JPH0545716B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention applies to cellulose fibers such as cotton, rayon, hemp, etc., and blends and interwoven products of these fibers with hydrophobic synthetic fibers such as polyester fibers, to reactive dyes, direct dyes, butt dyes, etc. The present invention relates to a printing paste that has sharp edges and has good permeability and level dyeing properties when printing using dyes or pigments. [Prior Art] In general, methods for printing cellulose fibers such as cotton, rayon, and linen use reactive dyes, direct dyes, butt dyes, and pigments as dyes, and sodium alginate, turpentine emulsion paste, and turpentine emulsion paste as base pastes. Water-swollen products such as guar gum paste, modified starch, and CMC,
PH adjuster, reduction inhibitor, binder (pigment printing),
A printing and dyeing paste is created by appropriately combining a discharge printing agent, etc., and after printing, drying, baking, steaming,
Applying fixing processes such as chemical padding, steam, and alkaline shock, soaping (other than pigment printing),
Perform finishing process. Compared to hydrophobic synthetic fibers such as polyester fibers,
In the above-mentioned treatment process for cellulose fibers, a particular practical problem is the problem of so-called poor penetration, in which the printing dyeing paste printed with a viscosity suitable for printing does not penetrate sufficiently to the back surface in the printing process. This cannot be improved by a fixing process such as steaming. This lack of penetration of printing dyeing paste not only leads to poor quality of the printed product, but also causes unevenness when the back side of filament fabrics such as rayon is worn as clothing due to friction and the back side of the printing turns over to the front side. This causes complaints about so-called thread return, which looks like dyeing. For these reasons, it is an important unresolved technical problem in textile printing factories to ensure that the printing paste sufficiently penetrates into the back surface during printing. Unlike hydrophobic synthetic fibers, cellulose fibers suffer from insufficient penetration of printing pastes, because the fibers themselves are hydrophilic, so only the water in the printed color pastes selectively absorbs. Moreover, it is thought that this is because it is instantaneously absorbed into the fibers, increasing the viscosity of the color paste. For the purpose of solving the lack of penetration of printing dye paste in conventional cellulose fiber printing, for example, ethylene oxide adducts of C ₃ to C ₁₈ alcohols and alkylphenols, and their sulfates, highly sulfated products of castor oil, and sulfosuccinic acid type anions have been used. Attempts have been made to solve the problem by adding various surfactants such as surfactants and phosphate ester surfactants to the printing and dyeing paste, but none have been successful. In reality, methods have been considered such as increasing the mechanical conditions during printing, such as staking pressure, or making the color paste viscosity extremely low. It is difficult to balance color paste penetration and bleed (dye oozes out along with water from the edge of the mold, making the pattern unclear), and bleed-through is likely to occur. [Problems to be Solved by the Invention] The present inventors have implemented a conventional printing method and process by adding only a few percent to the conventionally used printing dyeing paste when printing cellulose fibers. By doing so, we discovered a material that does not cause bleeding at the edge of the handle and also provides sufficient permeability to the back surface, resulting in the present invention. [Means for Solving the Problems] The present invention provides the following features when printing cellulose fibers such as cotton, rayon, and hemp, and their blended and woven products.
