JPS61194284A - Resist stypl fiber composite structure and its production - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to resist dyeing of composite structures of polyester fibers and cellulose fibers that are dyeable under normal pressure with cationic dyes and disperse dyes or disperse dyes. More specifically, the polyester fibers and/or cellulose fibers in the base-dyed part of the composite structure are dyed with a dye that can be discharged by reduction, and the polyester fibers in the colored discharge-printed part! The present invention relates to a fiber composite structure in which fibers and cellulosic fibers are dyed to substantially the same hue with a pad dye, and a method for dyeing the same.

(Conventional technology J Conventionally, as an anti-contamination dyeing method for composite structures of polyester fibers and cellulose [a], +11 is a method of reduction discharge printing using a dye that can be discharged by reduction as a background dye and a pigment as an accent color. (2) Resistance dyeing using alkali-soluble disperse dyes and addition reaction-type reactive dyes for ground dyeing, and using alkali-resistant disperse dyes and /'''te#i substitution-reactive reactive dyes as 12 different colors. (3) An anti-contact dyeing method that uses an alkali-soluble disperse dye and an acidic displacement-reactive reactive dye for ground dyeing, and an alkali-resistant disperse dye and/or an alkaline-reactive reactive dye for the accent color (4) Anti-discharge printing is known, in which an alkali-soluble disperse dye and an addition reaction-type reactive dye are used for background dyeing, and a pad dye is used as an accent color.

(Problems to be Solved by the Invention) Since the method (1) above uses a pigment as an accent color,
If the texture of the fiber composite, that is, the cloth, is hardened, and the fastness of the pigment-printed area is not good, it is not possible to obtain a high-quality printed product. If a mixed product of Regiera polyester fiber and cellulose fiber M1 is dyed using a dip dyeing method using a normal disperse dye or an alkali-soluble disperse dye and a reactive dye, color discharge printing is impossible and ground dyeing VC cannot be applied. Therefore (
21, +31, (A method is used in which alkali-soluble disperse dyes and reactive dyes are applied by a puffing method or a squeezing method as in 41, followed by drying and steaming. Because there is almost no movement of the reactive dye in the polyester fiber part and the disperse dye in the cellulose fiber part, they remain on the fiber as unused undyed dye without being dyed. The disadvantages are that it is difficult to remove the dye, resulting in poor fastness, and that the dye utilization rate is low, resulting in high cost.

Furthermore, in the methods of K, +21, and +31, disperse dyes and reactive dyes are used as accent colors, resulting in high costs and poor fastness for the same reasons as the background dyeing part.

Method (4) uses pad dye as an accent color, but dyeing polyester fiber requires high-temperature steaming or high-temperature baking, and dyeing cellulose fiber with pad dye requires sufficient moisture. Since IC5t is required, dyeing in the presence of a sufficient amount of water under normal pressure, that is, normal pressure steaming, is performed first, so a considerable amount of the pad dye is consumed. The dyeing on the polyester fibers is considerably reduced and the so-called Mitscha phenomenon occurs, making it difficult to produce printed products with a high-quality feel.

c. Means for Solving the Problems The present inventors have conducted research to improve the problems that should be solved by the conventional method regarding the anti-staining method for composite structures of polyester fibers and cellulose fibers, and have developed the method of the present invention. The anti-contamination method was achieved.

That is, the present invention is a composite structure of polyester fibers and cellulose fibers that is dyeable under normal pressure with cationic dyes and disperse dyes, and the polyester fibers and/or cellulose fibers in the ground-dyed portion are reduced. The polyester fibers and cellulose-based N1. &1 is a fiber composite structure that is dyed with a pad dye to substantially the same hue, and is a composite made of polyester fibers and cellulose fibers that are dyeable to cationic dyes and disperse dyes or disperse dyes under normal pressure. A dye solution containing a dye as a main component that can be discharged by reduction is applied to the polyester fibers and/or cellulose fibers of the structure, and the necessary IMV is applied.
A polyester fiber and cellulose-based composite characterized in that after fixation treatment from C, a dye liquid or printing paste containing a pad dye, an alkaline agent, and a reducing agent is printed or partially applied, and a steam fixation treatment is performed at 90 to 110°C. This paper relates to a discharge dyeing method for structures.

