JPH0686716B2 - Discoloration-preventing dyeing method for polyester / cellulose mixed fiber - Google Patents

Description

The present invention relates to a color-preventive discharge printing method for polyester / cellulose mixed fibers, and more specifically, to alkali-extractable and alkali-resistant disperse dyes and vinyl sulfone type, monochlorotriazinyl type water-soluble dyes. TECHNICAL FIELD The present invention relates to a color-preventing discharge printing method in which a reactive reactive dye is used to perform discharge-proofing and coloring at the same time.

For example, Japanese Patent Publication No. 58-48674 is known as a color-preventing discharge printing method for polyester / cellulose mixed fibers. In this method, an alkali agent is used in a dyeing liquor or a printing paste containing an alkali labile dispersible alkaline dye and a water-soluble reactive dye. This alkaline agent is indispensable for fixing the water-soluble reactive dye, but it has a drawback that the alkali removable disperse dye is water-solubilized by the alkali during the fixing treatment, and dyeing on the polyester is significantly impaired. However, there is a problem that there is no industrial reproducibility. Further, since the dyeing solution or the printing paste which becomes the background color contains the alkali agent, the temporal stability of the alkali removable disperse dye and the water-soluble reactive dye is poor.

Therefore, the present inventors have focused on a method that does not use an alkaline agent in the above-mentioned dyeing liquor or printing paste in order to provide a color-preventive discharge printing method for polyester / cellulose mixed fibers which does not have the above-mentioned drawbacks.

However, in that case, in order to react the water-soluble reactive dye with the cellulose fiber, it is necessary to carry out an alkali fixing treatment in a subsequent step.

Alkali shock method is known as an alkali fixing treatment, but when this method using a concentrated alkali is applied to the color-preventing discharge printing method, in the step of dry heat or steam heat fixing,
It is generally considered that the alkali-drainable disperse dye dyed on the polyester fiber or the printing of the printing paste may decompose the water-soluble reactive dye reactively dyed on the cellulose fiber. Is not yet tried.

However, when the present inventors applied it in a coloring-preventing discharge method using a specific water-soluble reactive dye, unexpectedly, there is no problem as in the past, and the coloring-preventing discharge of polyester / cellulose mixed fiber is excellent. The present invention has been completed and the present invention has been completed.

That is, the gist of the present invention is to provide a polyester / cellulose mixed fiber with (1) a dye liquor or a printing paste containing an alkali-drainable disperse dye and a vinylsulfone-type water-soluble reactive dye as essential components and containing no alkali agent, (2) Containing an alkali-resistant disperse dye, a monochlorotriazinyl type water-soluble reactive dye, a vinyl sulfone-type water-soluble reactive dye stainproofing agent, an alkali agent and a mono- or di-lower alkyl ether of a polyalkylene glycol having an average molecular weight of 150 to 500 A method for coloring and preventing discharge printing of polyester / cellulose mixed fibers, which comprises printing a dyeing solution or a printing paste, (3) fixing by dry heat or steam, and (4) subsequently fixing by alkali.

Hereinafter, the present invention will be described in more detail.

Examples of the polyester fiber of the polyester / cellulose mixed fiber in the present invention include polyethylene terephthalate, polybutylene terephthalate, and modified polyesters obtained by modifying these with isophthalic acid or the like.

On the other hand, examples of the cellulose fiber include cotton, hemp, viscose rayon, polynodite crayon, copper ammonia rayon and the like. Examples of the form of the polyester / cellulose mixed fiber include woven and knitted products such as mixed spinning, mixed weaving, mixed weaving, and mixed knitting.

In the present invention, first, the above-mentioned polyester / cellulose mixed fiber is dyed in accordance with a conventional method with a dyeing solution or a printing paste which does not contain an alkali agent and contains alkali dispersible disperse dye and vinyl sulfone type water-soluble reactive dye as essential components. .

As the alkali-detachable disperse dye, a dye having at least one or more carboxylic acid ester group in the dye molecule, solubilized by alkali such as nitrothiazole dye,
Alternatively, various known dyes that are decomposed and do not dye polyester fibers can be used.

Further, as the vinyl sulfone type water-soluble reactive dyes, groups such as giving a -SO ₂ CH = CH ₂ group or a vinyl sulfone group according by thermal as reactive groups, for example, -SO ₂ CH ₂ CH ₂ OS
Various known water-soluble dyes having at least one O ₃ N _a group in the dye molecule can be used.

