JP2003049372A - Method of dyeing cellulosic fiber product with natural dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of dyeing cellulosic fiber products in high dye concentration with increased fastness in a shortened time with reproducibility by using pretreatment and after-treatment solutions and the dye liquors including no or reduced amounts of harmful matters under the good environment for dyeing with reduced environmental load of the waste liquid treatment. SOLUTION: The cellulosic fiber products are treated with an aqueous alkali solution including 3-50 wt.% of alkali based on 100 wt.% of the products at 50-110 deg.C and dyed with natural dyes using a mordant.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for dyeing a cellulose fiber product made of cotton, hemp, rayon, fiber, etc. with a natural dye such as a plant dye, an animal dye or a mineral dye using a mordant. It is a thing.

[0002]

2. Description of the Related Art Conventionally, this type of cellulose fiber product is
Generally, it was dyed with a reactive dye, a sulfur dye, a vat dye, a naphthol dye, a direct dye or an organic pigment.
When dyeing, these chemical dyes require a large amount of salts, alkalis or surfactants as leveling agents. On the other hand, since ancient times dyeing methods using natural dyes such as plant dyes as cellulosic fiber products to be dyed have been handed down as traditional industrial dyeing methods such as tie dyeing and wax dyeing, but these dyeing methods are all hand dyed. However, a general method is to immerse the natural fiber in a dye liquor for a long time at a low temperature or repeatedly dye it to obtain a color having a predetermined density.

[0003]

However, when dyeing with a chemical dye such as a reactive dye, the dye liquor contains harmful chemical substances, a strong alkaline liquid, and a harmful surfactant. Wastewater had to be treated before being discharged into a general river. In addition, when dyeing with natural dyes, there is a problem that dyeing fastness such as light fastness, wet fastness, rubbing fastness, washing fastness, etc. is extremely low, and special dyeing equipment is required, and a large amount of dyed products are required. However, there is a problem in that it cannot be dyed reproducibly and uniformly at low cost.

The object of the present invention is to provide a treatment liquid before and after dyeing and a dyeing liquid containing no or relatively no harmful substances, which improves the working environment at the time of dyeing and reduces waste liquid treatment. To provide a dyeing method for products. Another object of the present invention is to provide a method for dyeing a cellulose fiber product with high reproducibility in a short time at high concentration and high fastness with a natural dye. Still another object of the present invention is to provide a dyeing method capable of dyeing a cellulose fiber product with a natural dye inexpensively and in a large amount at a commonly used dyeing facility.

[0005]

The invention according to claim 1 is
50% by weight of an aqueous alkaline solution containing 3 to 50% by weight of the cellulose fiber product with respect to 100% by weight of the cellulose fiber product.
This is a method in which after treating at a temperature of up to 110 ° C., this cellulose fiber product is dyed with a natural dye using a mordant. By pre-treating a cellulose fiber product with an alkaline aqueous solution under the above-mentioned conditions, natural impurities such as pectin, fats and impurities are removed and hydrophilicity is obtained without changing the crystallinity of the fiber. Further, since the natural pigment acts on the fiber on the alkaline side, its affinity is improved. From these facts, the alkali pretreatment enhances the dyeability of the cellulose fiber product.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Cellulose fiber product The fiber product to be dyed in the present invention includes cotton, hemp,
It is a cellulosic fiber product such as rayon, kenaf, mitsumata, kozo, as well as filament yarn made from Manila hemp or bamboo. It can also be applied to a product made of a mixed fiber of cellulose fiber and other fiber. The forms of these products are fiber, web, top, sliver,
Examples thereof include threads, nets, knitted fabrics, woven fabrics, and non-woven fabrics. (b) Natural pigments and dyes The natural pigments include plant pigments, animal pigments, mineral pigments and the like. The plant pigments include gardenia, enju, yamamo, catechu, quintet, logwood, pomegranate, kariyasu, wood (haze), yellow leaf, yellow oak, Suou, tsurubami, kunugi, Chestnut, cedar, cypress, plum, indigo,
Akane, safflower, turmeric, stink tree, areca nut, persimmon astringent, tea and so on. In addition, examples of animal pigments include cochineal, purple shellfish, and rack dye. Further mineral pigments include
Examples include mud such as mulch and loess. The chemical composition of these pigments includes carotenoids such as carotene and xanthophyll, chlorophyll, flavonoids such as flavones, flavonols, anthocyans, chalcones, and aurones, quinones such as naphthoquinone and anthraquinone, polyphenols such as tannin, and indigo. Such as indole, other benzopyrans, alkaloids, diketones. The natural pigment of the present invention is used in the form of a solid (preferably powder) or a concentrated aqueous solution, which is dissolved or dispersed in water at a ratio of 0.001 to 50% by weight of the cellulose fiber product to be dyed. Melting temperature is 10
Keep below 0 ° C. In addition, dyeing with natural pigments is 25-11
10 to 12 at a temperature of 0 ° C., preferably 60 to 100 ° C.
It is carried out for 0 minutes, preferably for 20 to 40 minutes. If the temperature and the time are below the lower limits, the dyeing of the natural pigment to the cellulose fiber is not sufficient, and if the respective upper limits are exceeded, the cellulose fiber product is discolored after dyeing, or the pigment may fall off. The pH of the dye liquor is adjusted to 5.0 to 9.0. No salt is used for dyeing. Table 1 below
Shows the details of natural products containing typical dyes and their dyeing fastness. In Table 1, the light fastness is a value based on the JIS L 842 method when dyed with a natural dye of 3% concentration, and the washing fastness is also a value based on the JIS L 0844 A-2 method.

