EP0713940B1 - Process for dying fibrous materials containing wool - Google Patents
Process for dying fibrous materials containing wool Download PDFInfo
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- EP0713940B1 EP0713940B1 EP95810682A EP95810682A EP0713940B1 EP 0713940 B1 EP0713940 B1 EP 0713940B1 EP 95810682 A EP95810682 A EP 95810682A EP 95810682 A EP95810682 A EP 95810682A EP 0713940 B1 EP0713940 B1 EP 0713940B1
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- wool
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-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
- D06P1/6495—Compounds containing carbonamide -RCON= (R=H or hydrocarbons)
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
- D06P1/613—Polyethers without nitrogen
- D06P1/6136—Condensation products of esters, acids, oils, oxyacids with oxiranes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
- D06P1/6495—Compounds containing carbonamide -RCON= (R=H or hydrocarbons)
- D06P1/6497—Amides of di- or polyamines; Acylated polyamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65125—Compounds containing ester groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65131—Compounds containing ether or acetal groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/653—Nitrogen-free carboxylic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/16—Wool using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8209—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing amide groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/916—Natural fiber dyeing
- Y10S8/917—Wool or silk
Definitions
- the present invention relates to a new method for high temperature dyeing of Wool or wool-containing fiber materials.
- the present invention thus relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of a wool protection agent containing at least one compound of the formula colors, in which R and R 'independently of one another each represent hydrogen, C 1 -C 6 alkyl or a cation, R 1 , R 2 , R 1 'and R 2 ' are each independently hydrogen, C 1 -C 6 alkyl or halogen B is a radical of the formula - X - Z 1 - - X - Z 2 - X - or - NR 3 - (alk) 0-1 - Z 1 - (alk) - NR 3 '- means X is a functional group -O- or -NR 3 -, where in the rest of the formula (2b) both radicals X stand for a group -O- or both radicals X stand for a group -NR 3 -, R 3 and R 3 '
- C 1 -C 6 -alkyl generally means, for example, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl.
- the cation includes, for example, alkali metal or alkaline earth metal cations such as sodium, potassium, lithium. Understand calcium or magnesium cation, the ammonium cation or organic ammonium cations such as the mono-, di- or triethanolammonium cation.
- Halogen generally means, for example, fluorine, bromine or, in particular, chlorine.
- C 1 -C 4 alkylene generally means, for example, methylene, 1,1- or 1,2-ethylene, 1,2- or 1,3-propylene or 1,2-, 1,3-, 1,4- or 2 , 3-butylene.
- R or R 'in the meaning of an alkyl radical are preferably a C 1 -C 4 alkyl radical and particularly preferably methyl or ethyl.
- R or R ' is a cation, it is preferably a Alkali metal cation, e.g. around the sodium, potassium or lithium cation, Ammonium cation or around the cation of an organic amine, e.g. around the mono-, di- or triethanolammonium cation.
- R or R ' are particularly preferably each as a cation independently for the sodium, potassium or triethanolammonium cation.
- R and R 'independently of one another each preferably represent hydrogen or a cation and particularly preferred for hydrogen or the sodium or potassium cation.
- radicals R and R ' are preferably the same.
- the radicals R 1 , R 2 , R 1 'and R 2 ' independently of one another are preferably each hydrogen, C 1 -C 4 -alkyl or chlorine.
- the radicals R 1 , R 2 , R 1 'and R 2 ' are preferably the same. In a particularly preferred embodiment of the present invention, R 1 , R 2 , R 1 'and R 2 ' each represent hydrogen.
- R 3 and R 3 'independently of one another are preferably each hydrogen or C 1 -C 4 -alkyl and particularly preferably hydrogen, methyl or ethyl.
- the radicals R 3 and R 3 ' are preferably the same. In a particularly preferred embodiment of the present invention, R 3 and R 3 'each represent hydrogen.
- X preferably represents the functional group -O-.
- p, q and r independently of one another each preferably represent an integer from 0 to 8, where the sum of (p + q + r) is 2 to 8.
- Z 1 radicals correspond to the formula - (CH 2 -CH 2 -O) p - (CHY 1 -CHY 2 -O) q - wherein Y 1 and Y 2 have the meaning given above and p and q are each independently an integer from 0 to 8, the sum of (p + q) being 2 to 8.
- Z 1 particularly preferably represents a radical of the formula - (CH 2 -CH 2 -O) p - wherein p is an integer from 2 to 8 and especially 2 to 5.
- the preferences previously given for R apply independently for R "and the preferences given previously for R 1 " and R 2 "each independently apply for R 1 and R 2.
- the radical R" preferably has that the same meaning as R and R ', and the radicals R 1 "and R 2 " preferably have the same meaning as R 1 , R 1 ', R 2 and R 2 '.
- Z 2 stands for the remainder of a tri-, tetra- or polyamine or tri-, tetra- or polyol, then this in each case preferably has C 12 carbon atoms and particularly preferably 3 to 8 carbon atoms.
- Suitable tri, tetra or polyol residues Z 2 are the residue of glycerol, diglycerol, triglycerol, 1,1,1-tris (hydroxymethyl) propane, erythritol, pentaerythritol, arabitol, sorbitol or mannitol, in which free or partially hydroxyl groups in the form of an ester group of the formula (4b) given above.
- a group of particularly suitable radicals of the formula (2b) given above is characterized in that X denotes a group -O- and Z 2 for the rest of a tri, tetra, penta- or hexaol having 3 to 6 carbon atoms and stands in particular for the remainder of a tri- or tetraol having 3 or 4 carbon atoms, the free hydroxyl groups of which are partly or completely in the form of an ester group of the formula (4b) given above.
- Glycerol residues of the formula are particularly preferred as the residue of the formula (2b) wherein R "is hydrogen or a cation. If B in formula (1) represents a radical of the formula (2b ') given above, R, R' and R" preferably have the same meaning.
- alkylene radical (alk) carries substituents, this can be, for example, a hydroxy, C 1 -C 4 alkoxy or sulfate radical.
- the group (alk) preferably denotes an unsubstituted or substituted by hydroxy, C 1 -C 4 alkoxy or -OSO 3 H C 2 -C 4 alkylene radical and particularly preferably the 1,2-ethylene, 1,2- or 1 , 3-propylene or 2-hydroxy-1,3-propylene radical.
- B represents a radical of the formula (2c) given above, this preferably corresponds to the formula -NR 3 - (alk) 0-1 - (CH 2 -CH 2 -O) p - (CHY 1 -CHY 2 -O) q - (alk) - NR 3 ' in which R 3 and R 3 'are identical and each represent hydrogen, methyl or ethyl, (alk) represents an unsubstituted or substituted by hydroxy, C 1 -C 4 alkoxy or -OSO 3 H, C 2 -C 4 alkylene radical, Y 1 and Y 2 have the meaning given above and p and q are each independently an integer from 0 to 8, the sum of (p + q) being 2 to 8.
- B as the radical of the formula (2c) is particularly preferably a radical of the formula NH - (alk) 0-1 - (CH 2 -CH 2 -O) p - (alk) -NH - wherein (alk) is 1,2-ethylene, 1,2- or 1,3-propylene or 2-hydroxy-1,3-propylene and p is an integer from 2 to 8 and especially 2 to 5.
- a preferred embodiment of the present invention relates to the method using a compound of the above formula (1), wherein R and R 'are the same and each represent hydrogen or a cation, R 1 , R 2 , R 1 'and R 2 ' are the same and are each hydrogen, C 1 -C 4 alkyl or chlorine, B is a radical of the formula -O- (CH 2 -CH 2 -O) p - (CHY 1 -CHY 2 -O) q - (CHY 3 -CHY 4 -O) r or -OZ 2 -O- means of Y 1 and Y 2 one is methyl and the other is hydrogen, of Y 3 and Y 4 one is ethyl and the other is hydrogen, p, q and r are each independently an integer from 0 to 8, the sum of (p + q + r) being 2 to 8, Z 2 stands for the remainder of a tri, tetra or polyol having 3 to 12 carbon atoms, the free
- a particularly preferred embodiment of the present invention relates to the method using a compound of the formula wherein B represents a radical of the formula -O- (CH 2 -CH 2 -O) p - is R is hydrogen or the sodium or potassium cation and p is an integer 2 to 5.
