US3802841A - Nitro aromatic hydrocarbon,amino nitro aromatic & nitro aromatic phosphine oxides on aromatic polyamide-imide as light fading inhibitors for dyes thereon - Google Patents

Nitro aromatic hydrocarbon,amino nitro aromatic & nitro aromatic phosphine oxides on aromatic polyamide-imide as light fading inhibitors for dyes thereon Download PDF

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US3802841A
US3802841A US26244172A US3802841A US 3802841 A US3802841 A US 3802841A US 26244172 A US26244172 A US 26244172A US 3802841 A US3802841 A US 3802841A
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nitro aromatic
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textile article
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS, OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/64General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642Compounds containing nitrogen
    • D06P1/6422Compounds containing nitro or nitroso groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/392Nitroso compounds; Nitro compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS, OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/24Polyamides; Polyurethanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS, OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/24Polyamides; Polyurethanes
    • D06P3/242Polyamides; Polyurethanes using basic dyes
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92Synthetic fiber dyeing
    • Y10S8/924Polyamide fiber

Abstract

An improved process of dyeing or printing textile articles composed of thermostable polymers, i.e. aromatic polyamides and polyamide imides, and the textile articles so dyed or printed, wherein the dyeing or printing solution contacting the textile article contains as an adjuvant, in an amount sufficient to provide improved light fastness to the textile article, an ultraviolet light absorbing nitro aromatic compound. The nitro aromatic compound is preferably selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.

Description

United States Patent 1 Robin 7 1 Apr. 9, 1974 NITRO AROMATIC IIYDROCARBON, AMINO NITRO AROMATIC & NITRO AROMATIC PHOSPI-IINE OXIDES ON AROMATIC POLYAMIDE-IMIDE AS LIGHT FADING INHIBITORS FOR DYES THEREON [75] Inventor: Jean-Baptiste Robin, Dardilly,

France [73] Assignee: Rhone-Poulene-Textile, Paris,

France [22] Filed: June 14, 1972 [21] Appl. No.: 262,441

[52] U.S. Cl 8/165, 8/171, 8/172,

, 260/45.9 R [51] Int. Cl D06p 5/02 [58] Field of Search 8/165, 171

[56] References Cited UNITED STATES PATENTS 3,101,236 8/1963 Salvin 8/165 1/1965 Newland 260/459 R 4/1966 Newland 260/459 R OTHER PUBLICATIONS American Dyestuff Rep., Dec. 5, 1065-1071 [57] ABSTRACT An improved process of dyeing or printing textile articles composed of thermostable polymers, i.e. aromatic polyamides and polyamide imides, and the textile articles so dyed or printed, wherein the dyeing or printing solution contacting the textile article contains as an adjuvant, in an amount sufficient to provide improved light fastness to the textile article, an ultraviolet light absorbing nitro aromatic compound. The nitro aromatic compound is preferably selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.

21 Claims, N0 Drawings NITRO AROMATIC HYDROCARBON, AMINO NITRO AROMATIC & NITRO AROMATIC PHOSPHINE OXIDES ON AROMATIC POLYAMIDE-IMIDE AS LIGHT FADING INHIBITORS FOR DYES THEREON The present invention is directed to a novel improved process for dyeing or printing textile articles having a base of a thermostable synthetic polymer as well as the novel dyed or printed textile article itself. More specifically, the present invention is directed to such novel process and product wherein in the dyeing or printing of a textile article having a base of a thermostable synthetic polymer, improved light resistance is created by utilization as an adjuvant an ultraviolet light absorbing nitro aromatic compound.

Prior to the development of the present invention, it has been known that textile articles having a base of a thermostable polymer can be dyed with plastosoluble dyes. While such dyeing can be carried out utilizing plastosoluble dyes, this method is not totally satisfactory, particularly for dark colors. This is due to the fact that the plastosoluble dyes do not appreciably fix on the thermostable materials, even after addition of a carrier to the dye bath, the carrier generally improving the fixing of the plastosoluble dye. Still further, the shade which is obtained on the thermostable polymer textile article utilizing the plastosoluble dye is not sufficiently light fast. These disadvantages with respect to the dyeing of textile articles having abase of a thermostable polymer with plastosoluble dyes have led to the discarding of this method as commercially suitable.

