Classifications

• • 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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/15—Locally discharging the dyes
  • D06P5/17—Azo 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
  • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
  • D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means

Definitions

• the present invention relates to a method for the manufacture lu ng of ⁇ tzreservedrucken on textile materials consisting of hydbphoben fibers, preferably polyester fibers, or if such fibers in admixture with cellulose fibers contained, wherein to the textile material a confuseharmbarer disperse dye and optionally a bmwstoffbe responsibler disperse dye in the form of a dye liquor or applied printing paste and then dried or partially dried, is then printing and a discharge reserve printing paste, optionally containing in addition to the etchant or caustic resistant dyes in the desired pattern, and subsequent heat treatment at temperatures of 100-230 0 C.
• the textile material is colored at the printed areas by the indestructible dye.
• Colored prints on a dark background can also be obtained if the dark background is made with a mixture of an etchable and a differently colored, non-etchable dye.
• the dye can be dissolved in the hydrophobic fiber.
• the desired pattern is then printed on the dried or dried-on padded fabric with the etching printing paste and the padded and printed fabric is then subjected to a heat treatment, with the base dye immigrating into the polyester at the unprinted areas, i.e. is fixed and the dye is destroyed at the printed areas, i.e. no coloring takes place.
• this method is also called etching reserve pressure.
• etching reserve printing which is simple in itself, involves a number of technical difficulties which often make its use more difficult. It is usually not easy to completely destroy the base dye with the etchant. If this does not succeed, a colored residue remains on the etched areas, the shade of which can vary between yellow-brown and dull violet or reddish gray tones and which soils the white background at the etched areas. This leads to white etching which appears to be unclean or, in the event that a colored etching is to be produced, to a falsification of the shade of the etching-resistant dye.
• etching pastes which contain relatively strong reducing or oxidizing agents, such as sodium dithionite in combination with alkali, alkali formaldehyde sulfoxylates or even heavy metal salts, such as tin-2-chloride.
• strong etching agents such as sodium dithionite in combination with alkali, alkali formaldehyde sulfoxylates or even heavy metal salts, such as tin-2-chloride.
• this etchant are generally not bi l - lig, and in the case of Schwermetallrienstoff they represent an additional environmental burden or cause them additional expenses in sewage treatment.
• dyes that are resistant to such etchants, so that the selection of etch-resistant dyes that can be used to produce colored etchings is relatively small.
• Disperse dyes are required for the background coloring, which can be etched with pure white agents.
• Disperse dyes are known from German published patent application 26 12 740, 26 12 741, 26 12 742, 26 12 790, 26 12 791, 26 12 792 which contain at least two esterified carboxyl groups in their molecule. Such dyes saponify when treated with aqueous alkalis to form alkali-soluble dyes containing carboxylate groups.
• the use of such dyes as disperse dyes for dyeing polyester materials has the advantage that unfixed dye residues can be washed off the textile material by simple treatment with alkaline agents.
• the diazo or coupling components that are required for the production of dyes containing carboxylic acid ester groups are not common substances in the large chemical industry, but have to be produced separately for these types of dyes, which is generally uneconomical.
• the need to use pure white etchable dispersion dyes in the process of etching reserve printing on hydrophobic textile materials under relatively mild etching conditions could therefore not be satisfied by the types of dyes specified above.
• Y in addition also —NHCOZ, in which Z represents methyl, ethyl, propyl or i-propyl, which can be substituted by hydroxy, chlorine, bromine, cyano, phenyl or phenoxy or alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy group, Alkyl with 2 to 8 carbon atoms, which is interrupted one to three times by oxygen and can be substituted by hydroxy, phenyl, amino, N-alkylamino with 1 to 4 carbon atoms, R 1 is hydrogen, alkyl with 1 - 4 C atoms by chlorine, bromine, cyan, by alkoxycarbonyl having 1 to 2 C atoms in the alkoxy group optionally substituted by hydroxyl, methoxy, ethoxy, chlorine, bromine or cyan, by alkanoyloxy having 2 to 4 C atoms Phenoxyacetoxy, monosubstituted by alkylaminocarbonyloxy having 1 to 4 carbon atom
• R 2 alkyl with 1 to 4 carbon atoms which is monosubstituted by chlorine, bromine, cyan, by alkanoyloxy with 2 to 4 carbon atoms, alkylaminocarbonyloxy with 2 to 4 carbon atoms or hydroxy or disubstituted by hydroxy or simultaneously by chlorine and hydroxy may be substituted, alkenyl having 3 to 4 carbon atoms or alkyl having 3 to 8 carbon atoms, the carbon chain of which is interrupted by 1 to 3 oxygen atoms and may be substituted one or more times by hydroxyl, chlorine, bromine or cyano,
• Etching reserve printing paste which contains a base as etchant which produces at least a pH of 8 in 5% strength aqueous solution.
