JPS5839955B2 - Anti-settling agent for different dyes in mixed fibers - Google Patents

Description

[Detailed description of the invention] The present invention relates to a suspending agent for different dyes in mixed fibers.

For more details, please refer to the different types of dyes for mixed fibers that have excellent dyeing performance when dyeing mixed fibers of cationic dye-dyeable fibers and anionic dye-dyeable fibers with cationic dyes and anionic dyes in one bath. This invention relates to an anti-settling agent.

Recently, with the diversification of textile products, there has been an increase in the use of excellent materials that take advantage of the unique properties of each fiber and compensate for their shortcomings, such as blended fibers made by mixing different types of fibers, and blended fibers of mixed knitting and weaving.
Efficient dyeing processing of this material is a challenge for the dyeing processing industry.

Such blended fibers include cationic dye-dyeable fibers (
There are blended fibers of acrylic fibers, cationically dyeable polyester, etc.) and anionic dyes dyeable fibers (natural fibers such as cotton, rayon, hemp, wool, etc.; synthetic polyamide fibers; regular polyester fibers, etc.). To dye the flammable fiber side with a cationic dye,
A so-called two-bath dyeing method has been used in which the anionic dye-dyeable fiber side is dyed with an anionic dye, but it has the disadvantage that the dyeing process is complicated and takes a long time, and the dyeing cost is high.

As an improved method of this, the so-called IT dyeing method, which dyes acrylic fiber/wool blends and acrylic fiber/cellulose fiber blends in one bath, has already been put into practical use.
No. 19877, Japanese Patent Application Publication No. 1987-19182, Special Publication No. 1972
It has been reported in various publications such as No. 37118 and Japanese Patent Publication No. 53-25072.

However, these have the disadvantage that the dyes that can be used are limited due to dye absorption, mutual contamination of fibers, fastness, etc., and no satisfactory product has yet been found.

The present inventors have made extensive studies to solve these problems, and as a result, have arrived at the present invention.

That is, the present invention provides sulfates or phosphoric acids of alkylene oxide adducts of polycyclic phenols having 7 to 14 aromatic rings obtained by reacting phenols with a compound selected from the group consisting of styrenes and benzyl halides. For different dyes of mixed fibers, characterized in that it is made of salt and is used for single-bath dyeing of mixed fibers of cationic dye-dyeable fibers and anionic dye-dyeable fibers with cationic dyes and anionic dyes. It is an anti-settling agent.

A sulfate or an alkylene oxide adduct of a polycyclic phenol having 7 to 14 aromatic rings obtained by reacting the phenol used in the present invention with a compound selected from the group consisting of styrenes and halogenated benzyls. In the phosphate, phenols include phenol; naphthol; alkylphenol (phenol having a C7 to C20 alkyl group, such as methyl, ethyl, butyl, tertiary butyl, hexyl, octyl, nonyl, dimethyl, dinonyl, dodecylphenol, etc.); Arylphenol (phenylphenol, biphenylphenol,
(naphthylphenol, etc.); alkarylphenol (tolylphenol, xylylphenol, etc.); aralkylphenol (cumylphenol; benzylphenol, etc.); halogenated phenol (trichlorophenol, monochlorophenol, monobromophenol, etc.); and these phenols. Examples include formaldehyde or acetaldehyde condensates.

Among these, preferred are phenol, alkylphenol, aralkylphenol and halogenated phenol, and particularly preferred are phenol, nonylphenol, dinonylphenol, cumylphenol,
It is monochlorophenol.

Styrenes include styrene and substituted styrenes (alkyl-substituted styrenes, such as α-methylstyrene, β-
Halogen-substituted styrenes such as methylstyrene include α-chlorostyrene, β-chlorostyrene, α-guymustyrene, and ββ-β-chlorostyrene.

Examples of the benzyl halides include benzyl chloride and benzyl bromide.

Among styrenes and benzyl halides, styrenes are preferred; among styrenes, styrene,
and α-methylstyrene are preferred.

The method of reacting styrene with phenol is a known method, for example, Friedel-Crabz reaction (AIC#3,5bC).
7. The reaction is carried out at a temperature of 110 to 140° C. using an acidic catalyst such as H2SO4, H3PO4, activated clay, etc.).

In this case, the reaction product is one in which styrene is added to the phenol core, one in which styrene is further added to the added styrene, or one in which only styrene is polymerized first and this is added to the phenol core. Although it is obtained as a mixture, it can be used as it is.

The reaction is carried out in such proportions that a polycyclic phenol having 7 to 14 (preferably 9 to 12) aromatic rings is obtained.

When the polycyclic phenol has less than 7 aromatic rings, the effect of preventing precipitation due to the formation of a complex between the cationic dye and the anionic dye can only be exhibited in the case of a specific dye, and the range of use is limited.

Further, when the number of aromatic rings is more than 15, the precipitation prevention effect is excellent, but the dyeing properties of cationic dyes and anionic dyes are greatly affected.

