EP0713940A2 - Process for drying fibrous materials containing wool - Google Patents
Process for drying fibrous materials containing wool Download PDFInfo
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- EP0713940A2 EP0713940A2 EP95810682A EP95810682A EP0713940A2 EP 0713940 A2 EP0713940 A2 EP 0713940A2 EP 95810682 A EP95810682 A EP 95810682A EP 95810682 A EP95810682 A EP 95810682A EP 0713940 A2 EP0713940 A2 EP 0713940A2
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- wool
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- hydrogen
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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
-
- 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)
-
- 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
-
- 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 process for high-temperature dyeing wool or wool-containing fiber materials.
- auxiliaries in order to counteract fiber damage which occurs in particular during high-temperature dyeing.
- auxiliaries Many of the known auxiliaries contain formaldehyde or release formaldehyde when heated, which is not toxicologically harmless.
- 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 or colors, in which R and R 'each independently represent hydrogen, C1-C6-alkyl or a cation, R1, R2, R1 'and R2' are each independently hydrogen, C1-C6-alkyl or halogen, B is a radical of the formula - X - Z1 - (2a), - X - Z2 - X - (2b) or - NR3 - (alk) - Z1 - (alk) 0 ⁇ 1 - NR3'- (2c) means X is a functional group -O- or -NR3-, R3 and R3 'each independently represent hydrogen or C1-C6 alkyl, Z1 for a radical of the formula - (CH2-CH2-O) p - (CHY1
- C1-C6-alkyl generally means e.g. Methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl.
- Under cation are e.g. Alkali metal or alkaline earth metal cations such as the sodium, potassium, lithium, calcium or magnesium cation, the ammonium cation or organic ammonium cations such as e.g. understand the mono-, di- or triethanolammonium cation.
- Halogen generally means e.g. Fluorine, bromine or especially chlorine.
- C1-C4 alkylene generally means e.g. 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 C1-C4 alkyl radical and particularly preferred for methyl or ethyl.
- R or R ' is a cation
- it is preferably an alkali metal cation, e.g. around the sodium, potassium or lithium cation, ammonium cation or around the cation of an organic amine, e.g. the mono-, di- or triethanolammonium cation.
- R or R ' are particularly preferably each independently of the other the sodium, potassium or triethanolammonium cation.
- R and R 'independently of one another each preferably represent hydrogen or a cation and particularly preferably hydrogen or the sodium or potassium cation.
- radicals R and R ' are preferably the same.
- radicals R1, R2, R1 'and R2' independently of one another preferably each represent hydrogen, C1-C4-alkyl or chlorine.
- the radicals R1, R2, R1 'and R2' are preferably the same. In a particularly preferred embodiment of the present invention, R1, R2, R1 'and R2' each represent hydrogen.
- R3 and R3 'independently of one another preferably each represent hydrogen or C1-C4-alkyl and particularly preferably hydrogen, methyl or ethyl.
- the radicals R3 and R3 ' are preferably the same. In a particularly preferred embodiment of the present invention, R3 and R3 'each represent hydrogen.
- X preferably represents the functional group -O-.
- p, q and r each independently represent an integer from 0 to 8, the sum of (p + q + r) being 2 to 8.
- Z1 radicals correspond to the formula - (CH2-CH2-O) p - (CHY1-CHY2-O) q - (3a), wherein Y1 and Y2 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.
- Z1 particularly preferably represents a radical of the formula - (CH2-CH2-O) p - (3b), 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 for R1” and R2 "each independently apply the preferences previously given for R1 and R2.
- the radical R" preferably has the same meaning such as R and R ', and the radicals R1 "and R2" preferably have the same meaning as R1, R1', R2 and R2 '.
- Z2 stands for the rest of a tri-, tetra- or polyamine or tri-, tetra- or polyol, this has in each case preferably ⁇ 12 C atoms and particularly preferably 3 to 8 C atoms.
- Suitable tri, tetra or polyol radicals Z2 are the rest of glycerol, diglycerol, triglycerol, 1,1,1-tris (hydroxymethyl) propane, erythritol, pentaerythritol, arabitol, sorbitol or mannitol, in which free or partially hydroxyl groups Form of an ester group of the formula (4b) given above.
- a group of particularly suitable radicals of the above formula (2b) is characterized in that X represents a group -O- and Z2 for the rest of a tri, tetra, penta- or hexaol with 3 to 6 carbon atoms and in particular stands for the remainder of a tri- or tetraol with 3 or 4 carbon atoms, the free hydroxyl groups of which are partly or completely present 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) where R "is hydrogen or a cation.
- R represents a radical of Formula (2b ') given above, R, R' and R "preferably have the same meaning.
- alkylene radical (alk) carries substituents, this can e.g. be a hydroxy, C1-C4 alkoxy or sulfate.