[0007]

[Table 1]

(C) Alkali Aqueous Solution and Alkali Pretreatment Aqueous alkali solutions are potassium and sodium salts of silicic acid, potassium and sodium salts of secondary phosphoric acid, potassium and sodium salts of tertiary phosphoric acid, potassium carbonate. 1 or 2 selected from the group consisting of salts and sodium salts, potassium and sodium salts of pyrophosphoric acid, potassium and sodium salts of hydrogen carbonate, caustic soda and caustic potash.
Including more than one species. The blending ratio is 3 to 50% by weight, preferably 5 to 10% by weight, based on 100% by weight of the cellulose fiber product to be dyed. If it is less than the lower limit, the effect of the alkali pretreatment is poor, and if it exceeds the upper limit, the strength of the cellulose fiber is lowered, or it causes uneven dyeing. The alkaline pretreatment is carried out at a temperature of 25 to 110 ° C., preferably 60 to 100 ° C. for 5 to 30 minutes, preferably 5 to
20 minutes will be held. If the temperature and the time are less than the lower limits, respectively, the effect of the alkali pretreatment is poor, and if the temperatures and the times are more than the respective upper limits, the strength of the cellulose fiber is reduced and uneven dyeing occurs. For example, in the case where the cellulose fiber is cotton, alkali pretreatment with caustic soda having a Baume degree of 5 to 22 gives wrinkle-proof property to the cellulose fiber product, thereby improving gloss and dyeing fastness. (d) Mordant and mordant treatment In the dyeing method of the present invention, treatment of the cellulose fiber product with the mordant is essential. The mordant is one or more compounds selected from tannic acid, lye, ocher, iron acetate wood, iron oxide, copper oxide, aluminum oxide, tin oxide, aluminum acetate, aluminum sulfate and copper sulfate.
Tannic acid or lye is 1 to 100% by weight, preferably 5 to 20% by weight, of the cellulose fiber product which is the object to be treated. Further, loess, iron oxide, copper oxide, aluminum oxide containing alum, tin oxide, aluminum acetate, and aluminum sulfate are 1 to 30% by weight, preferably 5% by weight of the object to be treated.
10 to 10% by weight. When the ratio of the mordant is less than the lower limit, the color development of the natural dye is not sufficient, and even when it exceeds the upper limit, the effect is unchanged. Therefore, the mordant treatment is performed within the above range. The mordant treatment is 25 to 100 ° C., preferably 80 to 100.
It is carried out at a temperature of ° C for 5 to 40 minutes, preferably 5 to 20 minutes. If the temperature and time are less than the lower limits, the effect of the mordant treatment is poor, and if they exceed the upper limits, coloring and uneven dyeing due to the mordant occur and a desired hue cannot be obtained. There is also a method in which the mordant is previously made into a chelate compound with a chelating agent in order to uniformly react the mordant with the object to be treated. In this case, the chelate compound is reacted with the object to be treated, and then the chelate state is released to restore the function of the original mordant. This mordant treatment is performed before or after dyeing the cellulose fiber product with the natural pigment, before or after, or during dyeing. The timing of this mordant treatment is determined by the natural dye used, the mordant and the hue to be obtained. Table 2
Shown in.