These dyes are preferably mixed and used so as to be 1 to 30% by weight in the dye liquor or the printing paste.

Known additives may be further used in combination with the dye liquor or the printing paste. For example, a reduction inhibitor such as sodium m-nitrobenzenesulfonate is dyed in order to prevent the azo group of the alkali dispersible disperse dye or the vinyl sulfone-type water-soluble reactive dye from being reduced during the dry heat or steam heat treatment described below. A sequestering agent such as sodium tripolyphosphate is used to prevent adverse effects on dyeing due to metal ions in water, or a quenching agent is used to accelerate the dyeing of polyester by an alkali removable dye during dry heat or steam heat fixing treatment. Non-volatile acids such as acids, tartaric acid and malic acid may be added as appropriate.

About 0.1 to 0.3% by weight is suitable for these charges.

Next, an alkali-resistant disperse dye, a monochlorotriazinyl-type water-soluble reactive dye, and a vinylsulfone-type water-soluble reactive dye stain-proofing agent that cause a color difference on the polyester / cellulose mixed fiber dyed as described above, An accelerating agent that solubilizes or decomposes an alkali dispersible disperse dye, and further acts as a reaction catalyst between a monochlorotriazinyl type water-soluble reactive dye and cellulose fiber and an alkali dispersible disperse dye solubilizes or decomposes. The dyeing liquor or printing paste containing the polyalkylene glycol derivative as a component is printed by a conventional method.

As the alkali-resistant disperse dye, various known dyes that can be dyed well on the polyester fiber without solubilizing or decomposing the dye molecule by alkali can be used.

Further, as the monochlorotriazinyl type water-soluble reactive dye, as a reactive group, for example, Various known water-soluble dyes having one or more (R: an aryl group which may have an alkali group or a sulfone group) in the dye molecule can be used.

These dyes are preferably mixed and used so as to be 1 to 30% by weight in the dye liquor or the printing paste.

As the alkaline agent, an alkali metal carbonate, an alkali metal bicarbonate, an alkali metal phosphate, an alkali metal borate, an alkali metal silicate, an alkali metal hydroxide,
Alkali precursor compounds that generate alkali when heated in the presence of alkali metal fatty acid salts such as alkali metal acetates or water such as sodium trichloroacetate and sodium acetoacetate can be used.

Alkali metal carbonates are particularly preferable, and the amount thereof used is usually 2 to 5% by weight, preferably 3 to 4% by weight in the dye liquor or the printing paste.

As the vinyl sulfone-type water-soluble reactive dye stain-proofing agent, known sodium hydroxymethanesulfonate, glyoxalic acid sodium sulfite adduct and the like can be used.

The amount used is preferably 2 to 6% by weight, more preferably 3 to 4% by weight in the dye liquor or the printing paste of the color difference formulation.

Further, it is important to use a polyalkylene glycol derivative in a dyeing liquid or a printing paste of a color difference formulation as an accelerator for perfecting the dye resistance of the alkali dispersible disperse dye.

In the present invention, polyethylene glycol having an average molecular weight of 150 to 500, polypropylene glycol, a mono- or di-lower alkylated product of a copolymer of polyethylene glycol and polypropylene glycol is preferable, and particularly, a di-lower alkylated product of the above polyalkylene glycol. Is preferred.

The amount used is 3 to the dyeing solution or printing paste of the color difference formula.
20% by weight is preferable, and 8 to 15% by weight is particularly preferable. In addition to the above-mentioned essential components, 5% by weight of a monochloro-type reactive dye as a dyeing accelerating agent to the cellulose fiber
It is preferred to add some urea.

After printing with dyeing solution or printing paste of the above color difference formula,
By dry heat or steam heat fixing treatment, the alkali removable disperse dye is dyed on the polyester in the background color part, and the alkali resistant disperse dye is dyed on the polyester in the color difference part, and at the same time, the monochlorotriazinyl type water-soluble reactive dye React with the cellulose fibers.

Examples of the dry heat or steam fixation treatment include known methods such as thermosol method, high pressure steam method (HPS), and high temperature steam method (HTS).

Thermosole method at 190 ° -210 ° C for 45 seconds-90 seconds, high-pressure steaming method at 120 ° -130 ° C for 5 minutes-20 minutes, high temperature steaming method at 160 ° -185 ° C for 5 minutes-8 minutes. Appropriate to process.

