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
  • D06P1/44—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
  • D06P1/62—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 with sulfate, sulfonate, sulfenic or sulfinic groups
  • D06P1/628—Compounds containing nitrogen
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
  • D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
  • D06B11/0079—Local modifications of the ability of the textile material to receive the treating materials, (e.g. its dyeability)
• • 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
  • D06P3/10—Material containing basic nitrogen containing amide groups using reactive 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
  • D06P3/854—Textiles which contain different kinds of fibres containing modified or unmodified fibres, i.e. containing the same type of fibres having different characteristics, e.g. twisted and not-twisted fibres
• • 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
• • 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
• • 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
  • Y10S8/924—Polyamide fiber

Definitions

• the present invention concerns a dyeing process for the production of multi-colour effects on natural and synthetic polyamide fibre material, as well as the multicoloured fibre material produced thereby.
• Synthetic polyamide material has already been reserved using colourless fibre-reactive compounds, in which compounds however the fibre-reactive group must be bound to the rest of the molecule of the reserving agent via an -SO --bridge (cf. British Pat. No. 1,189,726).
• a process has now been found by which it is possible to permanently reserve not only natural but also synthetic polyamide fibre material, not only by printing but also by the padding method and the cold-storage process, and even by the exhaustion process.
• the present invention has a large range of possible applications. This process makes possible hitherto unattainable contrast effects on natural and synthetic polyamide fibre material in the most diverse conditions during its processing. In contrast to the hitherto known printing process, the variety of possible patterns is practically unlimited.
• a further important advantage of the present invention is that the amount of the reserving agent used which is fixed on the fibre is substantially higher than with previously known reserving agents.
• the polyamide material is first pretreated with an aqueous solution of at least one colourless fibre-reactive compound and preferably with a levelling agent, then combined with untreated fibre material and/or with at least one fibre material pretreated in a different manner, and then dyed with a dyestuff or mixture of dyestuffs having affinity for the fibre material.
• the colourless fibrereactive compounds according to the invention are fixed permanently on the fibre material, it is possible in this manner to obtain very beautiful multi-colour effects, e.g. tone-in-tone dyeings, i.e. dyeings which have the same colour in various tones.
• the portion which has been impregnated with the reserving agent according to the invention has a lighter shade than the untreated portion.
• the process according to the invention is characterised in that the colourless, fibre-reactive compound contains per molecule thereof at least one group of the Formula I NHCO--R wherein R represents either or of Formula II F 5 N/ C-Cl -NH-i: ⁇ -F
• fibre-reactive compound serving as reserving agent.
• colourless, fibre-reactive compounds are meant colourless organic compounds containing reactive groups which readily react with the fibre substrates, i.e. such which can form a covalent chemical bond.
• Aromatic radicals of these compounds can contain additional substituents such as, e.g. halogen atoms, hydroxyl groups, and low-molecular alkyl and alkoxy groups.
• the colourless, fibre-reactive compounds according to the invent are water-soluble.
• Suitable watersolubilising groups are, e.g. carboxylic acid groups, acid sulphuric acid ester groups and phosphoric acid ester groups, phosphoric acid groups, acylated sulphonic acid amide groups, and in particular, sulphonic acid groups.
• Particularly advantageous are compounds containing at least one sulphonic acid group.
• the term sulphonic acid group or carboxyl group embraces the free acid, and also salts of these acids, as well as the dissociated state of the acids.
• the colourless fibre-reactive compounds according to the invention are produced according to known methods.
• Preferred as reserving agents are the colourless fibrereactive compounds of the Formula III AD(BD),,A
• the colourless, reactive compounds are applied from aqueous preparations to the polyamide fibres.
• Suitable natural polyamide fibre is, in particular, wool.
• Synthetic polyamide fibres are obtained, for example, from the polycondensation products of adipic acid and hexamethylenediamine (Nylon 6.6), and sebacic acid and hexamethylenediamine (Nylon 6, or from the polymerisation products of e-caprolactam (Nylon 6), or w-aminoundecanoic acid (Nylon 1 l
• the reactive compounds can be applied to the fibre material by known methods, e.g. by the exhaust or impregnation process, whereby the whole substrate is subjected to a uniform treatment.