In view of the drawbacks of the use of plastosoluble dyes for the dyeing of textile articles having a base of thermostable polymer, it was proposed to introduce into the thermostable polymer acid sites so as to provide the fibers produced an affinity for basic dyes. While this procedure effectively allowed the dyeing of the fibers produced from the thermostable polymers to be dyed with basic dyes due to the affinity for the acid sites, it was unfortunately found that the dyeings or printings obtained had poor light fastness. Here again, this is an industrial or commercial drawback to this dyeing procedure.

The foregoing disadvantages of previously proposed processes for dyeing textile articles having a base of thermostable synthetic polymer have been overcome in accordance with the present invention wherein the textile articles having a base of the thermostable polymer are dyed or printed with a dyeing or printing solution or bath containing as an adjuvant at least one ultraviolet light absorbing nitro aromatic compound in an amount sufficient to provide improved light fastness to the textile article. Preferably, in accordance with the present invention, the nitro aromatic derivatives having the ability to absorb ultraviolet rays are selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.

Accordingly, it is a principal object of the present invention to provide a process for dyeing or printing textile articles having a base of a thermostable synthetic polymer and the article so dyed or printed, wherein such process eliminates the inherent deficiencies and disadvantages of previously proposed processes.

lt is a further object of the present invention to provide a novel improved process for dyeing or printing textile articles composed of thermostable synthetic 2 polymers, wherein the improvement resides in dyeing or printing such textile article utilizing as an adjuvant in the dyeing or printing solution at least one ultraviolet light absorbing nitro aromatic compound.

A still further object of the present invention comprises such improved process for dyeing or printing textile articles having a thermostable synthetic polymer base, wherein at least one ultraviolet light absorbing nitro aromatic compound selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides is employed as an adjuvant in an amount sufficient to provide light fastness.

A still further object of the present invention is to provide such a process for the production of textile articles dyed or printed and having improved light fastness, the textile articles containing 1 to 5 percent by weight of a nitro aromatic compound having the ability to absorb ultraviolet light.

Still further objects of the novel process and product of the present invention will become more apparent from the following more detailed description.

The foregoing objects and advantages of the present invention are achieved through a dyeing or printing process wherein a textile article composed of a thermostable synthetic polymer is dyed or printed with a dyeing or printing solution containing as an adjuvant, in an amount sufficient to provide improved light fastness to the textile article, an ultraviolet light absorbing nitro aromatic compound, Preferably, the nitro aromatic compound having the ultraviolet light absorbing property is selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.

in connection with the process of the present invention, the term textile article that can be effectively dyed or printed embraces not only textile fabrics but other articles in the form of yarns, flocks, knits, unwoven materials and the like. Accordingly, the textile article to be effectively dyed or printed in the process of the present invention can take any conventional form.

In accordance with the present invention, the expression thermostable synthetic polymer" is meant to embrace those synthetic polymers which have a high heat resistance, i.e. a heat resistance in the order of 350 to 500C. While such thermostable synthetic polymers can take various forms, the polymers most suited in carrying out the process of the present invention are of the aromatic polyamide type or polyamide-imide type.

The aromatic polyamides which are advantageously dyed or printed in accordance with the process of the present invention are well known thermally stable synthetic polymers which are conventionally prepared in the form of textile fibers, filaments and yarns in the 1 production of textile articles.

The aromatic polyamides are characterized predominantly by the recurring structural unit which do not form a polyamide during polymerization, the term lower referring to less than five carbon atoms.