As the alkylene oxide for obtaining the alkylene oxide adduct of polycyclic phenol, one or two alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide are used.
There may be more than one type, preferably ethylene oxide or two types, ethylene oxide and propylene oxide.

The method for producing the alkylene oxide adduct may be a known method, for example, NaOH, KOH, Na, C)-I
120-19 under pressure using an alkaline catalyst such as IONa
It can be added at a temperature of 0°C.

In the present invention, the amount of ethylene oxide in the alkylene oxide is usually 50% by weight or more, preferably 6% by weight or more.
It is 0 to 90% by weight.

When the ethylene oxide content is less than 50% by weight, a decrease in the precipitation prevention effect is observed.

The M conversion or phosphorylation to obtain the sulfate or phosphate of the alkylene oxide adduct of the polycyclic phenol is carried out by a known method, that is, sulfation using chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, sulfuric anhydride, or sulfamic acid. Examples include a method using a phosphorylating agent at 10 to 150°C using a phosphorylating agent, and a method using a phosphorylating agent such as phosphoric anhydride, phosphorus oxychloride, phosphoric acid, phosphorus pentachloride, or phosphorus trichloride at a temperature of 50 to 120°C. It will be done.

Examples of the above salts include metal salts (alkali metal salts, alkali metal salts, etc.) ammonium salts and amine salts (alkanolamines (mono-, di-, tri-, alkanolamines), alkylamines (mono-, di-, trialkylamines), etc.) can be given.

Salts can be produced by known methods.

Examples of the compounds used in the present invention are as follows.

In this example, polycyclic phenol refers to polycyclic phenol containing 7 to 14 aromatic rings.

In the water ring, EO is -CH2CH20CH3 shows, 0 -CH2C)(0 Show the side.

shows.

AO is alkylene okine [1] (phenol is naphthol + (styrenes or halogenated benzyls)) polycyclic phenol AO adduct sulfate or phosphate (here -(7CH
a) s indicates a styrene-side residue in which eight styrenes are bonded to one phenol nucleus, and the bond is a group that is formed by adding one styrene to the phenol nucleus, or a group that is formed by adding another styrene to the added styrene. The resulting group, styrene, was first polymerized, and this polymer was combined with the phenol nucleus to form a mixed group of the three groups, indicating that a total of eight styrene nuclei were bonded.

The meaning of this residue is the same in the following formulas.

) (2) Sulfate or phosphate of polycyclic phenol AO adduct from (alkylphenol + (styrenes or halogenated benzyls) reaction product [3] (aralkylphenol + (styrenes or halogenated benzyls) reaction) Sulfate or phosphoric acid of polycyclic phenol AO adducts (4) (halogenated phenols)
- (Styrenes or halogenated benzyls) Sulfate or phosphate of polycyclic phenol AO adduct from the reactant (5) (Formaldehyde or acetalkylene condensate of phenols) = (Styrenes or halogenated benzyls) ) Sulfate or phosphate of polycyclic phenol AO adducts from reactants [6] (Arylphenolic styrenes or halogenated benzyls) Polycyclic ** Sulfuric acid of phenol AO adducts from reactants Salt or Phosphate (7) Sulfate or Phosphate of Polycyclic Phenol AO Adduct from the Reactant of Alkaryl Phenol (styrenes or halogenated benzyl compounds) In one of the fibers of the mixed fiber in the present invention. In certain cationic dye dyeable fibers, the cationic dyes may be those commonly available commercially and used for dyeing.

Examples include basic dyes. Basic dyes include the New Edition Dye Handbook [edited by the Organic Synthesis Association, published in 1970, round neck (
Co., Ltd., pages 529 to 562.

In addition, in fibers dyeable with anionic dyes, anionic dyes include direct dyes, acid dyes, acid mordant dyes, mordant dyes, reactive dyes, and disperse dyes (ordinary disperse dyes containing anionic dispersants). and fluorescent brighteners (anionic type).

The anionic dyes described in the above-mentioned New Edition Dye Handbook can also be used.

Specifically, direct dyes are listed on pages 317-390, acidic dyes are listed on pages 393-526, acidic mordants and mordant dyes are listed on pages 565-597, and reactive dyes are listed on pages 881. - those listed on pages 942, disperse dyes listed on pages 725-816, and fluorescent brighteners listed on pages 819-816.
Examples include those listed on page 836.

Of course, any dye that is not listed in the Dye Handbook and that is already commercially available can be used.

The mixed fibers of cationic dye-dyeable fibers and anionic dye-dyeable fibers are the same as those mentioned above.

When dyeing blended fibers with a cationic dye in one bath using the compound of the present invention (hereinafter referred to as the suspending agent of the present invention), the amount of the suspending agent used in the dye bath is usually 0.
1 to 5 g/l (per solid content).

Moreover, it is usually 1 to 5% o, w, f (bath ratio 1:10).

