactive Red 24 (inorganic / organic 5.1) 6%
Acid Red 138 (Inorganic / organic 3.2) 4.5%
Diethylene glycol dimethyl ether 1.5%
Pure water balance (reactive dye IOB value)-(acidic dye IOB value) = 1.9 (≧ 1.5)
<Ink C>
Reactive Blue 19 (inorganic / organic value 4.2) 6.0%
Acid Blue 138 (Inorganic / organic 2.6) 4.5%
Diethylene glycol dimethyl ether 1.5%
Remaining pure water (Reactive dye IOB value)-(Acid dye IOB value) = 1.6 (≧ 1.5)
For each ink (reactive dye IOB value) within 4-6 (reactive dye group minimum IOB value)-(acid dye group maximum IOB value) = 1 (≥1)

  The coating amount ratio of the inks A, B, and C was 4: 1: 2.

[Comparative Example 4]
<Ink D>
Reactive Yellow 2 (inorganic / organic value 4.7) 6.0%
Acid Yellow 19 (Inorganic / organic value 3.8) 4.5%
Diethylene glycol dimethyl ether 1.5%
Remaining pure water (Reactive dye IOB value)-(Acid dye IOB value) = 0.9 (<1.5)
<Ink E>
Reactive Red 24 (inorganic / organic 5.1) 6.0%
Acid Red 265 (Inorganic / organic 4.1) 4.5%
Dimethylene glycol dimethyl ether 1.5%
Pure water balance (reactive dye IOB value)-(acidic dye IOB value) = 1.0 (<1.5)
<Ink F>
Reactive Blue 176 (Inorganic / Organic value 8.2) 6.0%
Acid Blue 138 (Inorganic / organic 2.6) 4.5%
Dimethylene glycol dimethyl ether 1.5%
Pure water balance (reactive dye IOB value)-(acidic dye IOB value) = 5.6 (≧ 1.5)
(Reactive dye group IOB value) 4-6 outside (reactive dye group minimum IOB value)-(acid dye group maximum IOB value) = 0.6 (<1)

The coating amount ratio of inks D, E, and F was 4: 1: 2. The results of evaluation of Reference Example 5 and Comparative Example 4 are shown in Table 5.

[ Reference Example 6 , Comparative Example 5]
In the ink jet textile printing method, a full color image including a gradation pattern in addition to the patterns of the above reference and comparative examples was printed under the following application conditions.

Prior to full color image recording, the same fabric as in Reference Example 5 and Comparative Example 4 was used, and a pretreated fabric treated under the same conditions was prepared.

  A full-color image was imparted to the pretreatment cloth using inks in which reactive dyes and acid dyes were mixed in yellow, red, and blue colors described later. After air drying, steaming was performed for 20 minutes with 160 ° C. heating steam. The steamed dough was thoroughly washed with running water, and then washed with hot water at 40 ° C. for 10 minutes using 50 times the amount of water relative to the fabric weight. Furthermore, it was treated at 40 ° C. for 10 minutes in a fix bath containing Dimafix ESB (manufactured by Meisei Chemical Industry Co., Ltd., an anionic fix agent) at a rate of 2 g / L, washed with water and dried.

The inkjet printing apparatus used was an on-demand serial scanning inkjet printing apparatus, and the application conditions were a nozzle diameter of 100 μm, a driving voltage of 100 V, a frequency of 5000 Hz, a resolution of 360 dpi, and an ink application amount of 1 to 15 g / m ^{2 for} each color. Evaluation was performed according to the same criteria as the above-mentioned Examples , Reference Examples, and Comparative Examples.

[ Reference Example 6 ]
The same three inks A, B, and C used in Reference Example 5 were used.

[Comparative Example 5]
The same three inks D, E, and F as those used in Comparative Example 4 were used.

Claims (3)

A dyeing method for dyeing a composite fiber product composed of cellulose fibers and synthetic polyamide fibers by using two or more reactive dyes and two or more acid dyes mixed together ,
As the reactive dye, one having an inorganic / organic value of 4.0 to 6.0 is used.
As the acid dye, one having an inorganic / organic value of 1.0 to 4.0 is used,
As the reactive dye and acidic dye of the same hue, a reactive dye and an acidic dye having a value obtained by subtracting the inorganic / organic value of the acidic dye from the inorganic / organic value of the reactive dye is 1.5 or more , And
A value obtained by subtracting the maximum inorganic / organic value of the acid dye group consisting of the two or more acidic dyes from the minimum inorganic / organic value of the reactive dye group consisting of the two or more reactive dyes. By using reactive dyes and acid dyes that are 1 or more ,
A method for dyeing a cellulose / synthetic polyamide composite fiber product, wherein the cellulose fiber and the synthetic polyamide fiber are dyed as much as possible. The method for dyeing a cellulose / synthetic polyamide composite fiber product according to claim 1 , wherein an inkjet system is used for dyeing using the reactive dye and the acid dye. A cellulose / synthetic polyamide composite fiber product obtained by the dyeing method according to claim 1 or 2 .