Such aromatic polyamides are well known in the art and they and their preparation are described, for example, in Hill, Kwolek and Sweeny, U.S. Pat. No. 3,094,51 1, the entire disclosure of which is hereby incorporated by reference. The description of Hill et al., column l, line 48, to column 5, line 20, is particularly incorporated. Aromatic polyamides may be obtained by reacting a diisocyanate or a diacid such as described in US. Pat. No. 3,642,715.

The aromatic polyamides are also reaction products of an aromatic diacid chloride with an aromatic diamine, the aromatic diacid chloride being of the formula wherein Ar, is a divalent aromatic radical, i.e. it contains resonant'unsaturation, and Hal is a halogen atom from the class consisting of chlorine, bromine, and fluorine. The aromatic radical may have a single, multiple, or fused ring structure. One or more hydrogens of the aromatic nucleus may be replaced by non-polyamideforming groups such as lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy, and the like. The terms lower alkyl and lower alkoxy" and lower carbalkoxy" refers to groups containing less than five carbon atoms.

' Diacid chlorides which may be utilized to prepare the polyamides include isophthaloyl chloride and lower alkyl isophthaloyl chlorides, such as methyl-, ethyl-, propyl-, etc., isophthaloyl chlorides. There may be more than one alkyl group attached to the aromatic ring as in the case of dimethyl, trimethyl, tetramethyl, diethyl, triethyl, and tetraethyl isophthaloyl chlorides. It is not necessary that all of the alkyl substituent groups be the same because compounds such as 2- 'methyl-4 ethyl isophthaloyl chloride and 2-methyl-4- ethyl-S-propyl isophthaloyl chloride may be utilized,

.the total number of carbon atoms in all the substituentgroups (non-polyamide-forming groups) attached to the aromatic ring in the latter two compounds being three and six, respectively. In place of an alkyl group, the aromatic ring in isophthaloyl chloride may be substituted with one or more lower alkoxy groups such as, for example, methoxy-, ethoxy-, propoxy-, butoxy-, etc., isophthaloyl chlorides. As with alkyl-substituted isophthaloyl chlorides it is desirable that the total number of carbon atoms in the alkoxy groups attached to the aromatic ring be less than about five, but it is not necessary that all of the alkoxy groups be the same. Representative of such compounds are vdimethoxy-, trimethoxy, tetramethoxy-, and diethoxy-isophthaloyl chlorides, and 2-methoxy-4-ethoxy isophthaloyl chloride. Halogen-substituted isophthaloyl chlorides as examplified by chloro-, bromo-, and fluoroisophthaloyl chlorides may be used. More than one halogen may be attached to the aromatic ring and dihalo isophthaloyl chlorides. such as dichloro-, dibromo-, difluoro-, or chlorobromo chlorofluoro-isophthaloyl chlorides'are useful as are similar trihalo and tetrahalo isophthaloyl chlorides. The halogens in these compounds may be the same or different as in the case of the dihalo compounds.

Other isophthaloyl chlorides which may be used include nitro and lower carbalkoxy isophthaloyl ch rides. One or more of the latter groups may be attached to the aromatic nucleus along with one or more alkyl, alkoxy, or halogen groups. Thus, it will be apparent that the aromatic radical of the isophthaloyl chloride may contain one or more of any combination of lower alkyl, lower alkoxy, halogen, nitro, phenyl, lower carbalkoxy, or other nompolyamide-forming groups.

In addition to isophthaloyl chlorides and substituted isophthaloyl chlorides specified above, corresponding unsubstituted and substituted terephthaloyl chloride may also be used. The substituted terephthaloyl chlorides correspond to the substituted isophthaloyl chlorides described above and include lower alkyl, lower alkoxy, halogen, nitro, phenyl, and carbalkoxy substituted terephthaloyl chlorides. There may be one or more or a combination of these substituents attached to the aromatic ring so long as the total number of carbon atoms in all the substituents does not exceed nine. Representative terephthaloyl chloride compounds which may be mentioned include, in addition to the terephthaloyl chloride itself, methyl-, ethyl-, propyl-, butyl-, etc., terephthaloyl chlorides, methoxy-, ethoxy-, propoxy-, butoxy-, etc., terephthaloyl chlorides, chloro-, bromo-, dichloro-, chlorobromo-, etc., terephthaloyl chlorides and nitro and lower carbalkoxy terephthaloyl chlorides.

