JPS6146593B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for improving the color fastness of a dyed object dyed using a reactive dye. Objects dyed with reactive dyes generally have superior color fastness compared to objects dyed with direct dyes, but they are still unsatisfactory in terms of washing fastness, water fastness, sweat fastness, etc. Moreover, since the covalent bond between the fiber and the reactive dye undergoes hydrolysis in the air and is gradually broken, there is a drawback that the color fastness of the dyed object decreases over time. For this reason, conventionally, in order to improve the color fastness of the dyed object, it has been usual to treat the dyed object with a dilute aqueous solution of a condensate of dicyandiamide and formalin or a condensate of a polyamine such as ethylenediamine or diethylenetriamine and dicyandiamide after dyeing. It is being done. However, the above-mentioned treatment has disadvantages in that the color of the dyed object becomes marked and a decrease in light fastness cannot be avoided. In addition, in recent years, a method has been developed to improve color fastness using equimolar reaction products of secondary amines and epihalohydrin (Japanese Patent Publication No. 43-243) and polyamine sulfone (Japanese Patent Publication No. 18165-1977).
Even when these are used, color fastness such as washing fastness, water fastness, sweat fastness, etc. cannot be sufficiently improved, and polyamine sulfone has a strong bonding strength with dyes. Because it is not strong, the amount of the compound used is inevitably large, and because the main chain of the compound has a sulfone group, it is susceptible to alkaline hydrolysis and the molecule is cleaved by depolymerization. There is a tendency for the color fastness of treated dyed objects to gradually decrease over time. In view of the current situation, the present inventors have made various efforts to improve the color fastness of dyed objects. As a result, when dyed objects are immersed in an aqueous solution of a compound with a low degree of polymerization having the following general formula [ ] as a basic structural unit, this treatment may cause discoloration, decrease in light fastness, and decrease in abrasion fastness. They discovered that it was possible to sufficiently improve color fastness such as washing fastness, water fastness, sweat fastness, chlorine water fastness, etc., without any problems, and completed the invention related to Japanese Patent Application No. 128232-1983. The present invention provides a method for further improving various fastness properties found in the above invention, particularly washing fastness, alkali and acid hydrolytic fastness, and sweat fastness. That is, the present invention improves the color fastness of a dyed object dyed using a reactive dye. [In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a methyl group. HX represents an organic or inorganic acid. ] A polymer consisting of a repeating monomer unit represented by the above general formula [], and (b) a repeating monomer unit represented by the above general formula [ ] and the monomer blended in an amount of up to 1/2 mole with respect to the monomer forming the unit. Relating to a method for improving the color fastness of a dyed object, which comprises treating the dyed object under alkaline conditions up to pH 11 using a water-soluble polymer selected from copolymers consisting of units of other polymerizable monomers. . The method of the present invention is advantageously applied to dyed objects such as cellulose products, protein products, synthetic polyamide products, etc. that have been dyed with reactive dyes. etc. may be used. Further, as the reactive dye, any of various known ones can be used, but dyes having two or more reactive groups capable of reacting with amino groups or hydroxyl groups are particularly preferred. Typical examples of the dye include those having a dichlorotriazinyl group, a dichloroquinoxaline group, a trichloropyrimidine group, a monochlorodifluoropyrimidine group, a vinylsulfonyl group, etc. as a reactive group. According to the method of the present invention, various wet fastnesses of dyed objects dyed with the above-mentioned reactive dyes can be highly improved without causing any discoloration, decrease in light fastness, decrease in chlorine water fastness, etc. In particular, according to the method of the present invention, compared to conventional methods using quaternary amine salt polymers, it is possible to prevent the dye from falling off due to hydrolysis during long-term storage of dyed objects, and it