JPS6350583A - Dyeing of cellulosic fabric - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cellulose fabric.
cfabric) staining.

Traditional technology The textile industry is concerned with fashion, especially the color of dyed materials (5ha
They are very susceptible to rapid changes in fashion and have to adapt to such changes in order to quickly meet the demands of the field. In order to respond rapidly to such changes, dyeing must be carried out at the final product or fabric stage.

This is because dyeing at the fiber or yarn stage requires lengthy processing after the dyeing stage to convert the material into the final product.

One way to speed up the response to tonal changes in fashion is to produce specifically dyeable fabrics. Fabrics can therefore be produced with generally acceptable patterns using yarns that differ only in their dyeability.

When such fabrics are dyed with appropriate trendy colors, a tone-on-tone pattern is created.
after) is formed. Alternatively, the fabric may be made with a generally popular pattern by weaving or knitting yarns that differ only in their affinity for dyes. This fabric is then dyed with suitable different classes of dyes to obtain a cross-dyed effect.

Therefore, for large-scale manufacturing, one
All you have to do is secure a stock of fabrics in order of type. The fabric can be cut to length and immediately dyed in a specific shade without having to keep a stock of every possible color scheme. A further development of this technique is to apply the same principles to the manufacture of garments made from treated fabrics, which are then dyed after manufacture.

Despite the development of synthetic fibers, cellulose-based fibers still account for the majority of the world's annual fiber production. Several properties of cellulosic fibers make them highly desirable as fibers in the textile industry. However, unlike synthetic fibers, it is not possible to control the range of increased dyeability and time the production of cellulosic fibers.Cellulosic materials are usually produced using dyes with anionic properties, at least in the adsorption stage. dyed. A conventional technique for tunable dye incorporation into cotton and other cellulosic fibers is to make the fibers hydrophobic, for example by esterification with acetic anhydride, thereby increasing the fiber's receptivity to anionic dyes.
ity). By weaving or knitting yarns treated to reduce dye uptake by this method with untreated yarns, dye uptake on the untreated yarns is relatively high and dye uptake on the treated yarns is relatively high. Fabrics with little or no incorporation are produced. Although this method provides a visual effect, its scope of application is limited. The treatment agents used may also be used to improve other desirable properties of the cellulosic material, such as moisture content.
regain), etc. A further development of this method is to use phthalic anhydride or other cyclic anhydrides as a treatment agent to reduce the receptivity of cellulosic materials to anionic dyes; , has been shown to impart affinity for cationic dyes not normally used in the dyeing of cellulosic fibers.
des to Celulosics)%
Lupton et al., American Dyestuff Reporter
ffReporter), March 1976, p. 56].

British Patent Specification GB-A-1521204, GB-A
-1550716 and GB-A-2119367, the treatment of cellulosic materials improves their affinity for anionic dyes, thereby improving the color yield of dyed materials, which is the intended purpose.
yield) and wash-fast
ness) has been described.

The particular treatment agent used reacts with the hydroxyl groups of the cellulose to introduce cationic groups along the polymer chain;
It is believed that the cationic group acts as a specific staining site for anionic dye ions.

DISCLOSURE OF THE INVENTION The present invention relates to dyeable cellulosic fabrics comprising cellulosic fibers that have been subjected to a treatment to increase their affinity for anionic dyes and fibers with different dye affinities.

According to the present invention, different dyeing effects can be obtained depending on the combination and form of cellulose used. For example, if a cellulosic yarn that has been treated to increase its affinity for anionic dyes is used, untreated cellulosic yarns and/or other cellulosic yarns that have been treated to increase their affinity for anionic dyes to different degrees may be used. May be used. The use of such dyes results in fabrics that can be specifically stained. Such fabrics exhibit interesting tone-on-tone effects when treated with conventional cellulosic anionic dyes.