[0009]

[Table 2]

(E) Morphological stabilizing treatment and / or thickening treatment (cationizing treatment / anionizing treatment) The present invention is a shrink-proof, wrinkle-proof, fluff-proof, anti-pilling, softening agent for cellulose fiber products to be treated. For the purpose of morphological stability such as treatment or thickening, it is preferable to treat the cellulose fiber product with an aqueous solution containing a colorless reactive substance having two or more polyfunctional groups. This morphological stabilization treatment or thickening treatment is performed before or after dyeing. The morphological stabilization treatment or the deep dyeing treatment is performed after the cellulose fiber product is treated with the alkaline aqueous solution and before the mordant treatment, or together with the treatment with the alkaline aqueous solution. The content of the reactive substance in the treatment liquid is 1 to 50 relative to 100% by weight of the cellulose fiber product.
% By weight, preferably 10 to 20% by weight. If the proportion of the reactive substance is less than the lower limit, the morphological stability or the deep-dyeing effect is not sufficient, and even if it exceeds the upper limit, the effect remains unchanged. Be seen. Further, the morphological stabilization treatment or the deep dyeing treatment is 25 to 100.
C., preferably 80-100.degree. C., for 5-30 minutes,
It is preferably carried out for 10 to 20 minutes. If the temperature and time are below the respective lower limits, the effect of the morphological stabilization treatment or the deep dyeing treatment is poor, and if the respective temperatures and the time are above the respective upper limits, the adsorption of the natural pigment to the cellulose fibers is significantly hindered. Examples of the reactive substance include a cationizing agent and an anionizing agent.

Examples of the cationizing agent include reactive nitrogen-containing compounds such as quaternary ammonium salts, polyfunctional quaternary ammonium salts, glycidyl trimethyl ammonium chloride, and cationic surfactants. The cationization treatment with the reactive nitrogen-containing compound also has the effect of increasing the dyeing density. Further, as the anionizing agent, 2,4-dichloro-s-triazin-6-yl-p-aminosalicylic acid sodium salt, 2,4-dichloro-s-triazin-6-yl-m-aminophenylphosphonic acid sodium salt Salt, 2,4-dichloro-s-triazin-6-yl-aniline, 2,4-dichloro-s-triazin-6-yl-pn-butyl-aniline, 2,4-dichloro-s-
Triazin-6-yl- (1-naphthylamine), dichlorotriazinyl sulfanilic acid sodium salt, dichlorotriazinylmethanilic acid sodium salt, (1, 3, 5
-Triacryloylhexahydro-s-triazine) triacrylformal, 1,3,5-tris- (2-methylacryloyl) -hexahydro-s-triazine,
1,3,5-Tris- (2-methylacryloyl) -hexahydro-es-triazine, 1,3,5-tris-
(2-Propylacryloyl) -hexahydro-S-
Triazine, 1,3,5-tris- (2-isopropylacryloyl) -hexahydro-s-triazine, 1,
3,5-Tris- (2-butylacryloyl) -hexahydro-s-triazine, 1,3,5-tris- (2-
Isobutylacryloyl) -hexahydro-s-triazine, 1-acryloyl-3,5-bis- (2-ethylacryloyl) -hexahydro-s-triazine, 1-
(2-Butylacryloyl) -3,5-bis- (2-ethylacryloyl) -hexahydro-es-triazine, 2,4-dichloro-6- (o-chloroanilino)-
1,3,5-triazine, 2,4-dichloro-4-hydroxy-1,3,5-triazine, triacryloyl-
Hexahydro-1,3,5-triazine and 1-ethoxy-4- (dichloro-1,3,5-triazinyl) -naphthalene, triaryl cyanurate, triaryl isocyanurate, trimetalyl isocyanurate, microbutanyl (2- p-chlorophenyl-2- (1h-1,2,
4-triazol-1-yl-methyl)) is included.