The one-bath dyeing method in the present invention may be the same as a conventional method except for using the suspending agent of the present invention.

For example, in one-bath dyeing, the amount of cationic dye used is usually 0.01 to 8% o, w, f.

The amount of anionic dye used is usually 0.01 to 10% O, W
, f.

The bath ratio is usually 1:5 to 1:100.

Moreover, the pH in the bath is usually 3 to 7.

Furthermore, in the bath (if necessary, acids (acetic acid, formic acid, sulfuric acid, etc.) for pH adjustment, salts (sodium acetate, ammonium acetate, ammonium sulfate), antifoaming agents for dye resistance to improve level dyeing, etc. Dyeing aids such as level dyeing of cationic dyes,
Relaxation dyeing agent: Leveling and slowing dyeing agents for anionic dyes such as direct dyes, acid dyes, chrome mordant dyes, and metal-containing complex salt dyes, dispersing and leveling agents for disperse dyes, dyeing carriers, etc. may be added at the same time. .

Next, as an example, the dye bath prescription, dye bath adjustment method, and dyeing method in a one-bath dyeing method for acrylic/wool fiber will be explained.

The dye bath recipe is as follows. acid dye
0.01-10% o-w, f-force ionic dye 0
．． 01-8% Relaxing agent for liver-on dyes: Appropriate amount (depending on the dye brand) Precipitating agent of the present invention: 1% O, We f
Formic acid: 1% 〃 Ammonium acetate: 2% 〃 Mover salt: 4% 〃 To prepare the dye bath, first mix the cationic dye solution and the auxiliary agents (precipitating agent, slow dyeing agent) to make a homogeneous solution, then add the anionic dye solution. Preferably, it is prepared by adding a dye solution.

The pH in the dye bath is adjusted to 4-5. In the dyeing method, the dyeing temperature and dyeing time may be according to the usual dyeing method for mixed fibers of acrylic/wool fibers, for example, the dyeing temperature is 40 to 98° C., and the dyeing time is 1 to 1.5 hours.

The anti-settling agent of the present invention has the following effects.

1. Since the anti-settling agent of the present invention has very good anti-settling ability, it can be used in a wide variety of ways without limiting the dyes to be used.

2. By using the anti-settling agent of the present invention, cross-contamination between cationic dyes and anionic dyes is reduced, and vividly dyed fabrics can be obtained.

The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Synthesis of suspending agent (A) A reaction vessel equipped with a reflux condenser and a dropping device (capacity 101
) was charged with 940 g of phenol and 330 g of activated clay, and 832 g of styrene monomer was added at a temperature of 110 to 130°C.
0 g was added dropwise to form styrene.

After the reaction and aging, the mixture was filtered to remove activated clay to obtain 9200 g of octastyrylphenol in the form of a pale brown transparent viscous liquid.

4,630 g of this compound was added to an autoclave reaction pot (capacity: 2
0A), charged with 50 g of caustic force, dehydrated under reduced pressure, replaced with nitrogen, and heated to a temperature of 170 to 190°C and a pressure of 5.
5500 g of ethylene oxide was injected and reacted in about 1 hour under conditions of kg/crlt G or less.

After injection, aging reaction was carried out at the same temperature for about 1 hour, and polyoxyethylene (25) octastyrylphenyl ether (the number in (') indicates the number of moles of oxyalkylene was produced at 25°C in the form of a yellowish-white paste.

) 19,620 g was obtained. Subsequently, 9620 g of the above reaction product and 500 g of perchlorethylene as a solvent were placed in a glass-lined reaction vessel (capacity 201) equipped with a pressure reducing device.
0g and 583g of chlorosulfonic acid were added to
The dropwise reaction was carried out for about 1 hour within a temperature range of .degree.

After removing hydrochloric acid at about 40°C for 5 hours and neutralizing with 750 g of triethanolamine, perchloroethylene was distilled off under reduced pressure to obtain a water-soluble (bound sulfuric acid/solid matter = 3.5) brown paste-like compound. [Suspension inhibitor (A) of the present invention] 105
50 g was obtained.

(2) Dyeing using anti-settling agent (A) Kayara Light Yellow F8G (manufactured by Nippon Kayaku Co., Ltd., direct dye) 0.5% o, w, f- (for all fibers, the same applies below)
Solid content of suspending agent (A) 1% o, w, f, Sodium acetate 0.4% o, w, f, Acetic acid (90%) 0.5% o
, w, f, Ionetsu IL EC (manufactured by Sanyo Kadai Co., Ltd., cationic dye slow dye agent) 0.75% o, w, f, and Eisen Cachilon Pink FGH (manufactured by Hodogaya Chemical Co., Ltd., cationic dye ) A dye liquor is prepared by mixing 0.5% o and wf in this order.