In addition to the single ring diacid chlorides specitied above, multiple ring diacid chlorides in which the acid chloride groups are oriented meta or para with respect to each other are also useful in this invention. Exemplary of such compounds are 4,4- methylenedibenzoyl chloride, 4,4'-oxydibenzoyl chloride, 4,4-sulfonyldibenzoyl chloride, 4,4'-dibenzoyl chloride, 3,3-oxydibenzoyl chloride, 3,3-sulfonyldibenzoyl chloride, and 3,3'-dibenzoyl chloride, the cor responding bromides and fluorides, and similar compounds in which one or both of the aromatic rings contains one or more or a combination of lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy groups.

The diamines useful as reactants in forming the aromatic polyamides are compounds of the formulas HgN-AI'y-JQHg and R HNAt' NHR where R is hydrogen or lower alkyl and Ar, is a divalent aromatic radical as defined above and the --Nl-l and NHR groups are oriented meta or para with respect to each other. The diamines may contain single or multiple rings as well as fused rings. One or more hydrogens of the aromatic nucleus may be replaced by nonpolyamide-forming groups such as lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy as mentioned above. The aromatic nucleus of the diamines may be identical to any of the aromatic radicals mentioned above for the diacid chlorides, and the diamine utilized in any given instance may contain the same or different aromatic radical as the diacid chloride utilized. The total number of carbon atoms in the substituent groups attached to any aromatic ring should not exceed nine.

Exemplary diamines which may be utilized in this invention include meta-phenylene diamine and lower alkyl substituted meta-phenylene diamine such as methyl-, ethyl-, propyl-, etc., meta-phenylene diamine; N,N'-dimethylmetaphenylene diamine, N,N'-diethylmetaphenylene diamine, etc. There may be more than one alkyl group attached to the aromatic ring as in the case of dimethyl, trimethyl, tetramethyl, diethyl, triethyl, and triisopropyl meta-phenylene diamine. The alkyl substituent groups need not be the same because compounds such as 2-methyl-4-ethyl meta-phenylene diamine and 2-methyl-4-ethyl-5-propyl metaphenylene diamine may be utilized. In place of an alkyl group, the aromatic ring may be substituted with one or more lower alkoxy groups suchas, for example, methoxy-, ethoxy-, propoxy-, butoxy-, etc., meta-phenylene diamine. Other representative aromatic diamines which may be utilized include dimethoxy, trimethoxy, tetramethoxy, diethoxy meta-phenylene diamine, and 2 methoxy-4-ethoxy meta-phenylene diamine. Halogensubstituted meta-phenylene diamine as exemplified by chloro, bromo, and fluoro meta-phenylene diamine may be utilized. More than one halogen may be attached to the aromatic ring. The halogens in these compounds may be the same or different as in the case of the dihalo compound. Other meta-phenylene diamines which may be used include nitro and lower carbalkoxy meta-phenylene diamines. One or more of the latter groups may be attached to the aromatic nucleus along with one or more alkyl, alkoxy, or halogen groups so long as the total number of carbon atoms in the substituents attached to an aromatic ring does not exceed nine.

in addition to meta-phenylene diamine and substituted meta-phenylene diamines specified above, the corresponding unsubstituted and substituted paraphenylene diamine compounds may also be used. There may be one or more or a combination of substituents attached to the aromatic ring so long as the total number of carbon atoms in all substituents attached to an aromatic ring does not exceed nine.

in addition to the single ring aromatic diamines specified above, multiple or fused ring aromatic diamines in which the amino groups are oriented meta or para with respect to each other are also useful in this invention. Exemplary of such compounds are 4,4- diphenylmethene 4,4-oxydiphenyldiamine, 4,4'-sulfonyldiphenyldiamine, 4,4'-diphenyldiamine, 3,3-oxydiphenyldiamine, 3,3'-sulfonyldiphenyldiamine, and 3,3'-diphenyldiamine, and the corresponding compounds in which one or both of the aromatic rings contains one or more or a combination of lower alkyl, lower alkoxy, halogen, nitro, sulfonyl, lower carbalkoxy groups and the total number of carbon atoms in the substituent groups attached to an aromatic ring does not exceed nine.