is also possible to prevent the dye from falling off due to hydrolysis during long-term storage of dyed objects. The color fastness to decomposition can be greatly improved. The reason why the above-mentioned particularly remarkable effect is expressed by the method of the present invention is not yet clear, but when the above-mentioned specific water-soluble polymer is used to treat the dyed object under alkaline conditions up to pH 11, The secondary amino groups in the above polymer chemically react with the unreacted groups remaining in the reactive dye molecules dyed on textile products, etc., and are firmly fixed to the surface of textile products etc. through covalent bonds. This is thought to be due to the generation of a molecular weight reactive dye layer. In any case, the method of the invention makes it possible to obtain products with markedly improved color fastness, in contrast to conventional methods based on ionic bonding. In the method of the present invention, it is essential to use a water-soluble polymer selected from (a) and (b) above.
The homopolymer shown in (a) among the above polymers has the general formula [In the formula, R ₁ , R ₂ and HX are the same as above] It can be produced by cyclization polymerizing a compound represented by the following formula using a radical polymerization catalyst. The polymerization method at this time may be according to a known method. Examples of the radical polymerization catalyst include ammonium persulfate, hydrogen peroxide, benzoyl peroxide, tertiary butyl hydroperoxide, azobisisobutyronitrile, and cumene hydroperoxide. Examples of the solvent include water and polar solvents such as methanol, ethanol, isopropanol, n-propanol, formamide, dimethyllumamide, dioxane, acetonitrile, and dimethyl sulfoxide. In addition, for the polymerization reaction, for example, 100 parts by weight of the compound of the general formula [] is dissolved in 20 to 100 parts by weight of a solvent, 0.05 to 10 parts by weight of a radical polymerization catalyst is added, and if necessary, acidic sodium sulfite, sulfuric acid dichloromethane, etc.
This can be carried out by using 0.01 to 5 parts by weight of a reducing agent such as iron or copper sulfate. It is preferable that the polymerization temperature is usually 70 to 110°C and the polymerization time is usually about 10 to 50 hours, and the polymerization reaction is advantageously carried out while blowing nitrogen gas. Other copolymerizable monomer units in the copolymer shown in (b) in the above water-soluble polymer include:
Typically, the unit represented by the formula -SO ₂ - [], the general formula [In the formula, R ₁ and R ₂ are the same as above. Y represents a halogen atom. ] Examples include units represented by these and acrylic monomer units. When introducing the unit represented by the above formula [] into a copolymer, for example, the reaction may be carried out while blowing sulfur dioxide gas into the cyclization polymerization reaction system of the compound represented by the above general formula []. When introducing the unit represented by the above general formula [], the following general formula is often introduced into the cyclization polymerization reaction system of the compound represented by the above general formula []. [In the formula, R ₁ , R ₂ and Y are the same as above] A compound represented by the following may be present as a comonomer. Similarly, when introducing an acrylic monomer unit, acrylic acid, methacrylic acid, acrylamide, etc. may be used as a comonomer. , methacrylamide, alkali metal or ammonium salts of acrylic or methacrylic acid, lower alkyl esters of acrylic or methacrylic acid, tertiary or quaternary amino substituted lower alkyl esters, tertiary or quaternary amino and hydroxy substituted A lower alkyl ester or the like may be present. Among the units introduced using the above acrylic monomer, particularly preferred units are represented by the following formula []. [In the formula, R ₃ is H or CH ₃ , Y is NH ₂ , OH, ONa,
OK, CNH ₄ , OCH ₃ , OC ₂ H ₅ , OC ₂ H ₄ N
_{( CH3} ) ₂ , _{OC2H4N ( C2H5 ) 2 ,} OC2H4N _{( CH3} ) _3.C , OC2H4N _{( CH3 )} ( _C2H5 ) _2.C , _OCH2CH (OH) _CH2N ( _CH3 ) ₂ , or _OCH2CH (OH) _CH2N ( _CH3 ) _3.C . ] The manufacturing conditions for the homopolymer may be similar to those for the homopolymer shown in (a) above, and the amount of copolymerizable monomer is 1/2 mol based on the compound represented by the general formula [] above. The copolymer thus obtained can exhibit substantially the same effects as the homopolymer shown in (a) above. The water-soluble polymer obtained as described above is preferably Sephadex G-25 (Pharmacia.