At a bath ratio of 1:30, equal weights of Cashmilon (manufactured by Asahi Kaoru Co., Ltd., acrylic fiber) 52 count double yarn and 40 count cotton double yarn were added to the above dye solution at 40°C and heated from 40°C to 100°C for 6 hours.
After increasing the temperature for 0 minutes and dyeing at 100°C for 30 minutes, anhydrous sodium sulfate 30% O, W, F was added.

It was further dyed at 100°C for 30 minutes, slowly cooled to 60°C over 20 minutes, washed with running water, and dried.

The resulting cashmilon and cotton dyed yarns were uniformly dyed in pale pink and yellow, respectively.

In addition, if the cashmilon yarn was directly dyed, there was almost no contamination of the cationic dye on the cotton yarn.

Example 2 (1) Synthesis of suspending agent (B) 636 g of cumylphenol was reacted with 3422 g of styrene monomer using the same apparatus (but capacity: 51) and method as in Example 1 to produce undecastyryl, a brown viscous substance. 3870 g of cumylphenol was obtained.

Next, 2712 g of the above compound and 30 g of caustic potassium as a catalyst were placed in an autoclave reaction vessel (capacity 10#), and after vacuum dehydration and nitrogen substitution, the temperature was 100 to 120°C.
Ethylene oxide 3960% under pressure of 5kg/c/lG or less. ! A mixture of li' and 580 g of propylene oxide in a liquefied state was injected in its entirety and subjected to an addition reaction to obtain 6890 g of polyoxyethylene (45) polyoxypropylene (randomly added undecastyryl cumyl phenyl ether) in the form of a pale yellow paste. Ta.

6890 g of this compound was sulfated with 233 g of chlorosulfonic acid using 4000 g of perchlorethylene as a solvent using the same apparatus as in Example 1 (but with a capacity of 1011), neutralized with 300 g of triethanolamine, and then the perchloroethylene was distilled off under reduced pressure. Soluble in water (bound sulfuric acid/solids = 2.
0) brown paste-like compound [settling prevention agent of the present invention (
B)) 72oo, 9 was obtained.

(2) Dyeing using anti-settling agent (B) Astrazonero-70LL (manufactured by Bayer, cationic dye) 0.5% 0. w, f, and suspending agent (B
) with a solid content of 1% o, w, f, in acetic acid.
Adjust to H4,5.

At a bath ratio of 1:30, cashmiron jersey and wool serge were added to this dye by five people of the same type, and the temperature was raised from 50°C to 80°C over 15 minutes. , acidic mordant dye) 0.5%o
, w, f.

Furthermore, the temperature was raised from 80°C to 100°C over 10 minutes,
After dyeing at the same temperature for 60 minutes, add sulfuric acid to adjust the dye bath to pH
3.5 and dye at 100°C for 30 minutes.

Next, after slowly cooling to 70℃, dichromic acid power IJ0.25
% o, w, f, were added, the temperature was raised to 100°C over 15 minutes, chroming was performed at the same temperature for 20 minutes, the mixture was gradually cooled to 60°C, washed with running water, and then dried.

The cashmilon and wool dyed products thus obtained had uniform hues of yellow and blue, respectively, and staining of cashmilon with acid medium dyes and wool with cationic dyes was hardly observed.

In addition, when the fastness of dyed products was evaluated, as shown in Table 1,
The result was the same as when cashmilon was dyed with a cationic dye and wool was dyed with an acid medium dye in separate baths.

(Fastness test method) Light fastness JIS L 0841-74 Washing fastness JIS L 0844-76 (A-2 method) Botting fastness JIS 0875-75 Rubbing fastness JIS 0849-67 (Dry method) Example 3 ( 1) Synthesis of suspending agent (C) Using the same apparatus as in Example 1 (but with a capacity of 51), 31 g of α-methylstyrene monomer was added to 660 g of nonylphenol.
86.9 was reacted to obtain 3690 g of nona-methylstyrylnonylphenol as a brown viscous substance.

Next, 2564 g of this compound was placed in an autoclave reaction vessel (
Capacity 101) and caustic strength IJ30. ! After charging 9, dehydration under reduced pressure and nitrogen substitution were performed, and the temperature was 170 to 190°C.
Pressure 5kg/crli, 3520g of ethylene oxide under conditions of G or less, temperature 100-120℃, pressure 5kg/CI? An addition reaction of 928g of propylene oxide was carried out under conditions below LG to form a light yellow paste of polyoxyethylene (40) polyoxypropylene (8) nona α.
- 6660 g of methylstyryl nonylphenyl ether was obtained.

Next, 6660 g of this compound was charged into a glass-lined reaction vessel (capacity 1011), heated to 50 to 60°C, and 280 g of urea and 220 g of sulfamic acid were gradually added with stirring.

Then, the temperature was raised to 100 to 110°C, and the reaction was carried out at the same temperature for 5 hours.

After cooling, a small amount of ammonia water was added to adjust the pH to 7.5 to form a pale yellowish brown paste compound [settling inhibitor of the present invention].
C)) 7100 g was obtained.