- the compounds of the formula (1) used according to the invention can be prepared in a manner known per se, for example by using a compound of the formula H-B'-H wherein B 'is a radical of the formula - X - Z 1 - - X - Z 2 - X - or - NR 3 - (alk) 0-1 - Z 1 - (alk) - NR 3 '- means X, Z 1 , R 3 , R 3 'and (alk) each have the meaning given above and Z 2 , when X is -NR 3 -, represents the rest of a tri-, tetra- or polyamine, or if X -O- is the residue of a tri-, tetra- or polyol which has 12 12 C atoms, in any order with the acid hydrides or mono-acid chlorides of carboxylic acids of the formulas and wherein R, R ', R ", R 1 , R 1 ', R 1 ",
- the preferred compounds of formula (1) wherein R, R 'and R “, R 1 , R 1 ' and R 1 " and R 2 , R 2 'and R 2 "are each identical, can advantageously be prepared by using one Reacting compound of formula (5) with an acid anhydride or mono acid chloride from a carboxylic acid of formula (6a) given above in a molar excess.
- R, R ', R "are each hydrogen or a cation and R 1 , R 1 ', R 1 ", R 2 , R 2 'and R 2 "are each hydrogen can advantageously be prepared by reacting a compound of formula (5) with maleic anhydride in a molar excess.
- the reaction of the compound of formula (5) with the compounds of formula (6a) (6b) and (6c) advantageously take place at elevated temperature, e.g. at a temperature of 15 up to 150 ° C and preferably at 80 to 120 ° C instead.
- the response time can be within further limits fluctuate, with a reaction time of approx. 1 to 10 hours and has proven to be practical for 1 to 5 hours.
- the products of formula (1) obtained in the reaction can either be directly or but e.g. after previous dilution with one or more suitable solvents can be used as wool protection.
- Solvents suitable for dilution are e.g. Water or alkylene glycols liquid at room temperature or Alkylene glycol ethers such as Polyethylene glycol 200, propylene glycol, diethylene glycol, Dipropylene glycol, triethylene glycol, tripropylene glycol or their monomethyl, Monoethyl, monobutyl, dimethyl, diethyl or dibutyl ether, e.g.
- alkylene glycols is preferred as a diluent for the wool protection agents according to the invention.
- the compounds of the formula (5), (6a), (6b) and (6c) are known per se or can be obtained by methods known per se.
- the wool protection agents used according to the invention can contain one or more of the compounds of the formula (1).
- An embodiment of the present invention is characterized in that a wool protection agent containing at least one compound of the formulas (1) and wherein R and Z 1 have the meanings given above, used. It is also possible to use wool protection agents which contain a compound of the formula (1) and a further compound with a wool-protecting action, for example 3-chloro-1,2-propanediol.
- the compounds of the formula (1 ') can be prepared in an analogous manner, for example by adding the acid halide or acid anhydride of a compound of the formula (6a) given above, in which R 1 and R 2 are each hydrogen, with approximately equimolar amounts of a compound of the aforementioned formula (5), in which B 'is a radical of the formula (2a) in which X is -O-.
- the wool-containing fiber material is first treated with the wool preservative pretreated in an aqueous bath and then by adding the dye colors to this bath. You can also proceed in such a way that you can dye the material at the same time treated with the wool preservative and the dye in an aqueous bath.
- the wool protection agent in an amount of e.g. 0.1 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 1 to 10% by weight and particularly preferably 1 to 6% by weight, based in each case on the weight of the material to be dyed, use.
- the wool-containing fiber material can be wool alone or mixtures from e.g. Trade wool / polyamide or wool / polyester. Thereby mixtures are made Wool and synthetic polyamide preferably with anionic dyes and Mixtures of wool and polyester fibers preferably with dispersion and anionic Dyes colored. Suitable anionic dyes and disperse dyes are Known specialist.
- the fiber material can be in various stages of processing, e.g. in Form of yarn, flake, sliver, knitwear, such as knitwear or knitted fabric, as Nonwoven fabric or preferably as a fabric.
- the mixed fiber materials are preferably fiber mixtures Wool and polyester, which are usually in a proportion of 20 to 50 Parts by weight of wool are present to 80-50 parts by weight of polyester.
- the one for the procedure preferred fiber blends contain 45 parts of wool and 55 parts of polyester fibers.
- the liquor ratio can be within a wide range in the process according to the invention Range can be selected; it is e.g. 1: 1 to 1: 100 and preferably 1:10 to 1:50.
- the dyebath can also be customary Additives included.
- Additives included.
- Mineral acids, organic acids and / or their salts which serve to adjust the pH of the dyebath, continue Electrolytes, leveling, wetting and defoaming agents and, if it is dyeing deals with wool / polyester mixtures, carriers and / or dispersants.
- the dye bath has a pH of e.g. 4 to 6.5 and preferably 5.2 to 5.8 on.
- the process according to the invention is generally carried out at a temperature of e.g. 60 to 130 ° C carried out.
- the dyeing is expediently carried out the pull-out process, e.g. at a temperature in the range of 60 to 106 ° C, preferably 95 to 98 ° C.
- the dyeing time can vary depending on the requirements, however, it is preferably 60-120 minutes.
- the dyeing of the polyester / wool mixed fiber materials is advantageously carried out in a single bath from aqueous liquor after the exhaust process. It is preferably dyed according to the so-called high-temperature processes in closed, pressure-resistant equipment at temperatures above 100 ° C, expediently between 110 and 125 ° C and preferably at 118-120 ° C and optionally under pressure.
- the mixed fiber materials can also be added using the usual carrier dyeing process Temperatures below 106 ° C, e.g. in the temperature range from 75 to 98 ° C in the presence one or more carriers are colored.
- the dyeing of the polyester / wool mixed fiber materials can be carried out in such a way that the first thing to be dyed is the wool preservative and, if necessary, the carrier treated and then colored. You can also proceed in such a way that you dye the material at the same time with the wool protection agent, the dyes and, if necessary, auxiliaries treated.
- the textile mixed fiber material is preferably added to a fleet, which contains the wool protection agent and possibly other conventional auxiliaries and a Has temperature of 40-50 ° C, and treated the material for 5 to 15 minutes Temperature. Then you raise the temperature to about 60 to 70 ° C, give the dye , heats up slowly to the dyeing temperature and then dyes about 20 to 60, preferably 30 up to 45 minutes at this temperature. At the end the fleet is heated to around 60 ° C cooled and the colored material worked up as usual.
- a setting is an unwanted one during the dyeing process fixation of the wool fibers, which is caused by rearrangement of the wool contained disulfide bridges is caused.
- Such undesirable fixations can e.g. in a deformation (flattening) of the wool yarns on bobbins, one Compacting the wool fibers as well as expressing a loss in the volume of the wool.
- the antisetting effect of a wool protection agent can e.g. based on A.M. Wemys and M.A. White, Proc. Ind. Japan-Australia, Joint Symp. On objective measurement, Kyoto (1985), page 165, can be determined by making rondelles from wool test fabric punched out, folded in the middle and sewn together at the edge. The candidates are then in pressed state dyed in the presence of the wool protection agent, then the Fabric pattern opened and one thread pulled out. After a recovery period the angle of the threads is measured in warm water. The more that happened before compressed yarn has opened and the more the measured angle Approaching 180 °, the better the anti-setting effect of the wool protection agent. On measured angle of approx. 120 to 180 ° and in particular 140 to 180 ° shows a good one Anti-setting effect.
- Parts mean parts by weight, Percentages by weight.
- Example 2 18.4 parts of glycerol, 55.9 parts of maleic anhydride and 0.3 part of tributylamine are placed in a sulfonation flask. The mixture is carefully warmed to about 100 ° C. and then left to stir at this temperature for about 5 hours. The titration of the carboxyl groups indicates the end of the reaction. It is cooled to about 50 ° C., diluted with 40 parts of water and neutralized to pH 6 by adding about 303 parts of 2N sodium hydroxide solution. After filtering off undissolved particles, the compound of the formula is obtained as a 20% solution.
- Example 5 20.1 parts of 1,1,1-trihydroxymethylpropane, 41.9 parts of maleic anhydride and 0.3 part of tributylamine are placed in a sulfonation flask. The mixture is carefully warmed to about 100 ° C. and then left to stir at this temperature for about 5 hours. The titration of the carboxyl groups indicates the end of the reaction. 58 parts of the product of the formula are obtained as a viscous oil.
- Example 6a If the procedure is as described in Example 6 and, instead of the aqueous preparation according to Example 1, 1.7 parts of a mixture consisting of 93 parts of the product according to Example 1 and 7 parts of 3-chloro-1,2-propanediol are obtained, also a dye with good properties and without negatively influencing the wool quality.
- Example 6b If the procedure described in Example 6 is followed and 2 parts of a mixture consisting of 50 parts of the product according to Example 1 and 50 parts of the product according to Example 5a are used instead of the aqueous preparation according to Example 1, a coloration with good properties is also obtained and without affecting the wool quality.
