JPS6220308B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new dyeing aid and its use in the dyeing of synthetic fiber materials. Many synthetic fibers have hydrophobic properties.
This makes dyeing these fibers difficult and creates practical problems. When these synthetic fiber materials are dyed with aqueous dispersions of disperse dyes or in the presence of cationic dyes without a carrier, they generally do not dye hydrophobic materials and dyeing at the boiling point of water is not successful. . As a method for dyeing this textile material, a carrier is usually used to promote the dyeing onto the material. However, we have discovered a new dyeing aid that not only contributes to dye adhesion to these materials, but also contributes to dye migration, improves the uniformity of dyeing, and increases the dyeing rate to at least 30%. . This new auxiliary agent also has the effect of cleaning the fiber material at the same time. The present invention comprises at least (a) tetralin (tetrahydronaphthalene) or preferably an alkylbenzene or a mixture thereof, (b) an anionic surfactant, (c) a water-immiscible non-aromatic solvent and optionally (d) Dyeing aids comprising polar solvents and/or (e) nonionic surfactants. Preferably, the dye liquor contains the following components. (a)+(b)+(c) (a)+(b)+(c)+(e) or especially (a)+(b)+(c)+(d) or (a)+( b)+(c)+(d)+(e) The alkylbenzene to be used as component (a) is, for example, a mixture of alkylbenzenes obtained by catalytic reduction of petroleum components. In particular, it is a benzene derivative having one or more methyl and/or ethyl groups. These compounds include, inter alia, toluene, xylene, trimethylbenzene, tetramethylbenzene, methyl-ethylbenzene,
Dimethyl-ethylbenzene, trimethyl-ethylbenzene and ethylbenzene or mixtures thereof. Particularly satisfactory results are obtained when using mixtures of methylethylbenzene and trimethylbenzene or mixtures of dimethyl-ethylbenzene, tetramethylbenzene and trimethyl-ethylbenzene. Mixtures of alkylbenzenes and tetralin can also be used as component (a). The anionic surfactant of component (b) is preferably an alkylene oxide adduct, such as alkylene oxide, especially ethylene oxide and/or
An inorganic compound obtained by adding propylene oxide or styrene oxide to an organic hydroxide, carboxyl compound, amino compound and/or amide compound or a mixture thereof having an aliphatic hydrocarbon residue having at least 4 carbon atoms. Acidic addition products containing ether or ester groups of acids or organic acids. These acidic ethers or esters may be in the form of the free acid or in the form of salts such as alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts. These anionic surfactants can be added by a known method, i.e., 1 mol, preferably more than 1 mol, for example 2 to 60 mol, of ethylene oxide or propylene oxide or ethylene oxide and propylene oxide, alternately in any order, to the above-mentioned organic compound. addition and then etherification or esterification of the addition product and optionally derivatization of the ether or ester into its salt form. Its basic substances are higher fatty alcohols, i.e., alkanols or alkenols having 8 to 22 carbon atoms, alicyclic alcohols, phenylphenols, benzylphenols, having one or more alkyl groups and having a total number of carbon atoms in the alkyl groups. Amines with alkylphenols of at least 4, fatty acids with 8 to 22 carbon atoms, aliphatic and/or cycloaliphatic hydrocarbon residues with at least 8 carbon atoms, in particular aliphatic with these radicals Amines, hydroxyalkylamines, hydroxyalkylamides and aminoalkyl esters of fatty acids or dicarboxylic acids and higher alkylated aryloxycarboxylic acids. Component (b) is, for example, the formula (In this formula, Q is R ₁ -O-, R ₂ -CO-O- or R ₃ -N<, and R ₁ is an aliphatic hydrocarbon residue having 8 to 24 carbon atoms, and 10 to 24 carbon atoms. 22 is a cycloaliphatic hydrocarbon residue, an O-phenylphenyl group or an alkyl phenyl group having 4 to 16 carbon atoms in the alkyl part, and R ₂ is an aliphatic hydrocarbon residue having 7 to 21 carbon atoms. , R ₃ is an aliphatic hydrocarbon residue having 12 to 22 carbon atoms, especially 12 to 18 carbon atoms, and Y ₁ and
One of _Y2 is a hydrogen atom, a methyl group or a phenyl group, the other is a hydrogen atom, X is an acid residue of an inorganic acid or dicarboxylic acid containing an oxygen atom, or _-CH2COOH , m is a number from 1 to 50, preferably from 1 to 30, and q is 1 or 2 when Q is R ₃ N<, in which case the two substituents bonded to the nitrogen atom are the same group or mutually different groups). As component (b), especially the formula or (In these formulas, R ₁ , R ₂ , R ₃ , Y ₁ , Y ₂ , X and m have the meanings already given, and r and s
is an integer whose sum is from 2 to 15) Compounds represented by the following are suitable. Surfactants of formula (2) are preferred compounds. The group R ₁ -O- is, for example, an alcohol having at least 8 or more carbon atoms, preferably 10 to 24 carbon atoms, such as 2-ethyl-hexyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol,
Stearyl alcohol, oleyl alcohol, arachidyl alcohol or behenyl alcohol or hydroabiethyl alcohol or alfol or o-phenylphenol or alkylphenols such as butylphenol, hexylphenol, n-octylphenol, n-nonylphenol, p-t-octyl phenol,
pt-nonylphenol, decylphenol,
Derived from dodecylphenol, tetradecylphenol or hexadecylphenol. Straight-chain primary alcohols are important as alphals. The number after the name refers to the average number of carbon atoms in the alcohol. Some representative examples of alphaol are alphaol (6-8), (8-
10), (10~14), (12), (16), (18), (20~22
). The group R ₂ -COO- is, for example, a fatty acid having 8 to 22 carbon atoms, such as caprylic acid, capric acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, coconut oil acid, tallow Derived from acids, decenoic acid, linoleic acid, linolenic acid, oleic acid, ricinoleic acid, eicosenoic acid, docosenoic acid or culpanodonic acid.
R ₃ is the number of carbon atoms, preferably 12 to 22, particularly 16 to
22 alkyl or alkenyl group.