- the group (alk) preferably means an unsubstituted or substituted by hydroxy, C1-C4-alkoxy or -OSO3H C2-C4-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 -NR3 - (alk) - (CH2-CH2-O) p - (CHY1-CHY2-O) q - (alk) 0 ⁇ 1 - NR3 '(2c'), wherein R3 and R3 'are the same and each represent hydrogen, methyl or ethyl, (alk) is an unsubstituted or substituted by hydroxy, C1-C4-alkoxy or -OSO3H-C2-C4-alkylene radical, Y1 and Y2 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) - (CH2-CH2-O) p - (alk) 0 ⁇ 1 - NH - (2c ⁇ ), 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, R1, R2, R1 'and R2' are the same and are each hydrogen, C1-C4-alkyl or chlorine, B is a radical of the formula - O - (CH2-CH2-O) p - (CHY1-CHY2-O) q - (CHY3-CHY4-O) r (2a ') or - O - Z2 - O (2b ⁇ ) means of Y1 and Y2 one is methyl and the other is hydrogen, of Y3 and Y4 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, Z2 represents the remainder of a tri-, tetra- or polyol having 3 to 12 carbon atoms, the free hydroxyl
- 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 - (CH2-CH2-O) p - (2a *) 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 (5), wherein B 'is a radical of the formula - X - Z1 - (2a), - X - Z2 - X - (2b) or - NR3 - (alk) - Z1 - (alk) 0 ⁇ 1 - NR3'- (2c) means X, Z1, R3, R3 'and (alk) each have the meaning given above and Z2, when X is -NR3-, represents the rest of a tri-, tetra- or polyamine, or if X is -O-, for the rest of a tri-, tetra- or polyol, in any order with the acid hydrides or mono acid chlorides of carboxylic acids of the formulas and wherein R, R ', R ", R1, R1', R1", R2, R2 '
- R, R ', R "each represent hydrogen or a cation and R1, R1', R1", R2, R2 'and R2 "are each hydrogen, can be advantageously 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) takes place advantageously at elevated temperature, e.g. at a temperature of 15 to 150 ° C and preferably at 80 to 120 ° C instead.
- the reaction time can fluctuate within wide limits, a reaction time of approximately 1 to 10 hours and preferably 1 to 5 hours having proven to be practical.
- the compounds of the formula (1 ') can be prepared in an analogous manner, for example by the acid halide or acid anhydride of a compound of the above formula (6a), in which R1 and R2 are each hydrogen, with approximately equimolar amounts of a compound of the above formula (5), in which B 'is a radical of the formula (2a), where X is -O- means.
- the products of the formula (1) and (1 ') obtained in the reaction can either be used directly or, e.g. after dilution with one or more suitable solvents, they can be used as wool protection agents.
- Solvents suitable for dilution are e.g. Water or alkylene glycols or alkylene glycol ethers such as e.g. 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.
- 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).
- One embodiment of the present invention is characterized in that a wool protection agent containing at least one compound of the formulas (1) and (1 ') is used. It is also possible to use wool protection agents which contain a compound of formula (1) or (1 ') and another compound with a wool protection effect, e.g. 3-chloro-1,2-propanediol.
- the wool-containing fiber material is first pretreated with the wool protection agent in an aqueous bath and then dyed by adding the dye to this bath. It is also possible to treat the material to be dyed simultaneously with the wool preservative and the dye in an aqueous bath.
- the wool protection agent in an amount of, for example, 0.1 to 20 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 1 to 10 wt .-% and particularly preferably 1 to 6 wt .-%, each based on the weight of the material to be used.
- the wool-containing fiber material can be wool alone or a mixture of e.g. Trade wool / polyamide or wool / polyester.
- Mixtures of wool and synthetic polyamide are preferably dyed with anionic dyes and mixtures of wool and polyester fibers are preferably dyed with disperse and anionic dyes. Suitable anionic dyes and disperse dyes are known to the person skilled in the art.
- the fiber material can be in various stages of processing, e.g. in the form of yarns, flakes, sliver, knitwear such as knitwear or knitted fabrics, as a nonwoven fabric or preferably as a woven fabric.
- the mixed fiber materials are preferably fiber blends of wool and polyester, which are generally present in a proportion of 20 to 50 parts by weight of wool to 80-50 parts by weight of polyester.
- the fiber mixtures preferred for the process contain 45 parts of wool and 55 parts of polyester fibers.
- the liquor ratio can be selected within a wide range in the process according to the invention; it is e.g. 1: 1 to 1: 100 and preferably 1:10 to 1:50.
- the dyebath can contain other customary additives.
- other customary additives e.g. Mineral acids, organic acids and / or their salts, which serve to adjust the pH value of the dye bath, further electrolytes, leveling agents, wetting agents and defoamers and, if dyeing wool / polyester mixtures, carriers and / or dispersant.
- the dye bath has a pH of e.g. 4 to 6.5 and preferably from 5.2 to 5.8.
- 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 by the exhaust process, for example at a temperature in the range from 60 to 106 ° C., preferably from 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 an aqueous liquor using the exhaust process.
- Dyeing is preferably carried out by the so-called high-temperature process in closed, pressure-resistant apparatus 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 processed by the usual carrier dyeing process at temperatures below 106 ° C, e.g. in the temperature range from 75 to 98 ° C in the presence of one or more carriers.
- the dyeing of the polyester / wool mixed fiber materials can be carried out by first treating the material to be dyed with the wool protection agent and, if appropriate, the carrier, and then dyeing. One can also proceed in such a way that the material to be dyed is treated simultaneously with the wool preservative, the dyes and, if appropriate, auxiliaries.
- the textile mixed fiber material is preferably added to a liquor which contains the wool protection agent and, if appropriate, other customary auxiliaries and has a temperature of 40-50 ° C., and the material is treated at this temperature for 5 to 15 minutes.
- the temperature is then increased to about 60 to 70 ° C., the dye is added, the mixture is slowly heated to the dyeing temperature and then dyeing is carried out at this temperature for about 20 to 60, preferably 30 to 45 minutes. Finally, the liquor is cooled to about 60 ° C and the colored material is worked up as usual.
- Another advantage of the method according to the invention relates to the reduction in the setting which is achieved by the presence of a compound of the formula (1) or (1 ') in the dyebath.
- a setting is an undesired fixation of the wool fibers that occurs during the dyeing process, which is caused by rearrangement of the disulfide bridges contained in the wool.