• the operation is performed in aqueous baths at temperatures of from 80 to 110C, preferably at 90 to 100C; the pH-value of the preparations is 4 to 7, preferably 4 to 6, and is adjusted, if necessary, with organic acids.
• Suitable organic acids are such having one to four carbon atoms, especially formic and acetic acid.
• the preparations can contain further agents, such as e.g. salts, or surface-active agents such as wetting and dispersing agents. Suitable ratios of goods to liquor are between 1 10 and l 40.
• the impregnating baths which can also be in a coazervated form, contain approximately the same additives and, optionally, also thickeners.
• the impregnating process can be carried out, for example, on a padding machine, at temperatures between and 40C.
• the fixing of the fibre-reactive compounds is effected by a cold-storage process of, e.g., 2 to 48 hours duration at room temperature, or by a short duration steaming process.
• the substrate is then washed, and dyed in admixture with fibre material of a different type.
• the fibre-reactive compounds are so fixed on the fibre that they are fast to boiling.
• the amounts in which the colourless, fibre-reactive compounds can be used can vary within wide limits, and are adjusted according to the desired depth of colour of the multicolour effects, and also according to the dyestuffs used. Suitable amounts are about 0.1 to 10 percent by weight, preferably 0.2 to 2 percent by weight, for synthetic polyamide fibre material, and l to 6 percent by weight for W001, relative to the fibre material.
• the material treated according to the invention with the colourless, fibre-reactive compounds is then combined with material not pretreated and/or with at least one fibre material pretreated in a different manner, the combining of the materials being effected, e.g. by mixing, carding, twisting, weaving, embroidering, or knitting.
• pretreated in a different manner is meant that material is used which has been pretreated either with another fibre-reactive compound, or with different concentrations of the same compound.
• the polyamide fibre material pretreated according to the invention can be combined not only with untreated and/or differently pretreated polyamide fibre material, but also with other organic fibres, e.g. with cellulose fibres, especially cotton, polyester or polyacrylonitrile fibres.
• suitable dyestuffs having affinity for the fibre should be used.
• the obtained fibre mixtures are then dyed in the next stage of the process with a dyestuff or dyestufi' mixture having affinity for the fibre, the dyeing being performed in the usual manner, advantageously in the presence of the usual dyeing auxiliaries.
• the usual dyeing auxiliaries are, e.g., condensation products from fatty amines and ethylene oxide, which can be, in addition, quaternised and/or esterified; fatty alcohol/ and alkylphenol/ethylene oxide addition products, which can, optionally, likewise be esterified, and condensation products of fatty acids with lower alkanolamines, as well as polyglycol ethers of these condensation products.
• Suitable as dyestuffs for the process according to the invention are the usual anionic wool dyestuffs which can belong to very diverse classes of dyestuffs. These can be, for example, the commercially important dyestuff classes of the azo, anthraquinone, phthalocyanine, nitro or formazane dyestuffs which can also contain metals bound in complex linkage such as copper, nickel, chromium or cobalt. Suitable azo dyestuffs are, principally, monoazo dyestuffs, e.g.
• phenylazobenzene phenylazonaphthalene, phenylazohydroxyor -aminopyrazole, phenylazoacylacetylarylamide, or those of the analogous naphthylazo series, whereby the aromatic nuclei can be suitably substituted.
• disand polyazo dyestuffs are also suitable.
• the anionic wool dyestuffs which can be used according to the invention can in particular also contain substituents which have affinity to the fibre material, for example substituents having a portion which can be split off as an anion, e.g. mobile fluorine, chlorine, or bromine atoms or sulfo-oxy groups, or double bonds which are capable of addition such as vinyl sulfonyl or vinyl carbonyl groups, or both types of reactive configurations such as in a,B-dichloroor dibromo-acroylamino groups. From the standpoint of dyeing, both those classes of anionic wool dyestuffs which are strongly acid as well as those which dye weakly acid to neutral are suitable.