A water-soluble material selected from the group consisting of a homopolymer of acryloylmorpholine and a copolymer of 10% by weight or more of acryloylmorpholine and 90% by weight or less of one or more monomers represented by the following formula () The present invention relates to a color paste composition for textile printing which contains a polymer in an amount of 0.5 to 5% as a pure polymer content. In the above formula, R ₁ represents hydrogen or -CH ₃ , and X
represents -OH or _-NH2 . Acryloylmorpholine used in the present invention has a chemical structure represented by the following formula (). When the polymer pure content is less than 0.5%, the effect is poor, and even when it is used in excess of 5%, no corresponding effect is observed and it is not practical. Further, the molecular weight of the polymer is preferably 1,000 to 100,000. If it is less than 1,000, no penetration effect will be observed, and if it is more than 100,000, it will adversely affect the fluidity of the printing paste, so it is not suitable. The water-soluble polymer may include acryloylmorpholine alone or a mixture thereof with acrylamide, acrylic acid, or methacrylic acid, such as mercaptan,
Using common chain transfer agents such as lower alcohols,
It can be easily produced by known general methods such as single or copolymerization at 60 to 100°C in an aqueous medium. The water-soluble polymer used in the present invention is particularly characterized in that it contains a morphoyl group. It is thought that this morphoyl group forms an ionic bond with water in the colored paste, and also forms a coordinate bond with the dye, and is used as a dye solubilizer. Therefore, when a color paste containing the above-mentioned water-soluble polymer is printed on cellulose fibers, the color paste has the effect of uniformly and sufficiently penetrating the water and dyes present in the color paste into the interior of the fibers. It is presumed that this is the case. Conventional surfactants are based on the idea of improving the permeability of colored paste by lowering the interfacial tension between fibers and colored paste, and are fundamentally different from the present invention. The color paste composition of the present invention can be prepared by a known method. Namely, a base paste using one or more of sodium alginate, a half emulsion paste made of sodium alginate and a turpentine emulsion, a locust bean gum paste, a guar gum paste, an etherified starch, CMC, etc., and a reaction paste. Dyes, vat dyes, direct dyes or pigments, hygroscopic agents such as urea, polyethylene glycol, glycerin, reducing agents such as Rongarit C, dechlorin, baking soda, sodium sesquicarbonate, sodium trichloroacetate, soda ash, etc.
By mixing the water-soluble polymer with substances commonly used in printing pastes, such as PH regulators, octyl alcohol, silicone-based antifoaming agents, and, if necessary, anionic and nonionic surfactants. It can be carried out. When printing is carried out, it can be carried out by a conventional method, for example, by printing colored paste onto the fiber material and fixing it in a dry or undried state. As the printing method, there are conventional methods such as manual printing, or methods using an auto screen printing machine, a rotary printing machine, a roll printing machine, etc.
As the fixing method, a steaming method, a baking method, an alkali shock method, an alkali pad steam method, etc. can be applied. After fixing, wash, soap, and finish. [Example] Hereinafter, the present invention will be further explained with reference to Examples.
The present invention is not limited to this. The molecular weight referred to herein is the molecular weight measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance. Synthesis Example 1 152 g of deionized water was placed in a 300 ml reaction vessel and heated to 85°C. Under nitrogen atmosphere and stirring, 80 g of acryloylmorpholine and 4 g of 2-
A mixture of mercaptoethanol and 4 g ammonium persulfate dissolved in 10 g deionized water,
They were added simultaneously over a period of about 1 hour. During the dropwise addition, strong heat generation due to polymerization was observed. Then 2 at 90℃
The reaction was continued for an hour to complete the polymerization. After cooling, 48%
The pH was adjusted to 7 by neutralizing with sodium hydroxide. The molecular weight of this polymer measured by GPC was approximately 4,000. Synthesis Example 2 152 g of deionized water was placed in a 300 ml reaction vessel and heated to 85°C. Under nitrogen atmosphere and stirring, 40 g of acryloylmorpholine, 40 g of acrylamide, and 4 g of 2-mercaptoethanol were added.
A mixture of 40 g of deionized water and 4 g of ammonium persulfate dissolved in 10 g of deionized water was added to the
Strong heat generation due to polymerization was observed during the simultaneous addition over a period of time. Thereafter, the reaction was continued at 90°C for 2 hours to complete the polymerization. After cooling, it was neutralized with 48% sodium hydroxide and adjusted to pH 7. The molecular weight of this polymer measured by GPC was approximately 4,000. Synthesis Example 3 In a 300ml reaction vessel, add 129g of deionized water and 23g of
of isopropanol and heated to 81°C. Under nitrogen atmosphere and stirring, a mixture of 16 g of acryloylmorpholine and 64 g of acrylic acid, and 10 g
4 g of ammonium persulfate dissolved in deionized water was simultaneously added dropwise over a period of about 1 hour. During the dropwise addition, strong heat generation due to polymerization was observed. Then 82
The reaction was continued at ℃ for 2 hours to complete the polymerization. After cooling
The pH was adjusted to 7 by neutralizing with 48% sodium hydroxide. The molecular weight of this polymer measured by GPC is approximately
It was 20,000. Comparative synthesis example 1 Put 72g of deionized water into a 300ml reaction vessel,
Heated to 80°C. Under nitrogen atmosphere and stirring, 80
A mixture of 1 g of acrylamide, 80 g of deionized water, 4 g of 2-mercaptoethanol, and 4 g of ammonium persulfate dissolved in 10 g of deionized water were added dropwise simultaneously over about 1 hour. During the dropwise addition, strong heat generation due to polymerization was observed. then 85
The reaction was continued at ℃ for 2 hours to complete the polymerization. After cooling
The pH was adjusted to 7 by neutralizing with 48% sodium hydroxide. The molecular weight of this polymer measured by GPC is approximately
It was 4000. Comparative synthesis example 2 In a 300 ml reaction vessel, 129 g of deionized water and 23 g
of isopropanol and heated to 81°C. Under nitrogen atmosphere and stirring, 80 g of acrylic acid and 4 g of ammonium persulfate dissolved in 10 g of deionized water were simultaneously added dropwise over about 1 hour.