- Such undesirable fixations can, for example, result 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 punching rondelles out of wool test fabric, folding them in the middle and sewing them together at the edge. The test specimens are then dyed in the pressed state in the presence of the wool protection agent, the fabric samples are then opened and a thread is pulled out in each case. After a recovery period in warm water, the angle of the threads is measured. The more the previously compressed yarn has opened and the closer the measured angle approaches 180 °, the better the anti-setting effect of the wool protection agent. A measured angle of approximately 120 to 180 ° and in particular 140 to 180 ° indicates a good 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, one obtains the compound of formula 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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Abstract
Beschrieben wird 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
oder
färbt, worin die Variablen die in den Ansprüchen angegebenen Bedeutungen haben. Nach dem Verfahren sind reibechte egale Färbungen ohne Einbussen an die Wollqualität erhältlich.A process is described for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials are present in the presence of a wool preservative containing at least one compound of the formula
or
colors in which the variables have the meanings given in the claims. According to the process, true-to-life dyeings are available without sacrificing wool quality.
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zum Hochtemperatur-Färben von Wolle oder wollhaltigen Fasermaterialien.The present invention relates to a new process for high-temperature dyeing 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 dye wool or wool-containing fiber materials in the presence of auxiliaries in order to counteract fiber damage which occurs in particular during high-temperature dyeing. Many of the known auxiliaries contain formaldehyde or release formaldehyde when heated, which is not toxicologically harmless.
Es wurde nun überraschend ein verbessertes Verfahren zum Hochtemperatur-Färben von wollhaltigen Fasermaterialien gefunden, welches auf der Verwendung einer neuen Klasse von Wollschutzmitteln basiert.Surprisingly, an improved process for high-temperature dyeing of wool-containing fiber materials has now been found, which is based on the use of a new class of wool protection agents.
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 - Z₁ - (2a),
- X - Z₂ - X - (2b)
oder
- NR₃ - (alk) - Z₁ - (alk)₀₋₁ - NR₃'- (2c)
bedeutet,
X eine funktionelle Gruppe -O- oder -NR₃- ist,
R₃ und R₃' unabhängig voneinander je Wasserstoff oder C₁-C₆-Alkyl bedeuten,
Z₁ für einen Rest der Formel
- (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (CHY₃-CHY₄-O)r- (3)
steht,
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 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
- NR₃ - CO - CR₁"= CR₂"- CO - O - R" (4a)
vorliegen, oder, wenn X -O- ist, für den Rest eines Tri-, Tetra- oder Polyols steht, dessen freie Hydroxygruppen teilweise oder vollständig in Form einer Estergruppe der Formel
- O - CO - CR₁" = CR₂"- CO - O - R" (4b),
vorliegen,
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
R₁, R₂, R₁ 'and R₂' are each independently hydrogen, C₁-C₆-alkyl or halogen,
B is a radical of the formula
- X - Z₁ - (2a),
- X - Z₂ - X - (2b)
or
- NR₃ - (alk) - Z₁ - (alk) ₀₋₁ - NR₃'- (2c)
means
X is a functional group -O- or -NR₃-,
R₃ and R₃ 'each independently represent hydrogen or C₁-C₆ alkyl,
Z₁ for a radical of the formula
- (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (CHY₃-CHY₄-O) r - (3)
stands,
of Y₁ and Y₂ one is methyl and the other is hydrogen,
of Y₃ and Y₄ 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,
Z₂ when X is -NR₃- stands for the rest 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
- NR₃ - CO - CR₁ "= CR₂" - CO - O - R "(4a)
are present, or, if X is -O-, represents the remainder of a tri-, tetra- or polyol, the free hydroxyl groups of which are partially or completely in the form of an ester group of the formula
- O - CO - CR₁ "= CR₂" - CO - O - R "(4b),
are present
R "independently have the meaning of R and R₁" and R₂ "each independently have the meaning of R₁ and R₂, and
(alk) is an optionally further substituted C₁-C₄ 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, C₁-C₆-alkyl generally means e.g. Methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl or straight-chain or branched pentyl or hexyl. Under cation are e.g. Alkali metal or alkaline earth metal cations such as the sodium, potassium, lithium, calcium or magnesium cation, the ammonium cation or organic ammonium cations such as e.g. understand the mono-, di- or triethanolammonium cation. Halogen generally means e.g. Fluorine, bromine or especially chlorine. C₁-C₄ alkylene generally means e.g. 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 C₁-C₄ alkyl radical and particularly preferred for 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.When R or R 'is a cation, it is preferably an alkali metal cation, e.g. around the sodium, potassium or lithium cation, ammonium cation or around the cation of an organic amine, e.g. the mono-, di- or triethanolammonium cation. R or R 'are particularly preferably each independently of the other 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 preferably 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 R₁, R₂, R₁ 'and R₂' independently of one another preferably each represent hydrogen, C₁-C₄-alkyl or chlorine. The radicals R₁, R₂, R₁ 'and R₂' are preferably the same. In a particularly preferred embodiment of the present invention, R₁, R₂, R₁ 'and R₂' 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.R₃ and R₃ 'independently of one another preferably each represent hydrogen or C₁-C₄-alkyl and particularly preferably hydrogen, methyl or ethyl. The radicals R₃ and R₃ 'are preferably the same. In a particularly preferred embodiment of the present invention, R₃ and R₃ '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 each independently represent an integer from 0 to 8, the sum of (p + q + r) being 2 to 8.
Besonders bevorzugte Reste Z₁ entsprechen der Formel
- (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (3a),
worin Y₁ und Y₂ die zuvor angegebene Bedeutung haben und p und q unabhängig voneinander je eine ganze Zahl von 0 bis 8 sind, wobei die Summe von (p+q) 2 bis 8 beträgt.Particularly preferred Z₁ radicals correspond to the formula
- (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (3a),
wherein Y₁ and Y₂ 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.
