JP2751806B2 - Dye fixative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a dye fixing agent for reactive dyes. In particular, the present invention relates to a dye fixing agent that improves dyeing fastness, such as sweat fastness and chlorine fastness, of a dyed product dyed with a reactive dye.

[0002]

2. Description of the Related Art Reactive dyes are widely used for dyeing cellulosic fibers because of their vivid hue and good wet fastness. However, a drawback of reactive dyes is that the dyes are oxidized and discolored by chlorine contained in tap water and bleach, and as a countermeasure, a dye fixing agent having a property of improving chlorine fastness has been developed. ing.

For example, homopolymers of monoallylamine derivatives (JP-A-58-31185), copolymers of monoallylamine derivatives and diallylamine derivatives (JP-A-60-110987), tertiary amino group-containing acrylamide derivatives and diallylamine Copolymers with derivatives (JP-A 1-272887).

[0004]

However, in the above allylamine-based dye fixatives, although a considerable effect is recognized, at present, the performance required for improving chlorine fastness in the market is becoming higher, and cellulose fiber is now used. From a practical point of view, no satisfactory effect has yet been obtained. In addition, during the heat treatment when applying these allylamine-based dye fixing agents to a printed fabric, yellowing due to the dye fixing agent may be observed in a white area, which may be a problem. Further, with respect to a Turqus blue dye which is frequently used as a vivid color, an allylamine-based dye fixing agent does not show an effect of improving the color fastness, and improvement is desired.

Accordingly, the present invention provides a dye fixing agent which can solve the above-mentioned problems and can improve the color fastness, such as the chlorine fastness and the sweat fastness, of a dyed product dyed with a reactive dye. It is something to offer.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, using a polymer having a vinylamine structure which has not been used as a dye fixing agent, By post-processing the dyed cellulosic fiber dyed with the reactive dye, chlorine fastness,
The present inventors have found that dyeing fastness such as sweat fastness is remarkably improved, and arrived at the present invention. That is, the present invention relates to a dye fixing agent used for a cellulosic fiber dyed with a reactive dye, and comprises a structural unit represented by the following general formula (1):
A polymer containing 0 mol% (hereinafter, referred to as “ N-vinyl amide unit _” ) and 10 to 98 mol% of a structural unit represented by the following general formula (2) (hereinafter, referred to as “vinyl amine unit”) and / or a salt thereof: And a dye fixative comprising:

[0007]

Embedded image

[0008]

Embedded image (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

The above-mentioned polymer has a particularly preferable composition as a dye fixing agent, in which one N-vinylamide unit (1) is used.
0 to 60 mol%, and the amount of the vinylamine unit (2) is 40 to
It contains 90 mol%. Further, the polymer has a reduced viscosity value of usually 0.01 to 10 dl / g measured at 25 ° C. as a 0.1 g / dl solution in 1 N saline solution. Considering the case of commercialization as a dye fixing agent in the form of an aqueous solution, the value of the reduced viscosity is 0.1.
More preferably, it is 1 to 5 dl / g . The amino group in the general formula (2) may be unneutralized, or may be a salt with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, sulfamic acid, and metasulfonic acid. May be formed.

The method for producing the above-mentioned polymer as the dye fixing agent of the present invention is not particularly limited, but it is usually a compound represented by the following general formula (3) (hereinafter collectively referred to as "N-vinylamide"). (Co-polymerized), and then
A method of partial hydrolysis is employed.

[0011]

Embedded image (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

Examples of the N-vinylamide include N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and the like, and N-vinylformamide is particularly preferred from the viewpoint of polymerizability, handleability and the like. Also,
Since the above polymer is used as a dye fixing agent after being partially hydrolyzed, a polymer obtained by copolymerizing a vinyl compound copolymerizable with N-vinylamide within a range not impairing its properties may be used. The monomers of the copolymerization component include (meth) acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylamide, (meth) acrylic esters, vinyl esters, vinyl ethers,
Nonionic monomers such as vinyl alcohol and allyl ether, (meth) acrylic acid, α, β-unsaturated dicarboxylic acid, sulfoalkyl (meth) acrylamide, sulfoalkyl (meth) acrylate, (meth) allylsulfonic acid, And cationic monomers such as dialkylaminoalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylamide, allylamine, diallylamine and salts or quaternary ammonium compounds thereof. It is not limited to these.

