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
  • 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
  • D06P1/90—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 dyes dissolved in organic solvents or aqueous emulsions thereof
  • D06P1/92—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 dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
  • D06P1/928—Solvents other than 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
  • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
• • 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
• • 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
  • D06P1/90—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 dyes dissolved in organic solvents or aqueous emulsions thereof
  • D06P1/92—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 dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents
  • D06P1/922—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 dyes dissolved in organic solvents or aqueous emulsions thereof in organic solvents hydrocarbons
  • D06P1/924—Halogenated hydrocarbons
• • 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
  • Y10S8/907—Nonionic emulsifiers for dyeing
• • 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
  • Y10S8/92—Synthetic fiber dyeing
  • Y10S8/922—Polyester fiber

Definitions

• ABSTRACT Water is dispersed in inert, non-polar fluorocarbon with a non-ionic emulsifier which is soluble in the water and fluorocarbon and contains a hydrophobic fluoroaliphatic portion and a hydrophilic solubilizing portion, to provide a water-in-fluorocarbon emulsion useful in the dyeing of textiles.
• This invention relates to emulsions of water in fluorocarbon, to the preparation of said emulsions, and to the use of said emulsions in the dyeing of textiles.
• Organic solvents evaluated for this purpose include perchloroethylene, which is strongly absorbed by some textiles and consequently is not readily removed and recovered.
• Most of the dyes used have substantial solubility in these solvents, requiring relatively high concentration initially, because of the relatively poor partition coefficient between solvent and fiber, and the relatively large fraction of the dye which is retained in the solvent and remains as unrecoverable residue after the distillation step of the solvent recovery.
• fluorinated materials have been proposed for use in dyeing in lieu of organic solvents. Characteristically, such fluorinated materials are substantially inert to the dyes and the textile fabrics involved and they neither dissolve in the textile fabric nor show any substantial dissolving power toward the dyes. Rather than a merephysical mixtue of dye and fluorinated material, a small amount of water is dispersed throughout the fluorinated material. Dyes are associated primarily with the water phase and are retained with the water by the fabric. Substantially all of the fluorinated material, in fairly pure form, is recovered from the process, and almost all of the dye supplied to the system remains on the fabric. Although even slight losses of the relatively expensive fluorinated material would be economically significant, such unavoidable losses are more than compensated for by the increased efficiency of dye utilization.
• relatively stable water-in-fluorocarbon emulsions useful as carriers for dyes in the dyeing of textiles, are provided by using as the emulsifier an inert, non-ionic emulsifier which is soluble in the fluorocarbon phase and contains one or more fluoroaliphatic non-polar hydrophobic moieties and also contains one or more solubilizing hydrophilic nonionic moieties which render the emulsifier soluble or even miscible in water.
• the fluoroaliphatic moieties in the emulsifiers used in this invention are generally monovalent aliphatic moieties. They can be straight chain, branched chain, and, if sufficiently large, cyclic, or combinations thereof, such as alkylcycloaliphatic radicals. At least percent of the non-catenary carbon valence bonds in thefluoroaliphatic moiety areattached to fluorine atoms.
• the fluoroaliphatic skeletal chain can include catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms, such hetero atoms providing stable linkages between fluorocarbon groups and not interfering with the inert character of the fluoroaliphatic moiety or radical.
• fluoroaliphatic moiety can have a large number of carbon atoms, not more than 20 carbon atoms will be adequate and preferred since larger radicals usually represent a less efficient utilization of fluorine than is possible with smaller fluoroaliphatic moieties.
• the fluoroaliphatic moiety will have 3 to 20 carbon atoms, preferably 6 to about 12, and will contain 4078 weight percent, preferably 50-77 weight percent, carbon-bonded fluorine. While the fluoroaliphatic moiety can be completely fluorinated, e.g.
• substituents on the carbon chain can be non-ionic, non-polar substituents such as chlorine, bromine, or hydrogen atoms, such substituents not adversely affecting the stability of the emulsifier molecule nor its solubility in the fluorocarbon phase, which can be as low as 0.01 weight percent.
• the water solubilizing moieties in the emulsifiers used in this invention are polar hydrophilic moieties which are non-ionic, since the ionic hydrophilic moieties which are non-ionic, since the ionic hydrophilic moieties have a tendency to form fluorocarbon-inwater emulsions under most conditions.