It is appropriate that the molecular weight is about 10,000 or less, more preferably about 500 to 5,000, as measured by a gel filtration method using a filler such as Fine Chemical Co., Ltd., Sweden) as a filler. The treatment of the dyed object of the present invention using the polymer thus obtained can be carried out in the same manner as conventional methods, except that the pH of the bath containing the polymer and in which the dyed object is to be treated is made alkaline to 11 or less. For example, typically, the above polymer is applied to the fiber at 0.1
After creating an aqueous solution containing ~2.0% by weight, its pH
is adjusted to the above range, and the object to be dyed is immersed in the dye for a predetermined period of time, then washed with water and dried. The bath ratio (dyed material: water) is usually 1:10 to 20, the treatment temperature is usually room temperature to 100°C, and the treatment time is usually 5 to 30 minutes. In the present invention, in particular, the pH of the above-mentioned treatment liquid is made alkaline to 11 or less. Since the aqueous solution of the water-soluble polymer itself is approximately neutral (usually pH approximately 6.5 to 7), this is carried out by adding an appropriate pH adjuster to this aqueous solution. Examples of pH adjusters include soda carbonate, Examples include potassium carbonate, sodium acetate, sodium bicarbonate, sodium phosphate, sodium silicate, sodium trichloroacetate, and other suitable buffers.The amount of pH adjuster (alkali) to be used depends on the pH of the above aqueous solution (processing solution). It can be determined as appropriate to make the pH of the treatment solution alkaline to 11 or less, and it is usually about 0.05 to 1 g/g.Even if a large amount of pH regulator is added and the pH of the treatment solution exceeds 11, the effect of the present invention will improve accordingly. Rather, it may reduce the water solubility of the water-soluble polymer, and it may not be possible to expect a uniform color fastness improvement effect over the entire object to be treated.Also, if a pH adjuster is not used or the amount used is too small, If the pH of the solution is neutral or weakly acidic, such as 7 or less, the effects of the present invention cannot be expected.A particularly suitable pH is about 8.5 to 10.5, and a pH around 10 can provide the best color fastness. The above-mentioned treatment in the present invention is carried out, for example, by using a water-soluble polymer of about 0.1 to 2.0
It can also be carried out by preparing a solution containing % by weight and, if necessary, a fiber processing resin and/or a fluorescent dye and having a specified pH value of 11 or less, and pad-treating the dyed material to be treated with this solution. can. Through the above treatment, the reactive groups of the reactive dye dyed onto the product and the aliphatic secondary amino groups of the water-soluble polymer are strongly bonded by covalent bonds, resulting in color fastness that cannot be seen with conventional methods. Significantly improved dyed products can be obtained. In the present invention, after treatment with the water-soluble polymer,
By washing with water and drying as necessary, the desired dyed product can be obtained, and this can also be further heat-treated or steam-treated as necessary.
The above drying can usually be carried out at about 100 to 120°C for 2 to 10 minutes, heat treatment can usually be carried out at about 130 to 180°C for 1 to 5 minutes, and steam treatment can usually be carried out at about 100 to 170°C.
It can be carried out for 1 to 5 minutes at 100°C. In order to explain the present invention in more detail, synthesis examples of water-soluble polymers used in the present invention are listed below as reference examples, and then examples are listed. Reference Example 1 100 g of diallylamine hydrochloride and 40 g of water are placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a gas introduction tube, and a thermometer, and the mixture is stirred to dissolve uniformly. The internal temperature was raised to 80°C while blowing nitrogen gas through the gas introduction tube, and 80°C of tertiary butyl hydroperoxide was added from the dropping funnel while stirring.
% butanol solution are added dropwise over 1 hour. The reaction is exothermic and the internal temperature rises to approximately 90°C. Approximately 90 minutes after dripping