As the polymerization method, any of radical polymerization and ionic polymerization may be used, but radical polymerization is preferred because the molecular weight can be easily controlled. As the polymerization initiator for radical polymerization, any of the usual general initiators can be used, but an azo compound is preferable in order to obtain a polymer with a high yield. Particularly preferred initiators are 2,
Hydrochloride and acetate of 2'-azobis- 2 -amidinopropane, sodium salt of 4,4'-azobis-4-cyanovaleric acid, and hydrochloride and sulfate of azobis-N, N'-dimethyleneisobutylamidine No. The amount of the polymerization initiator to be used is usually 0.01 to 1% by weight based on the monomer.

The polymerization can be carried out by known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. The polymerization reaction is generally carried out in an inert gas stream, usually 3 times.
It is performed under a temperature condition of 0 to 100 ° C. The solution polymerization is usually carried out with an aqueous solution having a monomer concentration of 5 to 60% by weight, and the suspension polymerization is usually carried out with a monomer concentration of 20 to 8% by weight.
A method in which a 0% by weight aqueous solution is polymerized in a water-in-oil type dispersion state using a hydrophobic solvent and a dispersion stabilizer. As the emulsion polymerization, usually, an aqueous solution having a monomer concentration of 20 to 60% by weight is subjected to hydrophobic treatment. And a method of polymerizing in an oil-in-water type or water-in-oil type emulsified state using the above-mentioned solvent and emulsifier.

The desired polymer can be obtained by subsequently partially hydrolyzing the N-vinylamide (co) polymer obtained as described above. The hydrolysis may be performed under any of acidic conditions and basic conditions, but is more preferably performed under basic conditions from the viewpoint of corrosion of the reactor. In the case of acidic hydrolysis, the amino group of the vinylamine unit generated by hydrolysis is in the form of a salt,
On the other hand, in the case of basic hydrolysis, the amino group is in a free form, but after the hydrolysis, an acid may be added to convert a part or all of the free amine to a salt form. Various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, sulfamic acid, and metasulfonic acid can be used as the acid in this case.

The acid compound used in the acidic hydrolysis is preferably a strongly acidic compound, and examples thereof include hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, and methanesulfonic acid. In view of the solubility of the hydrolyzate in water, monovalent acids are preferred. Examples of the basic compound used for the basic hydrolysis include sodium hydroxide, potassium hydroxide, lithium hydroxide, quaternary ammonium hydroxide, ammonia, low molecular primary amine, secondary amine and the like.

The amount of the acid or base used is usually 0.1 to 5 moles per mole of the amide group in the N-vinylamide (co) polymer, and is appropriately used according to the desired modification rate. . The reaction temperature is in the range of 50 to 110 ° C and the reaction time is 1 to
Performed for a period of 8 hours. Further, the hydrolysis is not limited to the aqueous solution state, but can be carried out in various situations, and may be a mixed solvent system of water and alcohol, a heterogeneous solvent system of water and hexane, toluene, or the like. Further, a method may be used in which a gaseous acid is brought into contact with a water-containing solid polymer.

As for the composition of the obtained polymer, the molar fraction of vinylamine units of the general formula (2) is substantially the same as the hydrolysis rate of the N-vinylamide (co) polymer, and Is applied in the range of 10 to 98%, preferably 40 to 90%. If it is less than 10%, the dye fixing effect is significantly reduced, which is not preferable. In addition, at the time of the above-mentioned hydrolysis, hydrolysis may be optionally performed by adding a gelling inhibitor such as hydroxylamine hydrochloride and hydroxylamine sulfate for the purpose of preventing gelation caused by impurities. In general, it is particularly preferable to carry out the hydrolysis after the treatment with the gelling inhibitor in the hydrolysis.

The method for treating a dyed product with the dye fixing agent of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Cellulose fibers to which the dye fixing agent of the present invention is applied include cotton, rayon, and the like, and can be applied to a mixture of cellulose fibers with other fibers such as polyester and silk. The reactive dye for dyeing cellulose fibers is not particularly limited as long as it is a general dye, and a water-soluble anionic dye is reacted with a vinyl sulfone group, a dichlorotriazine group, a monochlorotriazine group, a dichloroquinoxaline group, or the like. An organic dye having a group is exemplified, and examples of the dyeing method include ordinary immersion dyeing, continuous dyeing, and print dyeing.

As a method of treating a dyed product with the dye fixing agent of the present invention, for example, a dyed product to be treated is immersed in an aqueous solution of 1 to 5 g / l of the above polymer, then squeezed with a mangle or the like, and then heat dried And the above polymer, from 0.1 to 5
g / l of an aqueous solution to be treated, usually at room temperature to 8
After immersion at 0 ° C. for about 5 to 30 minutes, it may be washed with water and dried.