In particular, it is suitable to perform the fixing treatment at 170 ° to 180 ° C. for about 5 to 7 minutes by the high temperature steaming method.

Then, an alkali fixing treatment is performed to react the vinyl sulfone type water-soluble reactive dye in the ground color portion with the cellulose fiber.

As the alkali fixing treatment, a concentrated solution of alkali hydroxide or / and alkali metal, and / or sodium silicate, etc.
The most suitable method is 10 to 15 seconds at ° to 98 ° C.

After the alkali fixing treatment, washing with water, soaping treatment by a known method, and drying are carried out to obtain a high quality polyester / cellulose mixed fiber colored and discharge-proofed product.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

In the examples, "part" means "part by weight".

Example 1 A polyester / cotton (65/35) woven fabric was immersed in a dyeing solution having the following background color formulation, squeezed to a draw ratio of 70%, and intermediately dried at 100 ° C. for 2 minutes. Next, the printing paste of the following color difference formulation was overprinted in a polka dot pattern using a flat screen, dried at 100 ° C for 2 minutes, treated with HTS at 175 ° C for 7 minutes, and then in the following alkaline bath at 90 ° C for 15 seconds. Alkali fixation treatment, washing with water,
I soaped. As a result, a clear colored discharge-proof article having a yellow polka dot pattern on a uniform scarlet background was obtained.

Ground color prescription DIANIX Yellow A5G-FS paste 10 parts DIANIX RED A2B-FS paste 50 parts (all are alkaline dispersible dyes manufactured by Mitsubishi Kasei Co., Ltd.) DIAMirror red GD 40 parts DIAMirror red F3B 5 parts DIAMirror yellow GGL 5 parts (all are manufactured by Mitsubishi Kasei Co., Ltd., vinyl sulfone type reactive dye) Sodium m-nitrobenzenesulfonate 1 part (reduction inhibitor) Sodium tripolyphosphate 1 part (sequestering agent) Citric acid 3 parts Water 885 parts Total amount 1000 parts Color difference formulation Danix Yellow H2G-Liquid 50 parts (Mitsubishi Kasei Co., Ltd., alkali resistance disperse dye) Diaclone Yellow 5G 50 parts (Mitsubishi Kasei Co., monochlorotriazinyl reactive dye) Anhydrous sodium carbonate 30 50 parts of part urea _{CH 3 OC 2 H 4 O 4} CH 3 150 parts of registration stall HWS 30 parts (Meisei chemical Co., , Vinylsulfone reactive dyes proof Discharge) Nitsukakamu MA39 12% aqueous solution of 500 parts (Nicca Chemical Co., CMC-based sizing agent) 200 parts of 38 ° Be NaOH aqueous solution 50 parts of anhydrous sodium carbonate 140 parts total amount 1000 parts alkali bath of water Anhydrous sodium sulfate 100 parts Water 650 parts Total 1000 parts Comparative Example 1 Similar to Example 1 except that 20 parts of sodium trichloroacetate was further added to the dyeing solution of the background color formulation in Example 1 and fixing treatment in an alkaline bath was not performed. Carried out. As a result, the density of the ground-colored scarlet was remarkably lower than that of Example 1, and the commercial value was poor.

Comparative Example 2 In Example 1, CH ₃ OC ₂ H ₄ O ₄ CH ₃ of the color difference formulation was added to HOC.
It was changed to ₂ H ₄ O ₄ H was prepared in the same manner as in Example 1.
As a result, the difference in color yellow was extremely low as compared with Example 1, and the color was dull.

Example 2 A polyester / rayon (65/35) woven fabric was immersed in a dyeing solution having the following background color formulation, squeezed to a drawing ratio of 65%, and intermediately dried at 100 ° C. for 2 minutes. Then, the printing paste of the following color difference formulation was overprinted in a polka dot pattern with a flat screen,
Dry at 0 ° C for 2 minutes, treat with HTS at 180 ° C for 6 minutes, then perform alkali fixation treatment at 95 ° C for 10 seconds in an alkaline bath (Fixer RC-PD, Hoechst, sodium metasilicate aqueous solution), and wash with water. , Soaped. As a result, an excellent colored and discharge-proofing product having a clear red dot pattern on a uniform brown background was obtained.

