JPS5828393B2 - How to use cellulose - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves one-bath pad dyeing or one-phase printing of textile products containing cellulose fibers using a dye solution or color paste containing a reactive dye that can directly react and bond with cellulose fibers. Regarding the method.

Cellulose fibers have long been indispensable in the clothing field due to their unique properties, but on the other hand, synthetic fibers such as acrylic fibers and polyester fibers have recently been used to improve various functions. Active efforts are also being made to combine them with

Direct dyes and reactive dyes are generally used for dyeing cellulose fibers, and reactive dyes in particular provide vivid color tones and relatively good color fastness, so they almost satisfy the high demands of current consumption levels. It is widely used.

On the other hand, when dyeing synthetic fibers that are combined with cellulose fibers, different dye types and dyeing conditions are used than when using the above dyes for cellulose fibers.

For example, high-temperature dyeing using disperse dyes is commonly used for polyester fibers such as T/C blends.

In this way, the dyeing process of composite fiber materials containing cellulose fibers is complicated because a fixing process is required for each dye component, and the color tone of the dyed product may become dull because the optimum dyeing conditions cannot be adopted. There are also various concerns about deterioration in quality, such as a decrease in color fastness.

Furthermore, in the case of cellulose fibers, when used as spring/summer materials, some color fastness problems may arise even if reactive dyes are used.

That is, although the general color fastness is relatively good, the complex fastness against wet rubbing, perspiration, sunlight, etc. causes problems in practice when the concentration of the dye used becomes high.

Therefore, in the dyeing of textile products containing cellulose fibers, there is a strong desire for technological development aimed at both streamlining the process and improving quality, such as improving color fastness.

Furthermore, regarding process rationalization in pad dyeing and textile printing, for example, the alkali shock method, the print dry method, and recently the union color method have been developed.

Furthermore, resin processing has been adopted to improve color fastness and reduce residual shrinkage during washing and ironing.

However, a sufficient method has not yet been found to simultaneously satisfy these three major drawbacks of composite fiber materials containing cellulose fibers.

For example, the prodione resin method is known as a method for simultaneously performing dye fixation and resin processing, in which a reactive dye is used together with an aminoplast resin initial condensate and a strong acidic catalyst, and dry heat baking is performed under acidic conditions. .

However, under acidic conditions, the reactive dye does not bond sufficiently with cellulose fibers, leaving problems with color development, fastness, etc.

Furthermore, when a vinyl sulfone-based reactive dye is used, the dye often comes off during washing.

Furthermore, even when urea-formalin monomers, N-methylol acrylamide, etc. are used in a simultaneous method, a two-phase method is required to ensure sufficient dye fixation, and the problem of free formalin generation arises in dyed products.

The method of the present invention solves the above-mentioned three major drawbacks in dyeing cellulose fiber composite fiber materials at once.

That is, the present invention provides a method for pad dyeing or printing using a dye solution or color paste containing a reactive dye that can directly react and bond with cellulose fibers. A hexahydrotriazine compound and an active hydrogen-containing sulfonic acid represented by the general formula (where Y is H, NH2, an aminoalkyl group having 1 to 3 carbon atoms, and X is hydrogen or an alkali metal) are combined into the above general formula ( 1) to the hexahydrotriazine compound in a molar ratio of 1.0 or less, further adding a halogenated acetate, and p
This is a dyeing process for cellulose fiber products, which is characterized by pad dyeing or printing using a dye solution or colored paste in which H is adjusted to 7 or less.

According to the method of the present invention, a heating-phase fixing method is possible, and it has a remarkable effect on improving the color fastness of the dyed product and reducing shrinkage during washing.

Generally 1,3,5-triacryloyl-hexahydro-
Hexahydrotriazine compounds represented by the above general formula (1), represented by s-triazine, have been studied for a long time for the purpose of modifying cellulose fibers.

For example, US Pat. No. 3,016,281 describes a method for improving the dimensional stability and wrinkle resistance of cellulose fibers using similar compounds.

However, it has been difficult to apply hexahydrotriazine compounds to cellulose fibers due to their poor solubility.

In the present invention, the sulfonic acid compound of the above general formula (2) is added to hexahydrotriazine at a molar ratio of 1.0 or less, and a portion thereof is reacted to effect sulfonation.

The presence of this sulfonate makes it extremely easy to water-solubilize the remaining unreacted hexahydrotriazine, and, like the unreacted hexahydrotriazine, it undergoes a crosslinking reaction with cellulose fibers under alkaline conditions, resulting in cellulose fibers. significantly suppresses the degree of water swelling.

Therefore, after crosslinking is formed, it not only prevents shrinkage during washing but also improves various types of wet fastness, as in the case of using a known hexahydrotriazine compound alone.

On the other hand, in pad dyeing and textile printing, a one-phase method is desirable in order to streamline the processing process.

In this case, the reactive dye and hexahydrotriazine coexist and simultaneously react with the cellulose fiber under alkaline conditions.