[0021]

(Production example of polymer)

191 kg of demineralized water was charged into a 0.7 m ³ reactor equipped with a stirrer, a nitrogen inlet tube, and a cooling tube, and nitrogen was passed through the system at room temperature to perform degassing. Subsequently, the temperature was raised to 70 ° C., and 6 kg of a 10% aqueous solution of 2,2′-azobis-2-amidinopropane dihydrochloride was added. There, N-vinylformamide 6
9.9 kg (85.7% purity) and 30.1 kg of demineralized water were added, and a monomer solution adjusted to pH 6.5 with a 1N aqueous sodium hydroxide solution was added over 2 hours.

One hour after the start of the addition, 2,2 'is further added.
-10% of azobis-2-amidinopropane dihydrochloride
3 kg of an aqueous solution was added, and the reaction was carried out for 3 hours even after the addition of the monomer solution to obtain a 20% by weight solution of an N-vinylformamide polymer. 0.1 g / dl of the polymer in 1N saline
Was measured at 25 ° C. with an Ostwald viscometer to find that the reduced viscosity was 0.5 dl / g.

(Polymer A) The above-mentioned aqueous solution of N-vinylformamide polymer 18.5 k
g in a reactor equipped with a stirrer and a temperature controller, and 3.98 kg of a 35% by weight aqueous sodium hydroxide solution was added.
The temperature was raised and basic hydrolysis was performed at 80 ° C. for 5 hours. Thereafter, the temperature was returned to room temperature, and 2.12 kg of a 25% hydrochloric acid aqueous solution was added to adjust the pH to 7.5. When the obtained polymer was analyzed by colloid titration and ¹³ C-NMR spectrum measurement, the N-vinylformamide unit (1) was 43 mol%,
The amount of the vinylamine unit (2) was 57 mol%.

(Polymer B) 800 g of the N-vinylformamide polymer aqueous solution was placed in a reactor equipped with a stirrer and a temperature controller, 2.06 g of hydroxylamine sulfate was added thereto, and the mixture was stirred at 50 ° C. for 1 hour. After adding 215 g of a 35% by weight aqueous sodium hydroxide solution, the temperature was raised and basic hydrolysis was carried out at 80 ° C. for 5 hours. Thereafter, the temperature was returned to room temperature, and 98 g of a 25% aqueous hydrochloric acid solution was added to adjust the pH to 7.5. When the obtained polymer was analyzed, it was 35 mol% of N-vinylformamide units (1) and 65 mol% of vinylamine units (2).

(Polymer C) Instead of 215 g of a 35% by weight aqueous sodium hydroxide solution, 243 g of a 35% by weight aqueous sodium hydroxide solution was added.
Basic hydrolysis was carried out in the same manner as in the production method of polymer B except that 111 g of 5% hydrochloric acid was used. When the obtained polymer was analyzed, the number of N-vinylformamide units (1) was 2
5 mol% and 75 mol% of the vinylamine unit (2).

(Polymer D) 287 g of 35% by weight aqueous sodium hydroxide solution was added to 35%
Basic hydrolysis was carried out in the same manner as in the method for producing polymer B except that 130 g of hydrochloric acid was used. When the obtained polymer was analyzed, N-vinylformamide unit (1) was 10 mol% and vinylamine unit (2) was 90 mol%.

[Evaluation test of chlorine fastness] A 4 g / l aqueous solution of each of the above polymers A to D was prepared. Next, a cotton cloth continuously dyed at a concentration of 1.0% is immersed in this solution using the following reactive dye, and mangled.
For 90 seconds. The aperture ratio at that time is 70
%Met. The dyes used were Cibacron Blue 3R (manufactured by Ciba Geigy) and Kayashion Gray P-NR (manufactured by Nippon Kayaku Co., Ltd.).

Similarly, a 4 g / l aqueous solution of a polymer of monoallylamine hydrochloride (polymer E) was prepared and treated in the same manner as described above, and this was used as a comparative example. The continuous dyed cloth used for the test was dyed under the following conditions.

[0029]

Table 1 Dyeing bath formulation (g / l) Dye 100 Sodium alginate 0.5 Urea 100 Soda ash 15 Sodium metanitrobenzene sulfonate 5

Processing method Processing is performed in the following order. Pad dry (105 ° C. × 3 minutes) Baking (160 ° C. × 2 minutes) Soaping (90 ° C. × 5 minutes) Next, the chlorine fastness of the treated dyed cloth was measured according to JIS L-08.
84 (weak and strong test). The results are summarized in Table 1.