Y ₁ and Y ₂ are preferably hydrogen atoms. r+
The value of s is preferably 6-8. Y ₁ and Y ₂ are 1
May have different meanings within one molecule. When R ₃ is an alkyl group, it is, for example, n-dodecyl, myristyl, n-hexadecyl, n-heptadecyl, n-octadecyl, arachidyl or behenyl. _R3
When is an alkenyl group, it is, for example, a dodecenyl, hexadecenyl, oleyl or octadecenyl group. The hydrocarbon residue of the aliphatic amine, which is a starting material necessary for the production of the preferred addition product represented by formula (4), may be saturated or unsaturated, and may be branched or linear. Good too. The number of carbon atoms in this hydrocarbon residue is preferably 16-22. The amine may be chemically pure or in the form of a mixture. This amine mixture is preferably obtained by deriving the corresponding amine from natural fats such as tallow, soybean oil or coconut oil. Single amines include dodecylamine, hexadecylamine, heptadecylamine, octadecylamine, tallowamine, arachidylamine, behenylamine and octadecenylamine (oleylamine). Ethylene oxide can be added to the amine, or propylene oxide and/or styrene oxide can be added to attach a methyl or phenyl group to the ethylene oxide group. Propylene oxide is preferably used in a mixture with ethylene oxide. Preferably 5% propylene oxide per mole of amine
~15 moles, using more than 10 moles of ethylene oxide. The addition of styrene oxide is advantageously carried out before the addition of ethylene oxide. In this case amine 1
Preferably 1 mol of styrene oxide and 15 to 30 mol of ethylene oxide are used per mole. The acid residues X are derived from organic, preferably aliphatic dicarboxylic acids having 2 to 6 carbon atoms, such as maleic acid, malonic acid, succinic acid or especially sulfosuccinic acid or by reaction with halogenacetic acids. be able to. X is especially derived from a number of polyhydric oxyacids such as orthophosphoric acid or sulfuric acid. The acid residues X are preferably in the form of salts, eg alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts. These salts are, for example, sodium, potassium, calcium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts. Sodium and ammonium salts are preferred. alkylene oxide unit

[Formula] is usually a unit in the form of ethylene oxide or 1,2-propylene oxide, but in the latter case it is a unit of formula (2) in mixed form with a unit of ethylene oxide.
Contained in the compounds of ~(4). A preferred component (b) is the formula (2) in which R ₁ is an alkyl group having 4 to 12 carbon atoms, an o-phenylphenyl group, or an alkyl group or alkenyl group having 12 to 18 carbon atoms, and m is 2 to 15. Among them, the expression (In this formula, R ₄ is an octyl group or a nonyl group, m ₁ is 2 to 10, and X ₁ is sulfuric acid or o-
Anionic surfactants having a residue derived from phosphoric acid (in the form of the free acid or the sodium or ammonium salt) are particularly suitable compounds. In formula (4), R ₃ is an alkenyl group or especially an alkyl group having 16 to 22 carbon atoms, Y ₁ and Y ₂ are both hydrogen atoms, and the sum of r and s is 2 to 10, especially 4 to 10, in which X is _-SO3M and M is a sodium atom or _-NH4 , are particularly important compounds. As the water-immiscible non-aromatic solvent used as component (c), water-immiscible aliphatic, araliphatic and/or cycloaliphatic solvents are particularly suitable. Such solvents include, for example, monohydric or dihydric aliphatic alcohols having at least 5 carbon atoms, such as n-amyl alcohol, 2-ethylbutanol, trimethylhexanol, neopentyl glycol, and araliphatic alcohols, such as benzyl alcohol and furfuryl. Alcohols, and esters such as acetic acid-
_C1 - _C5 -alkyl esters, such as methyl, ethyl or propyl esters of acetate, phenyl acetate, benzyl acetate, methyl or ethyl lactate, cyclic diesters of carbonic acid and glycols, especially propylene glycol,
Amides such as acetoacetic acid diethylamide, N,
N-diethylthiourea, tributyl phosphate, polyhalogenated paraffins or aliphatic or cycloaliphatic hydrocarbons. The aliphatic hydrocarbons preferably have as low a melting point as possible (eg below -20°C) and a high boiling point (eg 300°C).
or higher) and has a low viscosity (for example, 5 to 60 at 50℃).
centistokes) paraffin oil is preferred. Cycloaliphatic hydrocarbons are also especially cyclopentane, cyclohexane and decalin. component
Preferred compounds as (c) are water-immiscible aliphatic solvents and especially n-amyl alcohol or paraffin oil. Furthermore, the dyeing aid of the present invention contains a polar solvent (d).
Water and/or water-miscible organic solvents may be included. This additive has the function of obtaining uniformity of the emulsion. Water-miscible organic solvents include, for example, aliphatic _C1 - _C4 alcohols such as methanol, ethanol or propanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, diacetone alcohol,
Ethers and acetates such as diisopropyl ether, diphenylene oxide, dioxane, tetrahydrofuran, monoalkyl ethers of glycols such as ethylene glycol monomethyl-, -ethyl- and butyl-ethers and diethylene glycol monomethyl- or -ethyl ether, tetrahydrofurfuryl alcohol, Pyridine, acetonitrile, γ-butyrolactone, N,N-dimethylformamide, N,N-
Examples include dimethylacetamide, tetramethylurea, and tetramethylene sulfone. It is also possible to use mixtures of these solvents. Preference is given to using isopropanol, β-ethoxyethanol and diacetone alcohol. In addition to components (a), (b), (c) and (d), the new dyeing aids according to the invention may contain nonionic surfactants as component (e). Component (e) preferably comprises from 1 to 100 mol of an alkylene oxide such as ethylene oxide and/or propylene oxide, an aliphatic monoalcohol having at least 4 and preferably 8 carbon atoms or a trihydric to 6 hydric alcohol having from 2 to 9 carbon atoms.