- Example 7 100 parts of a wool fabric with a m2 weight of 180 g are in 1000 parts of an aqueous liquor containing 4 parts of ammonium sulfate, 2.0 parts of the product according to Example 1 and 0.5 parts of a naphthalenesulfonic acid condensate product for 10 minutes at 50 ° C treated; the pH of the liquor is previously adjusted to about 6 with acetic acid. Then 3 parts of the dye of the formula added and a further 5 min. treated. The dyeing liquor is then removed within approx. 45 min. heated to approx. 98 ° C and the tissue for 60 min. colored at this temperature. Then allow to cool to approx. 60 ° C, rinse as usual and dry the dyed fabric. You get a rub-fast, level blue color without negatively influencing the wool quality.
- Example 7a If the procedure is as described in Example 7 and, instead of the aqueous preparation according to Example 1, 1.7 parts of a mixture consisting of 93 parts of the product according to Example 1 and 7 parts of 3-chloro-1,2-propanediol are obtained, also a dye with good properties and without negatively influencing the wool quality.
- Example 7b If the procedure described in Example 7 is followed and 2 parts of a mixture consisting of 50 parts of the product according to Example 1 and 50 parts of the product according to Example 5a are used instead of the aqueous preparation according to Example 1, a coloration with good properties is also obtained and without affecting the wool quality.
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Description
Die vorliegende Erfindung betrifft ein neues Verfahren zum Hochtemperatur-Färben von Wolle oder wollhaltigen Fasermaterialien.The present invention relates to a new method for high temperature dyeing of Wool or wool-containing fiber materials.
Es ist bekannt, Wolle oder wollhaltige Fasermaterialien in Gegenwart von Hilfsmitteln zu färben, um so Faserschädigungen entgegenzuwirken, welche insbesondere beim Hochtemperatur-Färben auftreten. Viele der bekannten Hilfsmittel enthalten Formaldehyd oder setzen beim Erhitzen Formaldehyd frei, was toxikologisch nicht unbedenklich ist.It is known to add wool or wool-containing fiber materials in the presence of auxiliaries dyeing in order to counteract fiber damage, especially when high-temperature dyeing occur. Many of the known auxiliaries contain formaldehyde or release formaldehyde when heated, which is not toxicologically harmless.
Aus der EP-A-0 393 037 sind Wollschutzmittel bekannt, welche im Unterschied zu den Wollschutzmitteln der nachfolgenden Formel (1) als Rest Z1 einen Alkylenrest enthalten.From EP-A-0 393 037 wool protection agents are known which, in contrast to the wool protection agents of the following formula (1), contain an alkylene radical as the Z 1 radical.
Es wurde nun überraschend ein verbessertes Verfahren zum Hochtemperatur-Färben von wollhaltigen Fasermaterialien gefunden, welches auf der Verwendung einer neuen Klasse von Wollschutzmitteln basiert.It has now surprisingly become an improved process for high temperature dyeing wool-containing fiber materials found, which is based on the use of a new class based on wool preservatives.
Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum Färben von
wollhaltigen Fasermaterialien mit anionischen Farbstoffen, welches dadurch
gekennzeichnet ist, dass man diese Materialien in Gegenwart eines Wollschutzmittels
enthaltend mindestens eine Verbindung der Formel
R1, R2, R1' und R2' unabhängig voneinander je Wasserstoff, C1-C6-Alkyl oder Halogen
sind
B einen Rest der Formel
X eine funktionelle Gruppe -O- oder -NR3- ist, wobei im Rest der Formel (2b) beide
Reste X für eine Gruppe -O- oder beide Reste X für eine Gruppe -NR3- stehen,
R3 und R3' unabhängig voneinander je Wasserstoff oder C1-C6-Alkyl bedeuten,
Z1 für einen Rest der Formel
von Y3 und Y4 der eine Rest Ethyl und der andere Rest Wasserstoff ist,
p, q und r unabhängig voneinander je eine ganze Zahl von 0 bis 20 sind, wobei die Summe
von (p+q+r) 2 bis 20 beträgt,
Z2, wenn X -NR3- ist, für den Rest eines Tri-, Tetra- oder Polyamins steht, dessen freie
Aminogruppen teilweise oder vollständig in Form einer Acylaminogruppe der Formel
oder, wenn X -O- ist, für den Rest eines Tri-, Tetra- oder Polyols welcher ≤ 12 C-Atome
aufweist, steht, dessen freie Hydroxygruppen teilweise oder vollständig in Form einer
Estergruppe der Formel
R" unabhängig die Bedeutung von R und R1" und R2" je unabhängig die Bedeutung von
R1 und R2 haben, und
(alk) ein gegebenenfalls weitersubstituierter C1-C4-Alkylen-Rest ist.The present invention thus relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of a wool protection agent containing at least one compound of the formula
R 1 , R 2 , R 1 'and R 2 ' are each independently hydrogen, C 1 -C 6 alkyl or halogen
B is a radical of the formula
X is a functional group -O- or -NR 3 -, where in the rest of the formula (2b) both radicals X stand for a group -O- or both radicals X stand for a group -NR 3 -,
R 3 and R 3 'each independently represent hydrogen or C 1 -C 6 alkyl,
Z 1 for a radical of the formula
of Y 3 and Y 4 one is ethyl and the other is hydrogen,
p, q and r are each independently an integer from 0 to 20, the sum of (p + q + r) being 2 to 20,
Z 2 , when X is -NR 3 -, stands for the remainder of a tri-, tetra- or polyamine, the free amino groups of which are partially or completely in the form of an acylamino group of the formula
or, if X is -O-, stands for the remainder of a tri-, tetra- or polyol which has 12 12 C atoms, the free hydroxyl groups of which are partially or completely in the form of an ester group of the formula
R "independently have the meaning of R and R 1 " and R 2 "each independently have the meaning of R 1 and R 2 , and
(alk) is an optionally further substituted C 1 -C 4 alkylene radical.
Hierbei bedeutet C1-C6-Alkyl generell z.B. Methyl, Ethyl, n- oder iso-Propyl, n-, iso-, sec.- oder tert.-Butyl oder geradkettiges oder verzweigtes Pentyl oder Hexyl. Unter Kation sind z.B. Alkalimetall- oder Erdalkalimetallkationen wie das Natrium-, Kalium-, Lithium-. Calcium- oder Magnesium-Kation, das Ammonium-Kation oder organische Ammonium-Kationen wie z.B. das Mono-, Di- oder Triethanolammonium-Kation zu verstehen. Halogen bedeutet generell z.B. Fluor, Brom oder insbesondere Chlor. C1-C4-Alkylen bedeutet generell z.B. Methylen, 1,1- oder 1,2-Ethylen, 1,2- oder 1,3-Propylen oder 1,2-, 1,3-, 1,4- oder 2,3-Butylen.Here, C 1 -C 6 -alkyl generally means, for example, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl. The cation includes, for example, alkali metal or alkaline earth metal cations such as sodium, potassium, lithium. Understand calcium or magnesium cation, the ammonium cation or organic ammonium cations such as the mono-, di- or triethanolammonium cation. Halogen generally means, for example, fluorine, bromine or, in particular, chlorine. C 1 -C 4 alkylene generally means, for example, methylene, 1,1- or 1,2-ethylene, 1,2- or 1,3-propylene or 1,2-, 1,3-, 1,4- or 2 , 3-butylene.
R oder R' in der Bedeutung eines Alkylrests stehen bevorzugt für einen C1-C4-Alkylrest und besonders bevorzugt für Methyl oder Ethyl.R or R 'in the meaning of an alkyl radical are preferably a C 1 -C 4 alkyl radical and particularly preferably methyl or ethyl.
Bedeuten R oder R' für ein Kation, handelt es sich vorzugsweise um ein Alkalimetall-Kation, z.B. um das Natrium-, Kalium- oder Lithium-Kation, Ammonium-Kation oder um das Kation eines organischen Amins, z.B. um das Mono-, Di- oder Triethanolammonium-Kation. Besonders bevorzugt stehen R oder R' als Kation je unabhängig voneinander für das Natrium-, Kalium- oder Triethanolammonium-Kation.If R or R 'is a cation, it is preferably a Alkali metal cation, e.g. around the sodium, potassium or lithium cation, Ammonium cation or around the cation of an organic amine, e.g. around the mono-, di- or triethanolammonium cation. R or R 'are particularly preferably each as a cation independently for the sodium, potassium or triethanolammonium cation.
R und R' stehen unabhängig voneinander je bevorzugt für Wasserstoff oder ein Kation und besonders bevorzugt für Wasserstoff oder das Natrium- oder Kalium-Kation.R and R 'independently of one another each preferably represent hydrogen or a cation and particularly preferred for hydrogen or the sodium or potassium cation.
Die Reste R und R' sind vorzugsweise gleich.The radicals R and R 'are preferably the same.