The evaluation values in Table 1 show the grade of discoloration and fading of the treated dyed cloth before and after the test, and are shown in Gray Scale for Assessing Cha.
ngein Color Fastness Test)
See SL0804). This evaluation value is 5, 4-5,
4,3-4,3,2-3,2,1-2,1
The higher the value, the less discoloration.

Therefore, according to Table 1, when the polymers A to C of the dye fixing agent of the present invention were used, the chlorine fastness was remarkably improved as compared with the case where no treatment was carried out. It can be seen that the effect is greater than the hydrochloride polymer E.

[0033]

[Table 2] Note) a: weak test, b: strong test

[Evaluation test of sweat fastness]
A g / l aqueous solution was prepared. Next, a cotton cloth continuously dyed at a concentration of 10% was immersed in this solution using the following reactive dye, mangled, and heat-treated at 150 ° C. for 90 seconds. The drawing ratio at that time was 70%.
The dyes used were Kayashi on Red P-4BN and Kayashi on Turkey P-NGF (manufactured by Nippon Kayaku Co., Ltd.).

The continuous dyed cotton cloth used for the test was dyed in the same manner as in the above-mentioned evaluation test of chlorine fastness. Next, the sweat fastness of the treated dyed cloth was measured according to JIS L-0.
848 (alkaline sweat method). In the test method, a dyed cotton cloth immersed in an alkaline artificial sweat solution is brought into contact with a white cotton cloth or a silk cloth to examine the color transfer from the dyed cotton cloth. The results are summarized in Table-2. The evaluation values in Table 2 show white cloth (cotton, silk) contamination before and after the test in terms of grade, and a gray scale test (Gr.
ey Scale for Assessing Staining in Color Fastness T
est) (see JIS L0805). This evaluation value is 5, 4-5, 4, 3-4, 3, 2-3,
It is classified into 2, 1-2, and 1 means that the higher the numerical value, the less the contamination and the better the fastness.

[0036]

[Table 3] Note) a: cotton cloth, b: silk cloth

[Evaluation Test of Heat Treatment Yellowing] Each of Polymers A to E
And a mixed aqueous solution of 3 g / l of a 4 g / l aqueous solution of Fluorescent Dye and Hakkor BRK (manufactured by Showa Chemical Industry Co., Ltd.). Next, a cotton broad cloth was immersed in this solution, mangled, and heat-treated at 150 ° C. for 90 seconds. The drawing ratio at that time was 70%. Next, the whiteness of the treated cloth was measured using a Macbeth Color Eye MS-2020 colorimeter.
(Manufactured by Macbeth) and determined as Hunter White Index (WI value). In addition, this WI value means that the larger the value is, the whiter it is. The results are shown in Table-3.

[0038]

[Table 4] Note) Original fabric WI value: 88

[0039]

As described above, according to the dye fixing agent of the present invention, the dye fastness, such as the fastness to chlorine and the fastness to sweat, of the dyed product dyed with the reactive dye can be remarkably improved.

Continuation of front page (72) Inventor Shigeji Uchida 4-23 Besshicho, Sabae-shi, Fukui Prefecture (72) Masayuki Maeno 3-9-1 Kitayotsui, Fukui-shi, Fukui Prefecture (56) References JP-A-2-142810 (JP, A) JP-A-6-2288 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06P 5/08

Claims (4)

(57) [Claims] 1. A dye fixing agent used for a cellulosic fiber dyed with a reactive dye, comprising 2 to 90 mol% of a structural unit represented by the following general formula (1) and a general formula (2): A dye fixing agent comprising a polymer containing 10 to 98 mol% of a structural unit represented by the formula: and / or a salt thereof. Embedded image Embedded image (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2. Polymerization of a compound represented by the following general formula (3) alone or a mixture of a compound represented by the following general formula (3) and another vinyl compound copolymerizable with the compound. The dye fixing agent according to claim 1, comprising a polymer obtained by subjecting the polymer to partial hydrolysis. Embedded image (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 3. A compound represented by the following general formula (3):
The dye fixative according to claim 2, which is -vinylformamide. 4. A polymer having a concentration of 0.1 g / d in a 1N saline solution.
of reduced viscosity measured at 25 ° C.
The dye fixing agent according to any one of claims 1 to 3, wherein the amount is 1 to 10 dl / g .