nonionic alkylene oxide adducts added to 1 mole of aliphatic alcohols or phenols optionally substituted by alkyl, benzyl or phenyl groups or fatty acids having 8 to 22 carbon atoms; It is. The aliphatic monoalcohols used to prepare component (e) are water-insoluble monoalcohols having at least 4 carbon atoms, preferably from 8 to 22 carbon atoms. This alcohol may be in a saturated or unsaturated state, and may be branched or linear,
Moreover, it may be a single compound or a mixture. It is possible to react natural alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols such as in particular 2-ethylhexanol, trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or the alkylene oxides with the aforementioned alphors. can. Other aliphatic alcohols that can be reacted with alkylene oxides are trihydric to hexahydric alkanols. The alkanols are preferably alkanols having 3 to 6 carbon atoms, in particular glycerin, trimethylolethane, trimethylolpropane, erythritol, mannite, pentaerythritol and sorbitol. The trihydric to hexahydric alcohol is preferably reacted with propylene oxide or ethylene oxide or a mixture of these alkylene oxides. Optionally substituted phenols include, for example, phenol, benzylphenol, dibenzylphenol, benzyl-(nonyl)phenol, o-phenylphenol or an alkyl group having from 1 to 16 carbon atoms, preferably from 4 to 4 carbon atoms.
12 alkylphenols are suitable. These alkylphenols are, for example, p-cresol, butylphenol, tributylphenol, octylphenol and especially nonylphenol. The fatty acids are preferably fatty acids having from 8 to 22 carbon atoms and may be saturated or unsaturated, such as caprylic, capric, pelargonic, lauric, myristic, palmitic or stearic acids or decenelic acids. acids, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, oleic acid, linoleic acid, linolenic acid or ricinoleic acid. The preferred alkylene oxide reaction product used as component (e) has the formula (In this formula, R ₅ is a hydrogen atom, an alkyl group or alkenyl group having 4 to 18 carbon atoms, an o-phenylphenyl group, or an alkyl phenyl group having 4 to 12 carbon atoms in the alkyl part) , one of Z ₁ and Z ₂ is a hydrogen atom and the other is a methyl group, Z is 1 to 15, and the sum of n ₁ and n ₂ is 5 to 10). This component (e) is preferably used together with component (b) of formula (2) or (5). The dyeing aid of the present invention may optionally contain a fatty acid salt of a polyvalent metal as an additive, which acts as a foaming inhibiting component (f) and preferably has a content of 0.2 to 5% based on the total dyeing aid. % by weight may be included. These metal salts are, for example, magnesium, calcium, strontium, barium, zinc or aluminum fatty acid salts. Fatty acid salts of alkaline earth metals or aluminum are preferred. The salt is either a mono-, di- or tri-fatty acid salt or a mixture thereof. It should be a solid agglomerate at room temperature. Suitable fatty acids are the fatty acids mentioned above, which can be saturated or unsaturated and preferably have 8 to 22 carbon atoms. The new dyeing aid formulation of the present invention consists of components (a), (b),
(c) and optionally (d), (e) and/or (f) may be prepared by simply stirring together, a homogeneous clear mixture being obtained which is storage stable at room temperature. Motsu. This dyeing auxiliary formulation advantageously comprises 30 to 80% by weight of component (a), 5 to 30% by weight of component (b), 5 to 20% by weight of component (c), 5% to 5% by weight of component (d), based on the total formulation. ~40% by weight, component (e)
0-10% by weight preferably 3-10% by weight and ingredients
(f) 0 to 5% by weight, preferably 0.2 to 5% by weight. The new dyeing auxiliary of the present invention specifically addresses the need for diffusion and dye migration when dyeing synthetic fiber materials. The invention therefore relates to a method for dyeing synthetic fiber materials with cationic dyes or disperse dyes, characterized in that the synthetic fiber materials are dyed in the presence of the dyeing auxiliary according to the invention. In this case it is preferred to use disperse dyes. The amount of the dyeing aid of the present invention used in the dye bath is:
0.5 to 6% by weight based on the weight of the dyed product, preferably 1
~4% by weight. Fiber materials, in particular textile materials, which can be dyed in the presence of the dyeing aids according to the invention are, for example, cellulose ester fibers such as cellulose-21/2-
Acetate fibers and cellulose-triacetate fibers, synthetic polyamide fibers such as synthetic polyamide fibers made from ε-caprolactam, synthetic polyamide fibers made from adipic acid and hexamethylene diamine and synthetic polyamide fibers made from ω-aminoundecanoic acid. , for example aromatic polyamide fibers derived from poly(meta-phenylene-isophthalamide), polyacrylonitrile fibers, modacrylic fibers, acid-modified polyester fibers and especially linear polyester fibers. Among them, cellulose ester fibers, polyamide fibers and polyester fibers are preferably dyed using disperse dyes, and polyacrylonitrile fibers, acid-modified polyester fibers and aromatic polyamide fibers are preferably dyed using cationic dyes. Linear polyester fibers are, for example, synthetic fibers obtained by condensation of terephthalic acid and ethylene glycol or isophthalic acid or terephthalic acid and 1,4-bis-(hydroxymethyl)-cyclohexane, and terephthalic acid and isophthalic acid with ethylene glycol. It is a copolymer with Acrylic fibers that can be dyed by the method of the invention include the usual types of polymers or copolymers of acrylonitrile. In the case of acrylonitrile copolymers, the acrylonitrile content should preferably account for at least 80% by weight relative to the total weight of the copolymer. Acid-modified polyester fibers include, for example, terephthalic acid or isophthalic acid, ethylene glycol and 1,2- or 1,3-dihydroxy-3-(3
-sodium sulfopropoxy)-propane,
2,3-dimethylol-1-(sodium sulfopropoxy)-butane, 2,2-bis-(3-sodium sulfopropoxyphenyl)-propane or 3,5-dicarboxy-benzenesulfonic acid or sulfonated terephthalic acid, sulfone It is a condensation product of 4-methoxybenzenecarboxylic acid or sulfonated diphenyl-4,4'-dicarboxylic acid. These fiber materials may be in the form of blends with other fibers, such as polyacrylonitrile/polyester blends, polyamide/polyester blends, polyester/cotton blends, polyester/viscose blends, and polyester/wool blends. can also be used. The textile material to be dyed can be in various states of processing. For example, it may be a non-textile material, a textile article such as a knitted or woven fabric, a thread in spun form or a muff. Cationic dyes suitable for the method of the invention belong to various dye classes. The cationic dyes are in particular the customary salts of cationic dyes, such as chlorides, sulfates or metal halides, such as zinc chloride di- Heavy salt. These chromophores are, for example, azo dyes, in particular monoazo or hydrazone dyes, diphenylmethane dyes, triphenylmethane dyes, methyl or azomethine dyes, coumarin dyes, ketonimine dyes, cyanine dyes, xanthene dyes, azine dyes, oxazine dyes or thiazine dyes. It is.