This compound was soluble in water with a combined sulfuric acid/solids ratio of 2.1.

(2) Dyeing using a sedimentation preventive agent (C) A bath consisting of a solid content of the sedimentation prevention agent (C) of 1% o, w, f and anhydrous sodium sulfate 5% o, w, f is prepared.

The pH was adjusted to 4 with acetic acid, and equal weights of cashmiron jersey and nylon knitted jersey were added and treated at 40°C for 10 minutes (bath ratio 1:30).

After that, 0.5% O, W, F, Maxilon Yellow 6GL (Ciba Geigy, cationic dye) was dissolved and added.

Neolan Red GRE (manufactured by Ciba Geigy, metal-containing complex salt dye) 0.5% dissolved in advance after treatment at the same temperature for 5 minutes
Add o, w, f, heat up to 100°C over 45 minutes, and dye at the same temperature for 30 minutes.

After cooling to below 90°C, diluted sulfuric acid was added to adjust the pH to 3.5, and the temperature was raised to 100°C again.

After dyeing at the same temperature for 60 minutes, it is slowly cooled and washed with water.

2 in a 60°C bath containing 0.5 g/l of water wash-off valve ionic activator.
Soap for 0 minutes, then wash with water and dry.

At the same time, dyeing is carried out in the same manner without using the suspending agent (C).

When the cashmilon and nylon dyed products obtained in this way were not used with the suspending agent (C), they were both indistinct and partially covered with tar-like substances, whereas with the suspending agent (C) When using this method, cashmilon had a clear and uniform hue of yellow and nylon had a clear and uniform hue of red, and no tar-like substances were observed.

Example 4 (1) Synthesis of suspending agent (D) 165 g of α-methylstyrene was added to 257 g of monochlorophenol using the same apparatus (but capacity 31) as in Example 1.
2 g was reacted to obtain 1870 g of hepta-α-methylstyryl monochlorophenol, which is a light brown viscous substance.

Next, a mixture of 1980 g of ethylene oxide and 360 g of 1,2-butylene oxide in a liquefied state was added to 955 g of the above compound using the same apparatus as in Example 2 (but with a capacity of 5 A), and a yellow paste-like polyoxy Ethylene (45), polyoxybutylene (5) buta-methylstyryl monochlorophenyl ether 319
0 gwo4t, =.

Transfer 1000g of this compound to a glass-lined reaction vessel (capacity 3JI?) and heat at 50-60°C with 21.5g of phosphorus pentoxide.
was gradually added and reacted at the same temperature for 3 hours.

Next, this phosphoric oxide was poured into a 1 to 2% aqueous solution of caustic soda prepared in advance to neutralize it, and a yellowish brown transparent liquid compound (precipitating agent (1) of the present invention) of about 50% aqueous solution was obtained.
)) zo2og was obtained.

The bound phosphate/solids for this compound was 2.3.

(2) Dyeing using anti-settling agent (D) Paranyl Yellow 30 (manufactured by BASF, disperse dye) 0.5% o, w, f
,, commercially available methylnaphthalene carrier 6% o, w,
f,, Sodium acetate 1% o, w, f,, Suspension inhibitor (D)
Solid content of 1% o, w, f, and Eisenkatylon Bink FGH (manufactured by Hodogaya Chemical Co., Ltd., cationic dye) 0.5%
Mix o, w, f in this order and adjust the pH to 4.0 with acetic acid.
Prepare a dye solution adjusted to 5.

At a bath ratio of 1:30 and at 60°C, large amounts of Beslon (manufactured by Toho Rayon Co., Ltd., acrylic fiber) jersey and Tetron (manufactured by Toshi Co., Ltd., polyester fiber) jersey of the same type were prepared.
The temperature is raised to 100°C over 40 minutes, dyed at the same temperature for 60 minutes, then slowly cooled to 60°C, washed with running water, and dried.

The dyed Veslon jersey and Tetron jersey thus obtained have uniform hues of bright pink and yellow, respectively, and contamination with disperse dyes for Veslon and cationic dyes for Tetron is negligible. It was very little.

Example 5 (1) Synthesis of suspending agent (E) β-naphthol 288 was placed in a reaction vessel (capacity 21) equipped with a dropping device.
g, and 1 g of anhydrous aluminum chloride were added, and the temperature was raised to 140 to 150°C.

1518 g of benzyl chloride was added dropwise over about 6 hours to react.

After further reacting at the same temperature for 5 hours, the mixture was cooled to 60°C and neutralized with caustic soda.

The catalyst was removed by filtration to obtain 1320 g of hexabenzyl β-naphthol as a pale brown viscous liquid.

To 684 g of this compound, 2640 g of ethylene oxide was added using the same method as in Example 1 (but with a capacity of 57). ? The mixture was added to obtain 3400 g of polyoxyethylene (60) hexabenzyl β-naphthyl ether in the form of a pale yellow soft solid.