In the method of the present invention, it is possible to carry out ground dyeing at normal pressure by a one-dip method in order to use polyester fibers that can be easily dyed in deep colors with cationic dyes and disperse dyes or disperse dyes at normal pressure. The utilization rate of the dye used is high, and the effect of reducing dye cost is particularly large for dark colors. Further, high color fastness can be easily obtained due to the high utilization rate of the dye and sufficient washing after background dyeing. In particular, it is possible to perform reduction washing on the dyed edges of polyester fibers if necessary, and it is easy to obtain high fastness in dark colors. In methods (2), (3), and (4) in which a mixture of a disperse dye and a reactive dye is applied simultaneously, reduction cleaning cannot be performed. Next, regarding the accent color part, in the present invention, polyester fibers and cellulose fibers are simultaneously dyed using only a pad dye as an accent color in a single normal pressure sdaming process, so polyester fibers and cellulose fibers are It is possible to dye both to substantially the same hue, and even in a pattern with a large area of the accent color part, so-called blemishes do not occur, and it is possible to print with a high-class feel.

In addition, since only the pad dye is used and the polyester fibers and cellulose fibers are simultaneously dyed, the dye usage rate is extremely high and cleaning after printing is easy, making it easy to obtain a high degree of durability. Another feature of the present invention is that the process is simple compared to other polyester fibers and cellulose fiber cutting and discharge dyeing methods, and the conditions of each process are easy to control, making it easy to obtain stable quality. . As described above, according to Kine 151JK, it is possible to obtain a discharge-resistant discharge-printed product of a composite structure of high-grade polyester fibers and cellulose fibers at a relatively low cost.

The polyester fibers used in the present invention that are dyeable at normal pressure with cationic dyes, disperse dyes, or disperse dyes are those that can be dyed to a sufficiently deep color with cationic dyes, disperse dyes, or disperse dyes at normal pressure. It is polyester fiber.

The polyester fibers that are dyeable under normal pressure with cationic dyes and disperse dyes or disperse dyes used in the present invention are:
A specific example is given below.

Mainly contains an acid component (80 moles or more) mainly consisting of terephthal Wl or its ester-forming component, and a glycol component consisting of one or more selected from ethylene glycol, tetramethylene glycol #, and L4-cyclohexanedimethanol. (A terephthalate-based polyester obtained from a glycol component of 80 mole or more is used as a paste, and an ester-forming component having a sulfonic acid metal salt group as the K(4) component, and addition of components other than the (4) component as the a3) component. It is a fiber obtained by spinning a polyester obtained by appropriately selecting and copolymerizing components. -dicarboxylic acid, 5-(4-sulfophenoxyfisophthalic acid), and glycols containing a sulfone-dicarboxylated 14#L group. It's ester.

[F]) Specific examples of components include acid components such as isophthalic acid, adipine acid, sebacic acid, glutaric acid, and naphthalene dicarboxylic acid, and diethylene glycol, triethylene glycol, and cyphthylene glycol, with a molecular weight of 100.
Examples include polyether glycol having a molecular weight of 500 or less, adducts of ethylene oquinide, and KtI'ftL< include isophthalic acid, glutaric acid, polyethylene oxide adducts having a molecular weight of 500 or less, and diethylene glycol. The silicic acid component and the component (8) can be selected as appropriate within a range that does not particularly impair the physical properties of the fibers, but the component (4) is preferably selected to be 67 R or less relative to the silicic acid component. Alternatively, a glycol component of 6 molt or less is selected. ω) As a component,
A weight of less than 6.5% based on total polymer weight is selected. Also[
F]) Diethylene glycol, triethylene glycol, etc. in the ingredients not only actively add mosquito compounds, but also cause the monoglycol component to self-condense during polymerization, resulting in copolymerization in the polymer. Of course, this is fine.