That is, because the first treated cellulosic yarn absorbs more dye than the untreated fibers, the treated yarns absorb more dye than the untreated yarns and/or the first treated yarns. In contrast, the yarn has an affinity for anionic dyes that is intermediate between that of the first treated yarn and that of the untreated yarn.

Alternatively, or in addition, the yarn may be treated to increase its affinity for anionic dyes, and the yarn may be treated to increase its affinity for cationic dyes, which are not normally used for dyeing cellulosic materials. If such a fabric is dyed with both anionic and cationic dye Q1, only a tone-on-tone effect will be produced.

[Cross-dying] A distinct color effect, known as cross-dying, appears due to yarns being specifically modified by absorbing different types of dyes.

Yarns with different dye affinities may be obtained by treating cellulose in yarn form, or by treating cellulosic fibers and yarn rubbing the treated fibers.

Generally, the most useful fabrics are obtained by using cellulosic yarns that have been treated to increase their affinity for anionic dyes, along with yarns that have different dye affinities. For example, suitable weaving, knitting or tufting of different yarns.
fting) i This makes it possible to obtain a fabric that can be specifically dyed with a design selected from a wide range of designs, which fabric can be custom dyed with the desired color scheme. The anti-fog effect is obtained whether or not yarns treated to increase their affinity for dyes are used with untreated yarns.In fabrics or garments,
Although any number of yarns having different dye affinities may be combined, in practice it is appropriate to combine only four or five yarns. Dyed fabrics, which thus have different color ranges, are obtained by incorporating yarns that have been subjected to a treatment that imparts an affinity for cationic dyes.

Another method of obtaining a specifically dyeable fabric according to the invention is to apply one or more treatment agents to different areas of the surface of an untreated open fabric, such as by printing.

In addition, the blended fibers according to the invention may be used to produce non-woven fabrics consisting of individual fibers treated by different methods, the effects of which are generally The disadvantage is that unless the fibers are specially arranged, it will result in a variegated fabric. It is also advantageous to produce cellulosic yarns from mixed fibers with different dye affinities according to the invention. In this way, a yarn with predetermined and constant dyeing properties may be obtained. The dye affinity of the treated fibers (accordingly, for example, by adjusting the amount of treated and untreated fibers in the yarn)
The dye affinity of the dye can be adjusted to the required level. It is also possible to mix anionically and cationically treated fibers to obtain yarns with desired properties.

Furthermore, according to one aspect of the present invention, by forming a yarn from a blend of fibers treated to impart anionic groups to cellulose and untreated fibers, cationic dyes having predetermined dyeing properties can be obtained. It is possible to produce dyeable yarns.

The fabric according to the invention may be dyed in certain lengths, for example after it has been made into a garment. Accordingly, in accordance with the present invention there is provided a dyeable garment made from a fabric according to the present invention.

The cellulose-based fibers used in the present invention, preferably fibers in yarn form or fibers to be later converted into yarn form, are treated with a treatment agent capable of reacting with cellulose molecules to introduce cationic groups into the cellulose molecules. may be treated with anionic dyes to increase their affinity for anionic dyes. Treatment agents used to increase the affinity for anionic dyes include British Patent Specification GB-A-1521240
Examples include those described in No. 1550716 and No. 2119367. However, preferred cationic treating agents are those represented by the following formula [I]; or group 1 such as a chlorine atom, a fluorine atom or a methylsulfone group, R is an alkyl group or a substituted alkyl group or an aryl group or a substituted aryl group, such as methyl,
ethyl, n-propyl, n-hexyl, phenyl or naphthylmethyl, etc.). The group R is planar (
The planar) group is preferred. Treatment agents of this type generally exhibit a relatively good affinity for cellulose molecules.

The reason for this is not completely understood.

This is thought to be because, since the group R is located in contact with the substantially planar cellulose molecule, the planar group is subject to larger van der Waals forces than the non-planar group, which has a very weak interaction with the cellulose molecule. .

The affinity for anionic dyes may be varied by treatment with different amounts of treatment agents. In general, processing agents have a maximum concentration; above this concentration, no effective change in affinity is observed; below this concentration, affinity changes with the concentration of the processing agent used. do.