Furthermore, 3300 g of the above compound was added to the same apparatus as in Example 3 (
However, the capacity is 51), the method is 112g of sulfamic acid,
Sulfate with 140g of urea, neutralize with a small amount of ammonia water,
Pale brown paste compound (settling inhibitor (E) of the present invention)
) 3500g was obtained.

This compound is soluble in water and the bound sulfuric acid/solids are 2.
It was 1.

(2) Dyeing using an anti-settling agent (E) A cationically dyeable polyester (CDP)/wool blend fabric (50:50) was dyed using the anti-settling agent (E) in the following manner.

(Dye solution) Waste Chemical Concentration ■ Reactive dye for wool Lanazole Elo-4G (manufactured by Ciba Geigy) 0.275% o, w, f Lanazole Red B (manufactured by Ciba Geigy) 0.08 tt Lanazol Fill-3G (manufactured by Ciba Geigy) ) 0.55 g ■ Albegar B (manufactured by Ciba Geigy, leveling agent) 1 ■ Anhydrous sodium sulfate 5 ■ Ionet TD-276 (manufactured by Sanyo Kaisha, carrier) 3 g/l Sodium acetate
0.5% o, w, f.

Acetic acid (Adjusted to pH: Anti-settling agent (E) Solid content 1% o, w, f.

Cationic dye for CDP Eisenkatilon Yellow C1) RLH [Manufactured by Hodogaya Chemical Co., Ltd.] 0.35% o, w, f.

Eisenkatylon Red CI) FBLH ()0.0125 tt Eisenkatyron Blue CD-RLH (tt )0.65 tt Aqueous ammonia (adjusted to pH 8) [Phase] Acetic Acid
(〃 4 〃 ) (Dyeing method) A dye solution (pH 4) at 40°C mixed with chemicals ■～■ in a bath ratio of 1
: Add CDP/wool blend fabric (50:50) at 40
The temperature was raised to 80°C over a period of 30 minutes, then the chemical (1) was added, the temperature was maintained for 10 minutes, and then the temperature was raised to 100°C over a period of 30 minutes.

After dyeing at 100°C for 60 minutes, the temperature was lowered to 80°C, the pH was adjusted to 8 by adding drug ①, and the same temperature was maintained for 20 minutes.
The temperature drops to ℃.

Add the drug [phase], adjust the pH to 4, maintain the same temperature for 20 minutes, wash with water, and dry.

At the same time, dyeing is carried out in the same manner without using the suspending agent (E).

When the CDP/wool blend fabric dyed in this way did not use the sedimentation prevention agent (E), it was unevenly dyed and tar-like substances were partially attached, whereas the sedimentation prevention @ ( When used in E), it had a uniform dark green hue.

In addition, when the fastness of the CDP/wool blend fabric dyed using the suspending agent (E) was evaluated, the light fastness was grade 5 to 6;
The washing fastness (wool stain) was 5th grade, and the rubbing fastness (dry) was 5th grade.

Reference Examples 1 to 8 In order to examine the anti-settling effect of the anti-settling agent of the present invention, the compound of the present invention (product of the present invention) and a known compound (comparison) were used as the anti-settling agent for combinations of various cationic dyes and anionic dyes. The anti-precipitation effect was checked using the following products:

The precipitation prevention effect was determined by the following test method, and judgment was made by visual judgment.

(Test method) 1 test solution (100CC) prepared according to the prescribed procedure
After heating to 00° C. and simmering at the same temperature for 80 minutes, suction filtration was performed using a Sutsche filter (Toyo Roshi 45A) L, and dye residue on the filter paper was visually determined.

The criteria for judgment are as follows.

○: No dye aggregates △: 〃 Slightly present ×: 〃 Considerably present × × 2 〃 Significantly present Reference example 1 Cationic dye - Acid dye (leveling type and milling type) 1. Test solution concentration 1 Contaminant (%) 5ol) pH adjustment mixing c
c number ■ Cationic dye 0.5 5 10
■ Anti-settling agent 1.0 5 10 ■ Acid dye 0.5 5 10 ■ Water 5 70 total
100*pH adjustment was performed with acetic acid (pH adjustment in the following reference examples was performed using the same method).

2. Solution preparation procedure After mixing (approximately 60°C) (about 60°C), mix (1) and add (2).

3. Dye (1) Cationic dye (C-1) Cachilon Yellow 3GLH [manufactured by Hodogaya Chemical ■] (C-2) Maxilon Brilliant Pink B [manufactured by Ciba Geigi ■] (C-3) Astrazone Red 5BL [Manufactured by Bayer ■] (C-4) Nistrol Yellow N-2RL [Manufactured by Sumitomo Chemical ■] (C-5) Cachiron Red Ni-GLH [Manufactured by Hodogaya Chemical ■] (C-6) Diacrylic Blue GRL-H [ Manufactured by Sumitomo Chemical ■] The above cationic dyes were also used in Reference Examples 2 to 8 below.