Ground color prescription DIANIX Yellow AN-FS paste 50 parts DIANIX RED A2B-FS paste 12 parts DIANIX Blue A2R-FS 8 parts (all are alkaline dispersible dyes manufactured by Mitsubishi Kasei Co., Ltd.) DIAMirror Mirror 6R 12 parts DIAMirror Orange 3R 45 parts Dia Mirror Black B 12 parts (all are vinyl sulfone type reactive dyes manufactured by Mitsubishi Kasei Co., Ltd.) Sodium m-nitrobenzenesulfonate 1 part Sodium tripolyphosphate 1 part Tartaric acid 3 parts Water 856 parts Total quantity 1000 parts Example 3 A polyester / cotton (50/50) nit was immersed in a dyeing solution of the following background color formulation, squeezed to a drawing ratio of 75%, and intermediately dried at 100 ° C. for 3 minutes. Next, overprint the floral pattern of the following differential color prescription with a flat screen at 100 ° C.
It was dried for 2 minutes at 200 ° C. for 90 seconds, then treated with thermosol at 90 ° C. for 90 seconds, then subjected to the alkali fixing treatment described in Example 1, washed with water and soaped. As a result, a color-preventing discharge-printed product having a good part having a yellow floral pattern on a uniform dark blue background was obtained.

Ground color prescription Dianix Blue A2R-FS 13 parts Dyanix Bio-Areto A-3B-FS 17 parts Dyanix Yellow A-N FS Pace 6 parts (both manufactured by Mitsubishi Kasei Co., Ltd. alkaline dispersible dye) DIAMIRROR BLUE RN 60 parts DIA Mirror Bio-Oreto 5R 20 parts Dia Mirror Black B 20 parts (all are vinyl sulfone type reactive dyes manufactured by Mitsubishi Kasei Co., Ltd.) Sodium m-nitrobenzenesulfonate 1 part Sodium tripolyphosphate 1 part Citric acid 3 parts Water balance Total amount 1000 parts Color difference Prescription DIANIX Yellow H2G-P Liquid 40 parts (Alkali-resistant disperse dye manufactured by Mitsubishi Kasei Co., Ltd.) DIACRON Yellow 5G 60 parts (Monochlorotriazinyl reactive dye manufactured by Mitsubishi Kasei) Anhydrous sodium carbonate 30 parts Urea 50 parts CH _{3 OC 2 H 4 O 8 CH} 3 130 parts of registration stall HWS 30 parts (Meisei of Ltd.) was stamped indicia printing paste of fabric below ground color formulation 1000 parts of sodium alginate 10% aqueous solution 550 parts Water balance the total amount Example 4 Polyester / cotton (65/35), the difference between the first embodiment described The printing paste of the color formulation was overprinted on the entire surface and then processed according to the method described in Example 1. As a result, a clear colored discharge-proof article having a yellow polka dot pattern on a uniform scarlet background was obtained.

Ground color prescription Dyanyx yellow A5G-FS paste 8 parts Dyanix red A2B-FS paste 40 parts (all are alkali dispersible disperse dyes manufactured by Mitsubishi Kasei Co., Ltd.) DIA Mirror red GD 32 parts DIA Mirror red F3B 4 parts DIA Mirror yellow GGL 4 parts (all are vinyl sulfone type reactive dyes manufactured by Mitsubishi Kasei Co., Ltd. m-Nitrobenzenesulfonic acid 1 part Sodium tripolyphosphate 1 part Citric acid 3 parts Alginic acid half emulsion 550 parts Water 357 parts Total 1000 parts

Claims (1)

[Claims] 1. A polyester / cellulosic mixed fiber is provided with (1) a dyeing solution or printing paste containing an alkali removable disperse dye and a vinyl sulfone type water-soluble reactive dye as essential components and containing no alkali agent, and (2) alkali resistance. Disperse dyes and monochlorotriazinyl type water-soluble reactive dyes, dye-staining agents for vinyl sulfone type water-soluble reactive dyes, alkali agents, and dye liquors containing mono- or di-lower alkyl ethers of polyalkylene glycol having an average molecular weight of 150 to 500 as components. Alternatively, a color-prevention discharge printing method for polyester / cellulose mixed fibers, which comprises printing a printing paste, (3) fixing by dry heat or steam, and (4) subsequently fixing by alkali.