By continuing stirring at ℃, a pale brown paste is obtained. The polymerization rate measured by colloid titration method was 90%. The intrinsic viscosity of the above polymer determined in a 0.1N potassium chloride solution was 0.13 at 30°C. When the molecular weight distribution of this polymer was measured by a gel permeation method (using Cephadex G-50 as a filler, gel bed φ26 x 400 cm, flow rate 3 ml/hour), the molecular weight of most of the polymers was in the range of 1,000 to 4,000. Reference Example 2 135 g of diallylamine hydrochloride and 250 g of water are placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a gas inlet tube, and the mixture is stirred to dissolve uniformly. After raising the internal temperature to 50°C and blowing in sulfur dioxide gas for about 15 minutes, 50 g of a 10% aqueous solution of ammonium persulfate was added dropwise over 1 hour. During this time, continue to blow sulfur dioxide gas. After blowing in 64 g of sulfur dioxide gas for about 2 hours and continuing the stirring reaction at 50°C for 10 hours, in order to remove free sulfur dioxide gas,
Blow in nitrogen gas. A pale yellow, slightly viscous, transparent liquid is thus obtained. The polymerization yield measured by colloid titration was 92%. The intrinsic viscosity of the obtained polymer determined in a 0.1N potassium chloride solution was 0.15 at 30°C. In addition, when the molecular weight distribution of this polymer was determined by gel filtration method, most of the molecular weight distribution was
It was in the range of 1500-5000. Reference Example 3 135 g of diallylamine hydrochloride and 100 g of water are placed in a reaction vessel equipped with a stirrer, a reflux condenser, a metering pump, a gas inlet tube, and a thermometer, and the mixture is stirred to dissolve uniformly. Next, increase the internal temperature to 50℃ while blowing in nitrogen gas.
20ml of ammonium persulfate 20% aqueous solution per minute.
Add at a rate of 0.2 ml. Five minutes after the start of addition, 180 g of a 20% acrylamide aqueous solution was gradually added dropwise over 3 hours. The reaction is exothermic, and the temperature of the reaction solution is raised to 55°C, and the same temperature is maintained until the dropwise addition of acrylamide is completed. If the stirring reaction is continued for 10 hours, a yellow transparent viscous liquid is obtained. The polymerization yield determined by colloid titration was 75%. The intrinsic viscosity of the resulting polymer determined in a 0.1N aqueous potassium chloride solution was 0.09 at 30°C. Furthermore, when the molecular weight distribution of this polymer was measured by a gel filtration method, most of the molecular weight distribution was in the range of 500 to 2,500. Reference Example 4 135 g of diallylamine hydrochloride, 80 g of diallyldimethylammonium chloride, and 100 g of water are placed in a reaction vessel equipped with a stirring device, a reflux condenser, a dropping funnel, a thermometer, and a gas inlet tube, and are stirred to uniformly dissolve them. The internal temperature was raised to 60°C, and 40 g of a 20% aqueous solution of ammonium persulfate was gradually added dropwise over 2 hours from the dropping funnel while stirring and blowing nitrogen gas through the gas inlet tube. When the polymerization is continued at 60°C for 24 hours after the dropwise addition, a viscous light brown liquid is formed. The polymerization yield of this product was 85% by colloid titration.
The intrinsic viscosity of this polymer determined in a 0.1N potassium chloride solution was 0.11. Furthermore, when the molecular weight distribution of this polymer was determined by a gel filtration method, it was mostly in the range of 1000 to 3500. Comparative Reference Example 1 Put 100 g of diallyldimethylammonium chloride and 100 g of water into a reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, gas inlet tube, and thermometer, stir to dissolve uniformly, and then introduce nitrogen through the gas inlet tube. While blowing gas, the internal temperature was raised to 60℃, and while stirring, 1 g of 80% butanol solution of tert-butyl hydroperoxide was gradually added dropwise from the dropping funnel.Then, the temperature was stirred at the same temperature for 5 hours, and then the temperature was raised to 90℃. Raise the internal temperature, stop stirring, and let the mixture stand at the same temperature for 48 hours to polymerize.
A pale yellow viscous liquid is obtained. Take 50g of this and make 500ml