(2) Acidic dye (leveling type) (AR-1) Suminol Leveling Yellow GR [manufactured by Sumitomo Chemical ■] (AR-2) Diazid Fast Blue NP [manufactured by Mitsubishi Chemical ■] (AR-3) Solar Rhodamine B [ (manufactured by Sumitomo Chemical ■) (3) Acidic dye (milling type) (AM-1) Kayanol Milling Yellow 6GW [manufactured by Nippon Kayaku ■] (AM-2) Suminol Milling Red pG [manufactured by Sumitomo Chemical ■] (AM- 3) Irganol Scarlet RLS (manufactured by Ciba Geigy) 4. Precipitating agent (1) Poly[oxyethylene (15) oxypropylene (5)) octastyrylphenyl ether sulfate sodium salt (80%) 2. Invention product (F) (2) Poly[oxyethylene (40) oxypropylene (10)) lysocan styryl phenyl ether sulfate ammonium salt (100%); Invention product (G) (3) Poly[oxyethylene (40) stearyl alcohol ether] Comparative product (a) (4) Polyoxyethylene (20) lauryl alcohol ether sulfate sodium salt (80% aqueous solution);
Comparative product (b) 5. The sales method is shown in the test result table-2.

Reference example 2 Cationic dye - metal-containing complex dye (1. Test solution waste Drug concentration (%5ol) ■Cationic dye 0.5 ■Concentrated sulfuric acid o, i: Type 1 mixed cc number 0 0 Preservative agent ■Precipitation prevention Agent ■1: Type 1 metal-containing dye ■Water concentration (% sol) 1.0 0.5 Total 00 2. Solution preparation procedure After mixing ■, ■, and ■ thoroughly (about 30°C), mix ■; Add ■ 3. Dye (1) Metal-containing complex dye (Type 1) (M-1) Balalan Fast Red BEN (B, A
, S, F, ■] (M-2) Balaran Fast Blue RRN (B,
A, S, F, manufactured by ■] (M-3) Neo Lampurawn GRN [manufactured by Ciba Geigi ■] 4. Test results are shown in Table-3.

Reference example 3 Cationic dye-metallic complex dye (1:1, test solution type 2) Concentration change Chemical (%5ol) pH adjustment ■ Cationic dye 0.55 ■ Precipitating agent 0.55 Mixed cc number Concentration change Drug (%5ol) "Kansei mixed cc number"
1; Type 2 metal-containing dye 0.5 5 10■
Water 5 70 total 00 2. Solution preparation procedure Mix ■ and ■ well (approximately 60°C), mix ■, and add ■.

3゜Dye (1) Metal-containing complex salt dye (1:2 type) (M-4) Kaya Calan Scarlet GL [manufactured by Nippon Kayaku ■] (M-5) Lanasin Red 2GL 280% [manufactured by Mitsubishi Kasei ■] (M- 6) Lanier Yellow G [manufactured by Sumitomo Chemical ■] 4. Test results are shown in Table-3.

Reference example 4 Cationic dye - chromium dye 1, test solution Concentration, %5 o 1) pH adjustment ■ Cationic dye 0.5 5 1゜ ■ Precipitating agent 0.5 5 10 ■ Chromium dye 0.5 5 10 ■ Water 5 70 cc mixed
Count 100 2. Solution preparation procedure After mixing (approximately 60°C) ■ and ■, mix ■ and add ■.

3. Dye Chrome Dye (CR-1) Yamada Chrome Black FT Conk [Manufactured by Yamada Chemical ■] (eR-2) Sunchrome Black FT Conk [Manufactured by Sumitomo Chemical ■] (CR-3) Mitsui Chrome Black PB Conk [Manufactured by Sumitomo Chemical ■]
Manufactured by Mitsui Toatsu Chemical Co., Ltd.] 4. Test results are shown in Table-4.

Reference example 5 Cationic dye 1, test solution Reactive dye (for wool) Scraps Drug concentration (%5ol) pH adjustment mixing cc number■ Cationic dye 0.5 5 10■
Precipitating agent 0.5 5 10 ■Reactive dye 0.5 5 10 ■Water 5 70 total 00 2. Solution preparation procedure After mixing ■ and ■ (about 30°C), mix ■ and add ■.

3. Dye (1) Reactive dye (for wool) (RW-1) Trimaran Yellow F-30L [Made by Sand ■] (RW-2) Trimaran Red F-2BL [Made by Sand ■] (RW-3) Trimaran Blue F-2GL (manufactured by Sandoz) 4° Test results are shown in Table-4.

Reference example 6 Cationic dye - direct dye 1, test solution sterilizer Concentration * pH mixing (%5ol) adjustment cc number■Cationic dye 0.5 5 10■Settling inhibitor 0.5 5 10 ■Direct dye 0. 5 5 10 ■ Water 5 70 total
100 2. Solution preparation procedure After mixing (approximately 60°C) (about 60°C), mix (1) and add (2).