• the reactive dyestuffs which are derived, in particular, from water-soluble azo and anthraquinone dyestuffs, and contain, as reactive grouping, at least one acylamino radical derived from an a,B-unsaturated aliphatic carboxylic acid containing one to four carbon atoms, or at least one radical convertible by the elimination of acid into such an acylamino radical.
• acylamino radical derived from an a,B-unsaturated aliphatic carboxylic acid containing one to four carbon atoms
• reactive groupings are the radical derived from acrylic acid of the formula CH CH CO (IV) wherein X represents in each case a chlorine or bromine atom.
• the reactive groupings are preferably bound by way of a nitrogen atom to an aromatic ring of the dyestuff molecule.
• the dyestuffs contain as suitable watersolubilising groups, e.g. carboxylic acid groups or sulphonic acid groups. Preferred are such dyestuffs containing at least one sulphonic acid group.
• the polyamide fibre mixture can be dyed in the most diverse conditions during its processing, thus, for example, in loose form or as slubbing, tow, yarn, fabric, knitware, fibre-fleece, or carpet.
• the dyeing is performed in the exhaust process (ratio of goods to liquor ca. 1 20 to l 50) by known methods at temperatures of from 80 to l C, preferably 90 Br Br to 100C; or in the impregnating process on a padding machine at room temperature, whereby fixing of the dyestuff on the fibre is afterwards effected by a shortduration steaming process, or by storage at room temperature for a fairly long period of time, tag. 2 to 48 hours.
• the dye bath can also contain the auxiliaries usual in the dyeing industry, e.g. salts such as sodium sulphate or ammonium sulphate, acids such as acetic acid or formic acid, wetting agents or surface-active compounds as levelling agents, non-ionic compounds, e.g. urea or thiourea, and, optionally, thickeners, the lastmentioned being used especially in the impregnating liquors.
• auxiliaries e.g. salts such as sodium sulphate or ammonium sulphate, acids such as acetic acid or formic acid, wetting agents or surface-active compounds as levelling agents, non-ionic compounds, e.g. urea or thiourea, and, optionally, thickeners, the lastmentioned being used especially in the impregnating liquors.
• the pl-l-values of the dyeing preparations are be tween 4.5 and 6.5, and are adjusted with low-molecular acids, preferably with formic or acetic acid.
• a colourless fibre-reactive compound according to the invention in the pretreatment bath for the reservation of wool there are employed from 2 to 6 percent of a colourless fibre-reactive compound according to the invention, relative to the weight of the goods; 1 percent of an auxiliary consisting of a. 1 part of the adduct from 1 mol of a fatty amine (30 percent of hexadecylamine, 25 percent of octadecylamine and 45 percent of octadecenylamine) and 7 mol of ethylene oxide, quaternised with chloroacetamide, and
• the process according to the invention enables twoor multi-colour effects to be obtained on undyed fibre materials by dyeing in one dye bath, using one or more dyestuffs.
• the colourless, fibre-reactive compounds are so fixed on the fibre that they are fast to boiling, so that, in the actual dyeing process, no migration of these compounds on to the untreated material can occur.
• the process is simple to perform, and a minimum of operational stages is required for the process. No damage to the fibres occurs either during the pretreatment of during the actual dyeing process.
• Example 1 100 parts of wool yarn are treated for one hour at 100 in an aqueous preparation (ratio of goods to liquor 1 40) containing 6 percent of the colourless, fibre-reactive compound of the formula Br Br S0311 A 2.5 percent of acetic acid percent), and 1 percent of an auxiliary mixture consisting of a. 1 part of the adduct from 1 mol of a fatty amine (30 percent of hexadecylamine, 25 percent of octadecylamine and 45 percent of octadecenylamine) and 7 mol of ethylene oxide, quaternised with chloroacetamide, and b.
• the fibre material is wetted for 5 minutes at 50 in a preparation containing the auxiliary and the acid; the dyestuff is then added, the whole heated in 50 minutes to boiling, and dyeing carried out for 1 hour at this temperature. After cooling of the dye bath to 80, the pH- value is adjusted with ammonia to 8.5, and the fibre material then treated for 15 minutes. The dyed material is subsequently rinsed and dried.