By treating with the above anionizing agent,
The surface of the object to be treated is anionized. As a result, the binding between the cellulose fiber and the natural pigment is suppressed, the reduction in the friction fastness due to surface dyeing is improved, and the texture of the cellulose fiber product becomes soft. Further, triacryloyl-hexahydro-1,3,5-triazine, triazine derivative (trade name: Sandspace R) and the like cross-link with the cellulose fiber to improve the morphological stability of the fiber product. (f) Treatment or dyeing equipment For the alkaline pretreatment, morphological stabilization treatment, mordant treatment and dyeing of the present invention, the conventional equipment for chemical dyeing according to the form of the cellulose fiber product is used as it is, and special equipment or No equipment needed. That is, a conventional high-pressure or normal-pressure dyeing device for dyeing a chemical dye can be used. When the cellulosic fiber product is a cloth, a machine for spreading the cloth into a rope shape for dyeing, a machine for packing the cloth in a tumbler for dyeing, or the like can be used. Either batch or continuous equipment can be used. (g) Determine the complete exhaust concentration of the natural pigment according to the type of uncolored cellulosic fibers in the waste liquor, the type of natural pigment, and the dyeing concentration of the fiber product, and the amount of the natural pigment used from this complete exhaust concentration. To calculate.
By dyeing based on this calculated amount, it is possible to reduce the dye component in the waste liquid to almost zero, eliminate the coloring of the waste liquid, reduce the dye cost, and further improve the wet dyeing fastness of the dyed product. .

[0013]

EXAMPLES Next, examples of the present invention will be described together with comparative examples. <Example 1> The following series of treatments and dyeing were carried out using a jet type skein dyeing machine for a yarn made from Manila hemp (23/1). First, after putting the fiber-making yarn in the skein dyeing machine, 1 part of sodium phosphate tribasic (Na ₃ PO ₄ ) is added to 100% by weight of the fiber-making yarn.
An alkaline aqueous solution containing 0% by weight was placed in the dyeing machine. The alkaline aqueous solution was heated from 50 ° C. and treated at 100 ° C. for 10 minutes to treat the fiber-making yarn (alkaline pretreatment). After deliquoring, the papermaking yarn was thoroughly washed with water. Then, an aqueous solution containing 10% by weight of ferric oxide with respect to 100% by weight of the fiber-making yarn is put into a skein dyeing machine,
This liquid was heated from 50 ° C. and treated at 100 ° C. for 15 minutes to treat the fiber-forming yarn (pre-mordanting treatment). After deliquoring, the papermaking yarn was thoroughly washed with water. Next, a dye liquor containing 10% by weight of logwood with respect to 100% by weight of the fiber-making yarn is put into a dyeing machine and 50
Increase the temperature from 100 ℃ to 100 ℃ in 20 minutes,
The textile yarn was dyed for a minute. As a result, a navy blue dyed yarn was obtained. <Comparative Example 1> Except that the alkali pretreatment is not performed in Example 1,
As in Example 1, the same fiber yarns as in Example 1 were pre-morded and then dyed.