• the solubilizing moiety is generally a monovalent organic radical, such as a polyester moiety or, preferably, a poly(oxyalkylene) moiety, the nature and hydrophilicity of the solubilizing moiety being such as to render the emulsifier soluble in water at 25C. to the extent of at least 0.1 weight percent. Solubilization may even be strong enough to render the emulsifier miscible with water. For those emulsifiers only slightly soluble in water, compatibility can be determined by measuring the solubility of water in the emulsifier.
• the fluoroaliphatic hydrophobic moieties can be bonded or linked to the hydrophilic moieties by valence bonds or by any suitable linkage or radical which is free of polar groups, such as hydroxyl, carboxyl, and the like, and is stable to hydrolysis under conditions the emulsion is used.
• the linkage between the two moieties can be a polyvalent aliphatic linkages, e.g. CH C- H and CH CH(CH polyvalent aromatic, e.g.
• the emulsifiers used in this invention will contain 30 to 60 weight percent carbon-bonded fluorine, the fluorine content of the emulsifier residing in said fluoroaliphatic moieties to insure adequate solubility of the hydrophobic moieties in the fluorocarbon phase of the emulsion.
• the fluoroaliphatic moieties and hydrophilic moieties are balanced to insure solubility of the emulsifier in water and the fluorocarbon phase.
• One class of emulsifiers useful in preparing the waterin-fluorocarbon emulsions of this invention can be represented by the general formula:
• R is a fluoroaliphatic hydrophobic radical
• R is a solubilizing hydrophilic monovalent non-ionic organic radical
• O is a linkage through which R, and R are covalently bonded together
• n, and z are integers of l to 3.
• a particularly useful class of emulsifiers is that expressed in terms of the formula:
• emulsifiers falling within the scope of the above formulas are known in the art, e.g. U.S. Pat. Nos. 2,915,554 (Ahlbrecht and Morin) and 3,470,258 (Tesoro).
• the emulsifiers with poly(oxyalkylene) solubilizing moieties can be obtained by several methods, such as by the oxyalkylation or condensation of ethylene oxide and 1,2-propylene oxide with fluorinecontaining compounds having at least one Zerewitinoff active hydrogen atom, e.g. R SO N(R')CH CH(OH)C- H OH, where R is lower alkyl or hydrogen.
• Said oxyalkylation can be accomplished by known procedures, e.g.
• the emulsifiers used in this invention will be a mixture of compounds whose average composition is described by the formulas given above.
• the fluorocarbon phase of the emulsions of this invention is stable, inert, non-polar, oleophobic and hydrophobic, highly fluorinated liquid and usually will be a mixture of compounds having such nature.
• the fluorocarbons can be straight chained, branched, or cyclic, or a combination thereof, such as alkylcycloaliphatic, and can be saturated or contain ethylenic unsaturation.
• the skeletal chain of the fluorocarbon can include catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms, such hetero atoms providing stable linkages between fluorocarbon groups and not interfering with the inert character of the fluorocarbon.
• the fluorocarbon has about 6 to about 25 carbon atoms, the maximum number of carbon atoms being dictated by the desired volatility for processing ease. Generally, the fluorocarbon will have a boiling range between 55 and 200C, preferaby to C. Generally, the fluorocarbon will contain about 60 to 76 weight percent carbon-bonded fluorine. The fluorocarbon can contain some hydrogen or chlorine, i.e. less than about 5 atom percent on the basis of fluorine content, but is preferably substantially completely fluorinated.
• Fluorocarbons useful in this invention are known and readily available, usually as mixtures of fluorocarbons.
• U.S. Pat. Nos. 3,250,807, 3,250,808, and 3,274,239 disclose fluorinated oils, made by polymerization of perfluoropropylene oxide, which can be stabilized, e.g. as disclosed in U.S. Pat. Nos. 3,214,478, 3,242,218, and 3,342,875, to provide fluorocarbons useful in this invention, said stabilization converting functional or active end groups to inert carbon-bonded hydrogen or fluorine by reaction with fluorinating agents, protic bases, or ultraviolet radiation.
• 2,500,388, 2,519,983, 2,594,272, and 2,616,927 describe the preparation of inert, highly fluorinated compounds, such as hydrocarbons, ethers, and tertiary amines, said preparation involving electrochemical fluorination in anhydrous HF medium.
• Commercial fluorocarbons useful in this invention are 3M Companys Fluorinert liquids, e.g. FC-40, FC43, and FC-48, described in that companys bulletins Y1LBG(R) (87-1 )RC and Y-lFC-48(60.2)R.
• the emulsifier can be added to the water component or to the fluorocarbon component, and the two components mixed with agitation in any suitable fashion.
• the relative amount of the water component emulsified in the fluorocarbon component can vary from as much as a few weight percent to as much as 50 weight percent, based on the total weight of the emulsion.