Also, phthalocyanine or anthraquinone dye salts with external onium groups such as alkylammonium groups or cycloammonium groups and benzo-1,2-
Pyran dye salts can also be used. The disperse dyes used in the process of the invention, which are only very slightly soluble in water and exist mostly in the form of fine dispersions in the dye liquor, can be of various dye types, such as acudrine dyes, azo dyes, anthraquinone dyes. , coumarin dyes, methine dyes, perinone dyes, naphthoquinone imine dyes, quinophthalone dyes, styryl dyes or nitro dyes. It is also possible to use mixtures of cationic dyes or disperse dyes in the process of the invention. The amount of dye to be used in the dye liquor depends on the required dye density, but it is usually advantageous to use from 0.1 to 10% by weight, based on the weight of the fiber material. The dyeing aids of the invention are, for example, di- or tri-chlorobenzene, o-phenylphenol, benzylphenol, diphenyl, diphenyl ether, chlordiphenyl, methyldiphenyl, methyldiphenyl ether, butylbenzoic acid, methylbenzoic acid, phenyl Benzoic acid, dibenzyl ether, alkylphenylbenzoic acid, dimethyl phthalate, cyclohexanone, acetophenone, alkylphenoxyethanol, mono-, di- and tri-chlorophenoxy-ethanol or -
It can also be used in admixture with already known carriers based on propanol or pentachlorophenoxyethanol. This carrier is preferably 0.1 per dye liquor.
~2g or 5-30 for the entire dyeing aid of the present invention
Use % by weight. Depending on the textile material to be dyed, the dyebath may contain, in addition to the dye and the dyeing auxiliary according to the invention, oligomerization inhibitors, foaming inhibitors, anti-wrinkle agents, retarders and, in particular, dispersants. Good too. The purpose of the dispersant is inter alia to obtain a good dispersion of the disperse dye. Suitable dispersants are those commonly used for dyeing with disperse dyes. Preferred dispersants contain from 15 to 100 moles of ethylene oxide or preferably propylene oxide and from 2 to 2 carbon atoms.
6 polyhydric aliphatic alcohols such as ethylene glycol, glycerin or pentaerythritol or having at least two amino groups or having one amino group and one hydroxyl group and having a carbon number of 2
Sulfation or phosphorylation with amines of ~9.
Alkyl sulfonates which are addition products or have alkyl moieties of 10 to 20 carbon atoms, alkylbenzene sulfonates with linear or branched alkyl moieties of 8 to 20 carbon atoms, such as nonylbenzene sulfonate, dodecylbenzene sulfonate. , 1,3,5,7-tetramethyloctylbenzenesulfonate or octadecylbenzenesulfonate or alkylnaphthalenesulfonates such as bisnaphthylmethanesulfonate or sulfosuccinates such as sodium dioctylsulfosuccinate. It is also possible to use mixtures of anionic dispersants. Anionic dispersants usually take the form of their alkali metal, ammonium or amine salts. Such dispersants are preferably used in an amount of 0.1 to 5 g per dye liquor. Customary additives for dye baths, preferably electrolytes, such as salts such as sodium sulfate, ammonium sulfate,
Sodium or ammonium salts of phosphoric or polyphosphoric acids, ammonium acetate or sodium acetate and/or acids such as mineral acids such as sulfuric acid or phosphoric acid or organic acids, preferably lower aliphatic carboxylic acids such as formic acid, acetic acid or oxalic acid. It's good that it is. These acids usually adjust the pH of the dye liquor used in the method of the present invention to 4 to 6.5, preferably
Used to adjust to 4.5-6. Dyeing is preferably carried out by the exhaust method using aqueous dye liquors. The dye solution can be applied in a wide range, for example 1:4 to 1:
100, preferably 1:10 to 1:50. The temperature at which dyeing is carried out should be at least 70°C and usually not higher than 140°C. Preferably 80-130
Keep within the range of ℃. The dyeing of linear polyester fibers and cellulose triacetate fibers is carried out according to the so-called high-temperature process, in which dyeing is carried out in a closed, preferably pressure-tight vessel at temperatures above 100 DEG C., preferably from 110 DEG to 130 DEG C., optionally under pressure. Suitable confinement dyeing machines are, for example, dye circulation machines such as cheese dyers and beam dyers, winchbeck machines, jet dyers or rotary dyers, muff dyers, paddle or dyers. Cellulose-21/2-acetate fibers are preferably dyed at 80 DEG to 85 DEG C., and polyamide fibers and polyacrylonitrile fibers are preferably dyed at the boiling point of the aqueous bath (98 DEG C.). Dyeing of aromatic polyamide fibers or acid-modified polyester fibers is preferably carried out at a temperature of 80 to 130°C. According to the method of the invention, the material to be dyed can first be briefly treated with the dyeing auxiliary and then dyed, or the material to be dyed can be treated simultaneously with the auxiliary and the dye. In both of these dyeing methods, at the end of the dyeing the dye liquor is cooled to approximately 60°C and the dyed product is then washed with water and in some cases, for example when dyeing polyester fibres, it is carried out in the usual manner. Perform the reducing post-creation treatment in an alkaline medium according to the following. This dyed material is further washed and dried. According to the method of the present invention, synthetic fiber materials, particularly linear polyester fibers, can be dyed uniformly and with high dye density, and the dyed products exhibit good abrasion fastness and good dyeing degree. The use of the auxiliary agents according to the invention does not affect the other fastness properties of the dyeings, such as the light fastness properties. Next, in the description of Examples, parts mean parts by weight, and % means weight %. The reaction products listed below are the components