• Alkyl or alkoxy radicals even if they are part of other radicals, can be straight-chain or branched.
• alkyl radicals with 1 to 4 carbon atoms in the alkylsulfonyl and dialkylphosphono substituents which can represent X 1 9 X 2 or X 3 are methyl, ethyl, propyl, butyl and i-butyl.
• substituents which can represent Y 1 are: hydrogen, chlorine, bromine, methyl, ethyl, propyl, i-propyl, n-butyl, butyl-2, i-butyl, t-butyl, hydroxymethyl, a- or ⁇ -hydroxyethyl, a-hydroxy-n-propyl, -i-propyl, -n-butyl, -butyl-2 or -i-butyl, dihydroxypropyl; Methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, i-butoxy, sec.-butoxy, ß-hydro xyethoxy, ⁇ -hydroxypropoxy, y-hydroxypropoxy, ⁇ -hydroxybutoxy, ⁇ -hydroxybutoxy, ⁇ , y-dihydroxypropoxy; Methoxycarbonylmethoxy, ethoxycarbonylmethoxy, 2- (methoxycarbonyl) ethoxy, 2-
• Substituents for which Y 2 can represent are, for example, hydrogen, chlorine, bromine; Methyl, ethyl, propyl, i-propyl, n-butyl, butyl-2, i-butyl, t-butyl; Hydroxymethyl, a- or ⁇ -hydroxyethyl, a-hydroxy-n-propyl, -i-propyl, -butyl, -butyl-2.
• Alkyl radicals for which R 1 and / or R 2 can stand are, for example, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl; 2-chloro, 2-bromo or 2-cyanoethyl; 2- or 3-chloro, bromine or cyanopropyl; 2-, 3- or 4-chloro, bromine or cyanobutyl; 2,3-dihydroxypropyl, 2-hydroxy-3-chloropropyl; 2-acetoxy-, 2-propionyloxy- or 2-butyryloxyethyl, 2- or 3-acetoxy-, - propionyloxy- or-butyryloxypropyl, 3- or 4-acetoxy-, - propionyloxy- or-butyryloxy-butyl; Methyl, ethyl, propyl or butyl aminocarbonyloxethyl, methyl, ethyl, propyl or
• R 1 can furthermore be, for example: benzyl, phenethyl, phenoxyethyl, prop-3-yl, but-4-yl, but-3-yl or but-2-yl; Cyclohexyl, cyclopentyl; Methoxy, ethoxy, propoxy, hydroxyethoxy, chloroethoxy or methoxyethoxycarbonylethyl, carbonyl-1-methylethyl or carbonyl-2-methylethyl; 2-acetoxy, 2-propionyloxy or 2-butyryloxyethyl, 2- or 3-acetoxy, propionyloxy or butyryloxy propyl, 3- or 4-acetoxy, propionyloxy or butyryloxy butyl.
• Bases which are contained in the etching reserve printing paste as etching agents and which produce at least a pH of 8 in 5% aqueous solution are known in large numbers.
• bases are the hydroxides of the alkali and alkaline earth metals, salts of alkaline earth and alkali metals with weak organic or inorganic acids, such as, for example, alkali acetate, alkali metal carbonates or bicarbonates, trialkali phosphates, ammonia or else aliphatic amines, such as, for example, triethyl or tripropyl or tributylamine, ethanolamine, dinethyl- or diethylethanolamine, diethanolamine, methyl-, ethyl- or propyl-diethanolamine or triethanolamine.