Sulfonic acids containing active hydrogen, such as the aminosulfonic acid of general formula (2) above, have the effect of accelerating the reaction of reactive dyes and hexahydrotriazine to cellulose fibers in the same way as urea etc. As the amount of reaction increases, the amount of reaction (color yield and degree of crosslinking) becomes extremely large.

From these phenomena, it is desirable that the amount of the sulfonic acid added be within a molar ratio of 1.0 or less to hexahydrotriazine.

The method of the present invention has a completely different mechanism from the process of fixing reactive dyes that do not have direct reactivity with cellulose fibers.
For example, Pasazol Color, a type of commercially available reactive dye,
(manufactured by BASF, registered trademark) is bonded to cellulose fibers via a hexatriazine-based crosslinking agent, and such dyes do not directly react with cellulose fibers and therefore do not improve fastness.

However, in the method of the present invention, the reactive dye used is also directly reactively bonded to the cellulose fibers in the same manner as the hexatriazine compound.

The purpose of using a halogenated acetate in the method of the present invention is to control the pH during dye fixation.

These compounds generally have low heat resistance; for example, sodium trichloroacetate gradually decomposes when heated according to the reaction formula below.
Next, soda carbonate is produced from baking soda, changing the pH from acidic to neutral real alkaline.

This transition of pH from acidic to alkaline during heating has an important meaning in fixing dyes to composite fiber materials including cellulose fibers.

In other words, disperse dyes and cationic dyes are used together with reactive dyes in polyester-mixed products and acrylic-mixed products, but the pH of these dyes when fixed is weakly acidic or acidic, and many of them have poor stability in an alkaline atmosphere. Easily discolored or decomposed.

Therefore, when using the one-phase fixation method, the dye is first diffused onto the other fiber under acidic or weakly acidic conditions with a PR of 7 or less, and then the reactive dye is applied onto the cellulose fiber under alkaline conditions. should be fixed, and this pH
The use of the halogenated acetates mentioned above as a control is truly effective.

It is a well-known fact that disperse dyes and cationic dyes that have diffused into the fibers are relatively stable even in an alkaline atmosphere; The combined use of dye accelerants, fiber swelling agents, etc. to promote this is desirable even in illegal cases.

Furthermore, when a reactive dye and a cationic dye having different ionic properties are used in combination, consideration should naturally be given to the combined use of a suspending agent to prevent the formation of complex salts.

On the other hand, both the reactive dye and the hexahydrotriazine compound are relatively stable when the pH is acidic.

Therefore, under pre-adjusted acidic conditions, as the temperature rises, the dye first diffuses into the synthetic fiber for composite materials, and then as the pH gradually becomes alkaline due to thermal decomposition of the halogenated acetate, the reactive dye and hexahydrocarbon The triazine compound is diffused and fixed inside the cellulose fiber.

Not only in the case of composite fiber materials with synthetic fibers, but also in the case of cellulose fiber alone, it is better to gradually change the pH from acid to alkaline than to make the pH alkaline from the beginning with baking soda or soda carbonate. The color development efficiency and the crosslinking efficiency of the hexatriazine compound are good.

Furthermore, even in such cases, the presence of active hydrogen-containing sulfonic acid is effective in preventing bleeding and migration during the drying process, and also increases the rate of reaction and fixation between cellulose fibers and the above-mentioned reactive dyes. A vivid dyed product with extremely good fastness can be obtained.

The textile products containing cellulose fibers referred to in the present invention are cellulose fibers, for example, natural fibers such as cotton and hemp, or recycled cellulose fibers such as viscose rayon and Qubu Y, or these cellulose fibers and acetate, polyester, It refers to fibrous structures such as yarns, knitted fabrics, non-woven fabrics, etc., which are made of semi-synthetic fibers such as polyamide and acrylic fibers, mixed fibers such as synthetic fibers, blended fibers, and composites made by inter-knitting machines.

Reactive dyes that can bind directly to cellulose fibers include mono- and dihalogenotriazinyl groups, di- and trihalogenopyrimidinyl groups, methylsulfonylchloromethylpyrimidinyl groups, dichloroquizalinyl groups, sulfatoethylsulfonamide groups, and sulfatoethylsulfonamide groups. Those having reactive functional groups such as ethylsulfonyl group and vinylsulfonyl group are generally used, and among these, those having good compatibility with the hexahydrotriazine compound used in the present invention are desirable.

As a pH adjuster for adjusting the pH of the dye solution or color paste to 7 or lower in advance, it is preferable to use an organic carboxylic acid having 6 or less carbon atoms, such as formic acid, acetic acid, propionic acid, tartaric acid, oxalic acid, citric acid, and malic acid. etc., preferably P
It will be adjusted to H4-6.

This PH region is necessary for dyeing the mating fiber and at the same time can inhibit the hydrolysis of the reactive dye and hexahydrotriazine.