During the dropwise addition, strong heat generation due to polymerization was observed. Thereafter, the reaction was continued at 82°C for 2 hours to complete the polymerization. After cooling, it was neutralized with 48% sodium hydroxide and adjusted to pH 7. The molecular weight of this polymer measured by GPC was approximately 20,000. Example 1 45 parts of sodium alginate paste (6% base paste of Snow Algin M, which is sodium alginate manufactured by Fuji Chemical), 5 parts of urea, 3 parts of sodium bicarbonate, 0.5 parts of sodium metanitrobenzenesulfonate, Cibacron Scarlet G (manufactured by Civer Geigy) CI Reactive Red 33) 5 parts, octyl alcohol 0.5 parts,
5 parts of the aqueous polymer solution of Synthesis Example 1 and the remaining water such that the total amount was 100 parts were added and mixed uniformly. A floral pattern was printed on the refined polygon crayon fabric using a Tsujii autoscreen printing tester (manufactured by Tsujii Senki Kogyo Co., Ltd.) using 150 mesh gauze. After drying, it was steamed at 102°C for 7 minutes, washed with water, soaped at 90°C for 10 minutes using 2 g/1 Lipotol RK-5 (soaping agent manufactured by NICCA Chemical Co., Ltd.), washed with water, and then dried. The printed fabric thus obtained had no bleeding at the edge of the mold, had good permeability to the back side, and had good printing quality. In addition, for comparison, when a completely similar colored paste was prepared and printed in the same manner as in Synthesis Example 1, except that the polymerized aqueous solution was not added, it was found that it lacked penetration into the back side and the quality was poor. It was hot. The front and back sides of the above prints were printed by Macbeth Company 2020.
The results of measuring the dye density (K/S) with a colorimeter are shown first, and it has been demonstrated that the prints obtained in the examples of the present invention have good permeability to the back side.

[Table] Example 2 Half emulsion base glue (1:1 mixture of 6% base paste of Snow Algin M, which is sodium alginate manufactured by Fuji Chemical, and ST-1, which is turpentine emulsion manufactured by Nicca Chemical) 50 10 parts of urea, 3 parts of sodium bicarbonate, 0.5 parts of soda metanitrobenzenesulfonate, Diamira Black B (manufactured by Mitsubishi Kasei,
CI Reactive Black 5) 8 parts, Synthesis Example 1
5 parts of the aqueous polymer solution and the remaining water such that the total amount was 100 parts were added and mixed uniformly. A floral pattern was printed on the refined polygon crayon fabric using a Tsujii Aust Screen printing tester (manufactured by Tsujii Someki Kogyo Co., Ltd.) using 150 mesh gauze. After drying, it was steamed at 102°C for 7 minutes, washed with water, soaped at 90°C for 10 minutes using 2 g/1 Lipotol RK-5 (soaping agent manufactured by Nicca Chemical), washed with water, and then dried. The printed fabric thus obtained had no bleeding at the edge of the mold, had good permeability to the back side, and had good printing quality. In addition, when printing was carried out in the same manner using the polymer aqueous solutions of Synthesis Examples 2 and 3 instead of the polymer aqueous solution of Synthesis Example 1, it was found that the penetration into the back surface was significantly lower than that of the polymer aqueous solution of Synthesis Example 1. Although the quality was slightly inferior, a printed product of almost satisfactory quality was obtained. However, except for the case where the water-soluble polymer of Synthesis Example was not added to the colored paste and the polymers of Comparative Synthesis Examples 1 and 2 were used instead of the aqueous solution of the polymer of Synthesis Example 1, which was carried out for comparison. Printed articles printed in exactly the same manner all had insufficient penetration into the back side and were of poor quality. The front and back sides of the above prints were printed by Macbeth Company 2020.