• the water-in-fluorocarbon emulsions of this invention are relatively stable. Standing at room temperature, the emulsions generally do not separate into their two phases in less than about 15 minutes, although emulsions which separate in a short a period of time as /2 to 3 minutes can be used under conditions of continuous agitation.
• the emulsions of this invention are particularly suitable in the dyeing of textiles.
• the dye can be suspended in the fluorocarbon and the water and emulsifier subsequently added, or the water, emulsifier, and dye can be mixed and added to the fluorocarbon with suitable agitation.
• the emulsion can be made up in a separate reservior and subsequently added to the dyeing vessel or the fluorocarbon can be circulated through the dyeing vessel and the water-dye-emulsifier mixture added to the circulating fluid through, for example, a centrifugal pump which can provide the agitation necessary for adequate dispersion. It is generally preferable to prepare the complete emulsion prior to contact with the fabric.
• the dyes because of their generally more polar nature, associate themselves with the aqueous phase and the fluorocarbon phase remains relatively free of both water and dye.
• the relative amount of the water, fluorocarbon, and emulsifier components in the emulsion will vary, depending upon the particular class of fabrics used, the temperatures and times desired for treatment, and the specific dye involved. While the process is applicable to both batch and continuous processes, batch processing is conventional and will be used for the illustrative discussion. Generally sufficient fluorocarbon must be used to at least fill the system in the presence of the fabric to be treated, including sufficient to fill the reservoirs, connecting piping, pumps and other auxiliary equipment. The amount of dye used depends upon the particular fabric and the dye and the intensity of color desired. A mixture of dyes can be used to provide special effects or to provide suitable coloration of fabrics composed of a mixture of fibers.
• an amount of dye between about 0.2 and 5 percent by weight of the fabric is sufficient.
• the amount of water used depends not upon the amount of fluorocarbon present but on the amount of water required to uniformly wet-out the fabric. If too little water is used, only a portion of the fabric will be wet and only this portion will be dyed. Conversely, if too much water is used, an aqueous phase will remain after dyeing is complete, and this aqueous phase will retain dye. Such unused dye represents uneconomical loss and gives rise to pollution problems. It is not necessary to provide as much water as fabric can possibly hold. In general, the amount of water to be used as an aqueous phase will be about to 100 percent, preferably to 50 percent, by weight of the fabric.
• the amount of emulsifier to be used will be sufficient to provide the emulsion with the desired degree of stability, which will depend on conditions of use of the emulsion, e.g., the degree of agitation, mode of transport, equipment used for dyeing, etc. Generally, the amount of emulsifier will be about I to 25 weight percent, preferably 2 to 10 weight percent, based on the weight of the water phase
• the process is suitable for any of the dyeable textile fabrics, such as those based on cotton, wool, rayon, acetate, polyamide, polyester, polycrylonitrile or mixtures of such fibers. Because of the difficulties of dyeing by present techniques, the method is particularly suitable for dyeing of fabrics based wholly or in part on polyester fibers, such as poly(ethyleneterephthalate) fibers.
• the dyes are suitably those presently used to dye industrial and decorative fabrics, including those used for garments, drapery and upholstery.
• the dyes (including pigments) suitable for use in this invention are those which are water-wettable in the presence of fluorocarbon. While the process is suitable for use with substantive dyes, such as the conventional acidic or basic dyes, it is particularly beneficial in the application of disperse dyes, which have relatively low or moderate solubility in water and which require subsequent elevated temperature processing to insure satisfactory leveling, penetration, and permanence. Because of the much greater efficiency of application to the fabric, deep shades require the same amount of dye on the fabric as in conventional processes, but substantially less dye is used overall due to substantially complete retention of dye by the fabric.
• modifying and assisting components such as penetrants, carriers, levelers, and the like, as normally used in the dyeing industry, can also be added to the emulsion, although generally their use need not be as closely controlled, nor are such large quantities required, because of the improved efficiency of the process.
• the fluorocarbon has little or no solvent power toward oils, sizes, and other possible contaminants on the fiber, it is desirable .that the fabric be thoroughly scoured prior to dyeing.
• EXAMPLE l Into a one-lite glass cylinder with an outlet built at the bottom of the cylinder and an inlet at the top, the inlet and outlet being suitably connected by polyvinyl chloride tubing to a centrifugal pump, was placed 400 ml. of a mixture (commercially available as fluorinert FC-82) of isomeric fluorocarbons having a composition corresponding to CgFwO and C F and 0.8 gram of emulsifier, C F SO N(C I-I )C H O(C I-I O) H, and 8 grams of water in which was suspended 0.124 gram of SET YELLOW 4RL (Color Index No. 26074), a disperse dye.