When poured into acetone, a white precipitate forms. The precipitate was separated, thoroughly washed twice with 100 ml of acetone, and then dried in a vacuum desiccator to obtain 26.5 g of a deliquescent white solid. The molecular weight distribution of the obtained polymer by gel filtration method was mostly in the range of 1000 to 3000. Comparative Reference Example 2 According to Example 1 described in Japanese Patent Publication No. 43-18165, 16 parts of dimethyldiarylammonium chloride was added and dissolved in 32 parts of a 20% methanol solution of sulfur dioxide, and the solution was stirred while maintaining the temperature at 20°C. Five parts of a 5% methanol solution of t-butyl hydroperoxide was added dropwise to the bottom, stirring was continued for 2 hours, and the resulting polymer was separated, thoroughly washed with methanol, and dried under reduced pressure to obtain a white powder. Comparative Reference Example 3 According to Example 6 described in Japanese Patent Publication No. 43-18165, 97 parts of diarylamine was gradually added to 105 parts of concentrated hydrochloric acid under cooling to neutralize it to prepare an aqueous solution of diarylamine hydrochloride. Next, 160 parts of dimethylammonium chloride was dissolved in 160 parts of water and mixed with the above aqueous solution, and the resulting mixed aqueous solution of diarylamine hydrochloride and dimethyldiarylammonium chloride was mixed with 120 parts of sulfur dioxide while keeping the temperature below 30°C. After blowing, a solution of 3 parts of potassium persulfate dissolved in 60 parts of water was added, and polymerization was continued for 3 hours at a temperature below 50°C to obtain a syrupy aqueous solution, and a large amount of methanol was added to a portion of it to form a white precipitate. I got something. Example 1 A) Dyed fabric for test A No. 40 cotton broadcloth was used as the fabric to be dyed, and each of the following 6 types of reactive dyes was applied to the fabric in a proportion of 6% by weight of the fiber.
% concentration and dye according to the usual method at a bath ratio of 1:20. <Dye> a: Mikasion Brilliant Red 8BS (manufactured by Nippon Kayaku) b: Mikasion Navy Blue RBS (manufactured by Nippon Kayaku) c: Remazol Black B (manufactured by Hoechst) d: Mikasion Blue 3GS (manufactured by Nippon Kayaku) ) e: Mikasion Scarlet GS (manufactured by Nippon Kayaku Co., Ltd.) f: Procion Red MX-5B (manufactured by ICI) B) Treatment method A 0.025% by weight aqueous solution of the water-soluble polymer obtained in each reference example and comparative reference example was prepared. To this, about 0.2 g of soda carbonate was added to adjust the pH to 9.8, and each test dyed fabric was added to this aqueous solution or the above aqueous solution (pH 6.5) for which the pH was not adjusted for comparison at a bath ratio of 1:20 and a temperature of
After soaking at 60℃ for 20 minutes, wash with water and air dry. The following tests were conducted on the thus obtained treated fabric. C) Test method C-1 Color fastness to washing Each test fabric was placed in a container at 100% humidity and 60℃ and kept for 2 weeks (dye hydrolyzability due to long-term storage), JIS-L- 0844 Conduct the test according to A-4. C-2 Color fastness to acid hydrolysis Each test fabric was immersed in an aqueous solution containing 10 g of acetic acid and 0.5 g of a household detergent ("New Beads" manufactured by Kao Soap Co., Ltd.) at a bath ratio of 1:20, and the test fabric was dyed at 37°C. After holding for 20 hours, the absorbance of the test solution is measured using a spectrophotometer. The higher the concentration of the shed dye, the higher the absorbance. The acetic acid-detergent solution mentioned above was used as a reference solution. C-3 Color fastness to alkaline hydrolysis A test similar to C-2 above is conducted using an alkaline detergent solution containing 0.5 g of soda carbonate and 0.5 g of household detergent ("Newbeads"). C-4 Colorfastness against perspiration After holding each test fabric in a container at 100% humidity and 60°C for two weeks, test against acid perspiration according to JIS-L-0848 A method. Determine the contamination of the attached white cloth using gray scale. D) Results D-1 Dye fastness to washing The test solution after the washing test according to C-1 above was diluted twice with n-propyl alcohol containing 10% acetic acid, and the color fastness of each dye was measured using a spectrophotometer. Measure the absorbance at a specific wavelength. The higher the concentration of the shed dye, the higher the absorbance. As a reference solution, the washing solution used above was diluted twice with an n-propyl alcohol solution containing 10% acetic acid. The measurement wavelengths are as follows. Dye a...521 mμ b...590 mμ c...580 mμ d...603 mμ e...500 mμ f...512 mμ The results (absorbance) are shown in Table 1.