FI obtained by spinning these polyesters using a normal spinning method, drawing them, then heat setting and crimping them.
l, fiber is used in the present invention, and K is 2500m/
Other additional methods such as spinning at high speeds of more than 1 minute are required! ! The fibers obtained using the method are also incorporated. These fibers may be either staples or fits, and may be crimped yarns, textured yarns, or heat-processed yarns. It may also be a mixture of these fibers, and the cross-sectional shape may be circular, irregularly shaped, or hollow.

Furthermore, various compounding agents may be used during or at any stage after the production of polyester fibers, such as inorganic fillers such as silica, clay, kaolin, and calcium carbonate, and organic fillers such as organic phosphorus ester salts and sulfonates. Fibers containing additives or the like may also be used.

The polyester fibers that are dyeable under normal pressure with the cationic dyes, disperse dyes, or disperse dyes used in the present invention have a dyeing rate (D
7) When qi is a disperse dye, preferably son or more is 70
1 or more, more preferably 80% or more, and in the case of cationic dyes, 1 (is 50 or more, preferably 80% or more)
The fiber content is 0% or more, more preferably 90% or more.

(4 Disperse dye dyeing rate test tp> Cationic dye dyeing rate test included
Examples include natural cellulose fibers such as cotton and linen, viscose, polynosic rayon, and regenerated cellulose fibers such as E14 (D).

They may be staples or filaments. Composite mixtures of these polyester fibers and cellulose 1a and Ja include threads, wA fabrics, non-woven fabrics, rugs, raised blankets, strips, and gin; examples of composite forms include blends,
In addition to mixed fibers, interlaced fibers, multilayered structure fabrics, etc., composite yarns such as cover yarns and arbitrary structures using them can be mentioned.

The mixing ratio of polyester is 5-80 - preferably 10-7
It is 0chi.

To explain the cut-and-discharge method of the present invention, a dye solution containing a disperse dye and/or a cationic dye that can be discharged with a reducing agent, and a reactive dye and/or a direct dye that can be discharged with a reducing agent is applied. If necessary, after fixation treatment, printing or partial application of a dye liquid or printing paste containing a pad dye, an alkaline agent, and a reducing agent is applied, preferably after drying for 90 to 90 minutes.
Steam fixation treatment at 110°C is performed. After applying disperse dyes and/or cationic dyes that can be discharged by reduction, reactive dyes and/or direct dyes that can be discharged by reduction if necessary, quality issues such as clarity of the final product, bleeding at the edge of the mold, hot water contamination, etc. From the point of view of solidity and high firmness, it is desirable to wash with water for fixation and dry before applying a dye liquid or printing paste containing a pad dye, an alkaline agent, and a reducing agent. Dyeing with disperse dyes and/or cationic dyes, optionally reactive dyes, and/or direct dyes may be carried out by conventional methods. Composite structure made of polyester fibers and cellulose fibers dyeable with atmospheric pressure disperse dyes. In this case, only the polyester fibers can be dyed with disperse dyes, or
On the contrary, cellulose-based Tl
Only the T fibers may be dyed.Also, both polyester and cellulose fibers may be dyed using a combination K of disperse dyes and reactive dyes or disperse dyes and direct dyes.
Sara K.

Cellulosic fibers may be dyed using both reactive and direct dyes. Moreover, the combination of dyes used varies depending on the purpose. In the case of a composite structure of polyester fibers and cellulose fibers for the atmospheric pressure cation dyeable lid, the polyester fibers can be dyed with either disperse dyes or cationic dyes, making it possible to use even more diverse combinations of dyes.

