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
  • 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
  • D06P3/34—Material containing ester groups
  • D06P3/36—Material containing ester groups using dispersed dyestuffs
• • 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
  • Y10S8/921—Cellulose ester or ether

Definitions

• This invention relates to dyed materials and relates more particularly to dyed organic derivative of cellulose textile materials.
• gasfading which is also called acid-fading
• gas-fading may cause a material colored with a blue anthraquinone dye to take on a reddish hue, for example.
• this type of fading results from the presence in the atmosphere of certain oxides of nitrogen, which oxides are produced during combustion of coal, gas or other fuels.
• inhibitors comprising basic nitrogen compounds, e.g. amines, are often incorporated into the textile material, before, during, or after the dyeing thereof.
• the amine-type inhibitors show a tendency to discolor the textile material. This discoloration. is particularly noticeable where the textile material to which the inhibitor is applied has a basis of a cellulose ester of low hydroxyl content, since such textile materials are generally exposed during processing to much higher temperatures than are employed for textile materials made from other cellulose derivatives.
• textile materials of cellulose acetate of low hydroxyl content commonly known as cellulose triacetate
• heat-treated cellulose triacetate textile materials have very high safe ironing points, on'the order of 240 C.
• the O-fading of the colored material is particularly noticeable where the colored material is exposed to an atmosphere containing the aforesaid oxidative substances before the colored material has been heat-treated. This may take place when a fabric is dyed and then stored before heattreating.
• Another object of this invention is the provision of an organic derivative of cellulose textile material which,
• This invention finds its greatest utility when the organic derivative of cellulose is a cellulose ester of low hydroxyl content, since, as pointed out above, in the normal treatment and use of such cellulose esters the elevated temperatures employed will generally tend to discolor the usual basic nitrogenous gas fading inhibitors.
• These cellulose esters contain not above 0.29, preferably 0 to 0.12, hydroxyl groups per anhydroglucose unit in the cellulose molecules thereof.
• the invention is also applicable, however, to organic derivatives of cellulose having a higher hydroxyl content, e.g. ripened, secondary or partially esterified cellulose.
• the carbon-to-carbon unsaturation may be present in the organic derivative of cellulose molecule which comprises the textile material by being bound to the anhydroglucose units through their oxygen atoms, e.g. a cellulose acetate crotonate yarn having a low free hydroxyl content and a few percent of crotonyl groups can be heat treated and dyed with normally O-fading susceptible dyes without change in color.
• the carbon-to-carbon unsaturation is present in a substance which is added to the organic derivative of cellulose in any suitable manner before, during or after the dyeing thereof.
• it is incorporated into the organic derivative or cellulose before the latter is formed into filaments.
• the inhibitor may be added to the spinning dope, e.g.
• a solution of cellulose triacetate in a methylene chloride-containing solvent for example, a solvent comprising methylene chloride alone or admixed with a lower alkano l such as methanol, ethanol, propanol, isopropanol, or butanol or mixtures of such alkanols.
• the inhibitor may also be applied in the form of a solution or an aqueous dispersion thereof, to the organic derivative of cellulose after it has been formed into filaments, especially where the inhibitor would be only slightly soluble in the spinning dope, e.g. dimethallylidene pentaerythritol which has limited solubility in methylene chloride.
• a cellulosederivative which is inherently an inhibitor of O-fading due to the presence of unsaturations i.e. a cellulose derivative wherein some of the cellulose hydroxyl groups are esterified or etherified with unsaturated acids or alcohols, e.g. cellulose methallylsuccinate, allyl ether of cellulose acetate, methallyl ether of cellulose acetate propionate, and the like.
• the O-fadinig inhibition is achieved by adding unsaturated substances to a cellulose. ester of a lower alkanoic acid.