Example Lubafix Fluor P-3GL (Reactive dye manufactured by Bayer, registered trademark) 257.1.3.5-Triacryloyl-
Hexatriazine 30? , sulfamino acid soda 7.5
P Sodium trichloroacetate 21, urea 50? A pad bath made by adding water to alginate Noda 4.51 to make it 11 was adjusted to pH 5.0 with acetic acid, padded with rayon taffeta and cupra taffeta, and nipped at a squeezing rate of 70%.
After drying, it was steamed at 105° C. for 20 minutes.

For comparison, one of the above formulations was prepared without adding a triazine compound, and the other one was prepared with a pad dye bath in which 2Of sodium bicarbonate was added instead of sodium trichloroacetate, and processed in the same manner. .

The staining results are shown in Table 1.

The dyeing density was expressed as a /S value based on the reflectance R at the maximum absorption wavelength using the Kubelka-Munk equation.

Wet rubbing fastness was determined according to JIS L-0849 (1971), and water fastness was determined according to JIS L-0846 (1967) A method.

Example 2 DR for a textured fiber (Shantung ■) made of polyester 100d processed yarn and cupro 50d filament yarn
Yellow 3GL-8 (Union color manufactured by Osaka Godo) 1.
2 parts, 0.7 parts of DR Flu EB, 2.5 parts of 1,3,5-triacryloylhexahydro-s-triazine, 0.6 parts of taurine, Toho Salt A-30 (deep dyeing agent for polyester manufactured by Toho Chemical Co., Ltd.) 4 parts, 0.5 parts of sodium chlorate, and 4 parts of sodium chlorate.

A colored paste prepared from 3.0 parts of potassium acetate, 0.2 parts of acetic acid (48%), 3 parts of etherified CMC-based paste, and 5 parts of alginic acid was printed using a 100-mesh screen.

After drying, it was steamed at 118° C. for 30 minutes.

For comparison, printing was carried out in the same manner using the colored paste prepared without adding the above triazine compound and taurine.

Example 3 A polyester cotton (65:35) blended No. 45 twin yarn plain fabric was used, and 11 parts of Diamira, Brilliant, Blue B (reactive dye manufactured by Mitsubishi Kasei), Resolin, Flue FBL (dispersed dye manufactured by Bayer, registered trademark) were used. ) 19 parts, 1,3-diacryloyl-5-β-chloroethyloylhexamethylene S-triazine 28 parts, acidic sodium sulfite 3 parts, taurine 3 parts, f-oxyethylene glycol 20 parts, tribromo sodium acetate 20 parts A pad bath was prepared by adding 4 parts of tartaric acid and 10 parts of a modified locust bean sizing agent to water to make 1000 parts, and the pad bath was dried after padding.

Next, steaming treatment was performed at 130°C for 35 minutes, followed by soaping and finishing.

Further, according to the formulation of the method of the present invention, processing using a pad bath excluding the triazine compound was carried out as Comparative Example 1, and then processing using a pad bath excluding acidic sodium sulfite and taurine was carried out as Comparative Example 2.

Further, as Comparative Example 3, a pad bath was made from the above recipe without the alkali generator, and after steaming the pad in the same manner, 95% An alkaline shock method was performed with a 20 second pass at °C.

Example 4 Interwoven tricot made of nylon 70d filament yarn and rayon 50d filament yarn was mixed with 10 parts of Subranol Brilliant Red BB (acid dye manufactured by Bayer) and 10 parts of Trimalene Brilliant Red X-2B (reactive dye manufactured by Sandoz). parts, 28 parts of 1,3,5-I'loloetheroylhexahydro S-triazine, 5 parts of sodium r-aminoflovir sulfonate, 12 parts of sodium monochloroacetate, 8 parts of sodium trichloroacetate, 3 parts of ammonium sulfate, 8 parts of sodium alginate Immerse in a blended dye solution consisting of
0%) and dried at 80°C.

Next, after steaming at 102°C for 40 minutes, saw pinking was performed at 65°C with an ammoniacal weakly alkaline nonionic activator solution.

The obtained dyed product had a clear red color with a bluish tinge, and its color fastness against sunlight, washing, water, perspiration, friction, dry cleaning, etc. was grade 4 or higher in all cases.

As is clear from the above examples, according to the present invention, a dyed product having a high dye density and high color fastness can be obtained by a one-phase method, and its industrial value is extremely large.

Claims (1)

[Claims] 1. When pad dyeing or printing a textile product containing cellulose fibers using a dye solution or color paste containing a reactive dye that can directly react and bond with cellulose fibers, the general formula (where R is - A hexahydrotriazine compound represented by COCH-CH2 or C00H2CH2C1) and an active hydrogen-containing compound represented by the general formula (where Y is H, NH2, an aminoalkyl group having 1 to 3 carbon atoms, and X is hydrogen or an alkali metal). sulfonic acid is added to the hexahydrotriazine compound of the above general formula (1) in a molar ratio of 1.0 or less, further, a halogenated acetate is added, and p
A dyeing process for cellulose fiber products, which is characterized by pad dyeing or printing using a dye solution or colored paste in which H is adjusted to 7 or less.