Dyes that can be discharged by reduction that can be used are azo dyes. Next, a dyeing liquid and/or printing paste containing a pad dye, an alkaline agent, and a reducing agent are applied partially or printed, and if necessary, dried. The four methods of applying the dye solution and printing paste components are a transfer method using an engraved roll, and ordinary printing methods such as roller printing, screen printing,
There are rotary printing methods, etc.

Suitable pad dyes that can be used include indigo and thioindigo dyes. As alkaline agents, sodium aqueous, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, kashin sodium, rational potassium, trisodium phosphate, tripotassium phosphate, alkali metal salt of trichloroacetate, alkali acetate Examples include metal salts, etc. As a reducing agent, Redol C (NaH8O!・C
Hao 2 HtO), N*@Sfo@, etc., but Redol C is preferably used. Next, a fixing treatment is carried out, and the conditions are normal pressure steaming at 90 to 110°C, preferably 95 to 105°C.
C., time rJJ is preferably applied for 5 to 60 minutes, preferably 10 to 30 minutes. When such conditions are adopted in the present invention, polyester fibers and cells are bonded to each other under normal pressure.
It is also possible to color the fibers to substantially the same hue all at once.

As a finishing treatment, softening treatment, silicone-based or fluorine-based water repellent treatment, antifouling treatment, and other types of performance may be imparted.

(Example) Example-1 5-sodium sulfoisophthalic acid was more than 3 moles based on the total acid components, and CH was 3.0% by weight based on the total poly i-.

and 1.51i! A blended yarn (50:50 weight ratio) of polyester staple and polynosic regenerated cellulose fiber stable obtained by spinning ethylene terephthalate polyester copolymerized with % of diethylene glycol, drawing, and heat setting. A twill fabric consisting of font was loosened by a conventional method and printed according to the following recipe.As a comparison sample, a polyethylene/terephthalate fiber stable obtained by a conventional method and a polynosic regenerated cellulose fiber stable (50:50C + weight ratio) were used. ) °Twill printing made of blended yarn, dried printed fabric was steamed at 100°C for 20 minutes, and soaped in a conventional manner.Color density of the printed part of the printed fabric and dyeing of polyester and polynosic fiber parts Table 1 shows the observation results of the dyeing condition.Polyester fibers show the same pad dye dyeing properties as polynosic fibers under steaming conditions of 100℃ and 20 minutes, but regular polyester fibers are hardly dyed or dyed only under pressure to the extent of contamination. Not done.

Example-2 For the aftershock component, 5-sodium sulfoisophthalic acid was used at 3 moles or more, and for the total polymer, 3.0 weight -〇
〇lla Polyester fiber stable obtained by spinning ethylene terephthalate polyester copolymerized with 1.5% by weight diethylene glycol, drawing, and heat setting, and Polynosic's regenerated cellulose fiber staple (30 nia) A twill fabric consisting of yarns with a weight ratio of 0) &D was kneaded by a conventional method and dyed according to the following recipe.

vinegar acid
1-171, dried, and dyed the polynosic fibers with the following recipe. Part C was cold batch dyed by weight, then washed with water, soaped, hot water, washed with water, and dried. Then, a printing paste with the following formulation was printed and dried. Part C is part by weight] Okeslen Pink 1.0 part (Mitsui Toatsu, Pat dye] Mikesuren Hiolef) 4.01 (Mitsui Toatsu, Pat dye) Water 33
．． 0 # Redor C6.0 # Soda ash 6.01 yuan Glue 50.0 #
C. Pretische Gum and Starch] The printed and dried printed fabric was steamed at 100'C for 20 minutes and then soaped in the usual manner9.

As a result, an excellent purple discharge-printed cloth with a clear red background and sharp mold edges was obtained, and it also had a soft texture. The color fastness of the discharge printed fabric was as follows.