• unsaturated additives which can be used in accordance with the present invention include diallyl phthalate, diallyl suc cinate, acrylic or crotonic acid esters of monoor polyhydric alcohols or unsaturated polyesters of p'olyhydric alcohols and polycarboxylic acids.
• unsaturated polyesters are the linear esters of such saturated glycols as ethylene glycol, 1,2-propylene glycol,
• the unsaturated polyesters may also be formed from unsaturated glycols such as 1-allyloxy-2,3-propanediol, butcnediol and butyne diol and a polycarboxylic acid which may be unsaturated, e.g. the polyester of butyne diol and methallyl succinic anhydride, or saturated, e.-g. the polyester of butyne diol and succinic anhydride.
• unsaturated organic compounds may also be employed.
• a highly crotonate'd cellulose acetate crotonate can be added to cellulose acetate to bring the average degree of unsaturation Within the recited ranges.
• Allyl cellulose and other ethers or esters with a high degree of tunsaturation can be similarly employed.
• unsaturated hydrocarbons which are compatible with the organic derivative of cellulose in the amounts present. Examples of such hydrocarbons are the liquid homopolymers of butadiene and the liquid copolymers of butadiene and styrene (e.g. the product known as C-oil).
• Unsaturated ethers and acetals can also be employed, e;g.
• di-acro-lein acetal of pentaerythritol (dicrotonylidene pentaerythritol), triallyl cyanurate, and the like.
• trial'lyl cyanurate contains nitrogen atoms
• the compound is not basic since the nitrogen of the triaziue ring is not basic and does not result in the color change occasioned by conventional basic nitrogenous gas-fading inhibitors.
• Those additives are preferred which have relatively high molecular weights, e.g. at least 100 and preferably above 500. Such compounds have greater fastness to washing and will not be lost through vaporization during heat-treating.
• the unsaturation of the inhibiting group should be non-conjugated, i.e.
• polyesters having higher acid numbers give better O-fading resistance, they render processing somewhat more diflicu-lt so that additives of lower acid numbers are preferred,
• the preferred additives are non-volatile linear polyesters of molecular weights of at least about 500, possessing non-conjugated unsaturations in short side chains, and having acid numbers below about 50.
• the proportion of unsaturated additive employed is desirably in the range of about 1 to 10% by weight of the cellulose derivative. preferably about 1 to 3%.
• an amount of the inhibitor larger than that which is compatible with the organic derivative of cellulose or an amount sufiicient to change appreciably the physical properties of said onganic derivative of cellulose.
• ester to which the inhibitor is added is a cellulose acetate of very high acetyl value, preferably of acetyl value 61 to 62.5%, calculated as combined acetic acid.
• other organic acid esters of low hydroxyl content may be employed. Examples of such other esters are cellulose propionate, cellulose butyrate, cellulose acetate-propionate, cellulose acetate-butyrate and cellulose acetate-formate.
• the unsaturated O-fading inhibitors may also be incorporated into textile materials having a basis of other organic derivatives of cellulose such as those cellulose esters of higher hydroxyl content, e.g. cellulose acetate of acetyl value 53 to 56%, calculated as combined acetic acid.
• the coloring of the textile material may be carried out in a manner well known to the art, preferably by applying one or more dyestuffs of the type known as dispersed cellulose acetate dyestuffs.
• the material may be immersed in a heated aqueous bath having a temperature of, for example, 60 to 95 C. and containing one or more dispersed cellulose acetate dyestuffs together with a dispersing agent therefor, such as sodium lignosulfonate, sulfonated naphthalene-formaldehyde condensation product or soap.
• a dispersing agent therefor such as sodium lignosulfonate, sulfonated naphthalene-formaldehyde condensation product or soap.
• any desired hue may be imparted to the material by the use of appropriate mixtures of dyestuffs, as by using mixtures of varying amounts of red, blue and yellow dyestuffs.
• the blue dyestuff used is of the type which is highly resistant to gas-fading.
• This type of dyestutf may be described as those which show negligible fading when applied in the amount of 0.3% based on the fabric weight and in the absence of a gas-fading inhibitor to a'textile fabric of cellulose acetate of acetyl value 61.5%, and subjected to 3 units of gas-fading exposure in accordance with Test Method 23-52 as given in the Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists 1954, page 87.