• Alkaline earth metal hydroxides such as calcium hydroxide, alkali metal hydroxides such as sodium or potassium hydroxide, or alkali metal salts of weak inorganic acids such as sodium carbonate or trisodium phosphate are usually used as bases.
• the concentration of the base in the etching reserve printing pastes is expediently 25 to 250 g / kg, preferably 50 to 130 g / kg.
• the etching reserve printing pastes contain the usual additives contained in textile printing pastes, in particular thickeners such as alginates, starch products, synthetic polymeric thickeners, mineral oils, hydrotropic substances such as urea, as well as additives which promote wetting, penetration and dye absorption.
• thickeners such as alginates, starch products, synthetic polymeric thickeners, mineral oils, hydrotropic substances such as urea, as well as additives which promote wetting, penetration and dye absorption.
• nonionic detergents which are expediently contained in the etching reserve printing pastes, such as, for example, glycerol and / or polyglycols, such as polyethylene glycol with an average molecular weight of 300 to 400, is particularly favorable for the etching process.
• Preferred combinations X 1 / X 2 are nitro / methyl or ethylsulfonyl, nitro / trifluoromethyl, cyano / methyl or ethylsulfonyl, methylsulfonyl / methylsulfonyl, ethylsulfonyl / ethylsulfonyl.
• Very particularly preferred combinations X 1 / X 2 are nitro / cyan, nitro / nitro, nitro / methoxy or ethoxycarbonyl, cyan / cyan.
• Preferred combinations X 1 / X 2 / X 3 are methylsulfonyl / methylsulfonyl / alkoxycarbonyl, ethylsulfonyl / ethylsulfonyl / alkoxycarbonyl and nitro / methyl or ethylsulfonyl / alkoxycarbonyl, the alkoxy radical of the alkoxycarbonyl group carrying optionally substituted 1 to 4 carbon atoms.
• Very particularly preferred combinations of X 1 / X 2 / X 3 are N it ro / Cyan / Nitro, Nitro / nitro / Nitro, Nitro / Nitro / cyano, nitro / methoxy or ethoxycarbonyl / Nitro, Nitro / Cyan / optionally substituted alkoxycarbonyl, Nitro / nitro / optionally substituted alkoxycarbonyl, cyan / cyan / optionally substituted alkoxycarbonyl, nitro / nitro / aminosulfonyl or optionally substituted alkylaminosulfonyl, nitro / cyan / amino- or optionally substituted alkylaminosulfonyl or cyan / cyan / amino- or optionally substituted alkylaminosulfonyl.
• a further preferred group of dyes of the formula I comprises those dyes which are in the radicals R1 and / or R 2 and / or in the alkyl or alkoxy radicals which are Y1 or Y 2 and / or in the alkyl radicals which are Z stand, carry one or more hydroxyl groups.
• R1 and / or R 2 and / or in the alkyl or alkoxy radicals which are Y1 or Y 2 and / or in the alkyl radicals which are Z stand carry one or more hydroxyl groups.
• the 2-hydroxyethyl and the 2,3-dihydroxypropyl radical are particularly preferred.
• R 1 and R 2 are alkyl radicals with 3 to 8 carbon atoms, for Z alkyl radicals with 2 to 8 carbon atoms and for Y 1 and Y 2 alkoxy radicals with 3 to 8 carbon atoms, the carbon chain of the alkyl - and alkoxy radicals interrupted by 1 to 3 oxygen atoms and optionally substituted by hydroxy.
• Preferred dyes are also dyes of the general formula I which carry alkoxycarbonylalkyl groups in the radicals R 1 , Y 1 , Y and Z.
• Alkoxycarbonyl-methyl, alkoxycarbonyl-ethyl or alkoxycarbonyl-methylethyl radicals are particularly preferred for R 1 and alkoxycarbonyl- or alkoxycarbonyl-alkyl having 1 to 4 carbon atoms in the alkyl group for Z.
• Alkoxy radicals in the alkoxycarbonylalkyl groups which stand for R 1 or Z are preferably methoxy, ethoxy, i-propoxy, n-propoxy, methoxyethoxy or ethoxyethoxy.
• the process according to the invention is preferably suitable for textile materials which consist of hydrophobic fibers, in particular polyester fibers. However, it is also suitable for textile materials that predominantly use hydrophobic fibers alongside other fibers, e.g. Cell or cotton.