• FC-82 fluorinert FC-82
• isomeric fluorocarbons having a composition corresponding to CgFwO and C F and 0.8 gram of emulsifier, C F SO N(C I-I )C H O(C I-I O) H
• the circulating pump was operated until a stable emulsion was obtained, about 2 min. Twenty grams of an undyed piece of rayon-acetate velvet was loosely rolled and placed in the cylinder. Pumping was resumed. Within 5 min. a uniform deposition of the dye was obtained over the whole piece of fabric and substantially all of the water was absorbed, leaving a clear, almost colorless fluorocarbon phase. The dyed fabric was then dried and the dried fabric retained its uniformity of color.
• EXAMPLE 2 Using the equipment of Example 1, a water-influorocarbon emulsion was formed from 400 ml. of a C fluorocarbon mixture (boiling at about C. and commercially available as fluorinert" FC77), 0.2 g. of the emulsifier of Example 1, 4 ml. of water, and 0.15 g. of the dispersed dye Amocel Pink B (Color Index No. 60710). Fifteen g. of white polyester fabric was inserted in the cylinder and circulation continued until the dye was absorbed on the fabric, dye deposition being uniform throughout the fabric. The remaining fluorocarbon phase was clear and essentially colorless.
• EXAMPLE 3 Three water-in-fluorocarbon emulsions were prepared by different techniques using a C fluorocarbon mixture with a boiling point of about 100C. (and commercially available as EC-77) and the emulsifier used in Example 1.
• Example 4 The first run of Example 4 was repeated twice using an emulsifier of the formula C F SO N(CH )C H O(C H O) H, in one run x being 1 and in the other run x being 10. Results obtained were similar to those of Example 1.
• Example 6 The first run of Example 4 was repeated four times using an emulsifier of the formula C F SO N(C H )C H,O(C H O),H, where x varied for each run, viz. 1.29, 4.19, 6.7, and 9.2.
• the stability of the dispersions was better for the emulsifiers with lower ethylene oxide content.
• EXAMPLE 7 The first run of example 4 was repeated three times, using in each run different emulsifier, viz. C F SO N(- 2 5) 2 4 3 6 )3 v CF3(CF2)58C2H4O(C2- H4O)1H and C8F17SO2N(C2H5) 2 4 )a( 3 s )s
• the dispersions obtained remained stable while gently rolled in the bottle.
• said fluorocarbon having 6 to 25 carbon atoms and a skeletal chain which is straight chain, branched, cyclic, or combinations thereof and can contain catenary oxygen or trivalent nitrogen hetero atoms, or both kinds of said hetero atoms, said hetero atoms being bonded only to carbon atoms, said fluoroaliphatic moiety of said emulsifier containing 40 to 78 weight percent carbon-bonded fluorine and having 3 to 20 carbon atoms, said fluoroaliphatic moiety being straight chain, branched chain, cyclic, or combinations thereof, and having at least percent of the non-catenary carbon valence bonds attached to fluorine atoms and up to 25 percent of said valence bonds being bonded to non-ionic, non-polar substituents, and wherein the skeletal chain of said fluoroaliphatic moiety can contain catenary oxygen or
• hydrophilic moiety is poly(oxyalkylene) wherein the number of oxyalkylene units is in the range of 1 to 25.
• the emulsion of claim 1 further comprising a dye dispersed or dissolved in the aqueous phase of said emulsion.
• said fluorocarbon having 6 to 25 carbon atoms and a skeletal chain which is straight chain, branched, cyclic or combinations thereof and can contain catenary oxygen or trivalent nitrogen hetero atoms, or both kinds of said hetero atoms, said hetero atoms being bonded only to carbon atoms, said fluoroaliphatic moiety of said emulsifier containing 40 to 78 weight percent carbon-bonded fluorine and having 3 to 20 carbon atoms, said fluoroaliphatic moiety being straight chain, branched chain, cyclic, or combinations thereof and having at least 75 percent of the non-catenary carbon valence bonds attached to fluorine atoms and up to 25 percent of said valence bonds being bonded to non-ionic, non-polar substituents, and wherein the skeletal chain of said fluoroaliphatic moiety can contain catenary oxygen or tri
• the emulsion of claim 9 further comprising a dye dispersed or dissolved in the aqueous phase of said emulsion.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

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Cited By (10)

Citations (1)

• 1972
  • 1972-05-15 US US00253163A patent/US3792977A/en not_active Expired - Lifetime
• 1973
  • 1973-04-10 ZA ZA732472A patent/ZA732472B/xx unknown
  • 1973-05-04 NL NL7306231A patent/NL7306231A/xx unknown
  • 1973-05-14 BR BR3509/73A patent/BR7303509D0/pt unknown
  • 1973-05-14 BE BE131073A patent/BE799492A/xx unknown
  • 1973-05-14 AU AU55656/73A patent/AU452398B2/en not_active Expired
  • 1973-05-14 IT IT49926/73A patent/IT988181B/it active
  • 1973-05-14 CH CH683773D patent/CH683773A4/de unknown
  • 1973-05-14 JP JP48053473A patent/JPS4947681A/ja active Pending
  • 1973-05-14 FR FR7317304A patent/FR2184786A1/fr not_active Withdrawn
  • 1973-05-14 GB GB2286373A patent/GB1424098A/en not_active Expired
  • 1973-05-14 DE DE2324301A patent/DE2324301A1/de active Pending

Patent Citations (1)

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