Example 2 Cotton yarn (100/2) was subjected to the following series of treatments and dyeings using a high-pressure package dyeing machine. First, put the cotton thread in the dyeing machine, and then add Na ₃ PO ₄ to the cotton thread 1
An alkaline aqueous solution containing 10% by weight with respect to 00% by weight was put into the dyeing machine. This alkaline aqueous solution was heated from 50 ° C. and the cotton yarn was treated (alkaline pretreatment) at 100 ° C. for 10 minutes. After draining, the cotton thread was thoroughly washed with water. Then, a solution containing 50 g / l of cathionone UK and 20 g / l of caustic soda was put in a dyeing machine, the solution was heated from 30 ° C to 70 ° C, and the cotton yarn was treated (cationized) at 70 ° C for 30 minutes. . Then, add ferric oxide and copper sulfate to the cotton thread 10
Aqueous solutions containing 10% by weight and 10% by weight with respect to 0% by weight were put in a dyeing machine, and the solution was heated from 50 ° C. to treat cotton yarn at 100 ° C. for 10 minutes (pre-mordanting treatment). After draining, the cotton thread was thoroughly washed with water. Next, the rack die is cotton thread 1
A dye liquor containing 10 wt% to 00 wt% was put in a dyeing machine, and the dye liquor was heated from 50 ° C. to 100 ° C. in 20 minutes to dye cotton threads at 100 ° C. for 30 minutes. As a result, a cotton thread dyed in a dark engine color was obtained.

Comparative Example 2 The same cotton yarn as in Example 2 was cationized, dyed after mordanting as in Example 2, except that the alkali pretreatment was not carried out. <Comparative Evaluation 1> The dyeing density and dyeing fastness of each yarn of Examples 1 and 2 and Comparative Examples 1 and 2 were measured. The results are shown in Table 3. In Table 3, the light fastness is JIS L 0842 method,
Washing fastness is JIS L 0844 A-2 method, friction fastness is the same as JI
The SL 0849 method and the staining density were measured based on the CIELab method.

[0016]

[Table 3]

As is clear from Table 3, the K-S value of the dyeing density of the fiber-making yarn of Example 1 is about 1.75 times that of the fiber-making yarn of Comparative Example 1, and the color saturation is high. Was excellent. The fixing of the dye to the fiber of Example 1 was more satisfactory than that of the fiber of Comparative Example 1, and the fastness to washing and the fastness to rubbing were superior to those of Comparative Example 1. Further, the cotton yarn of Example 2 had a K / S value of the dyeing density of about 1.6 times that of the cotton yarn of Comparative Example 2, and was excellent in color saturation. The cotton yarn of Comparative Example 2 had a light density and a desired engine color could not be obtained. Example 2
The fixation of the dye to the cotton yarn of No. 2 was more satisfactory than that of the cotton yarn of Comparative Example 2, and the washing fastness and rubbing fastness were also superior to those of Comparative Example 2.

Example 3 100% ramie (ramie) yarn (40/2) was subjected to the following series of treatments and dyeings using a high-pressure package dyeing machine. First, after putting the ramie yarn in the dyeing machine, an alkaline aqueous solution containing 10% by weight of sodium silicate with respect to 100% by weight of the ramie yarn was put in the dyeing machine. This alkaline aqueous solution is heated from 50 ° C to 10 ° C at 100 ° C.
The ramie yarn was treated for a minute (alkaline pretreatment). After draining,
The ramie yarn was thoroughly washed with water. Then sand space R
A liquid containing (triazine derivative) at a rate of 50 g / liter was put into a dyeing machine, the liquid was heated from 30 ° C. to 100 ° C., and the ramie yarn was treated (anionization treatment) at 100 ° C. for 20 minutes. Next, an aqueous solution containing 10% by weight of aluminum sulfate with respect to 100% by weight of the ramie yarn was put into a dyeing machine, the temperature of this liquid was raised from 50 ° C, and the ramie yarn was treated at 100 ° C for 15 minutes (pre-mordanting treatment). After draining, the ramie yarn was thoroughly washed with water. Next, a dyeing liquor containing 5% by weight of gardenia to 100% by weight of the ramie yarn is put into a dyeing machine, and the dyeing liquor is heated from 50 ° C. to 100 ° C. in 20 minutes to dye the ramie yarn at 100 ° C. for 30 minutes. did. As a result, a very bright golden dyed ramie yarn was obtained.

<Comparative Example 3> The same ramie yarns as in Example 3 were anionized as in Example 3 except that the alkali pretreatment was not carried out in Example 3, and the dyeing was carried out with the mordanting. <Comparative Evaluation 2> Using each of the ramie yarns of Example 3 and Comparative Example 3, a cloth for a men's blazer was woven, and then the cloth was scoured and finished. Example 3 and Comparative Example 3
Each of the finished fabrics using was tested for wrinkle resistance, pilling, and washing shrinkage together with the dyeing density. The results are shown in Table 4. In Table 4, wrinkle resistance is according to Monsanto method, pilling is according to JIS L 1076 method,
The washing shrinkage was tested based on JIS L 1042 method. The staining density was determined by the same method as in the comparative evaluation.