• the white-etchable disperse dyes of the formula I can be applied to the textile material in the form of liquors or printing pastes.
• the textile material is impregnated with the dye liquor in a manner known per se, for example padded or splashed.
• the dye liquors can be one or more disperse dyes of the formula 1 in addition to the known dyeing aids, such as dispersing agents agents, wetting agents, foam suppressants and block aids.
• the impregnated fabric web is squeezed to a liquor absorption of 50 to 120%.
• the fabric webs are then dried by warm air with any preceding infrared radiation, the temperature being approximately 80 ° C., maximum approximately 90 ° C. with a corresponding reduction in time.
• the fabric webs prepared in this way are then printed with an etching reserve printing paste which contains one of the bases specified in more detail above as an etching agent and the known additives, in particular thickening agents, which are customary in printing pastes for textile printing.
• the impregnated and printed fabric webs are then subjected to a heat treatment between 100 and 230 ° C. In the lower temperature range of approximately 100 to 110 ° C., the heat is preferably supplied by superheated steam. For heat treatments that are carried out between 160 and 230 ° C, hot air is preferably used as the heat transfer medium.
• the textiles are post-treated in the manner customary for polyester , rinsed hot and cold and dried.
• a particular embodiment of the process according to the invention consists in that the dye liquor contains, in addition to dispersion dyes of the formula I, one or more dispersion dyes which are alkali-resistant and are therefore not destroyed by the alkaline etching reserve printing pastes to be used according to the invention. If one proceeds as above, then multicolored designs are obtained.
• the disperse dyes of the formula I can also be printed onto the fabric in the form of printing pastes and then overprinted with the etching reserve printing paste.
• the textile prints are then fixed and finished as described above.
• multi-colored designs are obtained.
• etching reserve printing pastes which in turn contain alkali-resistant disperse dyes are printed on the fund impregnated or printed with disperse dyes of the formula I. With subsequent fixation and completion of the textile materials as described above, multicolored designs are also obtained here.
• etching reserve prints can be applied not only to textile materials which consist of hydrophobic fibers, in particular polyester fibers, or predominantly contain such fibers, but also to textile materials which contain hydrophobic fibers, in particular polyester fibers, and cellulose fibers in comparable proportions.
• Such polyester / cellulose blended fabrics can have, for example, a weight ratio of polyester / cellulose of 75:25, 65:35 or 50:50.
• the dye liquor or printing paste which contains at least one white-etchable disperse dye of the formula I and optionally one or more etch-resistant disperse dyes, also contains at least one etchable reactive dye with a reactive residue of formula or or or in which X is hydrogen or a metal cation, in particular the sodium cation, and Hal is halogen, in particular chlorine or bromine, and optionally contains one or more etch-resistant reactive dyes and if the etching reserve printing paste contains an alkali metal sulfate or alkali metal hydrogen carbonate and optionally an aldehyde, and if not otherwise, in addition to alkali metal carbonate or alkali metal hydrogen carbonate work as already stated.
• the etchable reactive dyes to be used contain one of the above-mentioned fiber-reactive radicals of the formulas II to V.
• the radicals of the formulas II to IV have in common that they are in the presence of alkali with the elimination of a sulfate or Halide anion form a vinylsulfonyl group. This group formed in the presence of alkali fixes on cotton or cellulose in the same way as the vinylsulfonyl radical of the formula V bonded directly to the dye radical by adding an OH group of the cellulose to the vinyl double bond.
• Etchable reactive dyes which have one of the reactive radicals mentioned above can belong to all technically important dye groups.
• Suitable reactive dyes are the monoazo dyes CI-Yellow 13 to 17 and 72 to 74, -Orange 7, 15, 16, 23, 24, 55, -Red 21 to 23, 35 36, 50, 63, 103 to 107, 112 to 114, -Blue 28, -Brown 16; the disazo dyes CI-Blue 76, -Blue 98, -Black 5, 31; the mono- or disazo metal complex dyes CI-Violet 4.5, -Blue 20, -Brown 18; the anthraquinone dyes CI-Violet 22, -Blue 19 and 27; the phthalocyanine dyes CI-Blue 21, 38, 77, 91 and Green 14 called.