Die Reste R1, R2, R1' und R2' bedeuten unabhängig voneinander bevorzugt je Wasserstoff, C1-C4-Alkyl oder Chlor. Die Reste R1, R2, R1' und R2' sind vorzugsweise gleich. In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung bedeuten R1, R2, R1' und R2' je Wasserstoff.The radicals R 1 , R 2 , R 1 'and R 2 ' independently of one another are preferably each hydrogen, C 1 -C 4 -alkyl or chlorine. The radicals R 1 , R 2 , R 1 'and R 2 ' are preferably the same. In a particularly preferred embodiment of the present invention, R 1 , R 2 , R 1 'and R 2 ' each represent hydrogen.
R3 und R3' bedeuten unabhängig voneinander bevorzugt je Wasserstoff oder C1-C4-Alkyl und besonders bevorzugt Wasserstoff, Methyl oder Ethyl. Die Reste R3 und R3' sind vorzugsweise gleich. In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung bedeuten R3 und R3' je Wasserstoff.R 3 and R 3 'independently of one another are preferably each hydrogen or C 1 -C 4 -alkyl and particularly preferably hydrogen, methyl or ethyl. The radicals R 3 and R 3 'are preferably the same. In a particularly preferred embodiment of the present invention, R 3 and R 3 'each represent hydrogen.
X steht bevorzugt für die funktionelle Gruppe -O-.X preferably represents the functional group -O-.
p, q und r stehen unabhängig voneinander je bevorzugt für eine ganze Zahl von 0 bis 8, wobei die Summe von (p+q+r) 2 bis 8 beträgt.p, q and r independently of one another each preferably represent an integer from 0 to 8, where the sum of (p + q + r) is 2 to 8.
Besonders bevorzugte Reste Z1 entsprechen der Formel
Z1 steht insbesondere bevorzugt für einen Rest der Formel
Z 1 particularly preferably represents a radical of the formula
In den Formeln (4a) und (4b) gelten für R" unabhängig die zuvor für R angegebenen Bevorzugungen und für R1" und R2" je unabhängig die zuvor für R1 und R2 angegebenen Bevorzugungen. Der Rest R" hat bevorzugt die gleiche Bedeutung wie R und R', und die Reste R1" und R2" haben vorzugsweise die gleiche Bedeutung wie R1, R1', R2 und R2'.In formulas (4a) and (4b), the preferences previously given for R apply independently for R "and the preferences given previously for R 1 " and R 2 "each independently apply for R 1 and R 2. The radical R" preferably has that the same meaning as R and R ', and the radicals R 1 "and R 2 " preferably have the same meaning as R 1 , R 1 ', R 2 and R 2 '.
Steht Z2 für den Rest eines Tri-, Tetra- oder Polyamins oder Tri-, Tetra- oder Polyols, so weist dieses jeweils bevorzugt ≤ 12 C-Atome und besonders bevorzugt 3 bis 8 C-Atome auf.If Z 2 stands for the remainder of a tri-, tetra- or polyamine or tri-, tetra- or polyol, then this in each case preferably has C 12 carbon atoms and particularly preferably 3 to 8 carbon atoms.
Beispiele für geeignete Tri-, Tetra- oder Polyolreste Z2 sind der Rest von Glycerin, Diglycerin, Triglycerin, 1,1,1-Tris(hydroxymethyl)propan, Erythrit, Pentaerythrit, Arabit, Sorbit oder Mannit, worin freie Hydroxygruppen teilweise oder vollständig in Form einer Estergruppe der zuvor angegebenen Formel (4b) vorliegen.Examples of suitable tri, tetra or polyol residues Z 2 are the residue of glycerol, diglycerol, triglycerol, 1,1,1-tris (hydroxymethyl) propane, erythritol, pentaerythritol, arabitol, sorbitol or mannitol, in which free or partially hydroxyl groups in the form of an ester group of the formula (4b) given above.
Eine Gruppe von besonders geeigneten Resten der zuvor angegebenen Formel (2b) ist dadurch gekennzeichnet, dass X eine Gruppe -O- bedeutet und Z2 für den Rest eines Tri-, Tetra-, Penta- oder Hexaols mit 3 bis 6 C-Atomen und insbesondere für den Rest eines Tri- oder Tetraols mit 3 oder 4 C-Atomen steht, dessen freie Hydroxygruppen jeweils teilweise oder vollständig in Form einer Estergruppe der zuvor angegebenen Formel (4b) vorliegen.A group of particularly suitable radicals of the formula (2b) given above is characterized in that X denotes a group -O- and Z 2 for the rest of a tri, tetra, penta- or hexaol having 3 to 6 carbon atoms and stands in particular for the remainder of a tri- or tetraol having 3 or 4 carbon atoms, the free hydroxyl groups of which are partly or completely in the form of an ester group of the formula (4b) given above.
Insbesondere bevorzugt als Rest der Formel (2b) sind Glycerinreste der Formel
In Formel (2c) gelten für Z1 die unter der Formel (2a) angegebenen Bedeutungen und Bevorzugungen und für R3' unabhängig die zuvor für R3 genannten Bedeutungen und Bevorzugungen. Trägt der Alkylenrest (alk) Substituenten, so kann dies z.B. ein Hydroxy-, C1-C4-Alkoxy- oder Sulfatorest sein. Die Gruppe (alk) bedeutet vorzugsweise einen unsubstituierten oder durch Hydroxy, C1-C4-Alkoxy oder -OSO3H substituierten C2-C4-Alkylenrest und besonders bevorzugt den 1,2-Ethylen-, 1,2- oder 1,3-Propylenoder 2-Hydroxy-1,3-propylenrest.In the formula (2c) is defined and preferred under the formula (2a) are for Z 1 and R 3 'independently the meanings and preferred meanings mentioned above for R. 3 If the alkylene radical (alk) carries substituents, this can be, for example, a hydroxy, C 1 -C 4 alkoxy or sulfate radical. The group (alk) preferably denotes an unsubstituted or substituted by hydroxy, C 1 -C 4 alkoxy or -OSO 3 H C 2 -C 4 alkylene radical and particularly preferably the 1,2-ethylene, 1,2- or 1 , 3-propylene or 2-hydroxy-1,3-propylene radical.
Steht B für einen Rest der zuvor angegebenen Formel (2c), so entspricht dieser bevorzugt
der Formel
B steht als Rest der Formel (2c) insbesondere bevorzugt für einen Rest der Formel
Von besonderem Interesse für das erfindungsgemässe Verfahren sind Verbindungen der zuvor angegebenen Formel (1), worin B einen Rest der zuvor angegebenen Formel (2a) oder (2b) bedeutet und X für eine funktionelle Gruppe -O- steht. Compounds of are of particular interest for the process according to the invention Formula (1) above, wherein B is a radical of the formula (2a) above or (2b) means and X represents a functional group -O-.
Eine bevorzugte Ausführungsform der vorliegenden Erfindung betrifft das Verfahren unter
Verwendung einer Verbindung der zuvor angegebenen Formel (1), worin
R und R' gleich sind und je Wasserstoff oder ein Kation bedeuten,
R1, R2, R1' und R2' gleich sind und je Wasserstoff, C1-C4-Alkyl oder Chlor sind,
B einen Rest der Formel
von Y1 und Y2 der eine Rest Methyl und der andere Rest Wasserstoff bedeutet,
von Y3 und Y4 der eine Rest Ethyl und der andere Rest Wasserstoff ist,
p, q und r unabhängig voneinander je eine ganze Zahl von 0 bis 8 sind, wobei die Summe
von (p+q+r) 2 bis 8 beträgt,
Z2 für den Rest eines Tri-, Tetra- oder Polyols mit 3 bis 12 C-Atomen steht, dessen freie
Hydroxygruppen teilweise oder vollständig in Form einer Estergruppe der Formel
R" die Bedeutung von R und R1" und R2" je die Bedeutung von R1 und R2 haben.A preferred embodiment of the present invention relates to the method using a compound of the above formula (1), wherein
R and R 'are the same and each represent hydrogen or a cation,
R 1 , R 2 , R 1 'and R 2 ' are the same and are each hydrogen, C 1 -C 4 alkyl or chlorine,
B is a radical of the formula
of Y 1 and Y 2 one is methyl and the other is hydrogen,
of Y 3 and Y 4 one is ethyl and the other is hydrogen,
p, q and r are each independently an integer from 0 to 8, the sum of (p + q + r) being 2 to 8,
Z 2 stands for the remainder of a tri, tetra or polyol having 3 to 12 carbon atoms, the free hydroxyl groups of which are partially or completely in the form of an ester group of the formula
R "have the meaning of R and R 1 " and R 2 "each have the meaning of R 1 and R 2 .