It should be obvious from the foregoing description that any or all of the conventional aromatic polyamides having high heat resistance can be advantageously dyed or printed in accordance with the process of the present invention. In this regard, the present invention is not limited to any specific type of aromatic polyamide but any of those conventionally employed in the production of textile articles is applicable.

A further type of thermostable synthetic polymer suitably employed in accordance with the present invention is of the polyamide-imide type, i.e. polymers obtainedthrough the reaction of a diamine or one or its derivatives and an acid anhydride or one of its derivatives. Derivatives of diamines are aromatic diisocyanates such as toluylene diisocyanate, 4 4diisocyanatop ny an t 4,4.qiisocy nawsli hcnylnroranq 4 4'diisocyanatodiphenylether etc. Generally, in the production of the polyamide-imide type thermostable synthetic polymer, one or more diamines is reacted with a polycarboxylic acid or derivative, preferably a tricarboxylic acid. In this respect, any of the diamine reactants set forth above with respect to the preparation of the aromatic polyamide can be advantageously employed in connection with the production of polyamide-imide type thermostable synthetic polymers. The polycarboxylic acids which are advantageously employed in the production of the polyamide-imide type thermostable synthetic polymer, include, for example, benzenel ,2,4-tricarboxylic acid (trimellitic acid), benqrhen a 3t3f i hqrsyliquas sitnanht ene- 245 tricarboxylic acid, etc. Of course, derivatives of these acids can advantageously be employed. Still further, in the production of the polyamide-imide type thermostable synthetic polymer a dibasic acid or derivative thereof is generally employed in the reaction system so as to produce the amide-imide linkage. Such dicarboxylic acids include any of those previously discussed in connection with the preparation of the aromatic polyamide.

In connection with the applicable polyamide-imide type thermostable synthetic polymers suitably employed in accordance with the present invention, reference is made to U.S. Pat. No. 2,421,024 and British Pat. No. 570,858 which illustrate the preparation of such polymeric materials having fiber-forming characteristics. Accordingly, the disclosures of these references are herein incorporated by reference, noting again that any of the conventionally employed polyamideimide type thermostable synthetic polymers can be advantageously dyed or printed in accordance with the process of the present invention.

In addition to the aromatic polyamides and polyamideimide type thermostable synthetic polymers, other conventional thermostable synthetic polymers can be advantageously dyed or printed in accordance with the process of the present invention. For example, mention is made of the heterocyclic polymers prepared from diamino-diamido compounds and polycarboxylic acid derivatives as set forth, for example, in U.S. Pat. No. 3,639,342 as well as the polybenzimidazoles, described, for example, in various patent literature as well as in the Journal of Polymer Science, Vol. L, pages 51 l 539, 1961, under Polybenzimidazoles, New Thermally Stable Polymers" by Herward Vogel and C. S. Marvel. Similarly, polyamides such as described, for

example, in U.S. Pat. No. 3,179,632 and British Pat..

No. 1,058,390 find utility in the process of the present invention. Accordingly, as indicated previously, the expression thermostable synthetic polymer" is meant to embrace any and all of the foregoing and equivalent synthetic polymers having a high heat resistance, i.e. a heat resistance of 350 500C.

In addition to the employment of the polymers per se in the dyeing or printing process of the present invention, the thermostable synthetic polymers can be advantageously modified by introduction of acid groups which favor coagulation of the polymer in the spinning bath and give to the polymer an affinity for basic dyes. Such technique of modifying polymers by introduction of acid groups so as to provide an affinity for basic dyes is, of course well known in the art.