• Particularly preferred as etchable reactive dyes are those which contain at least one fiber-reactive radical of the formulas III or IV as reactive anchor.
• the amounts of the disperse and reactive dyes which are contained in the padding liquors or printing pastes in the treatment of mixed fabrics are, as usual, matched to the depth of color of the desired color and intensity of the reactive effect.
• the amount of dyes suitable for one of the fiber types involved also corresponds to the mass fraction of this fiber type in the total fiber mass.
• a padding liquor which is prepared for a base dyeing of a certain color shade, in the case that the mixed fabric predominantly contains cellulose fibers, a high proportion of etchable and possibly non-etchable reactive dyes and a low proportion of etchable and possibly non-etchable dispersion dyes and in the case that the substrate predominantly Contains polyester fibers, a high proportion or only disperse dyes and a low proportion or no reactive dyes.
• an etching reserve printing paste is used which, in addition to alkali carbonate or alkali hydrogen carbonate, also contains an alkali sulfite or alkali hydrogen sulfite as a reservation agent for the reactive dyes.
• the alkali hydrogen sulfite can also be replaced in whole or in part by an equivalent amount of an alkali hydrogen sulfite-aldehyde adduct.
• alkali hydrogen sulfite alkali hydrogen carbonate and an aldehyde
• alkali hydrogen sulfite alkali hydrogen carbonate
• the sodium or potassium salts preferably the sodium salts
• Aldehydes which may be present in the reserve pastes as alkali metal bisulfite adducts are in principle all those which are technically readily accessible, such as, for example, formaldehyde, acetaldehyde, glyoxal, benzaldehyde.
• aldehyde-alkali hydrogen sulfite adducts are in equilibrium with the individual components of the adduct, preference is given to those aldehydes which, in the free state, do not have too high a vapor pressure and therefore cannot give rise to unpleasant odors.
• Glyoxal for example, is particularly suitable for the use according to the invention.
• the use of separately prepared addition compounds of these two components offers particular advantages in the preparation of printing pastes which contain sodium bisulfite in combination with an aldehyde.
• the use of such an adduct avoids the troublesome foaming that can occur in the most unfavorable cases when printing pastes containing alkali metal bicarbonate are produced.
• the concentration of the total of the reservation agents in the printing pastes is expediently 25 to 250 g / kg, preferably 50 to 130 g / kg.
• etching reserve prints on polyester / cellulose blended fabrics are the same as in the treatment of fabrics which consist of polyester or predominantly contain polyester.
• the heat treatment a) inhibits the etchable dispersion and reactive dyes at the points printed with the etching reserve printing paste and fixes any non-reservable dispersion and reactive dyes that are present, b) fixes the dispersion dyes at the points not printed with etching reserve printing paste, and, if so the padding liquor or printing paste contained an alkali metal formate, and at the same time a fixation of the reactive dyes.
• Inhibition of the dye is to be understood here as meaning the change in the dye molecule caused by the reservation agent, which leads to the dye in question no longer staining the substrate. In the two-phase process, i.e.
• the reactive dyes are then fixed in the base coloring, i.e. in the areas not printed with etching reserve printing paste, in a manner known per se. Finally, the dyeings or prints on the blended fabrics are rinsed hot and cold and dried.
• a particular embodiment of the process according to the invention on blended fabrics consists in that the padding liquor or printing paste contains, in addition to etchable disperse and reactive dyes, additionally etch-resistant disperse and reactive dyes, which are therefore those used according to the invention Etching reserve printing pastes cannot be destroyed. If one proceeds as above, then multicolored designs are obtained.
• a further possibility for carrying out the process according to the invention in mixed fabrics is that etching reserve printing pastes are printed on the fund, which are sealed or printed with reservable dyes, which in turn contain dispersing and reactive dyes which are resistant to the reservation agent. With subsequent fixation and completion of the textile materials as described above, multicolored designs are also obtained here.
• the disperse dyes of the formula I are present in the padding liquors or in the printing pastes in finely dispersed form, as is customary and known for disperse dyes, while the reactive dyes which may be present are dissolved.