Eine besonders bevorzugte Ausführungsform der vorliegenden Erfindung betrifft das
Verfahren unter Verwendung einer Verbindung der Formel
Eine insbesondere bevorzugte Ausführungsform der vorliegenden Erfindung betrifft das
Verfahren unter Verwendung einer Verbindung der Formel
Die erfindungsgemäss verwendeten Verbindungen der Formel (1) können in an sich
bekannter Weise hergestellt werden, z.B. indem man eine Verbindung der Formel
X, Z1, R3, R3' und (alk) je die zuvor angegebene Bedeutung haben und Z2, wenn X -NR3-
ist, für den Rest eines Tri-, Tetra- oder Polyamins steht, oder, wenn X -O- ist, für den Rest
eines Tri-, Tetra- oder Polyols welcher ≤ 12 C-Atome aufweist, steht, in beliebiger
Reihenfolge mit den Säurenhydriden oder Monosäurechloriden von Carbonsäuren der
Formeln
X, Z 1 , R 3 , R 3 'and (alk) each have the meaning given above and Z 2 , when X is -NR 3 -, represents the rest of a tri-, tetra- or polyamine, or if X -O- is the residue of a tri-, tetra- or polyol which has 12 12 C atoms, in any order with the acid hydrides or mono-acid chlorides of carboxylic acids of the formulas
Die bevorzugten Verbindungen der Formel (1), worin R, R' und R", R1, R1' und R1" und R2, R2' und R2" jeweils identisch sind, können vorteilhaft hergestellt, indem man eine Verbindung der Formel (5) mit einem Säureanhydrid oder Monosäurechlorid von einer Carbonsäure der oben angegebenen Formel (6a) im molaren Überschuss umsetzt.The preferred compounds of formula (1), wherein R, R 'and R ", R 1 , R 1 ' and R 1 " and R 2 , R 2 'and R 2 "are each identical, can advantageously be prepared by using one Reacting compound of formula (5) with an acid anhydride or mono acid chloride from a carboxylic acid of formula (6a) given above in a molar excess.
Die insbesondere bevorzugten Verbindungen der Formel (1), worin R, R', R" je Wasserstoff oder ein Kation bedeuten und R1, R1', R1", R2, R2' und R2" jeweils Wasserstoff sind, können vorteilhaft hergestellt, indem man eine Verbindung der Formel (5) mit Maleinsäureanhydrid im molaren Überschuss umsetzt.The particularly preferred compounds of the formula (1) in which R, R ', R "are each hydrogen or a cation and R 1 , R 1 ', R 1 ", R 2 , R 2 'and R 2 "are each hydrogen, can advantageously be prepared by reacting a compound of formula (5) with maleic anhydride in a molar excess.
Die Umsetzung der Verbindung der Formel (5) mit den Verbindungen der Formel (6a), (6b) und (6c) findet vorteilhaft bei erhöhter Temperatur, z.B. bei einer Temperatur von 15 bis 150°C und vorzugsweise bei 80 bis 120°C statt. Die Reaktionszeit kann innerhalb weiter Grenzen schwanken, wobei sich eine Reaktionszeit von ca. 1 bis 10 Stunden und bevorzugt 1 bis 5 Stunden als praktikabel erwiesen hat.The reaction of the compound of formula (5) with the compounds of formula (6a) (6b) and (6c) advantageously take place at elevated temperature, e.g. at a temperature of 15 up to 150 ° C and preferably at 80 to 120 ° C instead. The response time can be within further limits fluctuate, with a reaction time of approx. 1 to 10 hours and has proven to be practical for 1 to 5 hours.
Die bei der Umsetzung erhaltenen Produkte der Formel (1) können entweder direkt oder aber z.B. nach vorheriger Verdünnung mit einem oder mehreren geeigneten Lösungsmitteln als Wollschutzmittel eingesetzt werden. Zur Verdünnung geeignete Lösungsmittel sind z.B. Wasser oder bei Raumtemperatur flüssige Alkylenglykole oder Alkylenglykolether wie z.B. Polyethylenglykol 200, Propylenglykol, Diethylenglykol, Dipropylenglykol, Triethylenglykol, Tripropylenglykol oder deren Monomethyl-, Monoethyl-, Monobutyl-, Dimethyl-, Diethyl- oder Dibutylether, z.B. Diethylenglykolmonomethylether oder - monoethylether, Diethylenglykoldimethylether oder -diethylether, Ethylenglykolmonobutylether oder -dibutylether oder Diethylenglykolmonobutylether oder -dibutylether. Bevorzugt ist die Verwendung von Alkylenglykolen als Verdünnungsmittel für die erfindungsgemässen Wollschutzmitteln.The products of formula (1) obtained in the reaction can either be directly or but e.g. after previous dilution with one or more suitable solvents can be used as wool protection. Solvents suitable for dilution are e.g. Water or alkylene glycols liquid at room temperature or Alkylene glycol ethers such as Polyethylene glycol 200, propylene glycol, diethylene glycol, Dipropylene glycol, triethylene glycol, tripropylene glycol or their monomethyl, Monoethyl, monobutyl, dimethyl, diethyl or dibutyl ether, e.g. diethylene glycol monomethyl ether or - monoethyl ether, diethylene glycol dimethyl ether or -diethyl ether, ethylene glycol monobutyl ether or -dibutyl ether or diethylene glycol monobutyl ether or dibutyl ether. The use of alkylene glycols is preferred as a diluent for the wool protection agents according to the invention.
Die Verbindungen der Formel (5), (6a), (6b) und (6c) sind an sich bekannt oder können nach an sich bekannten Methoden erhalten werden.The compounds of the formula (5), (6a), (6b) and (6c) are known per se or can can be obtained by methods known per se.
Die erfindungsgemäss eingesetzten Wollschutzmittel können eine oder mehrere der
Verbindungen der Formel (1) enthalten. Eine Ausführungsform der vorliegenden
Erfindung ist dadurch gekennzeichnet, dass man ein Wollschutzmittel enthaltend je
mindestens eine Verbindung der Formeln (1) und
Die Herstellung der Verbindungen der Formel (1') kann in analoger Weise erfolgen, z.B. indem man das Säurehalogenid oder Säureanhydrid einer Verbindung der zuvor angegebenen Formel (6a), worin R1 und R2 je Wasserstoff bedeuten, mit in etwa äquimolaren Mengen einer Verbindung der zuvor angegebenen Formel (5), worin B' einen Rest der Formel (2a), worin X -O- ist, bedeutet, umsetzt.The compounds of the formula (1 ') can be prepared in an analogous manner, for example by adding the acid halide or acid anhydride of a compound of the formula (6a) given above, in which R 1 and R 2 are each hydrogen, with approximately equimolar amounts of a compound of the aforementioned formula (5), in which B 'is a radical of the formula (2a) in which X is -O-.
Man geht z.B. so vor, dass man das wollhaltige Fasermaterial zuerst mit dem Wollschutzmittel in einem wässrigen Bad vorbehandelt und anschliessend durch Zugabe des Farbstoffs zu diesem Bad färbt. Man kann auch so vorgehen, dass man das Färbegut gleichzeitig mit dem Wollschutzmittel und dem Farbstoff in einem wässrigen Bad behandelt.One goes e.g. so that the wool-containing fiber material is first treated with the wool preservative pretreated in an aqueous bath and then by adding the dye colors to this bath. You can also proceed in such a way that you can dye the material at the same time treated with the wool preservative and the dye in an aqueous bath.
Es hat sich als praktikabel erwiesen, das Wollschutzmittel in einer Menge von z.B. 0,1 bis 20 Gew.-%, bevorzugt 0,1 bis 10 Gew.-%, besonders bevorzugt 1 bis 10 Gew.-% und insbesondere bevorzugt 1 bis 6 Gew.-%, jeweils bezogen auf das Gewicht des Färbeguts, einzusetzen.It has proven to be practical to use the wool protection agent in an amount of e.g. 0.1 to 20% by weight, preferably 0.1 to 10% by weight, particularly preferably 1 to 10% by weight and particularly preferably 1 to 6% by weight, based in each case on the weight of the material to be dyed, use.
Bei dem wollhaltigen Fasermaterial kann es sich um Wolle allein oder um Mischungen aus z.B. Wolle/Polyamid oder Wolle/Polyester handeln. Dabei werden Gemische aus Wolle und synthetischem Polyamid vorzugsweise mit anionischen Farbstoffen und Gemische aus Wolle und Polyesterfasern vorzugsweise mit Dispersions- und anionischen Farbstoffen gefärbt. Geeignete anionische Farbstoffe und Dispersionsfarbstoffe sind dem Fachmann bekannt.The wool-containing fiber material can be wool alone or mixtures from e.g. Trade wool / polyamide or wool / polyester. Thereby mixtures are made Wool and synthetic polyamide preferably with anionic dyes and Mixtures of wool and polyester fibers preferably with dispersion and anionic Dyes colored. Suitable anionic dyes and disperse dyes are Known specialist.