The cellulosic fibers used in the present invention, preferably fibers in yarn form or later converted into yarn form, can be treated with a treatment agent capable of reacting with cellulose molecules and introducing anionic groups into the cellulose molecules. It may be treated to impart affinity for cationic dyes.

According to another aspect of the present invention, a treatment agent having a similar structure having an anionic group is used in place of the cationic quaternary ammonium group of the cationic treatment agent, thereby converting the anionic group into cellulose. can be introduced into the system. Cellulose treated in this way therefore has an affinity for cationic dyes which are not normally used in Q) for dyeing cellulose. A suitable compound has the following formula (
It is a compound represented by I[]: [wherein Y has the same meaning as above, each of Z□ and Z2 represents an oxygen atom, an imino group, or an alkylimino group, and Ar1 and A r 2 are the same or may be different and each represents an unsubstituted or substituted phenyl group or a naphthyl group (however, Ar□ and Ar
At least one of 2 represents one or more anionic groups)].

Preferred anionic groups are sulfonic acid groups or salts thereof, but may also be, for example, carboxylic acid groups or phosphonic acids or salts thereof. A preferred compound has the following formula (I
fa): The treatment agents used in the present invention, whether cationic or anionic, are applied to the fibers/yarns at about 80° C., such as colorless reactive dyes. applied.

For example, the fibers/yarns are placed in a treatment solution at 20° C., then 40 parts NaCl per salt 1, e.g. Add Na2Co3. In this case, the temperature is raised to 80 DEG C. and maintained at this temperature for 1 DEG -2 hours. Amount of processing agent to be used (in general, 15% based on the weight of the fiber is the maximum amount to be used in practice; using more than this will hardly increase dye affinity, but different amounts of processing agent can be used) Shiruko (!:
Different processing may be performed depending on ζ.

Alternatively, as described above, different treatments can be achieved by printing the colorless treatments of the present invention onto woven fiber fabrics.

Dyeing of the fabric according to the invention can be carried out by conventional methods, provided that no additional electrolytes, such as sodium chloride, are added to the dyebath.

The contrast between treated and untreated yarns is increased. Dyeing of modified yarns or modified fibers treated with cationic treatment agents The dyes used can be any dyes commonly used for dyeing cellulose.

Cotton is suitable as the cellulose used in the present invention. However, other cellulosic materials may be used, especially flux, ramie or other bast fibers, viscose rayon, and cellulose acetate.)
. Practically speaking, the treatment method according to the present invention can also be applied to convert cellulose into viscose rayon or cellulose acetate. Thus, in the case of viscose rayon and cellulose acetate, wood pulp or cotton linters can be treated by the method of the invention. The treated cellulose feedstock may be converted to xanthate x conductors and then regenerated into viscose rayon, thus increasing the affinity of the resulting viscose rayon for dyes. Similarly, the affinity of cellulose acetate for dyes obtained by acetylation of treated cellulose feedstocks is increased. This method is the supply method of the present invention (preferably Q of the treated cellulose acetate). This is because the ester group of cellulose acetate will be hydrolyzed if this treatment is carried out after esterification.

The present invention will be briefly explained in the following examples.

Example 1 A solution of 18.4 g of cyanuric chloride dissolved in 500a3 of acetone was added to 50 g of a mixture of ice and water with thorough stirring. Aniline 9.3011 in acetone 500m
A solution of l-carbonate is mixed into the mixture.
Add IJum 10% solution 600I3 at once and adjust the pH to 6.
．． 5-7. Of this was retained. During this time, the temperature was maintained at 0-5°C. After stirring for one hour, the colorless product was collected by filtration, washed with distilled water until no chloride ions were detected, and dried at 70° C. overnight. The reconsolidated product number from toluene is therefore 2-anilino-4,6-dichloro-1,
18 g of 3,5-1-riazine (intermediate 1) was obtained.