Examples of (b) and (e). Component (b) B ₁ Ammonium salt of the acidic sulfuric ester of the addition product of 1 mol of ethylene oxide and 1 mol of Alfluor (1014) B ₂ Ammonium salt of the acidic sulfuric ester of the addition product of 1 mol of ethylene oxide and 1 mol of stearyl alcohol B ₃ Ammonium salt of the acidic sulfuric ester of the addition product of 1 mol of ethylene oxide and 1 mol of 2-ethyl-hexanol B ₄ Ammonium acid of the acidic sulfuric ester of the addition product of 35 mol of ethylene oxide and 1 mol of stearyl alcohol B ₅ Ethylene oxide Ammonium salt B of the acidic sulfuric ester of the addition product of 3 mol and 1 mol of tridecyl alcohol ₆ Ammonium salt of the acidic sulfuric ester of the addition product of 4 mol of ethylene oxide and 1 mol of hydroabiethyl alcohol B ₇ With 3 mol of ethylene oxide Ammonium salt of acidic sulfate ester of addition product with 1 mol of Alfor (2022) B ₈ Ammonium salt of acidic sulfuric ester of addition product of 3 mol of ethylene oxide and 1 mol of lauryl alcohol B ₉ 3 mol of ethylene oxide and 1 mol of butylphenol Ammonium salt of acidic sulfuric acid ester of addition product with B ₁₀ Ammonium salt of acidic sulfuric ester of addition product of 5 mol of ethylene oxide and 1 mol of tributylphenol B ₁₁ Addition product of 2 mol of ethylene oxide and 1 mol of nonylphenol Ammonium salt of acidic sulfuric ester B ₁₂ Ammonium salt of acidic sulfuric ester of addition product of 10 mol of propylene oxide and 10 mol of ethylene oxide with 1 mol of nonylphenol B ₁₃ Acidicity of addition product of 35 mol of ethylene oxide and 1 mol of nonylphenol Ammonium salt of sulfuric ester B ₁₄ Ammonium salt of acidic sulfuric ester of the addition product of 50 mol of ethylene oxide and 1 mol of nonylphenol B ₁₅ Ammonium salt of the acidic sulfuric ester of the addition product of 15 mol of propylene oxide and 1 mol of nonylphenol B ₁₆ Ammonium salt of acidic sulfuric acid ester of addition product of 6 moles of ethylene oxide and 1 mole of dodecylphenol B ₁₇ Ammonium salt of acidic sulfuric ester of addition product of 6 moles of ethylene oxide and 1 mole of pentadecylphenol B ₁₈ 8 moles of ethylene oxide Ammonium salt B of the acidic sulfuric ester of the addition product between and 1 mol of o-phenylphenol ₁₉ Ammonium salt of the acidic sulfuric ester of the addition product of 2 mol of ethylene oxide and 1 mol of coconut fatty acid B ₂₀ With 2 mol of propylene oxide Palm fatty acid 1
Ammonium salt of acidic sulfuric acid ester of addition product with mol B ₂₁ ethylene oxide 15 mol and stearic acid -
Ammonium salt B of the acidic sulfuric ester of the addition product with 1 mol of β-hydroxyethylamide ₂₂ Ammonium salt of the acidic sulfuric ester of the addition product of 2.5 mol of ethylene oxide and 1 mol of tallow amine ₂₃ Polybutylene glycol with an average molecular weight of 2000 Ammonium salt of acidic disulfate ester of _B24 Addition product of 2 moles of ethylene oxide and 1 mole of p-nonylphenol Sodium salt of acidic maleic acid ester _B25 Addition product of 2 moles of ethylene oxide and 1 mole of p-nonylphenol B ₂₆ Sodium salt of the acidic dimaleic ester of polypropylene glycol with an average molecular weight of 1000 B ₂₇ Ammonium salt of the acidic phosphoric ester of the addition product of 2 moles of ethylene oxide and 1 mole of nonylphenol B ₂₈ Acidic phosphoric acid ester B of the addition product of 10 moles of ethylene oxide and 1 mole of p-nonylphenol ₂₉ Sodium salt of carboxymethyl ether of the addition product of 4 moles of ethylene oxide and 1 mole of octylphenol B ₃₀ 3 moles of ethylene oxide and lauryl alcohol Di-(β-hydroxy-ethyl)-amine salt of the acidic sulfuric ester of the addition product with 1 mol B ₃₁ Sodium salt of the acidic sulfuric ester of the addition product of 2 mol of ethylene oxide and 1 mol of lauryl alcohol B ₃₂ Ethylene oxide 3 Sodium salt of the acidic sulfuric ester of the addition product between mol and 1 mol of lauryl alcohol B ₃₃ Ammonium salt of the acidic sulfuric ester of the addition product of 8 mol of ethylene oxide and 1 mol of tallow amine B ₃₄ 2.4 or 6 mol of ethylene oxide and tallow amine Ammonium salt of acidic sulfuric acid ester of addition product with 1 mol B ₃₅ Ammonium salt of acidic sulfuric ester of addition product of 3 mol of propylene oxide and 5 mol of ethylene oxide with 1 mol of tallow amine B ₃₆ 1 mol of styrene oxide and 8 ethylene oxide ammonium salt of the acidic sulfuric acid ester of the addition product between 8 moles of ethylene oxide and 1 mole of tallow amine B ₃₇ Sodium salt of the acidic sulfosuccinic acid half ester of the addition product of 8 moles of ethylene oxide and 1 mole of tallow amine B ₃₈ 8 moles of ethylene oxide and tallow amine Ammonium salt of acidic phosphoric acid ester of addition product with 1 mole B ₃₉ 5 moles of ethylene oxide and 2-ethyl-n