3. Dye (1) Direct dye (D-1) Kayarasu Spray Yellow F8G [manufactured by Nippon Kayaku ■] (I)-2) Sumilite Turquoise Blue G Conch [manufactured by Sumitomo Chemical ■] (D-3) Dyluminus Red 4BL [Made by Mitsubishi Kasei ■] 4. Test results are shown in Table-5.

Reference example 7 Cationic dye - reactive dye (for cellulose) 1, test solution preservative concentration * pH mixing (excellent 5 ol) adjustment cc number ■ cationic dye ■ anti-settling agent ■ reactive dye ■ water meter 2, solution preparation procedure Mix ■ and ■ (approximately 3 times and add ■).

3. Dye 0℃), then mix ■ (1) Reactive dye (for cellulose) (RC-1) Mikasion Blue 2R [Made by Mitsubishi Kasei] (RC-2) Remazol Brilliant Red 6BD [Made by Hoechst ■] (RC-3) Trimalene yellow -R [Made by Sand ■] 4. Test results It is shown in Table-5.

Reference example 8 Cationic dye-disperse dye 1, test solution agent concentration *pH (%5ol) adjustment mixed cc number ■Cationic dye 0.5 ■Settling inhibitor 0.5 ■Disperse dye 0.5 ■Water 2゜Total 100 Solution Preparation Procedure After mixing ■ and ■ (about 60℃), mix ■ and add ■.

3. Dye (1) Disperse dye (DI-1) Dianics Yellow 2G-8E [Made by Mitsubishi Kasei] (DI-2) Kayalon Polyester Red BH3 [Made by Nippon Kayaku ■] (D.I. 3) Sumikaron Blue B.R. [Manufactured by Sumitomo Chemical] 4. Test results It is shown in Table-6.

Acrylic/
Dyeing of wool woven fabric was carried out.

Anti-settling agent Inventive product (H): Poly[oxyethylene (20):) oxypropylene (7)) Octastyrylphenyl ether sulfate monoethanolamine salt (1oo%) Comparative product (Q: Poly[oxyethylene (20):) Nonylphenyl Formalin condensation of ether sulfate ammonium salt 5
Dye (30+) Dye Cationic dye: Astrazone Elo-7GLL (manufactured by Bayer) Acidic mordant dye: Sunchromine Fast Blue-MB (manufactured by Sumitomo Chemical Co., Ltd.) Example 2 was prepared using woven cashmilon knitted wool serge. The same treatment was carried out (however, the amount of dye used was 1% o, w, f).

The cashmilon and wool dyed fabrics using the invention product 0 thus obtained had uniform hues of yellow and blue, respectively, and there was almost no contamination of acidic mordant dyes for cashmilon or cationic dyes for wool. I couldn't.

On the other hand, in the dyed fabric using the comparative product (Q), no streaks were observed, but staining of cashmilon with acidic mordant dyes and staining of wool with cationic dyes was observed.

Furthermore, when the color fastness of each dyed fabric was evaluated, as is clear from the table below, the product of the present invention was superior to the comparative product in terms of stain fastness.

Example B In order to check the anti-settling effect of the anti-settling agent of the present invention, various combinations of cationic dyes and anionic dyes were used as the anti-settling agent, and the anti-settling effect was checked using the product of the present invention and a comparative product. The results are shown in Table-B and Table-C.

The test method was carried out in the same manner as in Reference Examples 1 to 8, and the results are shown according to the same criteria.

The anti-settling agent used was the product of the present invention CF (l: used in Example A) and the product of the present invention (■
): Poly[oxyethylene (35) oxypropylene (5)
) Theca α-methylstyrylphenyl ether phosphate ammonium salt (50%) Invention product (J): Poly[oxyethylene (50) oxypropylene (10
) Oxyethylene (10) ) Formalin condensation dimer of hebuta-α-methylstyrylphenyl ether sulfate jetanolamine salt (40%) Comparative product (C): The one used in Example A Comparative product (d): Poly [oxyethylene (5)] Formalin condensed trimer of dodecyl phenyl ether sulfate sodium salt (30 poly) Comparative product (e): Formalin condensed nonamer of poly[oxyethylene (30) ”]butylphenyl ether sulfate sodium salt (30 yen)

Claims (1)

[Claims] 1 Consists of a sulfate or phosphate of an alkylene oxide adduct of a polycyclic phenol having 7 to 14 aromatic rings obtained by reacting a phenol with a compound selected from the group consisting of styrenes and halogenated benzyls. , a precipitating agent for different dyes of mixed fibers, characterized in that it is used for one-bath dyeing of mixed fibers of cationic dye-dyeable fibers and anionic dye-dyeable fibers with cationic dyes and anionic dyes. .