A solution of 8.7 g of N,N-diethylethylenediamine dissolved in 30 cm of acetone was added to Intermediate 1 (18 g).
was carefully added to a solution containing 50 cm of acetone. After the initial reaction was completed, the mixture was refluxed for 1 hour,
After cooling, the crystalline product was collected by filtration, washed with acetone, and air-dried to give 23 g of the hydrochloride salt. By converting this hydrochloride to the free base, 2-anilino-4-(N,N-diethylethylenediamine)-6
-10Rho 1.3.5- 20g of triazine [Intermediate 2] was obtained.

A solution of 22 g of 2-fold excess of 1-(chloromethyl)-naphthalene dissolved in 50 CIIll of acetone was added to Intermediate 2.
(20 g) was added to a solution in which 100 cmf of acetone was dissolved. After refluxing for 30 hours, the colorless product was filtered from the hot solution and thoroughly washed with acetone.
By drying at 40°C under vacuum, the following formula [Ia]
Quaternary processing agent 1 (m, p, 179-18
1°C) (yield 92%): I Example 2 15.8g of 2-fold excess benzyl chloride was dissolved in 5°cm of acetone.
The solution in which Intermediate 2 (20 g) was dissolved in 100 G of acetone was added to the solution in which Intermediate 2 (20 g) was dissolved in 100 G of acetone.

After refluxing for 20 hours, the colorless precipitate was filtered from the hot solution, thoroughly washed with acetone (71), and evaporated under vacuum for 4 hours.
By drying at 0°C, the quaternary processing agent (m, p, 214-216°C) represented by the linear formula (Ib, ) is
6.5 g obtained (yield 95%): I [Ib) Example 3 Following the procedure for treating agents 1 and 2, intermediate 2 was refluxed in an acetone solution of the appropriate alkyl halide (this Therefore, roughly different quaternary treating agents were prepared. The required reaction time decreased with decreasing size of the alkyl substituent. For example, the reaction with methyl iodide required only a small amount of time (this It was ~3 hours.

Example 4 0.4 g of 1-naphthylamine-4-sulfonic acid
An aqueous solution of the sodium salt of the chain acid was prepared by dissolving in 500 I of M aqueous sodium hydroxide solution. This solution was mixed with Intermediate 1 (4.8 g) in acetone (30 cIR3).
was gradually added to the solution. During this time, the pH of the system was maintained at alkaline pH by adding a 2M aqueous solution of sodium I-IJ hydroxide. The temperature of the reaction mixture was increased to 40°C and the reaction mixture was kept at this temperature for 1 hour. The temperature of the system was then increased to 60° C. and the reaction mixture was kept at this temperature for roughly 2 hours under stirring. The product was filtered and washed with acetone to give a white paste under vacuum for 40 minutes.
3.7 g of treatment agent 3 of the following formula (Jla) were obtained by drying at <RTIgt; o
, w, f, (o, w, f, indicates based on fiber weight: on weight of fiber
) was dissolved in water, and the cellulose yarn soaked in water was immersed in this aqueous solution (60° C.). Sodium chloride (1 part water)
40 parts per 1,000 parts; straining ratio 50:1) was added in portions over about 10 minutes, and the treatment was continued at 60° C. for 45 minutes. The temperature was then raised to 80°C and sodium carbonate (water 1
20 parts per 000 parts) was added in portions and the reaction was continued at this temperature for 2 hours. The treated yarn was pulled up, rinsed, and then treated with a nonionic detergent (2% o, w, f,
) for 30 minutes at 60°C, then rinsed and dried.

In Examples 6 to 11 below, treatment agent 1 (10% o,
The yarn treated with w, f,) was used as the treated yarn.

Example 6 A bank of direct dye-treated and untreated yarns was coated with C.I. Direct Blue (c,1, DirectBlue).
) 1% O, W, F
:1) Stained together with odor. The bank was immersed at 60° C., the temperature was increased to 95° C. in 15 minutes, and staining was continued at this temperature G) for 35 minutes.