[0020]

[Table 4]

As is clear from Table 4, the fabric of the ramie yarn of Example 3 has a K / S value of the dyeing density of about 1.2 times that of Comparative Example 3 and is excellent in color saturation. Was there. The dough made from the ramie yarn of Example 1 was less likely to wrinkle as compared with that of Comparative Example 3, and it did not shrink even after washing, and pills were also difficult to occur.

Example 4 A circular knit product of 120d viscose rayon 100% was subjected to the following series of treatments and dyeings using a jet dyeing machine. First, after putting the knit product in the dyeing machine, an alkaline aqueous solution containing 5% by weight of caustic potash to 100% by weight of the knit product was put in the dyeing machine. This alkaline aqueous solution is heated from 50 ° C to 10 ° C at 100 ° C.
The knit product was treated (alkaline pretreatment) for minutes. After draining, the knit product was thoroughly washed with water. Then, an aqueous solution containing 6% by weight of tannic acid with respect to 100% by weight of the knit product was put into a dyeing machine, the temperature of the liquid was raised from 50 ° C., and the knit product was treated at 100 ° C. for 15 minutes (pre-mordanting treatment). After draining, the knit product was thoroughly washed with water. Next, a dyeing liquor containing 1% by weight of log wood to 100% by weight of a knit product is put in a dyeing machine, and the dyeing liquor is heated from 50 ° C. to 100 ° C. in 20 minutes to produce a knit product at 100 ° C. for 30 minutes. Stained.
After dyeing, it was drained, but was not washed with water, and the following mordant treatment was performed. That is, a stock solution of copper sulfate is put into a dyeing machine, and this solution is
The knit product was treated at 10 ° C. by raising the temperature from 80 ° C. for 10 minutes (post-mordanting treatment). As a result, a beautiful and deep green dyed knit product was obtained.

Comparative Example 4 The same knit product as in Example 4 was dyed by pre-mordanting and post-mordanting in the same manner as in Example 4 except that the alkali pretreatment was not carried out in Example 4. <Comparative Evaluation 3> The dyeing fastness of each knit product of Example 4 and Comparative Example 4 was measured. The results are shown in Table 5. In Table 5, sweat fastness was measured based on JIS L 0848 method. Other tests of fastness were performed based on the same test method as the comparative evaluation.

[0024]

[Table 5]

As is clear from Table 5, when the hues after dyeing of the knit products of Example 4 and Comparative Example 4 were compared, the knit product of Example 4 was green, whereas The knit product of Example 4 was a light gray color and did not give the desired hue. In addition, the knitted product of Example 4 was superior to the knitted product of Comparative Example 4 in each test result of light resistance, washing, sweat and wet friction.

[0026]

As described above, according to the present invention, the cellulose fiber product is contained in an amount of 3 to 50 with respect to 100% by weight of the product.
After treating with an alkaline aqueous solution containing 50% by weight at a temperature of 50 to 110 ° C., and dyeing the cellulose fiber product with a natural dye using a mordant, no harmful substances are contained in the treatment liquid and the dyeing liquid before and after dyeing. Relatively little work environment can be improved during dyeing, and waste liquid treatment can be reduced. Further, the cellulose fiber product can be dyed with high reproducibility with high density and high fastness in a short time with the natural dye. Further, it is possible to dye a large amount at a low cost with a commonly used dyeing equipment.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masuichi Mori             36-1 Kaimeijin Mitsuma, Bisai City, Aichi Prefecture F-term (reference) 4H057 AA02 BA32 CA03 CA37 CB03                       CB18 CB38 CB47 CB53 CB54                       CB58 CB60 CC01 CC02 CC03                       DA01 DA24 FA17 GA26 GA27                       HA01 JB01

Claims (8)