- Sodium salt component of acidic phosphoric acid ester of addition product with 1 mole of hexanol B ₄₀ Component of acidic sulfuric acid ester of addition product of 15 mole of ethylene oxide and 1 mole of dibenzylphenol (e) E ₁ 3 mole of ethylene oxide and 2-ethyl - reaction product with 1 mole of hexanol E ₂ reaction product between 5 moles of ethylene oxide and 1 mole of 2-ethyl-hexanol E ₃ reaction product between 3 moles of ethylene oxide and 1 mole of stearyl alcohol E ₄ 9 moles of ethylene oxide and alphaol (1014) Reaction product with 1 mole E ₅ Reaction product between 3 moles of ethylene oxide and 1 mole of hexadecyl alcohol E ₆ Reaction product between 6 moles of ethylene oxide and 1 mole of oleyl alcohol E ₇ 1 mole of ethylene oxide and 1 mole of phenol E ₈ Reaction product between 4 moles of ethylene oxide and 1 mole of p-cresol E ₉ Reaction product between 5 moles of ethylene oxide and 1 mole of tributylphenol E ₁₀ Reaction product between 8 moles of ethylene oxide and 1 mole of octylphenol Product E ₁₁ Reaction product of 9 moles of ethylene oxide and 1 mole of norphenol E ₁₂ Reaction product of 4 moles of ethylene oxide and 1 mole of nonylphenol E ₁₃ Reaction product of 6 moles of ethylene oxide and 1 mole of nonylphenol E ₁₄ Ethylene oxide 8 Reaction product of E ₁₅ with 1 mole of o-phenylphenol and 51 mole of propylene oxide and 5 moles of ethylene oxide with 1 mole of glycerin E ₁₆ Reaction of 51 mole of propylene oxide and 12 mole of ethylene oxide with 1 mole of glycerin Product E ₁₇ Reaction product of 3 moles of ethylene oxide and 1 mole of oleic acid E ₁₈ Polypropylene glycol (molecular weight 1000)
Reaction product of 2 moles of adipic acid with 1 mole of adipic acid E ₁₉ Reaction product of 12 moles of ethylene oxide and 12 moles of propylene oxide with 1 mole of C ₄ -C ₁₈ aliphatic alcohol E ₂₀ Reaction product of 80 moles of ethylene oxide and 1 mole of oleyl alcohol Reaction product E ₂₁ Reaction product of 12 moles of ethylene oxide and 12 moles of propylene oxide with 1 mole of C ₄ -C ₁₈ aliphatic alcohol and poly(oxyethylene) ₁₂ -poly(oxypropylene) ₁₂
-Mixture E with block polymer E ₂₂ 5 mol of ethylene oxide and 5 mol of propylene oxide with alphaol (12-14)
Example of reaction product with 1 mole 1 Polyester fibers are dyed using a dyeing aid (P ₁ ) obtained by mixing the following components. Component B ₂₈ 600 g n-amyl alcohol 300 g Diacetone alcohol 300 g Ethyl ethylbenzene and trimethylbenzene 1800 g 3000 g In a beam dyeing machine, 100 kg of polyethylene glycol terephthalate woven fabric is soaked in 1000 g of water. Raise the liquid temperature to 70℃ and add the following additives. Ammonium sulfate 2000g Dyeing aid P ₁ 3000g Formula Next, add 85% formic acid to adjust the pH of the dye liquor.
5.5, raise the liquid temperature to 120℃ in 30 minutes, and at this temperature
Perform staining for 30 minutes. Cool the dye solution, wash and dry the dyed item. In this way, an intensely dyed rubfast red dyeing is obtained. If the same dyeing process is carried out without using the above dyeing aid P ₁ , the dyeing result will be 40% lighter. If, in place of the dyeing auxiliary P ₁ , the same amounts of preparations P ₂ to P ₉ of the following composition are used in the process of Example 1, red dyeings which are likewise intensely dyed and exhibit rubfastness are obtained: get. Composition of P ₂ Methylethylbenzene and trimethylbenzene 2100g Paraffin oil 333g Component B ₁₁ 180g Water 180g Isopropanol 40g Component E ₁₉ or E ₂₁ 167g 3000g Composition of P ₃ Methylethylbenzene and trimethylbenzene 1800g Diphenyl 300g Paraffin oil 333g Component B ₁₁ 180g water 180g Isopropanol 40g Component E ₂₂ 167g 3000g Composition of P ₄ Component B ₂₈ 600g n-amyl alcohol 300g Diacetone alcohol 300g Methylethylbenzene and trimethylbenzene 1785g Magnesium stearate 15g 3000g Composition of _P5 Methylethylbenzene and trimethylbenzene 2100g Paraffin oil 333 g Component B ₁₁ 180g Water 180g Isopropanol 40g Component E ₁₁ 167g 3000g Composition of P ₆ Methylethylbenzene and trimethylbenzene 1050g Tetralin (tetrahydronaphthalene) 1050g Paraffin oil 333g Component B ₁₁ 180g Water 180g Isopropanol 40g Component E ₁₁ 167 g 3000g Composition of P ₇ Tetralin 2100g Paraffin oil 333g Component B ₁₁ 180g Water 180g Isopropanol 40g Component E ₁₁ 167g 3000g Composition of P ₈ Tetralin 1050g Xylene 1050g Paraffin oil 333g Component B ₁₁ 180g Water 180g Isopropanol 40g Component E ₁₁ 167g 3 000g Composition of P ₉ Methyl ethylbenzene and trimethylbenzene 900g Isobutanol 810g Component B ₂₈ 900g Component E ₁₀ 300g Monoethanolamine 90g 3000g When using auxiliary agent P ₄ , foaming is suppressed and quality can be maintained for a long period of time. Example 2 In a muff dyeing machine, 100 kg of spun polyethylene glycol terephthalate is soaked in 1200 kg of water and heated to 60°C. Add the following additives to the dye liquor. Ammonium sulfate 2400g Auxiliary agent P ₁ described in Example 1 2000g Formula (In this formula, p ₁ + p ₂ + p ₃ = 60) 2000 g of ammonium salt expressed by and the formula 200g of dye represented by 85% formic acid was added to adjust the pH of the dye bath to 5.