No sodium chloride was used in this staining process. The banks were washed with 2% O, W, F, non-ionic detergent at 60° C. for 30 minutes, then rinsed and dried (leakage ratio 50:1). The specific uptake of the dye by the treated and untreated yarns was clearly observed by visual observation and was also observed using a simple reflectance spectrophotometer [I C Varnish Micro Matsushi (1)]. , C.S., Micr.
Instrumental Color Systems (Instrumental Color Systems) manufactured by Match)
Reflectance measurements taken using an o1our system (2009) revealed that the dye uptake by the treated yarn was about 12 times that of the untreated yarn.

Example 7 After soaking banks of reactive dye-treated and untreated yarns in water, C.I. Reactive Blue (c-1, Rea
active Blue) 5 to 2% o, w, f.

They were placed together in a dye bath (50°C) containing (liquid ratio 50
:1). After 20 minutes of treatment at this temperature, sodium carbonate (20 parts per 1000 parts of water) was added and the temperature was raised to the boiling point. After dyeing at boiling point for 45 minutes, remove the bank, rinse, wash at boiling point for 30 minutes using 2% O, W, F non-ionic detergent (after applying this twice, rinse and dry. Reflectance measurements showed that the contrast between the treated and untreated yarns was more pronounced than when C.I. Direct Blue 1 was used.

Example 8 After soaking banks of vat dye-treated and untreated yarns in water, sodium hydroxide 5% o, w, f, sodium dithionite 5% o, w, f, and C.I.
Bat Yellow (c, 1, Vat Yellow)
3 (previously subjected to one reduction treatment at 50°C using sodium hydroxide and sodium dithionite) 2% o, w
, f, were placed together in a dye bath (25°C) containing. The final ratio in the dyebath was 60:1. dyeing 2
After 40 minutes at 5°C, the dyed banks were removed and oxidized in air.

After treatment with dilute acetic acid, there was a rinse followed by a boiling treatment with 2% non-ionic detergent for 20 minutes (liquid ratio 50:1). Visual and instrumental evaluation showed good contrast. It turns out that it can be obtained.

Example 9 After soaking the sulfur dye-treated yarn and the untreated yarn in water, sodium dithionite 15 No,w,f, sodium carbonate 7.5% o,w,f, and C.I. Black (c, I.

5olubilised 5ulfur Black
k) 1 15% o, w, f, containing dye bath (2
5°C) (liquid ratio 25:1). The dyebath was heated to the boiling point, held at this temperature for 40 minutes, and then cooled to 50° C. in 20 minutes. The sulfur dye solution was then squeezed out from the bank and subjected to air oxidation at room temperature, followed by 2% o.
Washed at 50°C using nonionic detergents w and f. The contrast obtained was very good (the color of the treated sample was completely black, while the color of the untreated sample was pale gray).

Example 10 After soaking treated and untreated yarns in water, 1% w
C.I. azoic coupling component (c, 1, A) dissolved in /V sodium hydroxide solution
Zoic Coupling Component
)34 2.25 N o, w, f, containing dye bath (
25°C) (liquid ratio 25:1). /% After pulling up the sink and squeezing out the excess dye, apply C.I. Azoic Diazo Component (c91, A
ZOic Diazo Component)8
One coupling reaction using C1 (15% w/v solution, liquid ratio 25:1) was carried out (25°C). The samples were rinsed with cold water, pickled in dilute hydrochloric acid for 20 minutes, and then rinsed with cold water containing 2% nonionic detergent and 5 parts of sodium carbonate. It was boiled in the solution for 20 minutes, then rinsed and dried.

Example 11 Acid dye treated yarn and untreated yarn were soaked in water and then treated with C.I. Acid Red (c-1, Ac1dRed).
Dye bath containing 1 y (OHW, f) of 88 (50 °C
) I put one. Raise the temperature to 90°C in 15 minutes,
Staining continued for 30 minutes. Rinse the bank.