• the untreated yarn has been dyed blue, while the treated yarn displays a level light blue shade.
• the goods to liquor ratio may vary between 1 l0 and l 40.
• a similar dyeing is obtained when the dyebath is heated to and dyed for minutes at this temperature.
• Example 2 100 parts of wool yarn are treated for one hour at and 0.6 percent Of the blue dyestuff given in Example 100 in an aqueous preparation (ratio of goods to lithe Untreated P has been y d gr y, While t e quor l 40) containing 6 percent of the colourless, treated part has a level light grey shade.
• the fibre material is after-treated as given in Exam- N NC ⁇ I ple l.
• the dyed goods are then rinsed and dried.
• the dyeing has good fastness properties, especially good wetfastness. 40
• Oz-NH-CHa The untreated yarn has been dyed red, while the 1:2 cobalt complex treated yarn has a level light pink shade.
• Example 3 if the dyestuff in Example 1 is replaced by a mixture percem of the bordeaux dyestuff of mg. @rmula of 0.12 percent of the yellow dyestufi of the formula OH OH I CH: 1 NH-CHg-CI-Ir-O CH; 1:2 cobalt complex Br and 0.2 percent of the grey dyestuff of the formula 0.3 percent of the red dyestuff of the formula OH OH HQN l! r I 0 CH;
• the pH-value of the 50 parts of the thus pretreated fabric and 50 parts of untreated fabric are dyed by the exhaust process at 100 with a dye liquor having, with a goods/liquor ratio of l 40, the following composition:
• the pH-value 2,0 percent of acetic acid 80 percent
• the fibre material Th l-L l f th d li is 5,0 Aft r d in th
• the dyed material iS subsedye liquor is adjusted with ammonia to a pH-value of quently rinsed, and then dried.
• the fibre material treated therein for 15 min- Th ntreated slubbing has been dyed red, whilst the utes at 80; the material is afterwards rinsed and dried.
• untreated slubbing displays a light pink shade.
• Example 7 100 parts of polyamide-6.6-yam (Nylon yarn) are Wool fabric is padded with the following preparation, and squeezed out to 100 percent weight increase: 300 parts urea, 320 parts of a 2.5 percent aqueous solution of a starch/ether thickening, 10 parts of the reaction product of coconut oil fatty acid with 1 mol of diethanolamine, 30 parts of the colourless compound of the formula SOaH 2 parts of acetic acid (80 percent),
• the impregnated fibre material is then stored for 48 hours at room temperature with the exclusion of air, and afterwards rinsed.
• the yarn is subsequently rinsed.
• the goods/liquor ratio can be varied between 1 l0 and l 40.
• the exhaust process may also be carried out for 30 minutes at 105.
• pretreated polyamide yarn 50 parts are combined with 50 parts of untreated polyamide yarn to a knitted fabric and dyed for 1 hour at 100 with an aqueous dyebath containing 0.3 percent of the yellow dyestuff given in Example 0.2 percent of the blue dyestuff given in Example 1, and
• a usual levelling agent can be added to the dyebath in order to avoid any occurrence of streakiness of the polyamide fibre material.
• a knitted fabric is thus obtained having a green twoshade efiect.
• Example 9 NaOOC less compound of that example is replaced by 0.5 percent of the colourless compound of the formula Br Br Br Br and the dyestuff mixture is replaced by 0.5 percent of the dyestuff given in Example 2; the untreated part has been dyed red, while the treated part has a level light pink shade.
• Example 10 Employing the procedure of Example 8, the colourless compound of that example is replaced by 1.5 percent of the colourless compound of the formula SOaH r rBr and the dyebath is replaced by 1 percent of the grey dyestuff given in Example 5 and 3 percent of ammonium sulfate; the untreated part has been dyed grey, while the treated part has a level light grey shade.
• Example 12 Similar results are obtained when the colourless fibre-reactive compound given in Example 8 is replaced by 1 percent of the colourless compound of the formula SOall IIN Hoa
• the dyebath is replaced by 1 percent of the dyestuff of the formula and 3 percent of ammonium sulfate; the untreated part has been dyed red, while the treated part has a level light pink shade.