Z₁ steht insbesondere bevorzugt für einen Rest der Formel
-(CH₂-CH₂-O)p- (3b),
worin p eine ganze Zahl von 2 bis 8 und besonders 2 bis 5 bedeutet.Z₁ particularly preferably represents a radical of the formula
- (CH₂-CH₂-O) p - (3b),
wherein p is an integer from 2 to 8 and especially 2 to 5.
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 the formulas (4a) and (4b), the preferences previously given for R apply independently for R "and for R₁" and R₂ "each independently apply the preferences previously given for R₁ and R₂. The radical R" preferably has the same meaning such as R and R ', and the radicals R₁ "and R₂" preferably have the same meaning as R₁, R₁', R₂ and R₂ '.
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.Z₂ stands for the rest of a tri-, tetra- or polyamine or tri-, tetra- or polyol, this has in each case preferably ≤ 12 C atoms and particularly preferably 3 to 8 C 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 radicals Z₂ are the rest of glycerol, diglycerol, triglycerol, 1,1,1-tris (hydroxymethyl) propane, erythritol, pentaerythritol, arabitol, sorbitol or mannitol, in which free or partially hydroxyl groups 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 above formula (2b) is characterized in that X represents a group -O- and Z₂ for the rest of a tri, tetra, penta- or hexaol with 3 to 6 carbon atoms and in particular stands for the remainder of a tri- or tetraol with 3 or 4 carbon atoms, the free hydroxyl groups of which are partly or completely present 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-Propylen- oder 2-Hydroxy-1,3-propylenrest.In formula (2c), the meanings and preferences given under formula (2a) apply to Z₁ and the meanings and preferences given above for R₃ independently for R₃ '. If the alkylene radical (alk) carries substituents, this can e.g. be a hydroxy, C₁-C₄ alkoxy or sulfate. The group (alk) preferably means an unsubstituted or substituted by hydroxy, C₁-C₄-alkoxy or -OSO₃H C₂-C₄-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
-NR₃ - (alk) -(CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (alk)₀₋₁ - NR₃' (2c'),
worin R₃ und R₃' gleich sind und je Wasserstoff, Methyl oder Ethyl bedeuten, (alk) für einen unsubstituierten oder durch Hydroxy, C₁-C₄-Alkoxy oder -OSO₃H substituierten C₂-C₄-Alkylenrest stehen, Y₁ und Y₂ die zuvor angegebene Bedeutung haben und p und q unabhängig voneinander je eine ganze Zahl von 0 bis 8 sind, wobei die Summe von (p+q) 2 bis 8 beträgt.If B represents a radical of the formula (2c) given above, this preferably corresponds to the formula
-NR₃ - (alk) - (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (alk) ₀₋₁ - NR₃ '(2c'),
wherein R₃ and R₃ 'are the same and each represent hydrogen, methyl or ethyl, (alk) is an unsubstituted or substituted by hydroxy, C₁-C₄-alkoxy or -OSO₃H-C₂-C₄-alkylene radical, Y₁ and Y₂ 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 steht als Rest der Formel (2c) insbesondere bevorzugt für einen Rest der Formel
NH - (alk) - (CH₂-CH₂-O)p- (alk)₀₋₁ - NH - (2cʺ),
worin (alk) 1,2-Ethylen, 1,2- oder 1,3-Propylen oder 2-Hydroxy-1,3-propylen ist und p eine ganze Zahl von 2 bis 8 und besonders 2 bis 5 bedeutet.B as the radical of the formula (2c) is particularly preferably a radical of the formula
NH - (alk) - (CH₂-CH₂-O) p - (alk) ₀₋₁ - NH - (2cʺ),
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.
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.Of particular interest for the process according to the invention are compounds of the formula (1) given above, in which B denotes a radical of the formula (2a) or (2b) given above and X represents a functional group -O-.
Von besonderem Interesse sind auch Verbindungen der zuvor angegebenen Formel (1'), worin R Wasserstoff oder ein Kation und Z₁ einen Rest der zuvor angegebenen Formel (3a) oder insbesondere (3b) bedeuten.Of particular interest are also compounds of the above formula (1 '), wherein R is hydrogen or a cation and Z₁ is a radical of the above formula (3a) or in particular (3b).
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
- O - (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (CHY₃-CHY₄-O)r (2a')
oder
- O - Z₂ - O (2bʺ)
bedeutet,
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
- O - CO - CR₁"= CR₂"- CO - O - R" (4b),
vorliegen, und
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,
R₁, R₂, R₁ 'and R₂' are the same and are each hydrogen, C₁-C₄-alkyl or chlorine, B is a radical of the formula
- O - (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (CHY₃-CHY₄-O) r (2a ')
or
- O - Z₂ - O (2bʺ)
means
of Y₁ and Y₂ one is methyl and the other is hydrogen,
of Y₃ and Y₄ 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,
Z₂ represents 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
- O - CO - CR₁ "= CR₂" - CO - O - R "(4b),
are present, and
R "have the meaning of R and R₁" and R₂ "each have the meaning of R₁ and R₂.