Das Fasermaterial kann in den verschiedensten Verarbeitungsstadien vorliegen, z.B. in Form von Garnen, Flocken, Kammzug, Maschenware, wie Strickware oder Gewirke, als Faservliesstoff oder vorzugsweise als Gewebe.The fiber material can be in various stages of processing, e.g. in Form of yarn, flake, sliver, knitwear, such as knitwear or knitted fabric, as Nonwoven fabric or preferably as a fabric.
Bei den Mischfasermaterialien handelt es sich vorzugsweise um Fasermischungen aus Wolle und Polyester, die in der Regel in einem Teilverhältnis von 20 bis 50 Gewichtsteilen Wolle zu 80-50 Gewichtsteilen Polyester vorliegen. Die für das Verfahren bevorzugten Fasermischungen enthalten 45 Teile Wolle und 55 Teile Polyesterfasern.The mixed fiber materials are preferably fiber mixtures Wool and polyester, which are usually in a proportion of 20 to 50 Parts by weight of wool are present to 80-50 parts by weight of polyester. The one for the procedure preferred fiber blends contain 45 parts of wool and 55 parts of polyester fibers.
Das Flottenverhältnis kann beim erfindungsgemässen Verfahren innerhalb eines weiten Bereiches gewählt werden; es beträgt z.B. 1:1 bis 1:100 und vorzugsweise 1:10 bis 1:50.The liquor ratio can be within a wide range in the process according to the invention Range can be selected; it is e.g. 1: 1 to 1: 100 and preferably 1:10 to 1:50.
Das Färbebad kann neben dem Farbstoff, Wasser und dem Wollhilfsmittel weitere übliche Zusätze enthalten. Zu erwähnen sind z.B. Mineralsäuren, organische Säuren und/oder deren Salze, die der Einstellung des pH-Werts des Färbebads dienen, weiterhin Elektrolyte, Egalisier-, Netz- und Entschäumungsmittel sowie, falls es sich um das Färben von Wolle/Polyester-Gemischen handelt, Carrier und/oder Dispergiermittel.In addition to the dye, water and the wool auxiliary, the dyebath can also be customary Additives included. Worth mentioning are e.g. Mineral acids, organic acids and / or their salts, which serve to adjust the pH of the dyebath, continue Electrolytes, leveling, wetting and defoaming agents and, if it is dyeing deals with wool / polyester mixtures, carriers and / or dispersants.
Das Färbebad weist einen pH-Wert von z.B. 4 bis 6,5 und vorzugsweise von 5,2 bis 5,8 auf. Das erfindungsgemässe Verfahren wird im allgemeinen bei einer Temperatur von z.B. 60 bis 130°C durchgeführt.The dye bath has a pH of e.g. 4 to 6.5 and preferably 5.2 to 5.8 on. The process according to the invention is generally carried out at a temperature of e.g. 60 to 130 ° C carried out.
Wenn das zu färbende Material Wolle allein ist, erfolgt die Färbung zweckmässig nach dem Ausziehverfahren, z.B. bei einer Temperatur im Bereich 60 bis 106°C, vorzugsweise 95 bis 98°C. Die Färbedauer kann in Abhängigkeit von den Erfordernissen variieren, beträgt jedoch vorzugsweise 60-120 Minuten.If the material to be dyed is wool alone, the dyeing is expediently carried out the pull-out process, e.g. at a temperature in the range of 60 to 106 ° C, preferably 95 to 98 ° C. The dyeing time can vary depending on the requirements, however, it is preferably 60-120 minutes.
Die Färbungen der Polyester/Wolle-Mischfasermaterialien erfolgen mit Vorteil einbadig aus wässriger Flotte nach dem Ausziehverfahren. Man färbt vorzugsweise nach dem sogenannten Hochtemperaturverfahren in geschlossenen, druckbeständigen Apparaturen bei Temperaturen von über 100°C, zweckmässig zwischen 110 und 125°C und vorzugsweise bei 118-120°C und gegebenenfalls unter Druck.The dyeing of the polyester / wool mixed fiber materials is advantageously carried out in a single bath from aqueous liquor after the exhaust process. It is preferably dyed according to the so-called high-temperature processes in closed, pressure-resistant equipment at temperatures above 100 ° C, expediently between 110 and 125 ° C and preferably at 118-120 ° C and optionally under pressure.
Die Mischfasermaterialien können auch nach dem üblichen Carrier-Färbeverfahren bei Temperaturen unter 106°C, z.B. im Temperaturbereich von 75 bis 98°C in Gegenwart eines oder mehrerer Carrier gefärbt werden.The mixed fiber materials can also be added using the usual carrier dyeing process Temperatures below 106 ° C, e.g. in the temperature range from 75 to 98 ° C in the presence one or more carriers are colored.
Das Färben der Polyester/Wolle-Mischfasermaterialien kann so durchgeführt werden, dass man das Färbegut zuerst mit dem Wollschutzmittel und gegebenenfalls dem Carrier behandelt und anschliessend färbt. Man kann auch so vorgehen, dass man das Färbegut gleichzeitig mit dem Wollschutzmittel, den Farbstoffen und gegebenenfalls Hilfsmitteln behandelt. Vorzugsweise geht man mit dem Textilmischfasermaterial in eine Flotte ein, die das Wollschutzmittel und gegebenenfalls weitere übliche Hilfsmittel enthält und eine Temperatur von 40-50°C aufweist, und behandelt das Material 5 bis 15 Minuten bei dieser Temperatur. Danach erhöht man die Temperatur auf ca. 60 bis 70°C, gibt den Farbstoff zu, erhitzt langsam auf die Färbetemperatur und färbt dann ca. 20 bis 60, vorzugsweise 30 bis 45 Minuten, bei dieser Temperatur. Am Schluss wird die Flotte auf etwa 60°C abgekühlt und das gefärbte Material wie üblich aufgearbeitet.The dyeing of the polyester / wool mixed fiber materials can be carried out in such a way that the first thing to be dyed is the wool preservative and, if necessary, the carrier treated and then colored. You can also proceed in such a way that you dye the material at the same time with the wool protection agent, the dyes and, if necessary, auxiliaries treated. The textile mixed fiber material is preferably added to a fleet, which contains the wool protection agent and possibly other conventional auxiliaries and a Has temperature of 40-50 ° C, and treated the material for 5 to 15 minutes Temperature. Then you raise the temperature to about 60 to 70 ° C, give the dye , heats up slowly to the dyeing temperature and then dyes about 20 to 60, preferably 30 up to 45 minutes at this temperature. At the end the fleet is heated to around 60 ° C cooled and the colored material worked up as usual.
Mittels des erfindungsgemässen Verfahrens ist es möglich, Wolle oder insbesondere Wolle/Polyester-Fasergemische bei hoher Temperatur unter einwandfreiem Schutz des Wollanteils, d.h. unter Erhaltung der wichtigen, fasertechnologischen Eigenschaften der Wolle, wie Reissfestigkeit, Berstbeständigkeit und Dehnung, zu färben. Hervorzuheben ist weiterhin, dass der Polyesteranteil bei Mischgeweben keine Angilbung zeigt.By means of the method according to the invention it is possible to use wool or in particular Wool / polyester fiber mixtures at high temperature with perfect protection of the Wool share, i.e. while maintaining the important fiber-technological properties of the Color wool, such as tear resistance, burst resistance and stretch. It should be emphasized furthermore that the proportion of polyester in mixed fabrics shows no yellowing.
Ein weiterer Vorteil des erfindungsgemässen Verfahrens betrifft die Verringerung des Settings, die durch die Anwesenheit einer Verbindung der Formel (1) im Färbebad erreicht wird. Als Setting bezeichnet man eine unerwünschte während des Färbeprozesses auftretende Fixierung der Wollfasern, welche durch Umordnung der in der Wolle enthaltenen Disulfid-Brücken verursacht wird. Solche unerwünschten Fixierungen können sich z.B. in einer Deformation (Verflachung) der Wollgarne auf Spulen, einer Kompaktierung der Wollfasern sowie in einem Verlust des Volumens der Wolle äussern.Another advantage of the method according to the invention relates to the reduction of the Settings achieved by the presence of a compound of formula (1) in the dye bath becomes. A setting is an unwanted one during the dyeing process fixation of the wool fibers, which is caused by rearrangement of the wool contained disulfide bridges is caused. Such undesirable fixations can e.g. in a deformation (flattening) of the wool yarns on bobbins, one Compacting the wool fibers as well as expressing a loss in the volume of the wool.