60℃ using 2% O, W, F non-ionic detergent
After washing for 30 minutes (liquid ratio 50:1), it was rinsed and dried. The visual contrast is good and dye uptake is approximately 10% lower in treated yarns than in untreated yarns.
It was 0 times.

Example 12 After soaking banks of acid dye treated and untreated yarns in water, C.I. Acid Red 13 was applied at 1% o, w, f.
, into a containing dyebath (50°C).

The temperature was increased to 90°C over 15 minutes and the staining was continued for 30 minutes.
It continued for minutes. Rinse the bank with 2% non-ionic detergent
o, w, f, (i) and washed at 60°C for 30 minutes (liquid ratio 50:1), rinsed and dried.

The contrast obtained was very good.

Example 13 Bank of yarn pretreated with O, W, F, dyeing cationic treatment 1 to 10 and anionic treatment 3 to 1
After soaking the bank of yarn pretreated with 0% O, W, F, C.I. Acid Red 881% O
,w,f,, C.I.Basic Yellow (c
,1,Ba5ic Yellow) 151%o,w
, f, and nonionic dispersant 5% o, w, f.

(II&Ratio 50:1)
. After increasing the temperature to 95°C and dyeing at this temperature for 30 minutes, the dyed bank is pulled out and rinsed.
It was then washed with non-ionic detergent (2% O, W, F) at 60°C for 30 minutes.

These banks are similar in shade 0 to other banks that were dyed separately using the appropriate single dye, indicating that no cross-staining occurred during the dyeing process. .

Example 14 Fabric A print paste was prepared containing the following ingredients: Treatment Agent 1 or Treatment Agent 2 1 part water
100 parts urea
20 parts sodium carbonate 3 parts thickening agent approx.
10 parts*) Non-ionic starch ether soluble in cold water (W, A.

5cholten's Chemische Fab
Commercial product Solvitose C5 from Richen B, V, ) A cotton fabric sample screen-printed with the above paste was subjected to steam treatment to fix the treatment agent, and then the remaining paste was removed by washing. Individual samples were then dyed as described above for combinations of treated and untreated yarns. For samples printed with a paste containing anionic treatment agent 3, this was dyed as follows: After soaking the fabric in water, apply C.I. Basic Yellow 15 at 1% O, W, f, containing dye bath (
50℃), raise the temperature to 90℃, and turn this F!
Staining was continued for 30 minutes at 50°C. Next, the fabric
After washing for 30 minutes at 60°C with non-ionic detergent 2% O, W, F, it was rinsed and dried. In all cases, the fabric had a tone-on-tone pattern with good contrast.

Example 15 Cellulose samples were treated with Treatment 1 at 10% O, W, F as described above for yarn treatment. The dry material was soaked in water for 15 minutes, filtered to remove as much water as possible, and then added to glacial acetic acid. After soaking for 30 minutes, the sample was filtered again, soaked in glacial acetic acid, and then filtered. A mixed acetylating agent consisting of 35 parts of glacial acetic acid and 15 parts of acetic anhydride per part (dry weight) was added.While stirring the mixture, a few drops of perchloric acid were added.

After standing for 45 minutes with occasional stirring (during which time the polymer dissolves in solution), the cellulose triacetate was precipitated by adding excess methanol. The precipitate is collected by filtration, thoroughly washed with water, suspended in one volume of water, neutralized to phenolphthalein using sodium carbonate, washed, subjected to one filtration treatment, and then dried. The product was soluble in a 9:1 mixed solvent of dichloromethane and methanol (IRl confirmed that almost complete acetylation of the hydroxyl groups had occurred).

This product was dyed as described in Example 11, except that the dyeing temperature was not 90 DEG C. but at the boiling point, and it showed a high affinity for acid dyes.

Cellulose pretreated with anionic treatment agent 3 at 10% O, W, F exhibited similar behavior on acetylation, resulting in a product that was easily dyed at the boiling point by basic dyes.