Eine besonders bevorzugte Ausführungsform der vorliegenden Erfindung betrifft das Verfahren unter Verwendung einer Verbindung der Formel
- O - (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (2aʺ)
oder
- O - Z₂ - O - (2bʺ)
steht, von Y₁ und Y₂ der eine Rest Methyl und der andere Rest Wasserstoff bedeutet, p und q unabhängig voneinander je eine ganze Zahl 0 bis 8 sind, wobei die Summe von (p+q) 2 bis 8 beträgt, und Z₂ für den Rest eines Tri-, Tetra- oder Polyols mit 3 bis 6 C-Atomen steht, dessen freie Hydroxygruppen teilweise oder vollständig in Form einer Estergruppe der Formel
-O-CO-CH=CH-CO-O-R (4b'),
worin R die oben angegebene Bedeutung hat, vorliegen.A particularly preferred embodiment of the present invention relates to the method using a compound of the formula
- O - (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (2aʺ)
or
- O - Z₂ - O - (2bʺ)
is of Y₁ and Y₂ is a methyl radical and the other radical is hydrogen, p and q are independently an integer 0 to 8, the sum of (p + q) being 2 to 8, and Z₂ represents the remainder of a tri, tetra or polyol having 3 to 6 carbon atoms, the free or partially hydroxyl groups in the form of an ester group of the formula
-O-CO-CH = CH-CO-OR (4b '),
where R has the meaning given above.
Eine insbesondere bevorzugte Ausführungsform der vorliegenden Erfindung betrifft das Verfahren unter Verwendung einer Verbindung der Formel
- O - (CH₂-CH₂-O)p - (2a*)
steht, R Wasserstoff oder das Natrium- oder Kalium-Kation bedeutet und p eine ganze Zahl 2 bis 5 ist.A particularly preferred embodiment of the present invention relates to the method using a compound of the formula
- O - (CH₂-CH₂-O) p - (2a *)
is R is hydrogen or the sodium or potassium cation and p is an integer 2 to 5.
Die erfindungsgemäss verwendeten Verbindungen der Formel (1) können in an sich bekannter Weise hergestellt werden, z.B. indem man eine Verbindung der Formel
H - B'- H (5),
worin B' einen Rest der Formel
- X - Z₁ - (2a),
- X - Z₂ - X - (2b)
oder
- NR₃ - (alk)- Z₁ - (alk)₀₋₁ - NR₃'- (2c)
bedeutet,
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 steht, in beliebiger Reihenfolge mit den Säurenhydriden oder Monosäurechloriden von Carbonsäuren der Formeln
H - B'- H (5),
wherein B 'is a radical of the formula
- X - Z₁ - (2a),
- X - Z₂ - X - (2b)
or
- NR₃ - (alk) - Z₁ - (alk) ₀₋₁ - NR₃'- (2c)
means
X, Z₁, R₃, R₃ 'and (alk) each have the meaning given above and Z₂, when X is -NR₃-, represents the rest of a tri-, tetra- or polyamine, or if X is -O-, for the rest of a tri-, tetra- or polyol, 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 ", R₁, R₁' and R₁" and R₂, R₂ 'and R₂ "are each identical, can advantageously be prepared by using a compound of formula (5) reacted with an acid anhydride or mono acid chloride from a carboxylic acid of the above formula (6a) in 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 formula (1), wherein R, R ', R "each represent hydrogen or a cation and R₁, R₁', R₁", R₂, R₂ 'and R₂ "are each hydrogen, can be advantageously 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) takes place advantageously at elevated temperature, e.g. at a temperature of 15 to 150 ° C and preferably at 80 to 120 ° C instead. The reaction time can fluctuate within wide limits, a reaction time of approximately 1 to 10 hours and preferably 1 to 5 hours having proven to be practical.
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 the acid halide or acid anhydride of a compound of the above formula (6a), in which R₁ and R₂ are each hydrogen, with approximately equimolar amounts of a compound of the above formula (5), in which B 'is a radical of the formula (2a), where X is -O- means.
Die bei der Umsetzung erhaltenen Produkte der Formel (1) und (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 the formula (1) and (1 ') obtained in the reaction can either be used directly or, e.g. after dilution with one or more suitable solvents, they can be used as wool protection agents. Solvents suitable for dilution are e.g. Water or alkylene glycols or alkylene glycol ethers such as e.g. 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. Preferred is the use of alkylene glycols as diluents 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 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 (1') verwendet. Es ist auch möglich, Wollschutzmittel zu verwenden, die eine Verbindung der Formel (1) oder (1') und eine weitere Verbindung mit wollschützender Wirkung, z.B. 3-Chlor-1,2-propandiol, enthalten.The wool protection agents used according to the invention can contain one or more of the compounds of the formula (1). One embodiment of the present invention is characterized in that a wool protection agent containing at least one compound of the formulas (1) and (1 ') is used. It is also possible to use wool protection agents which contain a compound of formula (1) or (1 ') and another compound with a wool protection effect, e.g. 3-chloro-1,2-propanediol.
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 pretreated with the wool protection agent in an aqueous bath and then dyed by adding the dye to this bath. It is also possible to treat the material to be dyed simultaneously 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, for example, 0.1 to 20 wt .-%, preferably 0.1 to 10 wt .-%, particularly preferably 1 to 10 wt .-% and particularly preferably 1 to 6 wt .-%, each based on the weight of the material to be used.
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 a mixture of e.g. Trade wool / polyamide or wool / polyester. Mixtures of wool and synthetic polyamide are preferably dyed with anionic dyes and mixtures of wool and polyester fibers are preferably dyed with disperse and anionic dyes. Suitable anionic dyes and disperse dyes are known to the person skilled in the art.
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 the form of yarns, flakes, sliver, knitwear such as knitwear or knitted fabrics, as a nonwoven fabric or preferably as a woven 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 blends of wool and polyester, which are generally present in a proportion of 20 to 50 parts by weight of wool to 80-50 parts by weight of polyester. The fiber mixtures preferred for the process 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 selected within a wide range in the process according to the invention; 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 contain other customary additives. Worth mentioning are e.g. Mineral acids, organic acids and / or their salts, which serve to adjust the pH value of the dye bath, further electrolytes, leveling agents, wetting agents and defoamers and, if dyeing wool / polyester mixtures, carriers and / or dispersant.