As indicated previously, textile articles composed at least in part of the thermostable synthetic polymers described above are dyed or printed in accordance with the present invention and a textile article having improved light fastness is obtained, by dyeing or printing the textile article through contact with a dyeing or printing solution containing a specifically identified adjuvant comprising an aromatic nitro compound having ultravioletlight absorbing capabilities. In this regard,

the aromatc nitro compounds which are employed as the adjuvant in accordance with the present invention are those compounds which contain in their molecule at least one aromatic ring having a nitro group. in this regard, the nitro aromatic compounds can be of the nitro aromatic hydrocarbon type such as, for example, nitrobenzene and alpha-nitronaphthalene or can be of the nitro aromatic amine type such as, for example, iamino 2-nitrobenzene, l-amino 3-nitrobenzene, lamino 4-nitrobenzene, l-acetylamino 4-nitrobenzene, l-methylZ-amino 4-nitrobenzene, l-methyl 3-nitro 4- aminobenzene, l-methyl 2-amino 5-nitroben2ene, 1- amino 2-methoxy 4-nitrobenzene, l-amino 2-nitro 4- phenetidine, l-methyl 3-methoxy 4-amino 6- nitrobenzene and 1,3-dimethyl 2-nitro 4- aminobenzene.

Still further, the nitro aromatic compound employed as the adjuvant in the dyeing or printing process of the present invention may be of the nitro aromatic phosphine type such as methyl-bis(N- nitrophen'yhphosphine oxide.

it should be readily recognized that the foregoing is merely a representative listing of suitable nitro aromatic compounds which can be advantageously employed in accordance with the present invention and, in fact, any nitro aromatic compound having the ability to absorb ultraviolet light can be advantageously employed as the adjuva'nt in the dyeing or printing process of the present invention so as to create improved light fastness for the textile article dyed or printed therewith. Accordingly, the present invention is not in any way to be limited to the specific nitro aromatic compounds exemplified above.

When employing the nitro aromatic compound as an adjuvant in the dyeing or printing bath or solution, the amount of such adjuvant is not critical and, the nitro aromatic compound need only be employed in an amount sufficient to create the desired light fastness in the dyed or printed textile article. Preferably, however, the amount of nitro aromatic compound employed should be that which allows l to 5 percent, preferably l.5 to 3 percent, by weight of the nitro aromatic compound torernain on the dyed or printed textile article, the percentages being based upon the weight of the textile material. Noting that from l to 5 percent, preferably 1.5 to 3 percent, by weight of the nitro aromatic compound should remain on the textile article, the amount of nitro aromatic compound to be employed in any particular dyeing or printing bath or solution can be easily calculated based upon the weight and pick-up of of the article to be dyed. Still further, due to the fact that the nitro aromatic compounds which adhere tothe textile article are those which provide the improved light fastness, those which are insoluble or just slightly soluble in water are preferred since such nitro aromatic compounds have been found to fix particularly well on the material to be dyed or printed.

The dyeing or printing solution into which the adjuvant is incorporated can be any typically employed solution or bath for dyeing or printing textile articles. in this regard, an aqueous solution of a suitable dye is advantageously utilized in accordance with the present invention, the dye bath or solution optionally containing other adjuvants such as carriers, equalizing agent, etc. It should be recognized in this regard, however, that the nature of the dye or printing bath or solution is not critical to the present invention and any such bath or solution conventionally employed can be utilized as long as the same contains the nitro aromatic compound as an adjuvant.