The results of measuring the dye density (K/S) using a colorimeter are shown in Table 2, and it has been demonstrated that printed materials using the compound of the present invention have good permeability to the back side.

[Table] Example 3 45 parts of sodium alginate paste (6% base paste of Snow Algin M, which is sodium alginate manufactured by Fuji Chemical), 5 parts of urea, 3 parts of sodium bicarbonate, 0.5 parts of sodium metanitrobenzenesulfonate, Diamira Black B ( Mitsubishi Kasei CI Reactive Black 5) 8 parts, octyl alcohol 0.5 part, Synthesis Example 1
Additive-free, 1 part, 3 parts, or 5 parts of polymer aqueous solution, respectively.
Add the remaining water so that the total amount is 100 parts,
Mixed evenly. Tsujii auto screen printing test machine (manufactured by Tsujii Dye Machinery Co., Ltd.) on scouring and bleaching broad cotton fabrics
The floral pattern was stamped using 150 mesh gauze. After drying, steam at 102℃ for 7 minutes, wash with water, and apply Lipotol RK-5 (Nicca Chemical Soaping Agent) 2.
It was soaped at 90° C. for 10 minutes using 1 g/1, washed with water, and then dried. Table 3 shows the results of measuring the dyeing density (K/S) of the front and back sides of the above print using a Macbeth Co., Ltd. 2020 colorimeter. It has been demonstrated that it has good penetration into the back side.

[Table] Example 4 Snow Algin M (sodium alginate manufactured by Fuji Chemical) 1 g/, sodium metanitrobenzenesulfonate 10 g/, Remazol Salt FD (alkali agent manufactured by Hoechst, West Germany) 50 g/, urea 50 g/
, Sumifix, Brilliant Blue R
liq (Sumitomo Chemical CI Reactive Blue 19) 150
A cotton broadcloth was scoured and bleached using a dye liquor containing 1.5 g/g/g/g/g of the dye dissolved in water, and then dried using a mangle at a squeezing rate of 80%. Next, 45 parts of the half emulsion base paste used in Example 2, 5 parts of urea, 5 parts of sodium bicarbonate, 5 parts of Procion Red P-8B (CI Reactive Red 31, manufactured by ICI, USA), and Sunresist RD-90 (NICCA A resist dyeing paste was prepared by adding 5 parts of the chemical resisting agent for reactive dyes, 5 parts of the polymer aqueous solution of Synthesis Example 1, and the remaining water such that the total amount was 100 parts. On the padding cloth prepared earlier, each resist dyeing paste was printed on the floral pattern using a Tsujii autoscreen printing tester using 150 mesh gauze, and after drying,
Steam at 102℃ for 7 minutes, wash with water, and add Lipotol.
It was soaped with 2 g of RK-5 (soaping agent manufactured by Nicca Chemical Co., Ltd.), washed with water, and then dried. In the thus obtained printed fabric, in the case where the aqueous solution of the polymer of Synthesis Example 1 was added to the resist dyeing paste, the front and back sides of the part printed with the resist dyeing paste were completely resist dyed, and It was a beautiful resist-dyed item with vivid red accents in that area. However, in the case of printed products in which the aqueous polymer solution is not added to the resist dyeing paste, the surface of the part printed with the resist dyeing paste is resist dyed and colored red, but the back side is colored blue, which is the background color. , which was unsatisfactory as a resist dyeing product.

Claims (1)

[Scope of Claims] 1. When printing a fiber material made of or containing cellulose fibers, a homopolymer of acryloylmorpholine and 10% by weight or more of acryloylmorpholine and a monomer represented by the following formula () 1. A color paste composition for printing, containing 0.5 to 5% as a pure polymer content of a water-soluble polymer selected from the group consisting of a copolymer with 90% by weight or less of one or more of the following. In the above formula, R ₁ represents hydrogen or -CH ₃ , and X
represents -OH or _-NH2 .