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 from 5.2 to 5.8. 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 by the exhaust process, for example at a temperature in the range from 60 to 106 ° C., preferably from 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 an aqueous liquor using the exhaust process. Dyeing is preferably carried out by the so-called high-temperature process in closed, pressure-resistant apparatus 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 processed by the usual carrier dyeing process at temperatures below 106 ° C, e.g. in the temperature range from 75 to 98 ° C in the presence of one or more carriers.
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 by first treating the material to be dyed with the wool protection agent and, if appropriate, the carrier, and then dyeing. One can also proceed in such a way that the material to be dyed is treated simultaneously with the wool preservative, the dyes and, if appropriate, auxiliaries. The textile mixed fiber material is preferably added to a liquor which contains the wool protection agent and, if appropriate, other customary auxiliaries and has a temperature of 40-50 ° C., and the material is treated at this temperature for 5 to 15 minutes. The temperature is then increased to about 60 to 70 ° C., the dye is added, the mixture is slowly heated to the dyeing temperature and then dyeing is carried out at this temperature for about 20 to 60, preferably 30 to 45 minutes. Finally, the liquor is cooled to about 60 ° C and the colored material is 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 wool or in particular wool / polyester fiber mixtures at high temperature with perfect protection of the wool content, i.e. dyeing while preserving the important fiber-technological properties of the wool, such as tear resistance, bursting resistance and elongation. It should also be emphasized 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) bzw. (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 in the setting which is achieved by the presence of a compound of the formula (1) or (1 ') in the dyebath. A setting is an undesired fixation of the wool fibers that occurs during the dyeing process, which is caused by rearrangement of the disulfide bridges contained in the wool. Such undesirable fixations can, for example, result 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 punching rondelles out of wool test fabric, folding them in the middle and sewing them together at the edge. The test specimens are then dyed in the pressed state in the presence of the wool protection agent, the fabric samples are then opened and a thread is pulled out in each case. After a recovery period in warm water, the angle of the threads is measured. The more the previously compressed yarn has opened and the closer the measured angle approaches 180 °, the better the anti-setting effect of the wool protection agent. A measured angle of approximately 120 to 180 ° and in particular 140 to 180 ° indicates a good 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
HOOC - CH=CH - CO - O - (CH₂-CH₂-O)₄ - CO -CH=CH - COOH
als viskoses Oel, welches anschliessend mit Dipropylenglykol zu einer Lösung mit 70% Aktivgehalt formuliert wird. Example 1: 285 parts of polyethylene glycol 200, 279 parts of maleic anhydride and 2 parts 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. 560 parts of the product of the formula are obtained
HOOC - CH = CH - CO - O - (CH₂-CH₂-O) ₄ - CO -CH = CH - COOH
as a viscous oil, which is then formulated with dipropylene glycol to a solution with an active content of 70%.
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
HOOC - CH=CH - CO - O - [CH(CH₃)-CH₂-O]₂ - CO -CH=CH - COOH
als viskoses Oel. Example 3 : 53.7 parts of dipropylene glycol, 74.5 parts of maleic anhydride and 0.8 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. 125 parts of the product of the formula are obtained
HOOC - CH = CH - CO - O - [CH (CH₃) -CH₂-O] ₂ - CO -CH = CH - COOH
as a viscous oil.
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
HOOC - CH=CH - CO - O - (CH₂-CH₂-O)₂ - CO -CH=CH - COOH
als viskoses Oel. Example 4 : 53.1 parts of diethylene glycol, 93.1 parts of maleic anhydride and 1 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. 140 parts of the product of the formula are obtained
HOOC - CH = CH - CO - O - (CH₂-CH₂-O) ₂ - CO -CH = CH - COOH
as a viscous oil.
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
HOOC - CH=CH - CO - O - (CH₂-CH₂-O)₄ - H
als viskoses Oel, welches anschliessend mit 16,1 Teilen Dipropylenglykol zu einer Lösung mit 70% Aktivgehalt formuliert wird. Example 5a : 25.5 parts of tetraethylene glycol, 11.9 parts of maleic anhydride and 0.12 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. 37.5 parts of the product of the formula are obtained
HOOC - CH = CH - CO - O - (CH₂-CH₂-O) ₄ - H
as a viscous oil, which is then formulated with 16.1 parts of dipropylene glycol to form a solution with an active content of 70%.
Beispiel 5b: In einem Sulfierkolben werden 62,5 Teile der Verbindung der Formel H₂N-(CH₂CH₂O)₂₃-CH₂CH₂-NH₂ (z.B. Jeffamine® ED 900), 11,2 Teile Maleinsäureanhydrid und 0,3 Teile Tributylamin vorgelegt. Man erwärmt vorsichtig auf ca. 100°C und lässt anschliessend ca. 2 Stunden bei dieser Temperatur rühren. Die Titration der Carboxylgruppen zeigt das Ende der Reaktion an. Man erhält ca. 70 Teile des Produkts der Formel
HOOC-CH=CH-CO-NH-(CH₂-CH₂-O)₂₃-CH₂-CH₂-NH-CO-CH=CH-COOH
als viskoses Oel Example 5b : 62.5 parts of the compound of the formula H₂N- (CH₂CH₂O) ₂₃-CH₂CH₂-NH₂ (for example Jeffamine® ED 900), 11.2 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 2 hours. The titration of the carboxyl groups indicates the end of the reaction. About 70 parts of the product of the formula are obtained
HOOC-CH = CH-CO-NH- (CH₂-CH₂-O) ₂₃-CH₂-CH₂-NH-CO-CH = CH-COOH
as a viscous oil
Beispiel 5c: 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
HOOC - CH=CH - CO - O - (CH₂-CH₂-O)₁₃ - CO - CH=CH - COOH
als viskoses Oel. Example 5c : 47.9 parts of polyethylene glycol 600, 14.9 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 and then at 120 ° C. for 1 hour. The titration of the carboxyl groups indicates the end of the reaction. 60 parts of the product of the formula are obtained
HOOC - CH = CH - CO - O - (CH₂-CH₂-O) ₁₃ - CO - CH = CH - COOH
as a viscous oil.