• dyestuifs are 1,8-dihydroxyp (beta hydroxyethyl) anilido 5 nitroanthraquinone; 1-hydroxy-4-anilido-anthraquinone; 1,8-dihydroxy- 4 m (alpha hydroxyethyl) anilido 5 nitroanthraquinone.
• the rate of dyeing may be increased by the use of a suitable dyeing assistant, e.g. pine oil, tripropyl phosphate, tributyl phosphata diethyl phthalate, methyl salicylate or an N,N-dihydroxyethyl fatty acid amide, such as N,N-dihydroxyethyl capramide.
• a suitable dyeing assistant e.g. pine oil, tripropyl phosphate, tributyl phosphata diethyl phthalate, methyl salicylate or an N,N-dihydroxyethyl fatty acid amide, such as N,N-dihydroxyethyl capramide.
• Such dyeing assistants may be applied to the material, as by padding, before dyeing or may be added to the dyebath.
• the ethylenically unsaturated O-fading inhibitor may also be applied to the textile material during the dyeing thereof. To this end the inhibitor may be dispersed in the aqueous dyebath
• the textile material may be colored by applying thereto a printing paste containing the desired dyestuffs.
• the textile material may be colored by passing it through a heated solution of the dyestuff in a liquid polyhydric alcohol such as ethylene glycol. Any other coloring methods known to the art may be employed.
• the textile material having a basis of a cellulose ester of low hydroxyl content is given a heat-treatment, preferably during or after the application of the coloring material thereto.
• This treatment serves to increase the penetration of the dye into the cellulose ester and increases the wa'sh-fastness, resistance to gas-fading, resistance .to orfading and resistance to crocking of the dyed material.
• Heat-treatment also effects an improvement in the physical properties of the textile material.
• it effects an improvement in the safe ironing temperature, its resistance to glazing, its resistance to shrinkage on pressing with moist steam, its resistance to mussing or wrinkling on laundering, its resistance todegt'adafor returning vaporized glycol to the mixture.
• heat-treatment of a fabric of cellulose acetate of low hydroxyl content raises its safe ironing temperature by at least about 20 C., e.g. up to 220 C. or higher. Heat-treatment generally results in an increase in the crystallinity and crystalline order index of the cellulose ester material.
• heat-treatment will depend somewhat on the particular textile material being treated, for example, on its Weight and construction.
• temperatures of 190 C. or above are employed.
• the material is heated to a temperature of about 220 to 235 .C. for about 7 to 30 seconds.
• temperatures e.g. 190 C.
• the heating time is considerably longer, for example to minutes.
• Still lower heat-treatment temperatures may be employed when the heat is applied by means of saturated steam under a pressure of for example to 40 pounds per square inch or by means of a heated bath of ethylene glycol or other polyhydric alcohol.
• the coloring and heat-treatment may be combined, as by subjecting the textile material for a sufficient period of time to a suitable liquid medium containing a dyestuff dispersed or dissolved therein.
• a suitable liquid medium containing a dyestuff dispersed or dissolved therein.
• the material may be dyed and heat-treated in an aqueous medium maintained under superatmospheric pressure at a temperature of 90 C. or above or in a solution of the dyestuff in hot ethylene glycol.
• the term heat-treatment as employed herein accordingly has reference to high temperature, and the like, as well as treatments at moderate temperatures with solvents or assistants to achieve similar improvements.
• the unsaturated O-fading inhibitors of this invention may be used in combination with amine-type gas-fading inhibitors.
• the amount and type of amine should be such that there is little discoloration pending application and 1% of an unsaturated polyester combined by the reaction of methallyl succinic anhydride and glycol.
• discoloration may be reduced by subjecting the textile material to a bleaching agent, after, or preferably before, the heat-treatment operation. 7
• Example I A mixture of 1 mole of methallyl succinic anhydride and 1.1 moles of ethylene glycol is heated and stirred under nitrogen atmosphere for 5 hours, on an oil bath kept at 200 C., in a vessel equipped with a condenser The resulting polyester, which has an acid number of 16 or 17, is purified by dissolving it in a mixture of 90% of methylene chloride and 10% of methanol and boiling the resulting solution in the presence of charcoal.