Increase the temperature to 115°C in 45 minutes and carry out staining at this temperature for 60 minutes. The bath is then cooled and the dyed material is washed and dried. In this way, a deep, uniformly dyed rubfast blue dyeing is obtained. When dyeing with a dye liquor that does not contain auxiliary agent P ₁ , the dyeing is
30% weaker. If the same process were carried out using customary carriers such as o-phenylphenol or trichlorobenzene instead of the auxiliary P ₁ , the uniformity of the dyeing would be clearly inferior. Example 3 formula 54g of dye, formula 27g of dye, formula 130g of dye, formula from 50% cotton and 50% polyethylene glycol terephthalate in an HT-Paddrol dyer containing 10 g of the dye, 3500 g of the dyeing aid P ₁ as described in Example 1 and 6000 g of ammonium sulphate. 100 kg of unwashed woven fabric containing 3.15 g of residual fat was soaked and treated at 40°C for 20 minutes. Next, add 10kg of (calcined) powdered salt to the dye solution and raise the temperature of the solution to 115℃ in 40 minutes. at this temperature
Stain for 30 minutes and then cool the bath. Wash and dry the dyed item. In this way, a deeply dyed, uniformly beige dyed fabric is obtained, the residual fat content of which is reduced to only 0.65%. Example 4 (a) 2.6% dye of formula (101), 0.8% dye of formula (102)
%,formula of dye 2.9% and ammonium sulfate 2g/
A dyeing machine (autoclave) containing an aqueous dye solution (3) adjusted to 5 with 85% formic acid.
Heat to 70°C and soak 50g of polyethylene glycol terephthalate fabric in it. The temperature of the dye solution
The temperature was raised to 130°C for 30 minutes, and staining was carried out at this temperature for 1 hour. After cooling, the dyed material is washed and processed together with the undyed fabric as described below. (b) A dye liquor containing 0.5 g of ammonium sulfate, 1 g of the dyeing aid P ₁ described in Example 1, 0.6 g of the ammonium salt of formula (7) described in Example 2 and 300 g of water is placed in an autoclave, and (a) Soak 5 g of dyed cloth and 5 g of undyed cloth. Close the autoclave and increase the temperature to 125 for 30 minutes
℃ and treat both fabrics at this temperature for 1 hour. Next, the autoclave is cooled and the cloth is washed and dried. A dyed product with a dye migration degree of 4 to 5 is thus obtained. If the same process is carried out without adding the dyeing aid P ₁ , the degree of dye transfer remains between 1 and 2. Migration level 1 means the worst result and 5 the best result. Example 5: Soak 100kg of acid-modified polyester fiber fabric in 1000ml of water at 60°C in a beam dyeing machine. Add the following additives to this dye solution. 80% acetic acid 2000g Anhydrous sodium sulfate 6000g Auxiliary agent P ₃ 2000g and formula 1100g of dye After these additives are mixed uniformly, the dye liquor is heated to 120°C for 40 minutes, and dyeing is carried out at this temperature for 60 minutes. The dye solution is then cooled and the cloth is washed and dried. In this way, a uniformly deep red dyed product is obtained. If the same process is carried out without the above auxiliary P ₃ , the dyeing result will be 20% lighter. Example 6: 100 kg of polyester yarn fabric is immersed in 1000 kg of water at 70°C in a jet dyeing machine. Add the following additives to this. Tetrasodium salt of ethylenediaminetetraacetic acid
750g 60% acetic acid 1000g Condensate of naphthalene-2-sulfonic acid and formaldehyde 1000g Auxiliary agent P ₅ 750g Formula 1113 g of dye of formula (103) and 1,8-diamino-4,5-dihydroxy-anthraquinone and 1,5-diamino-4,
Dye obtained by reacting a mixture of 8-dihydroxy-anthraquinones with formaldehyde
After uniformly mixing 180 g of these additives, the temperature of the dye liquor was raised to 125°C over 75 minutes, and dyeing was carried out at this temperature for 20 minutes. The bath is then cooled to 50°C and the dyed items are washed and dried. In this way, a red dyed cloth is obtained which is deeply dyed and exhibits friction fastness (fastness of 4 to 5). If the same process is carried out with a dye liquor without the auxiliary P ₅ , the dyeing result will be 25% lighter and the friction fastness will be poorer (fastness level 3). Example 7 100 kg of woven fabric made of 55% polyester fiber and 45% cotton was placed on a TH pad roll and heated to 60°C.
Soak in 4000. Add the following additives to this. Tetrasodium salt of ethylenediaminetetraacetic acid
800g Condensate of naphthalene-2-sulfonic acid and formaldehyde 2000g Sulfate of fatty amine polyglycol ether
2000g Auxiliary P ₅ 8000g and formula 43 parts of dye, formula 45 parts of dye and formula 4500 g of a dye mixture consisting of 12 parts of a 1:2-chromium complex of the dyestuff After these additives have been uniformly dispersed, acetic acid is added to bring the pH of the dye liquor to 5.5-6. Next, the temperature of the dyeing solution is increased to 120°C over 45 minutes, and dyeing is carried out at this temperature for 30 minutes. Lower the bath temperature to 45°C and wash and dry the dyed item. This gives a dense blue dyeing of a polyester-cotton fabric which is uniformly dyed and exhibits rubfastness. When dyed in the same way without adding auxiliary P ₅ , the dyeing of the polyester part is obviously lighter;
Friction fastness is also poor.