Beispiel 6: 100 Teile eines Mischgewebes, bestehend aus 55 % Polyester und 45 % Wolle, werden in einem Zirkulationsapparat mit einer Flotte, die
- 2,0 Teile des Produkts gemäss Beispiel 1,
- 0,5 Teile eines sulfatierten Fettaminpolyglycolethers,
- 1,0 Teile eines handelsüblichen Hilfsmittelgemisches (auf Basis carbonsäure- und phosphorsäure-aromatischer Verbindungen) und
- 2,0 Teile Natriumacetat
- 1,6 Gew.-% Farbstoff der Formel
- 60 Gew.-% Farbstoff der Formel
- 5,0 Gew.-% Farbstoff der Formel
- 4,0 Teile Farbstoff der Formel
- 3,3 Teile Farbstoff der Formel
- 15,0 Teile Farbstoff der Formel
der Flotte zugefügt werden. Darauf färbt man 40 min. bei 120°C und kühlt anschliessend die Färbeflotte auf 60°C ab. Darauf wird die übliche Nachwäsche durchgeführt. Man erhält eine reibechte, egale, rote Ton-in-Ton Färbung ohne Einbusse der Wollqualität. Example 6 : 100 parts of a mixed fabric, consisting of 55% polyester and 45% wool, are in a circulation apparatus with a liquor
- 2.0 parts of the product according to Example 1,
- 0.5 parts of a sulfated fatty amine polyglycol ether,
- 1.0 parts of a commercially available auxiliary mixture (based on carboxylic and phosphoric acid aromatic compounds) and
- 2.0 parts sodium acetate
- 1.6% by weight of dye of the formula
- 60% by weight of dye of the formula
- 5.0% by weight of dye of the formula
- 4.0 parts of dye of the formula
- 3.3 parts of dye of the formula
- 15.0 parts of dye of the formula
be added to the fleet. It is stained for 40 min. at 120 ° C and then cools the dye liquor to 60 ° C. The usual post-wash is then carried out. You get a rub-fast, level, red tone-on-tone coloring without loss of wool quality.
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 are used, then dyeings with good properties and without negatively influencing the wool quality are also obtained.
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 are used, then dyeings with good properties and without negatively influencing the wool quality are also obtained.
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 (16)
R₁, R₂, R₁' und R₂' unabhängig voneinander je Wasserstoff, C₁-C₆-Alkyl oder Halogen sind,
B einen Rest der Formel
- X - Z₁ - (2a),
- X - Z₂ - X - (2b)
oder
- NR₃ - (alk) - Z₁ - (alk)₀₋₁ - NR₃'- (2c)
bedeutet,
X eine funktionelle Gruppe -O- oder -NR₃- ist,
R₃ und R₃' unabhängig voneinander je Wasserstoff oder C₁-C₆-Alkyl bedeuten,
Z₁ für einen Rest der Formel
- (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (CHY₃-CHY₄-O)r - (3)
steht,
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 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
- NR₃ - CO - CR₁"= CR₂"- CO - O - R" (4a)
vorliegen, oder, wenn X -O- ist, für den Rest eines Tri-, Tetra- oder Polyols steht, dessen freie Hydroxygruppen teilweise oder vollständig in Form einer Estergruppe der Formel
- O - CO - CR₁"= CR₂"- CO - O - R" (4b),
vorliegen,
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.Process for dyeing wool-containing fiber materials with anionic dyes, characterized in that these materials in the presence of a wool protection agent containing at least one compound of the formula
R₁, R₂, R₁ 'and R₂' are each independently hydrogen, C₁-C₆-alkyl or halogen,
B is a radical of the formula
- X - Z₁ - (2a),
- X - Z₂ - X - (2b)
or
- NR₃ - (alk) - Z₁ - (alk) ₀₋₁ - NR₃'- (2c)
means
X is a functional group -O- or -NR₃-,
R₃ and R₃ 'each independently represent hydrogen or C₁-C₆ alkyl,
Z₁ for a radical of the formula
- (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (CHY₃-CHY₄-O) r - (3)
stands,
of Y₁ and Y₂ one is methyl and the other is hydrogen,
of Y₃ and Y₄ 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,
Z₂ when X is -NR₃- represents the rest of a tri-, tetra- or polyamine, the free one Amino groups partially or completely in the form of an acylamino group of the formula
- NR₃ - CO - CR₁ "= CR₂" - CO - O - R "(4a)
are present, or, if X is -O-, represents the remainder of a tri-, tetra- or polyol, the free hydroxyl groups of which are partially or completely in the form of an ester group of the formula
- O - CO - CR₁ "= CR₂" - CO - O - R "(4b),
are present
R "independently have the meaning of R and R₁" and R₂ "each independently have the meaning of R₁ and R₂, and
(alk) is an optionally further substituted C₁-C₄ alkylene radical.