• Example 11 To a spinning solution containing 21 parts of cellulose acetate of 61.5% acetyl value, in 79 parts ofa mixture of 90% of methylene chloride and 10% of methanol 7 there is added 0.63 part of the purified polyester produced in Example I. The solution is spun into yarn and woven into a fabric, which is then dyed with l-methylamin'o-4-hydroxy-ethylamino-anthraquinone and there- Thus, there may 'sponding to 4 on the International Gray Scale, after hours of the fading exposure. When the above example is repeated, except that the material of Example I is I omitted the dyed and heat-treated fabric shows a shade change corresponding to a rating of only 2-3 after 100 hours of fading exposure.
• Example III A mixture of 1 mole of methallyl succinic anhydride and 1.05 moles of ethylene glycol is heated and stirred under nitrogen atmosphere for 2 hours, on an oil bath kept at C., in a vessel equipped with a reflux condenser for returning vaporized glycol to the mixture and withdrawing water of condensation. The temperature is raised to 210-220 C. for 5 hours longer, the pressure is reduced to 190 mm. Hg and heating is continued for 3 hours. The resulting polyester, which has an acid number of 3.0 and a molecular weight of about 1000, is purified by dissolving it in a mixture of 90% by weightof methylene chloride and 10% by weight of methanol and boiling the resulting solution in the presence of charcoal.
• Example IV To a spinning solution containing 21 parts of cellulose acetate of 61.5% acetyl value, in 79 parts of a mixture of 90% of methylene chloride and 10% of methanol there is added 0.63 part of the purified polyester produced in Example 1H (1 methallyl group unsaturation for 23 anhydroglucose units) and .01 part of Interchemical Blue B dyestuff, ie a mixture of 1,4-bis-methylaminoanthraquinone and 1-methylamino-4-beta-hydroxyethylamino-anthraquinone. The solution is spun into yarn and woven into a fabric, which is then scoured for 10 minutes at 40 C.
• the number of units of color change AB is determined according to the following equation:
• the color change is only 5.2 units as compared with 15.3 for a control fabric similarly treated but containing no O-fading inhibitor.
• the fabric of this example is about as resistant to gasfading and ultraviolet light as the control containing no O-fading inhibitor.
• the presence of the inhibitor does not change the lack of affinityof the yarn for acid dyes v under standard wool-dyeing conditions, showing that the 75' inhibitor-containing "yarn could' be used for producing cross-dyed effects in wool blends.
• the viscosity characteristics of the inhibitor-containing dope are the same as those for the dope from which the control fabric is prepared.
• Example V (a) Cellulose acetate of 61.5% acetyl value is dissolved to form a 21% by weight solution in a 90-10 weight mixture of methylene chloride-methanol. The solution is divided into a test specimen and a control specimen there being added to the test specimen 3% by weight of the polyester of Example III, based on the cellulose acetate. Both solutions are spun to form filament yarns and the yarns are each Woven into fabrics. An inhibitor-containing fabric sample and an inhibitor-free fabric sample are prescoured at 180 F. for one hour in 0.5 gram per liter of soap.
• Inhibitor-containing and inhibitor-free scoured and unscoured samples are then dyed with 0.05% by weight of. the dyestuff l,8-dihydroxy-4-p-(beta-hydroxyethyl)- anilido-S-nitroanthraquinone and tested to determine the extent of O-fading after 40 hours exposure to an O-fading atmosphere.
• the fabrics containing no inhibitor undergo severe shade changes (a rating of 2) whether or not prescoured.
• the inhibitor-containing fabric which is not prescoured undergoes a very slight shade change (4-5) while the inhibitor-containing fabric which is prescoured undergoes a slight to moderate change (34).
• Samples of unscoured inhibitor-containing and inhibititor-free fabrics as produced in (a) are dyed for two hours at 176 F. with Eastone Red GLF, i.e. 2- methylsulfone 4 nitro 4' (N hydroxyethyl N- beta-difluoroethyl)-amino-azobcnzene.
• Eastone Red GLF i.e. 2- methylsulfone 4 nitro 4' (N hydroxyethyl N- beta-difluoroethyl)-amino-azobcnzene.
• the fabric is inhibitor-free its dye content is found to be 0.52% whereas the inhibitor-containing fabric picks up 0.73% of dyestuff, indicating that the inhibitor acts as a dyeing accelerant.