Der Antisetting-Effekt eines Wollschutzmittels kann z.B. in Anlehnung an A.M. Wemys und M.A. White, Proc. Ind. Japan-Australia, Joint Symp. on objective measurement, Kyoto (1985), Seite 165, bestimmt werden, indem man Rondelle aus Woll-Testgewebe ausstanzt, in der Mitte faltet und am Rand zusammennäht. Die Prüflinge werden dann in gepresstem Zustand in Gegenwart des Wollschutzmittels gefärbt, anschliessend die Gewebemuster geöffnet und jeweils ein Faden herausgezogen. Nach einer Erholungsphase in warmem Wasser wird der Winkel der Fäden gemessen. Je mehr sich das vorher zusammengepresste Garn geöffnet hat und um so mehr sich der gemessene Winkel an 180° annähert, um so besser ist der Antisetting-Effekt des Wollschutzmittels. Ein gemessener Winkel von ca. 120 bis 180° und insbesondere 140 bis 180° zeigt einen guten Anti-Setting-Effekt an.The antisetting effect of a wool protection agent can e.g. based on A.M. Wemys and M.A. White, Proc. Ind. Japan-Australia, Joint Symp. On objective measurement, Kyoto (1985), page 165, can be determined by making rondelles from wool test fabric punched out, folded in the middle and sewn together at the edge. The candidates are then in pressed state dyed in the presence of the wool protection agent, then the Fabric pattern opened and one thread pulled out. After a recovery period the angle of the threads is measured in warm water. The more that happened before compressed yarn has opened and the more the measured angle Approaching 180 °, the better the anti-setting effect of the wool protection agent. On measured angle of approx. 120 to 180 ° and in particular 140 to 180 ° shows a good one Anti-setting effect.
Die folgenden Beispiele veranschaulichen die Erfindung. Teile bedeuten Gewichtsteile, Prozente Gewichtsprozente.The following examples illustrate the invention. Parts mean parts by weight, Percentages by weight.
Beispiel 1: In einem Sulfierkolben werden 285 Teile Polyethylenglykol 200, 279 Teile
Maleinsäureanhydrid und 2 Teile Tributylamin vorgelegt. Man erwärmt vorsichtig auf ca.
100°C und lässt anschliessend ca. 5 Stunden bei dieser Temperatur rühren. Die Titration
der Carboxylgruppen zeigt das Ende der Reaktion an. Man erhält 560 Teile des Produkts
der Formel
Beispiel 2: In einem Sulfierkolben werden 18,4 Teile Glycerin, 55,9 Teile
Maleinsäureanhydrid und 0,3 Teile Tributylamin vorgelegt. Man erwärmt vorsichtig auf
ca. 100°C und lässt anschliessend ca. 5 Stunden bei dieser Temperatur rühren. Die
Titration der Carboxylgruppen zeigt das Ende der Reaktion an. Man kühlt auf ca. 50°C ab,
verdünnt mit 40 Teilen Wasser und neutralisiert bis pH 6 durch Zugabe von ca. 303 Teilen
2N Natriumhydroxidlösung. Nach dem Abfiltrieren von ungelösten Teilchen erhält man
die Verbindung der Formel
Beispiel 3: In einem Sulfierkolben werden 53,7 Teile Dipropylenglykol, 74,5 Teile
Maleinsäureanhydrid und 0,8 Teile Tributylamin vorgelegt. Man erwärmt vorsichtig auf
ca. 100°C und lässt anschliessend ca. 5 Stunden bei dieser Temperatur rühren. Die
Titration der Carboxylgruppen zeigt das Ende der Reaktion an. Man erhält 125 Teile des
Produkts der Formel
Beispiel 4: In einem Sulfierkolben werden 53,1 Teile Diethylenglykol, 93,1 Teile
Maleinsäureanhydrid und 1 Teil Tributylamin vorgelegt. Man erwärmt vorsichtig auf ca.
100°C und lässt anschliessend ca. 5 Stunden bei dieser Temperatur rühren. Die Titration
der Carboxylgruppen zeigt das Ende der Reaktion an. Man erhält 140 Teile des Produkts
der Formel
Beispiel 5: In einem Sulfierkolben werden 20,1 Teile 1,1,1-Trihydroxymethylpropan, 41,9
Teile Maleinsäureanhydrid und 0,3 Teile Tributylamin vorgelegt. Man erwärmt vorsichtig
auf ca. 100°C und lässt anschliessend ca. 5 Stunden bei dieser Temperatur rühren. Die
Titration der Carboxylgruppen zeigt das Ende der Reaktion an. Man erhält 58 Teile des
Produkts der Formel 
Beispiel 5a: In einem Sulfierkolben werden 25,5 Teile Tetraethylenglykol, 11,9 Teile
Maleinsäureanhydrid und 0,12 Teile Tributylamin vorgelegt. Man erwärmt vorsichtig auf
ca. 100°C und lässt anschliessend ca. 5 Stunden bei dieser Temperatur rühren. Die
Titration der Carboxylgruppen zeigt das Ende der Reaktion an. Man erhält 37,5 Teile des
Produkts der Formel
Beispiel 5b: In einem Sulfierkolben werden 47,9 Teile Polyethylenglykol 600, 14,9 Teile
Maleinsäureanhydrid und 0,3 Teile Tributylamin vorgelegt. Man erwärmt vorsichtig auf
ca. 100°C und lässt anschliessend ca. 5 Stunden bei dieser Temperatur und anschliessend
noch 1 Stunde bei 120°C rühren. Die Titration der Carboxylgruppen zeigt das Ende der
Reaktion an. Man erhält 60 Teile des Produkts der Formel
Beispiel 6: 100 Teile eines Mischgewebes, bestehend aus 55 % Polyester und 45 %
Wolle, werden in einem Zirkulationsapparat mit einer Flotte, die
in 1200 Teilen Wasser enthält und mit Essigsäure auf pH 5,5 eingestellt ist, 5 min. bei 40°C vorbehandelt. Darauf wird die Flotte innerhalb von 30 Minuten auf 120°C erhitzt, wobei bei 70°C 2,0 Teile der Farbstoffmischung bestehend aus
contains in 1200 parts of water and is adjusted to pH 5.5 with acetic acid, 5 min. pretreated at 40 ° C. The liquor is then heated to 120 ° C. in the course of 30 minutes, 2.0 parts of the dye mixture consisting of at 70 ° C.
Verwendet man anstelle der wässrigen Zubereitung gemäss Beispiel 1 1,5 Teile des Produkts gemäss Beispiel 2 oder 1,5 Teile des Produkts gemäss Beispiel 3 oder 2,0 Teile des Produkts gemäss Beispiel 4 oder 5,0 Teile des Produkts gemäss Beispiel 5, so erhält man ebenfalls Färbungen mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität.If, instead of the aqueous preparation according to Example 1, 1.5 parts of the Product according to Example 2 or 1.5 parts of the product according to Example 3 or 2.0 parts of the product according to Example 4 or 5.0 parts of the product according to Example 5, is obtained also dyeings with good properties and without adversely affecting the Wool quality.
Beispiel 6a: Verfährt man wie im Beispiel 6 beschrieben und verwendet anstelle der wässrigen Zubereitung gemäss Beispiel 1 1,7 Teile einer Mischung bestehend aus 93 Teilen des Produkts gemäss Beispiel 1 und 7 Teilen 3-Chlor-1,2-propandiol, so erhält man ebenfalls eine Färbung mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität. Example 6a: If the procedure is as described in Example 6 and, instead of the aqueous preparation according to Example 1, 1.7 parts of a mixture consisting of 93 parts of the product according to Example 1 and 7 parts of 3-chloro-1,2-propanediol are obtained, also a dye with good properties and without negatively influencing the wool quality.
Beispiel 6b: Verfährt man wie im Beispiel 6 beschrieben und verwendet anstelle der wässrigen Zubereitung gemäss Beispiel 1 2 Teile einer Mischung bestehend aus 50 Teilen des Produkts gemäss Beispiel 1 und 50 Teilen des Produkts gemäss Beispiel 5a, so erhält man ebenfalls eine Färbung mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität. Example 6b: If the procedure described in Example 6 is followed and 2 parts of a mixture consisting of 50 parts of the product according to Example 1 and 50 parts of the product according to Example 5a are used instead of the aqueous preparation according to Example 1, a coloration with good properties is also obtained and without affecting the wool quality.
Beispiel 7: 100 Teile eines Wollgewebes mit einem m2-Gewicht von 180 g werden in
1000 Teilen einer wässrigen Flotte enthaltend 4 Teile Ammoniumsulfat, 2,0 Teile des
Produkts gemäss Beispiel 1 und 0,5 Teile eines Naphthalinsulfonsäure-Kondensatprodukts
10 min bei 50°C behandelt; der pH-Wert der Flotte wird zuvor mit Essigsäure auf ca. 6
eingestellt. Danach werden 3 Teile des Farbstoffs der Formel
Verwendet man anstelle der wässrigen Zubereitung gemäss Beispiel 1 1,5 Teile des Produkts gemäss Beispiel 2 oder 1,5 Teile des Produkts gemäss Beispiel 3 oder 2,0 Teile des Produkts gemäss Beispiel 4 oder 5,0 Teile des Produkts gemäss Beispiel 5, so erhält man ebenfalls Färbungen mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität.If, instead of the aqueous preparation according to Example 1, 1.5 parts of the Product according to Example 2 or 1.5 parts of the product according to Example 3 or 2.0 parts of the product according to Example 4 or 5.0 parts of the product according to Example 5, is obtained also dyeings with good properties and without adversely affecting the Wool quality.