• the padding liquors or printing pastes which are to be used in the process according to the invention are also prepared in a manner known per se by mixing the liquor or printing paste constituents with the necessary amount of water and liquid finely dispersed or solid redispersible formulations of the disperse dyes and solutions or formulations of reactive dyes.
• Disperse dyes which can be combined with the dye of the formula I to produce multicolored designs, are the known commercial dyes from the group of azo or azomethine, quinophthalone, nitro or anthraquinone dyes.
• alkali-resistant disperse dyes are:
• disperse dyes of the formula I to be used according to the invention are e.g. from German Offenlegungsschriften 12 90 915, 17 19 066, 18 09 920, 19 62 402, French Patents 145 833, 865 904, 816 950 and 1 465 508 and from Journal of the Chemical Society, Perkin I, 1979, p. 2634, known.
• the disperse dyes of the formula I can be prepared in a manner known per se by diazotization and coupling, as described, for example, in Swiss patent 615 938 or in German patent application 16 44 144. Some of the disperse dyes of the general formula I can also be prepared in a manner known per se so that an amine of the formula VI in which X 1 is chlorine, bromine, nitro, cyano, alkylsulfonyl having 1 to 4 carbon atoms or phenylsulfonyl and X 2 is chlorine or bromine, diazotized and on an amine of the formula VII couples and in the dye of formula VIII thus obtained in which X 1 is chlorine, bromine, nitro, cyan, alkylsulfonyl having 1 to 4 carbon atoms or phenylsulfonyl and X 2 is chlorine or bromine, the radical representing chlorine or bromine is cyan, nitro, alkylsulfonyl having 1 to 4 carbon atoms , Aryl
• 10 parts of the dye of the formula are added in finely divided form to a padding liquor which contains 905 parts of water, 5 parts of citric acid and 60 parts of an acrylic acid-based polymerization product as an anti-migration agent per 1000 parts.
• This padding liquor is used to pad a polyester fabric based on polyethylene glycol terephthalate at 20 to 30 ° C with a squeezing effect of approx. 80%.
• the padded fabric is carefully dried at 60 to 80 ° C. After drying is overprinted with a printing paste containing 500 parts of an aqueous 10% St. John's wort ether thickener, 260 parts of water, 80 parts of calcined sodium carbonate, 80 parts of polyethylene glycol 400 and 80 parts of glycerol per 1000 parts.
• Example 1 Instead of the dye in Example 1, 20 parts of the dye used and otherwise proceed as indicated in Example 1. A blue print is obtained with very good coloristic properties, in particular good fastness to light, dry heat fixation, rubbing and washing, and a very good white background with sharp contours at the etched areas.
• Example 1 Instead of the dye in Example 1, 20 parts of the dye of the formula used and otherwise proceed as indicated in Example 1. You get a red print with very good coloristic properties, especially good light, dry heat fixation, rub and wash fastness and a very good white background with sharp contours.
• Example 1 instead of the dye in Example 1, 20 parts of the dye of the formula used and otherwise proceed as indicated in Example 1. An orange-colored print is obtained with very good coloristic properties, in particular good light, dry heat fixation, rub and wash fastness and very good white background with sharp contours.
• a mercerized mixed fabric of polyester / cotton 65:35 is padded with a batch consisting of 100 parts of a 20% liquid setting of the dye of the formula 40 parts of the liquid commercial form of CI Reactive Blue 122, 808 parts of cold water, 10 parts of sodium m-nitrobenzenesulfonate, 20 parts of a polyacrylic acid-based antimigrant, 2 parts of monosodium phosphate, 20 parts of sodium formate.
• the stock thickener consists of 230 parts of an aqueous 4% alginate thickener, 80 parts of an aqueous 10% starch ether thickener, 85 parts of water, 25 parts of an aqueous 10% solution of the condensation product of polyglycol 2000 with stearic acid and 80 parts of heavy gasoline.

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• 1980
  • 1980-10-31 DE DE19803041014 patent/DE3041014A1/de not_active Withdrawn
• 1981
  • 1981-09-28 US US06/305,998 patent/US4386935A/en not_active Expired - Fee Related
  • 1981-10-28 EP EP81109077A patent/EP0051261A1/fr not_active Ceased
  • 1981-10-30 JP JP56173110A patent/JPS57106785A/ja active Pending

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