Speed: mFIxs Cellulose samples were treated with Treatment 1 at 10% O, W, F as described for yarn treatment above. 1 part dried pretreated cellulose.

Immersed in 10 parts of 20% w/v sodium hydroxide solution (care was taken to ensure that the treatment was uniform). The treated cellulose was lifted after 15 minutes, squeezed out as much of the alkali as possible, and then carbon disulfide. The mixture and 10 parts were placed in a sealed container and left at room temperature for 18 hours.

The orange cellulose xanthate was separated from the reaction mixture and mixed with 20 parts of 10% w/v sodium hydroxide solution after removing excess carbon disulfide. This mixture
It was shaken until a homogeneous suspension of xanthate was obtained and then allowed to stand for 3 days, forming a bright yellow sodium cellulose xanthate solution.

Cellulose was regenerated with viscose rayon toss by extruding the solution through a syringe into a coagulation bath containing sodium sulfate, zinc sulfate, and sulfuric acid. 1.5
Desulfurization treatment in %w/v sodium sulfide (60~b) When dried regenerated cellulose was dyed in a bath containing C.I. Acid Red 88 as described in Example 1, the result was normal. showed superior dye affinity compared to regenerated cellulose prepared from cellulose.

Cellulose samples pretreated with anionic treatment agent 3 at 10% O, W, F behaved similarly to those treated with sodium hydroxide/carbon disulfide, and upon regeneration were shown to be resistant to basic dyes. yielding products with excellent affinity.

Example 17 Commercially available cellulose acetate and cellulose triacetate were soaked in water, and cationic treatment agent 1 was added at 10% o.
, w, f, were placed in a bath (50 °C) containing (liquid ratio 50
:1). The temperature was raised to 60°C for 10 minutes, and thorium chloride (80 parts per 1000 parts of water) was added in portions.
Treatment continued for 1 hour at 60°C. Sodium carbonate (1 part water)
20 parts per 000 parts) was added, the temperature was raised to 85° C., and the treatment was carried out at this temperature for 90 minutes. The samples were subjected to two detergent washes at 60° C. for 30 minutes, then rinsed and dried.

When staining was carried out using C.I. Acid Red at 2% O, W, F, as described above; cellulose acetate and cellulose triacetate treated with straining both showed a deep color tone. In the case of untreated samples of the same type, even when dyed using the same dye bath, only a few spots were colored.

When commercially available cellulose acetate and cellulose triacetate were treated with anionic treatment agent 3 using b) as described above, the amount of basic dye uptake was lower than that of untreated samples of the same type dyed using the same dye bath. increased.

These results indicate that dyeing sites can be incorporated into cellulose acetate and cellulose triacetate by pre-treating the cellulose feedstock from which the derivatives are made or by processing ready-made acetate or triacetate fibers. . However, in the latter case, since neither acetate nor triacetate is soluble in the solvents commonly used for the respective fibers, some changes were observed in the overall composition. This indicates that some of the ester groups were hydrolyzed during treatment with the treatment agent.

Claims (1)