[Claims] 1. An alkaline aqueous solution containing a cellulose fiber product in an amount of 3 to 50% by weight based on 100% by weight of the product is used.
A method of dyeing the cellulose fiber product with a natural dye using a mordant after treating at a temperature of 110 ° C. 2. An alkaline aqueous solution comprising potassium and sodium salts of silicic acid, potassium and sodium salts of secondary phosphoric acid, potassium and sodium salts of tertiary phosphoric acid, potassium and sodium salts of carbonic acid, and pyrophosphate. The method according to claim 1, which is an alkaline aqueous solution containing one or more selected from the group consisting of potassium salts and sodium salts, potassium salts and sodium salts of hydrogen carbonate, caustic soda and caustic potash. 3. The method according to claim 1, wherein the treatment of the cellulosic fiber product with a mordant is carried out before, after or before or after the cellulosic fiber product is dyed with a natural dye or before or during the dyeing.
The method described. 4. The mordant is one or more compounds selected from tannic acid, lye, ocher, iron acetate, iron oxide, copper oxide, aluminum oxide, tin oxide, aluminum acetate, aluminum sulfate and copper sulfate. The method according to claim 3, wherein 5. 1 to 50 relative to 100% by weight of said product, before or after dyeing the cellulose fiber product with a natural dye.
5. The cellulose fiber product is subjected to either one or both of a morphological stabilization treatment and a deep dyeing treatment with an aqueous solution containing 2% by weight of a colorless reactive substance having two or more polyfunctional groups. the method of. 6. The morphological stabilization treatment and the deep dyeing treatment are cationization treatment with a reactive nitrogen-containing compound, wherein the reactive nitrogen-containing compound is a quaternary ammonium salt, a polyfunctional quaternary ammonium salt, or glycidyl. The method according to claim 5, comprising at least one of trimethylammonium chloride and a cationic surfactant. 7. The morphological stabilization treatment is an anionization treatment with an anionizing agent, wherein the anionizing agent is 2,4-dichloro-s-triazin-6-yl-p-aminosalicylic acid sodium salt, 2,
4-dichloro-s-triazin-6-yl-m-aminophenylphosphonic acid sodium salt, 2,4-dichloro-
s-triazin-6-yl-aniline, 2,4-dichloro-s-triazin-6-yl-pn-butyl-aniline, 2,4-dichloro-s-triazin-6-yl-
(1-naphthylamine), dichlorotriazinylsulfanilic acid sodium salt, dichlorotriazinylmethanilic acid sodium salt, (1,3,5-triacryloylhexahydro-es-triazine) triacrylformal, 1,3,5 -Tris- (2-methylacryloyl)
-Hexahydro-s-triazine, 1,3,5-tris- (2-methylacryloyl) -hexahydro-S-
Triazine, 1,3,5-tris- (2-propylacryloyl) -hexahydro-es-triazine, 1,
3,5-Tris- (2-isopropylacryloyl)-
Hexahydro-s-triazine, 1,3,5-tris-
(2-Butylacryloyl) -hexahydro-s-triazine, 1,3,5-tris- (2-isobutylacryloyl) -hexahydro-s-triazine, 1-acryloyl-3,5-bis- (2-ethylacryloyl) −
Hexahydro-s-triazine, 1- (2-butylacryloyl) -3,5-bis- (2-ethylacryloyl) -hexahydro-es-triazine, 2,4-dichloro-6- (o-chloroanilino) -1, 3,5-triazine, 2,4-dichloro-4-hydroxy-1,3
5-triazine, triacryloyl-hexahydro-
1,3,5-Triazine and 1-ethoxy-4- (dichloro-1,3,5-triazinyl) -naphthalene, triaryl cyanurate, triaryl isocyanurate, trimethallyl isocyanurate, microbutanyl (2-p
At least one of -chlorophenyl-2- (1h-1,2,4-triazol-1-yl-methyl)).
The method described. 8. The method according to claim 7, wherein the morphological stabilization treatment with an aqueous solution containing an anionizing agent is performed after the cellulose fiber product is treated with the alkaline aqueous solution, before the mordant treatment, or together with the treatment with the alkaline aqueous solution. .