• the washfastness of the fabrics are equal.
• Example VI A mixture of 1 mole of methallyl succiuic anhydride and 1.05 moles of ethylene glycol is stirred with an equal weight of xylene under nitrogen atmosphere and heated to reflux using a system to condense and separate water vapor while returning xylene. After the theoretical quantity of water is collected, i.e. in about 4 hours, refluxing is continued for an additional 3 hours. The xylene is then distilled off and the temperature is raised slowly to 200 C. While the pressure is reduced to 5 mm. Hg and held for 20 minutes. After cooling, the polyester is purified as in Example III. Its acid number is 113.0 and its molecular weight is about 1000. It is incorporated into a spinning dope along with dye, spun, and tested as in Example IV. The dyed material after 70 hours exposure to an O-fading atmosphere undergoes aggregater change AE of 3.7 units.
• Example VII Allyloxypropanediol is substituted for the glycol in Example III to give a product with an acid number of 9.8 and a molecular weight of 850.
• the ester is incorpo rated into a spinning dope which is treated as in Example IV.
• the color change AE after 70 hours of O-fading is 3.1.
• Example IX The linear polyester of maleic anhydride and butene diol, prepared in the same manner as the polyester in,-
• Example VI and having an acid number of 5.2 and a molecular weight of 1307, is used in repeating the process of Example IV.
• the color change Ali is 5 .5 units after 70 hours of O-fading.
• Example X Succinic anhydride and butene diol are substituted for the anhydride and glycol in the process of Example VI and the resulting polyester exhibits an acid number of 1.6 and a molecular weight of 1300. It is used in repeating the process of Example IV and after 70 hours O-fading the fabric. undergoes a color change 31E of 5.6 units.
• Example XI A mixed cellulose acetate crotonate having a crotonyl value of 46% and an acetyl value of 20.2% calculated as the combined acids, is prepared as follows:
• the proportion of cellulose acetate crotonate solution added to the cellulose triacetate spinning dope is varied so that in successive runs the weight percentage of the cellulose acetate crotonate based on the cellulose triacetate is 3%, 4.5% and 10%.
• the dyestuff employed in Example IV is added to the modified spinning solutions and they are separately spun into filaments, beingafter treated as in Example IV. , The color change AE after 70 hours of O-fading are respectively 5, 4 and 3 units.
• Example XII Three parts by weight of cellulose are pretreated for 2 hours with 35% by weight of glacial acetic acid. At 0 C. the cellulose is mixed with an esterification mix comprising 2.5 parts of acetic anhydride, 3.15 parts of acetic. acid, 0.82 part of crotonic acid, 0.68 part of crotonic anhydride and'0.21 part of sulfuric acid. A peak temperature of 45 C. is reached in minutes and The resulting dope is mixed with Water to precipitate the cellulose mixed ester, which is washed with alcohol, ether and then dried.
• the ester has a crotonyl content of 4.2% and an acetyl content of 57.7%, calculated as combined acids, and has 0.09 free hydroxyl per anhydroglucose unit.
• the ester is dissolved, spun into yarn, and woven into a fabric which when subjected to O-fading: for 70 hours undergoes a colorchange AE of.3.4 units.
• Example XIII Dopes are prepared as in Example IV, substituting for the inhibitor there disclosed 3% based on the weight of the cellulose triacetate of the following compounds: diethyl phthalate, diallyl phthalate, diallylidene pentaei'ythritol, dicrotonylidene pentaerythritol, triallyl cyanurate, C-oil and the polyester of succinic anhydride and ethylene glycol. Fabrics prepared as in Example IV are tested for color change and the values are given in the following table along with those for fabrics produced in accordance with Examples IV and VI to XII.
• a heat-treated material exhibiting a safe-ironing temperature of at least 220 C. and having a basis of organic acid esterified cellulose containing at most 0.29 hydroxyl groups per anhydroglucose unit in the cellulose molecule thereof, there being present in said textile material at least one isolated non-conjugated aliphatic carbon-to-carbon unsaturation per 50 anhydroglucose units for protecting said textile material against O-fading when said material is colored with an anthraquinone dye, said unsaturation being present in molecules free of saltforming groups.