- (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q- (3a)
ist, worin Y₁ und Y₂ die im Anspruch 1 angegebene Bedeutung haben und p und q unabhängig voneinander je eine ganze Zahl von 0 bis 8 sind, wobei die Summe von (p+q) 2 bis 8 beträgt.Method according to one of claims 1 to 6, characterized in that Z₁ is a radical of the formula
- (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (3a)
is wherein Y₁ and Y₂ have the meaning given in claim 1 and p and q are independently an integer from 0 to 8, the sum of (p + q) being 2 to 8.
-(CH₂-CH₂-O)p- (3b),
worin p eine ganze Zahl von 2 bis 8 und insbesondere 2 bis 5 bedeutet, steht.Method according to one of claims 1 to 7, characterized in that Z₁ for a radical of the formula
- (CH₂-CH₂-O) p - (3b),
where p is an integer from 2 to 8 and in particular 2 to 5.
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
- O - (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (CHY₃-CHY₄-O)r (2a')
oder
- O - Z₂ - O (2bʺ)
bedeutet,
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
- O - CO - CR₁"= CR₂"- CO - O - R" (4b),
vorliegen, und
R" die Bedeutung von R und R₁" und R₂" je die Bedeutung von R₁ und R₂ haben.Process for dyeing wool-containing fiber materials with anionic dyes according to Claim 1, characterized in that these materials are dyed in the presence of a wool protection agent comprising at least one compound of the formula (1) given in Claim 1, in which
R and R 'are the same and each represent hydrogen or a cation,
R₁, R₂, R₁ 'and R₂' are the same and are each hydrogen, C₁-C₄-alkyl or chlorine,
B is a radical of the formula
- O - (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (CHY₃-CHY₄-O) r (2a ')
or
- O - Z₂ - O (2bʺ)
means
of Y₁ and Y₂ one is methyl and the other is hydrogen,
of Y₃ and Y₄ 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,
Z₂ represents the rest 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
- O - CO - CR₁ "= CR₂" - CO - O - R "(4b),
are available, and
R "have the meaning of R and R₁" and R₂ "each have the meaning of R₁ and R₂.
- O - (CH₂-CH₂-O)p - (CHY₁-CHY₂-O)q - (2aʺ)
oder
- O - Z₂ - O - (2bʺ)
steht, von Y₁ und Y₂ der eine Rest Methyl und der andere Rest Wasserstoff bedeutet, p und q unabhängig voneinander je eine ganze Zahl 0 bis 8 sind, wobei die Summe von (p+q) 2 bis 8 beträgt, und Z₂ für den Rest eines Tri-, Tetra- oder Polyols mit 3 bis 6 C-Atomen steht, dessen freie Hydroxygruppen teilweise oder vollständig in Form einer Estergruppe der Formel
- O - CO - CH = CH - CO - O - R (4b'),
worin R die oben angegebene Bedeutung hat, vorliegen.A process for dyeing wool-containing fiber materials with anionic dyes according to claim 1, characterized in that these materials in the presence of a wool protection agent containing at least one compound of the formula
- O - (CH₂-CH₂-O) p - (CHY₁-CHY₂-O) q - (2aʺ)
or
- O - Z₂ - O - (2bʺ)
stands, of Y₁ and Y₂ the one radical is methyl and the other radical is hydrogen, p and q are independently an integer 0 to 8, the sum of (p + q) being 2 to 8, and Z₂ for the rest of a tri, tetra or polyol having 3 to 6 carbon atoms, the free hydroxyl groups of which are partially or completely in the form of an ester group of the formula
- O - CO - CH = CH - CO - O - R (4b '),
where R has the meaning given above.
- O - (CH₂-CH₂-O)p - (2a*)
steht, R Wasserstoff oder das Natrium- oder Kalium-Kation bedeutet und p eine ganze Zahl 2 bis 5 ist.A process for dyeing wool-containing fiber materials with anionic dyes according to claim 1, characterized in that these materials in the presence of a wool protection agent containing at least one compound of the formula
- O - (CH₂-CH₂-O) p - (2a *)
is R is hydrogen or the sodium or potassium cation and p is an integer 2 to 5.
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 | ||
| CH1474/95 | 1995-05-18 | ||
| CH147495 | 1995-05-18 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0713940A2 true EP0713940A2 (en) | 1996-05-29 |
| EP0713940A3 EP0713940A3 (en) | 1998-05-06 |
| EP0713940B1 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 | Dyeing Method of Plywood of Wool and Polylactic Acid Fiber |
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 DE DE59510179T patent/DE59510179D1/en not_active Expired - Fee Related
- 1995-10-31 EP EP95810682A patent/EP0713940B1/en not_active Expired - Lifetime
- 1995-10-31 ES ES95810682T patent/ES2173161T3/en not_active Expired - Lifetime
- 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 NZ NZ280403A patent/NZ280403A/en unknown
- 1995-11-06 CA CA002162217A patent/CA2162217A1/en not_active Abandoned
- 1995-11-07 KR KR1019950039994A patent/KR100362618B1/en not_active Expired - Fee Related
- 1995-11-07 AU AU37707/95A patent/AU695343B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08209552A (en) | 1996-08-13 |
| ES2173161T3 (en) | 2002-10-16 |
| AU695343B2 (en) | 1998-08-13 |
| CA2162217A1 (en) | 1996-05-09 |
| AU3770795A (en) | 1996-05-16 |
| EP0713940B1 (en) | 2002-04-24 |
| DE59510179D1 (en) | 2002-05-29 |
| EP0713940A3 (en) | 1998-05-06 |
| KR960018057A (en) | 1996-06-17 |
| US5611820A (en) | 1997-03-18 |
| NZ280403A (en) | 1997-09-22 |
| KR100362618B1 (en) | 2003-03-15 |
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