Claims (1)

[Scope of Claims] 1 At least (a) tetralin and/or alkylbenzene, (b) an anionic surfactant, (c) a water-immiscible non-aromatic solvent and optionally (d) a polar solvent and (or) (e) A dyeing aid characterized by containing a nonionic surfactant. 2. The dyeing aid as described in 1 above, which comprises at least components (a), (b), (c) and (d). 3. The dyeing aid as described in 1 above, which is characterized by containing at least components (a), (b), (c) and (e). 4. The dyeing aid as described in 1 above, which is characterized by containing at least components (a), (b), (c), (d) and (e). 5. The dyeing aid as described in items 1 to 4 above, which contains an alkylbenzene as component (a). 6. The dyeing aid according to item 5 above, wherein the alkylbenzene (a) is a benzene compound substituted with a methyl group, an ethyl group, or both. 7 Component (b) is the formula (In this formula, Q is R ₁ -O-, R ₂ -CO-O- or R ₃ -N〓, and R ₁ is an aliphatic hydrocarbon residue having 8 to 24 carbon atoms, and 10 to 24 carbon atoms. 22 is a cycloaliphatic hydrocarbon residue, an o-phenylphenyl group or an alkyl phenyl group having 4 to 16 carbon atoms in the alkyl part, and R ₂ is an aliphatic hydrocarbon residue having 7 to 21 carbon atoms. , R ₃ is an aliphatic hydrocarbon residue having 12 to 22 carbon atoms, especially 12 to 18 carbon atoms, and Y ₁ and
One of Y ₂ is a hydrogen atom, methyl group or phenyl group, the other is a hydrogen atom, X is an acid residue of an inorganic acid or dicarboxylic acid containing an oxygen atom, or -CH ₂ COOH, m is a number from 1 to 50, preferably from 1 to 30, and q is 1 or 2 when Q is R ₃ -N, in which case the two substituents bonded to the nitrogen atom are the same 7. The dyeing auxiliary agent according to items 1 to 6 above, which is an anionic surfactant represented by: 8 Component (b) is the formula or [In these formulas, R ₁ , R ₂ , R ₃ , Y ₁ , Y ₂ , X and m have the meanings given in the previous section 7, and r and s are integers whose total is 2 to 15. ] The dyeing aid according to item 7 above, which is an anionic surfactant represented by: 9 Component (b) has 4 carbon atoms in which R ₁ is an alkyl moiety
~12 alkylphenyl group, o-phenyl group, or alkyl group or alkenyl group having 12 to 18 carbon atoms, and m is 2 to 15, anionic surfactant of formula (2) The dyeing aid according to item 8, characterized in that: 10 Component (b) is the formula (In this formula, R ₄ is an octyl group or a nonyl group, m ₁ is a number from 2 to 10, and X ₁ is a group derived from sulfuric acid or orthophosphoric acid.) 9. The dyeing aid according to item 9, wherein the acid moiety is a free acid or a sodium salt or an ammonium salt. 11 Component (b) is R ₃ is an alkenyl group or alkyl group having 16 to 22 carbon atoms, and Y ₁ and Y ₂
is a hydrogen atom, the sum of r and s is 2 to 10, X is -SO ₃ M, and M is a sodium atom or an ammonium group. The dyeing aid according to item 8 above, characterized by: 12. The dyeing aid as described in items 1 to 11 above, wherein component (c) is a water-immiscible aliphatic solvent. 13. The dyeing aid as described in items 1 to 12 above, wherein component (c) is n-amyl alcohol or paraffin oil. 14. The dyeing aid as described in items 1, 2 and 4 to 13 above, wherein component (d) is water, isopropanol, β-ethoxyethanol or diacetone alcohol. 15 Component (e) contains 1 to 100 moles of alkylene oxide to an aliphatic monoalcohol having at least 8 carbon atoms, a tri- to hexahydric aliphatic alcohol having 2 to 9 carbon atoms, optionally an alkyl group, a benzyl group, or The dyeing aid according to items 3 to 14 above, which is a nonionic alkylene oxide addition product added to 1 mole of a phenol or a fatty acid having 8 to 22 carbon atoms, which may be substituted with a phenyl group. . 16 Component (e) is the formula (In this formula, R ₅ is an alkyl group or alkenyl group having 8 to 18 carbon atoms, an o-phenylphenyl group, or an alkylphenyl group having 4 to 12 carbon atoms in the alkyl part, and among Z ₁ and Z ₂ one is a hydrogen atom and the other is a methyl group, z is a number from 1 to 15, and the sum of n ₁ and n ₂ is 5 to 10). The dyeing aid according to item 15 above, characterized by: 17. The dyeing aid according to items 15 and 16 above, characterized in that component (e) is used together with component (b) of formula (2) or formula (5). 18. The dyeing aid as described in items 1 to 17 above, which also contains a fatty acid salt of a polyvalent metal as component (f). 19 The preceding paragraph 1 is characterized in that it also includes carriers.
19. The dyeing aid according to items 1 to 18. 20 Component (a) is 30-80% by weight, component (b) is 5-30% by weight, component (c) is 5-20% by weight, component (d) is 5-40% by weight, based on the entire auxiliary agent. 20. The dyeing aid as described in items 1 to 19 above, which contains component (e) in an amount of 0 to 10% by weight. 21. The dyeing auxiliary agent according to item 20 above, which contains component (e) in an amount of 3 to 10% by weight based on the total amount of the auxiliary agent. 22 Add 0.2% polyvalent metal fatty acid salt to the entire auxiliary agent.
22. The dyeing aid as described in items 1 to 21 above, characterized in that it contains ~5% by weight. 23. The dyeing aid as described in items 1 to 22 above, which contains carrier in an amount of 5 to 30% by weight based on the total weight of the aid. 24 At least (a) tetralin and/or
Alkylbenzene, (b) anionic surfactant, (c)
a water-immiscible non-aromatic solvent and optionally (d)
A method for dyeing synthetic fiber materials with cationic or disperse dyes, characterized in that the synthetic fiber materials are dyed in the presence of a polar solvent and/or (e) a dyeing aid comprising a nonionic surfactant. 25 The preceding item 24, characterized in that polyacrylonitrile fibers, acid-modified polyester fibers, or aromatic polyamide fibers are dyed with a cationic dye.
The method described in. 26. The method according to item 24 above, characterized in that polyester fibers are dyed with a disperse dye. 27. The method according to item 24, further comprising using a dye bath containing an anionic dispersant. 28 Dyeing aid 0.5-6% by weight based on fiber material
The preceding item 24~, characterized in that a dye bath containing
27. The method described in 27. 29. The method according to items 24 to 28 above, characterized in that dyeing is carried out at a temperature of 80 to 130°C. 30. The method according to item 29 above, characterized in that dyeing is carried out at a temperature of 80 to 98°C. 31. The method according to item 29 above, characterized in that the polyester fiber is dyed at a temperature of 110 to 130°C. 32 at least one cationic or disperse dye and at least (a) tetralin and/or alkylbenzene, (b) anionic surfactant, (c) a water-immiscible non-aromatic solvent and optionally ( Dye liquor for dyeing synthetic fiber materials, characterized in that it comprises a dyeing auxiliary comprising d) a polar solvent and/or (e) a nonionic surfactant.