[Table] D-2 The color fastness results against acid hydrolysis are shown in Table 2 below in terms of absorbance.

[Table] D-3 The color fastness results against alkaline hydrolysis are shown in Table 3 below in terms of absorbance.

[Table] D-4 Color fastness to sweat The results are shown in Table 4 below in gray scale.

[Table] Example 2 The same dyed fabric as in Example 1 was prepared by adding 0.025% by weight of the water-soluble polymer obtained in Reference Example 1 and about 10% by weight of sodium carbonate.
By adding 0.05 to 1g/, the pH was adjusted to 7.4, 8.6, and
Treat in the same way using treatment solutions of 9.8, 10.2 and 11.0. The results of a similar color fastness test against acid and alkali hydrolysis of the treated fabric are as follows:
They are shown in Tables 5 and 6, respectively.

【table】

[Table] From Tables 5 and 6 above, it can be seen that the treatment of the present invention with a specific water-soluble polymer under alkaline conditions of pH 11 or less can significantly improve the color fastness to acid and alkali hydrolysis. . Furthermore, the dyed fabric obtained by the above-mentioned treatment of the present invention was extremely excellent in fastness to chlorine water. Comparative Example 1 No. 40 broad cotton was used as the dyed fabric, and each of the following three types of direct dyes was applied to it at 3% by weight based on the fiber weight.
and dye according to the usual method at a bath ratio of 1:20. <Dye> a: Sumilight Red-3B (manufactured by Sumitomo Chemical Co., Ltd.) b: Kayarasu Spralett-6BL (manufactured by Nippon Kayaku Co., Ltd.) c: Kayarasu Splattermize Blue GL (manufactured by Nippon Kayaku Co., Ltd.) The processing method is as follows: The same method as described in Example 1 B was used. However, the amount of polymer used was 1.5% based on the weight of the fiber. Using each of the polymers described in Reference Example 1 and Comparative Reference Example 3 as polymers, treated fabrics obtained by processing in accordance with the same treatment method as B in Example 1 were subjected to JIS treatment in the same manner as C in Example 1. -L-0844 According to No. A-2, color fastness test against washing was carried out.
Contamination of the attached white cloth was determined on a gray scale. The results are shown in Table 7 below.

[Table] Comparative Example 2 After adjusting the polymer obtained in Comparative Reference Example 2 to an aqueous solution of a predetermined pH according to the treatment method described in Example 1, B, color fastness to washing according to C-1 of Example 1. The test was conducted and the results obtained according to D-1 of Example 1 are shown in Table 8 below in the same manner as Table 1.

【table】

【table】

Claims (1)

[Claims] 1. In improving the color fastness of a dyed object dyed with a reactive dye, (a) the general formula [In the formula, R ₁ and R ₂ are the same or different and represent a hydrogen atom or a methyl group, and HX represents an organic acid or an inorganic acid. ] A polymer consisting of a repeating monomer unit represented by the above general formula [], and (b) a repeating monomer unit represented by the above general formula [ ] and the monomer blended in an amount of up to 1/2 mole with respect to the monomer forming the unit. A method for improving the color fastness of a dyed object, which comprises treating the dyed object under alkaline conditions up to pH 11 using a water-soluble polymer selected from polymers. 2. The method according to claim 1, wherein the water-soluble polymer has a molecular weight of 10,000 or less. 3 Units of other copolymerizable monomers represented by the formula -SO ₂ - [], general formula [In the formula, R ₁ and R ₂ are the same as above. Y represents a halogen atom. ] The method according to claim 1, wherein the acrylic monomer unit is at least one selected from the group consisting of the following units and acrylic monomer units. 4. The method according to claim 1, wherein the reactive dye is a dye having two or more groups capable of reacting with a hydroxyl group or an amino group.