• Example 13 Similar results are obtained when 100 parts of polyamide 6.6 yarn (Nylon yarn) are pretreated for one hour at 100 in a goods to liquor ratio 0f 1 40 with a bath containing 0.5 percent of the colourless compound given in Example 2, 2 percent acetic acid percent), and 1 percent of the auxiliary mixture given in Example the yarn is then rinsed; and otherwise dyeing is carried out as described in Examples 9 to 12.
• the contrast obtained by the subsequent dyeing is weaker.
• Example 14 Polyamide 6.6 yarn (Nylon yarn) is padded with the following preparation and then squeezed out to percent weight increase:
• the fibre material is subsequently steamed for 45 minutes at 100, and then rinsed.
• a usual levelling agent can be added to the dyebath in order to avoid any occurence of streakiness of the polyamide fibre material.
• a knitted fabric is thus obtained having a green twotone effect.
• A represents hribi- QJ reactive group of the Formula I:
• fects on natural and synthetic polyamide fiber material comprising the steps of pretreating the fiber material with an aqueous solution of a reserving agent which is a colorless fiber-reactive compound and optionally with a levelling agent having affinity for the fiber material, combining the treated fiber material with fiber material that has not been treated with said solution, and dyeing the combined fiber material with a dyestuff having affinity for the fiber material, the improvement wherein the colorless fiber-reactive compound contains at least two substituents per molecule selected from the group consisting of a substituent of formual I: NH CO R and a substituent of formula II:
• R is selected from the group consistingof WW .
• A is a substituent of formula I or formula II; B
• levelreactive compound is of the formula ling agent is a mixture of a. 1 part of the adduct from 1 mol of a fatty amine SOaH (30 percent of hexadecylamine, 25 percent of octa- Br Br decylamine and 45 percent of octadecenylamine) A NH-C o-oH-dm and 7 mol of ethylene oxide, quatemised with chloroacetamide, and b. 1 part of the ammonium salt of the acid sulphuric acid ester of the unquaternised adduct a. 14.
• the level- BY Y ling agent is employed in the dyeing of wool.
• said dye stuffs are selected from water-soluble, reactive azo or anthraquinone dyestufis which contain acyl amino substituents of a,B-unsaturated carboxylic acids having three carbon atoms.
• said dyestuffs are reactive dyestuffs which contain acyl amino substituents of a,B-unsaturated carboxylic acids having three carbon atoms and in the aor B-position a halogen atom.
• Dyed polyamide fibre material having a multicolour effect in which on at least one part of the fibre material a colourless fibre-reactive compound as re serving agent is bound to the fibre, the molecules of said colourless compound being bound to the fibre molecules via at least two group of the Formula I or II given in claim 1, which is bound to an aromatic carbon atom of said colourless compound.
• Dyed mixed fibre material having a multi-colour effect consisting in part of natural and/or synthetic polyamide fibre material, in which on at least one part of the polyamide fibre material a colourless fibrereactive compound as reserving agent is bound to the fibre, the molecules of said colourless compound being bound to the fibre molecules via at least one group of the Formula I or II given in claim 1, which is bound to an aromatic carbon atom of said colourless compound.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Coloring (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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Citations (5)

• 1970
  • 1970-06-11 CH CH880970A patent/CH554453A/xx unknown
  • 1970-06-11 CH CH880970D patent/CH880970A4/xx unknown
• 1971
  • 1971-06-08 US US00150930A patent/US3775045A/en not_active Expired - Lifetime
  • 1971-06-10 NL NL7107984A patent/NL7107984A/xx unknown
  • 1971-06-10 FR FR7121143A patent/FR2100749B1/fr not_active Expired
  • 1971-06-10 BE BE768329A patent/BE768329A/xx unknown
  • 1971-06-10 GB GB2737371A patent/GB1337598A/en not_active Expired
  • 1971-06-11 CA CA115411A patent/CA936308A/en not_active Expired

Patent Citations (5)

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