Light emission (JIS-L-0841, 20hrs,)
Class 4 washing (JIS-L-0844, A-2 method)
Class 4-5 friction (JI 5-L-0849J
Dry type 4I & Wet type 3rd class rapid sweat (JIS-L-0848
, A method) Class 4 alkaline sweat (JIS-L-0
848, A method) 4th grade water test (J I 5-
L-0846) Grade 4-5 dry cleaning (JIS-L-0860 petroleum-based) Grade 4-5 dry cleaning (JIS-L-0860 solvent-based) 4-
Grade 5 Example-3 An ethylene terephthalate polyester obtained by copolymerizing 4.5 mol of 5-sodium sulfoisoheptalic acid with the acid component was obtained by spinning, stretching, and heat setting in a conventional manner. A twill fabric made from yarn from a staple blended with fiber and rayon in a ratio of 35:65 was used to dye polyester using the same recipe as in Example-1. Rayon dyeing was carried out using the following recipe, followed by soaping using a conventional method, and after drying, printing paste was applied using the following procedure and drying was performed. Part C is part by weight) (6) Industhrene Indigo Blue-4BD 3 parts (BASF, pat dye) Water 35 Rudol C61 Soda ash 61 Yuan Glue 5θI (b) Mikethrene Green FFB 4 parts C Mitsui Toatsu, pat dye] Water 34 l Redor 0 61 Soda ash 61 yuan Glue
The Sol printed and dried printed fabric was sdamned at 100° C. for 20 minutes and 4 hours, and then saw pinked in the usual manner. As a result, a two-color printed fabric of blue and green, which was vertical on a red background and had sharp edges, was obtained. Then, diethylene glycol, 1.0 weight, and polyethylene glycol (average molecular weight 400), 1.5
A fill fabric 5c was obtained from a blend of polyester fiber stable and cotton (30 nia 0 in weight ratio) obtained by spinning ethylene terephthalate polyester copolymerized in a weight percent by a conventional method.

6 at 98℃ using the following dye solution recipe for polyester dyeing.
Staining was performed for 0 minutes.

Diamonds Yellow GF80.5%0Wf (Mitsubishi Kasei, disperse dye) Sodium acetate 1.01 #Naruto 3
After adjusting the pH to 5Kv4 with f/1 vinegar, cold batch staining was performed using the following recipe. 1
After 1 part by weight, soap, dry, and print with printing paste with the following recipe.
Dry.

The printed and dried printed fabric was steamed at 100° C. for 20 minutes and then soaped in a conventional manner. As a result, we were able to obtain discharge-printed fabric with white, pink, and green colors on a clear and solid yellow background.

Example-5 3.0 mol of 5-sodium sulfoino-heptatalic acid was added to the total acid component, and 350 mol of diethylene glycol was copolymerized to the total polymer.
A fill fabric was obtained from a blended yarn of polyester staple fiber and cotton in a weight ratio of 40:60, which was spun at a spinning speed of 0 m/min.

The same bath dyeing was done using the following recipe.

After noping and drying, print with printing paste using the following recipe.
Dry. One part by weight was printed, and the dried printed fabric was steamed at 100° C. for 20 minutes and then soaped in a conventional manner. As a result, a green printed fabric with sharp edges at the edge of the mold was obtained with a red background KIE dungeon.

Claims (1)

[Scope of Claims] 1. A composite structure of polyester fibers and cellulose fibers that is dyeable under normal pressure with cationic dyes and disperse dyes or disperse dyes; A fiber composite structure 2 in which the fibers are dyed with a dye that can be discharged by reduction, and the polyester fibers and cellulose fibers in the colored discharge dyed portion are dyed with a pad dye to substantially the same hue, a cationic dye and a disperse dye, or It is necessary to apply a dyeing liquid mainly composed of a dye that can be discharged by reduction to polyester fibers and/or cellulose fibers of a composite structure consisting of polyester fibers and cellulose fibers that are dyeable under normal pressure with disperse dyes. A composite structure of polyester fibers and cellulose, characterized in that after fixation treatment, a dye liquid or printing paste containing a pad dye, an alkaline agent, and a reducing agent is printed or partially applied, followed by a steam fixation treatment at 90 to 110°C. Discharge-proof dyeing method for objects