Beispiel 7a: Verfährt man wie im Beispiel 7 beschrieben und verwendet anstelle der wässrigen Zubereitung gemäss Beispiel 1 1,7 Teile einer Mischung bestehend aus 93 Teilen des Produkts gemäss Beispiel 1 und 7 Teilen 3-Chlor-1,2-propandiol, so erhält man ebenfalls eine Färbung mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität. Example 7a: If the procedure is as described in Example 7 and, instead of the aqueous preparation according to Example 1, 1.7 parts of a mixture consisting of 93 parts of the product according to Example 1 and 7 parts of 3-chloro-1,2-propanediol are obtained, also a dye with good properties and without negatively influencing the wool quality.
Beispiel 7b: Verfährt man wie im Beispiel 7 beschrieben und verwendet anstelle der wässrigen Zubereitung gemäss Beispiel 1 2 Teile einer Mischung bestehend aus 50 Teilen des Produkts gemäss Beispiel 1 und 50 Teilen des Produkts gemäss Beispiel 5a, so erhält man ebenfalls eine Färbung mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität. Example 7b: If the procedure described in Example 7 is followed and 2 parts of a mixture consisting of 50 parts of the product according to Example 1 and 50 parts of the product according to Example 5a are used instead of the aqueous preparation according to Example 1, a coloration with good properties is also obtained and without affecting the wool quality.
Claims (13)
- A process for dyeing wool-containing fibre materials with anionic dyes, which comprises dyeing said materials in the presence of a wool protective agent comprising at least one compound of formulawherein R and R' are each independently of the other hydrogen, C1-C6alkyl or a cation,
R1, R2, R1' and R2' are each independently of one another hydrogen, C1-C6alkyl or halogen,
B is a radical of formula
R3 and R3' are each independently of the other hydrogen or C1-C6alkyl,
Z1 is a radical of formula
one of Y3 and Y4 is ethyl and the other is hydrogen,
p, q and r are each independently of each other an integer from 0 to 20, and the sum of (p+q+r) is from 2 to 20,
Z2, if X is -NR3-, is the radical of a tri-, tetra- or polyamine some or all of whose free amino groups are in the form of an acylamino group of formula - A process according to claim 1, wherein R, R' and R" are identical and are each hydrogen or a cation.
- A process according to one of claims 1 and 2, wherein R1, R1', R1", R2, R2', R2", R3, R3' and R3" are identical and are each hydrogen.
- A process according to any one of claims 1 to 3, wherein B is a radical of formula (2a) or (2b) as shown in claim 1 and X is a functional group -O-.
- A process according to any one of claims 1 to 4, wherein Z1 is a radical of formula
- A process according to any one of claims 1 to 5, wherein Z1 is a radical of formula
- A process according to any one of claims 1 to 6, wherein X is a group -O- and Z2 is the radical of a tri-, tetra-, penta- or hexaol of 3 to 6 carbon atoms and in particular the radical of a tri- or tetraol of 3 or 4 carbon atoms, some or all of whose free hydroxyl groups are in the form of an ester group of the formula (4b) as indicated in claim 1.
- A process according to any one of claims 1 to 7, wherein B is a radical of formulain which R" is hydrogen or a cation.
- A process for dyeing wool-containing fibre materials with anionic dyes according to claim 1, which comprises dyeing said materials in the presence of a wool protective agent comprising at least one compound of formula (1) as indicated in claim 1, wherein
R and R' are identical and are each hydrogen or a cation,
R1, R2, R1' and R2' are identical and are each hydrogen, C1-C4alkyl or chloro,
B is a radical of formula
one of Y3 and Y4 is ethyl and the other is hydrogen,
p, q and r are each independently of one another an integer from 0 to 8, and the sum of (p+q+r) is from 2 to 8,
Z2 is the radical of a tri-, tetra- or polyol of 3 to 12 carbon atoms, some or all of whose free hydroxyl groups are in the form of an ester group of formula
R" has the meaning of R, and R1" and R2" each have the meaning of R1 and R2. - A process for dyeing wool-containing fibre materials with anionic dyes according to claim 1, which comprises dyeing said materials in the presence of a wool protective agent comprising at least one compound of formulawherein R is hydrogen or a cation, B is a radical of formula
- A process for dyeing wool-containing fibre materials with anionic dyes according to claim 1, which comprises dyeing said materials in the presence of a wool protective agent comprising at least one compound of formulawherein B is a radical of formula
- A process according to any one of claims 1 to 11, which comprises dyeing the wool-containing fibre material in the presence of 0.1 to 10% by weight of one or more than one compound of formula (1), based on the goods to be dyed.
- A process according to any one of claims 1 to 12 for dyeing wool/polyester blends by the exhaust process.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH333894 | 1994-11-08 | ||
| CH333894 | 1994-11-08 | ||
| CH3338/94 | 1994-11-08 | ||
| CH147495 | 1995-05-18 | ||
| CH147495 | 1995-05-18 | ||
| CH1474/95 | 1995-05-18 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0713940A2 EP0713940A2 (en) | 1996-05-29 |
| EP0713940A3 EP0713940A3 (en) | 1998-05-06 |
| EP0713940B1 true EP0713940B1 (en) | 2002-04-24 |
Family
ID=25687759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95810682A Expired - Lifetime EP0713940B1 (en) | 1994-11-08 | 1995-10-31 | Process for dying fibrous materials containing wool |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5611820A (en) |
| EP (1) | EP0713940B1 (en) |
| JP (1) | JPH08209552A (en) |
| KR (1) | KR100362618B1 (en) |
| AU (1) | AU695343B2 (en) |
| CA (1) | CA2162217A1 (en) |
| DE (1) | DE59510179D1 (en) |
| ES (1) | ES2173161T3 (en) |
| NZ (1) | NZ280403A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITBO20050638A1 (en) * | 2005-10-24 | 2007-04-25 | Manrico S P A | PROCEDURE FOR THE PRODUCTION OF YARN AND TEXTILE PRODUCTS IN CACHEMIRE, YARN AND PRODUCTS SO OBTAINED |
| KR100988978B1 (en) * | 2008-06-23 | 2010-10-20 | 한국염색기술연구소 | Process Of Dyeing For Wool/Polylacticacid-fiber Ply-yarn |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2781A (en) * | 1985-06-27 | 1993-09-01 | Ciba Geigy Ag | FOAM INHIBITOR FOR AQUEOUS SYSTEMS |
| US4778919A (en) * | 1986-02-25 | 1988-10-18 | Ciba-Geigy Corporation | Maleic or phthalic acid half esters of alkoxylated fatty amines |
| NZ225841A (en) * | 1987-08-19 | 1991-02-26 | Commw Scient Ind Res Org | Treatment of textile materials comprising keratinous fibres using maleic acid or fumaric acid derivatives |
| EP0420807A1 (en) * | 1989-09-27 | 1991-04-03 | Ciba-Geigy Ag | Addition products of alkylene and styrene oxide on arylalkanols |
-
1995
- 1995-10-31 ES ES95810682T patent/ES2173161T3/en not_active Expired - Lifetime
- 1995-10-31 EP EP95810682A patent/EP0713940B1/en not_active Expired - Lifetime
- 1995-10-31 DE DE59510179T patent/DE59510179D1/en not_active Expired - Fee Related
- 1995-11-06 NZ NZ280403A patent/NZ280403A/en unknown
- 1995-11-06 US US08/554,422 patent/US5611820A/en not_active Expired - Fee Related
- 1995-11-06 JP JP7287223A patent/JPH08209552A/en active Pending
- 1995-11-06 CA CA002162217A patent/CA2162217A1/en not_active Abandoned
- 1995-11-07 AU AU37707/95A patent/AU695343B2/en not_active Ceased
- 1995-11-07 KR KR1019950039994A patent/KR100362618B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0713940A3 (en) | 1998-05-06 |
| EP0713940A2 (en) | 1996-05-29 |
| JPH08209552A (en) | 1996-08-13 |
| KR100362618B1 (en) | 2003-03-15 |
| ES2173161T3 (en) | 2002-10-16 |
| AU3770795A (en) | 1996-05-16 |
| CA2162217A1 (en) | 1996-05-09 |
| AU695343B2 (en) | 1998-08-13 |
| DE59510179D1 (en) | 2002-05-29 |
| KR960018057A (en) | 1996-06-17 |
| NZ280403A (en) | 1997-09-22 |
| US5611820A (en) | 1997-03-18 |
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