Claims: 1. A dyeable cellulosic fabric comprising cellulosic fibers treated to increase their affinity for anionic dyes and fibers with different affinities. 2. (a) Cellulose fibers treated with a treatment agent that can react with cellulose molecules and introduce cationic groups into the cellulose molecules, and one of the following cellulose fibers (b) to (d): or more: (b) Cellulose fibers treated with a treatment agent capable of reacting with cellulose molecules to introduce anionic groups into the cellulose molecules. (c) cellulosic fibers treated with a treatment agent as defined in (a) above which imparts different levels of dye affinity, and (d) (a), (b) or Cellulosic fibers that are not treated by any of (c). 3. Specific dyeable cellulosic woven, knitted or tough yarns using cellulosic yarns that have been subjected to affinity-increasing treatments for anionic dyes and one or more yarns with different affinities. Tetsudofabrik. 4. (a) Cellulose yarn treated with a treatment agent capable of reacting with cellulose molecules to introduce cationic groups into the cellulose molecules, and one of the following cellulose yarns (b) to (d): or more: (b) A cellulosic yarn treated with a treatment agent capable of reacting with cellulose molecules to introduce anionic groups into the cellulose molecules. (c) a cellulosic yarn treated with a treatment agent as defined in (a) above which imparts different levels of dye affinity, and (d) (a), (b) or Cellulosic yarn not treated by any of (c). 5. A specifically dyeable cellulose-based woven, knitted or tufted fabric with a treatment agent that is capable of reacting with cellulose molecules and introducing cationic groups into the cellulose molecules printed on a portion of the surface of the cellulose-based fabric. Abritsk. 6. Cellulose-based woven, knitted or tuffed fabrics that can be specifically dyed, in which a treatment agent capable of reacting with cellulose molecules and introducing anionic groups into the cellulose molecules is printed on a portion of the surface of the cellulose fabric. Dofuabriksk. 7. The fabric according to any one of items 1 to 6, wherein the cellulose fiber or yarn is cotton. 8. Cellulose acetate or viscose rayon, where the fabric is obtained by reacting a treatment agent capable of introducing a cationic group into cellulose molecules with cellulose, and then converting the resulting cellulose into cellulose acetate or viscose rayon. 2. The fabric according to claim 1, which is a cellulose acetate or viscose rayon fabric containing fibers. 9. Cellulose acetate or viscose rayon, whose fabric is obtained by reacting a processing agent capable of introducing anionic groups into cellulose molecules with cellulose, and then converting the resulting cellulose into cellulose acetate or viscose rayon. 2. The fabric according to claim 1, which is a cellulose acetate or viscose rayon fabric containing fibers. 10. A treatment agent capable of reacting with cellulose molecules to introduce a cationic group into the cellulose molecules has the formula [I]: ▲ Formula,
There are chemical formulas, tables, etc.▼[I] (In the formula, represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. 11. The fabric according to item 10, wherein the processing agent is a compound represented by the formula [I a]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I a]. 12. The treatment agent that can react with cellulose molecules and introduce anionic groups into the cellulose molecules has the formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y has the same meaning as in item 10. , each of Z_1 and Z_2 represents an oxygen atom or an imino group or an alkylimino group, and Ar_1 and Ar_2 may be the same or different and each represents an unsubstituted or substituted phenyl group or a naphthyl group. However, Ar_1
At least one of Ar_2 and Ar_2 has one or more anionic groups. ) The fabric according to item 2, item 4, item 7 or item 9, which is a compound represented by: 13. The fabric according to item 12, wherein the processing agent is a compound represented by the formula [IIa]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[IIa]. 14. Cellulose fiber with the formula [II]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (In the formula, Y has the same meaning as in item 10, Z_1,
Z_2, Ar_1 and Ar_2 have the same meanings as in item 12. 15. The method according to item 14, wherein the compound is a compound when it is represented by the formula [IIa]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IIa]. 16. Receptivity to anionic dyes comprising reacting cellulose with a treatment agent capable of introducing cationic groups into the cellulose molecule and then converting the so treated cellulose to cellulose acetate or viscose rayon. An improved method for producing cellulose acetate or viscose rayon. 17. Improved receptivity to cationic dyes, comprising reacting cellulose with a treatment agent capable of introducing anionic groups into the cellulose molecule and then converting the thus treated cellulose to cellulose acetate or viscose rayon. A method for producing cellulose acetate or viscose rayon. 18. The method according to item 16, wherein the processing agent is the treatment agent according to item 10 or 11. 19. Cellulosic yarn comprising cellulosic fibers subjected to dye affinity increasing treatment and one or more cellulosic fibers having different dye affinities. 20. A fabric obtained by dyeing the dyeable fabric according to any one of items 1 to 13. 21. A dyeable garment produced from the fabric according to any one of items 1 to 13.