• a textile material dyed with a dye normally subject to O-fading said textile material having a basis of organic acid esterified cellulose containing at most 0.29 hydroxyl groups per anhydroglucose unit in the cellulose molecule thereof, there being present in said textile material at least one isolated non-conjugated aliphatic carbon-to-carbon unsaturation per 50 anhydroglucose units for protecting said dye against O-fading, said dye being highly resistant to gas fading as indicated by negligible fading when applied in the amount of 0.3% based on the fabric weight and in the absence of a gas-fading amass 10 a inhibitor to a textile fabric of cellulose triacetate hav ing an acetyl value of 61.5% by weight calculated as acetic acid and subjected to 3 units of gas-fading exposure in accordance with Test Method 23-52 of the American Association of Textile Chemists and Colorists.
• a heat-treated textile material exhibiting a safeironing temperature of at least 220 C. and having a basis of organic acid esterified cellulose containing at most 0.29 hydroxyl groups per anhydroglucose unit in the cellulose molecule thereof, at least one oxygen atom per 50 anhydroglucose units of the cellulosemolecule being bound to a radical containing an isolated nonconjugated aliphatic carbon-to-carbon unsaturation for protecting said textile material against O-fading when said material is colored with an anthraquinone dye.
• a heat-treated textile material exhibiting a safe ironing temperature of at least 220 C. and having a basis of cellulose acetate crotonate containing at most 0.29 hydroxyl groups per anhydroglucose unit in the cellulose molecule thereof, there being present at least one crotonyl group per 50 anhydroglucose units for protecting said textile material against O-fading when said material is colored with an anthraquinone dye.
• a textile material having a basis of an organic acid ester of cellulose and having incorporated therein a minor amount of compatible compound free of basic nitrogen groups and having isolated aliphatic non-conjugated carbon-to-carbon unsaturation for protecting said textile material against O-fading when said material is colored with an anthraquinone dyestulf.
• a textile material having as basis of a cellulose organic acid ester containing at most 0.29 hydroxy groups per anhydroglucose unit in the cellulose molecule thereof, said cellulose ester having incorporated therein a minor amount of a compatible compound free of salt-forming groups and having isolated non-conjugated aliphatic carbon-to-carbon unsaturation for protecting said textile material against O-fading when said material is colored with an anthraquinone dye, said compound selected from the group consisting of diallyl phthalate, diallyl succinate, acrylic esters of monohydric and polyhydric alcohols, crotonic esters of monohydric and polyhydric alcohols, unsaturated polyesters of polyhydric alcohols and polycarboxylic acids, unsaturated cellulose esters, unsaturated hydrocarbons, unsaturated ethers and unsaturated acetals.
• a textile material having a basis of cellulose acetate containing at most 0.29 hydroxyl groups per anhydroglucose unit in the cellulose molecule thereof, said cellulose acetate having incorporated therein an unsaturated compound free of basic nitrogen groups and containing a plurality of isolated non-conjugated aliphatic carbonto-carbon unsaturations.
• the unsaturated compound is a cellulose derivative selected from the group consisting of ethers and esters having isolated non-conjugated aliphatic carbon-to-carbon unsaturation, said derivative being present in an amount ranging from about 1 to 1 0% by weight of the cellulose acetate and including suflicient unsaturations to provide at least one unsaturation for each 50 anhydroglucose units of the cellulose acetate.
• a spinning solution comprising a solution in a solvent comprising methylene chloride, of a cellulose acetate having an acetyl value of at least 61%, calculated as combined acetic acid and, as an inhibitor of O-fading, a minor amount of a compound free of salt-forming groups and having isolated non-conjugated aliphatic carbon te-carbon unsaturation.

Landscapes

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

Priority Applications (2)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24855882

Family Applications (1)

Country Status (2)

Cited By (2)

Citations (5)

• 0
  • BE BE634967D patent/BE634967A/xx unknown
• 1958
  • 1958-01-24 US US710870A patent/US3021188A/en not_active Expired - Lifetime

Patent Citations (5)

Also Published As

Similar Documents