The dyes which are utilized in the dyeing or printing solution can be any conventional dye which has been employed in connection with the dyeing of the abovenoted thermostable synthetic polymers. Accordingly,

the present invention is not in any way to be limited to any specific dye or class of dyes. Preferably, however, the dyes employed in accordance with the present invention are the conventionally used plastosoluble dyes with basic dyes being most preferrred, particularly where the polymer has been modified by the inclusion of acid groups. Again, however, it should be clearly recognized that any conventionally employed dye can be advantageously utilized in carrying out the process of the present invention which, as previously noted, is

predicated upon the presence of the nitro aromatic compound in the dyeing or printing solution or bath.

in carrying out the dyeing or printing process of the present invention, it is not necessary to strictly adhere to rigid parameters although it can generally be said that the dyeing or printing should be carried out under such conditions that the nitro aromatic compound fixes on the textile material to be dyed in the amounts previously noted. Generally, it is preferred to carry out the dyeing or printing process of the present invention at a temperature between and 140C., most preferably about C., for a period of time of about 2 hours using a standard pressure dyeing autoclave. After the dyeing or printing operation, the textile article may be treated in any conventional manner although it is preferred to rinse the dyed or printed article with hot water, i.e. about 80C. The washed textile article may then be immersed in a bath which contains a conventional non-ionic wetting agent and, if benzaldehyde is used, as the carrier, sodium bisulfite may additionally be present. Dyeing of the textile article is then carried out in a conventional manner. Each of these after-treatments is one which is conventionally adopted in the dyeing or printing of textile articles.

As indicated previously, and as will be illustrated hereinafter, through the process of the present invention by employing the nitro aromatic compound as an adjuvant in the dyeing or printing of thermostable polymers, it is possible to produce dyed textile articles with high yield and good equalizing. Additionally, the articles dyed or printed in accordance with the present invention show improved light fastness without losing their wash resistance, resistance to treatment with solvents and resistance to wear.

The process of the present invention and product produced thereby will now be illustrated by the following examples, which examples are in no way to be deemed as limiting the scope of the present invention.

in these examples, Cl means Colour index, second edition 1956 (and supplements) published by the Society of Dyers and Colourists" and the American Association of Textile Chemists and Colorists."

indication of light fastness is established by a scale of indices going from I (very slight fastness) to 8 (exceptional fastness) according to the method of evaluating fastness to artificial light (xenon lamp) described on page l7l ff of the Code ECE de Solidite' [ECE Fastness Code], 1958 edition, first supplement 1963, and second supplement 1966, published by the Association pour l'Etude et la Publication des Methodes de Determination de Solidite' [Association for the Study and Publication of Methods of Determination of Fastness] 12, rue dAnjou, 75, Paris (8e).

Example 1 A fabric weighing 125 g/m made up in warp and weft of filaments of 235 dtex (210 den), of a polyamide-imide, obtained by the reaction of 100 moles of 4 4'diisocyanatodiphenylmethane, with 80 moles of trimellitic anhydride, 16 moles of terephthalic acid and 4 moles of sulfo-S-isophthalic sodium salt, is dyed in a bath with a pH of 3-4, containing: I

g of l-methyl 2-amino 4-nitrobenzene,

1.25 g of a basic dye orange Cl 48 040,

g of benzaldehyde as carrier,

l g of formic acid, I

amount sufficient for 1,000 g of water, with a bath ratio of l /20 (l g of material to be dyed per 20 cc of bath).

The fabric is dyed for 2 hours at 130C in an autoclave under pressure. The dyed fabric is then rinsed in hot water (80C) and immersed for 30 minutes in an aqueous bath heated to 95C and containing 5 cc/liter of sodium bisulfite solution 35Be' and l cc/liter of a condensate of ethylene oxide and a fatty alcohol. Drying is performed in an oven at 60C. The fabric which is obtained has an equalized orange dyeing and its light fastness is 5. In comparison, the light fastness of an identical control fabric dyed under the same conditions but without introduction of l-methyl 2-amino 4- nitrobenzene in the dye bath, is only 2-3. The improvement of the light fastness remains after washings and dry cleanings.

Example 2 A fabric identical with that described in Example 1 is dyed under the same conditions as Example 1, except the dye bath contains:

7.5 g of nitrobenzene,

2.5 g of a basic dye red Cl 48 020,

20 g of benzaldehyde as carrier,

1 g of formic acid,

amount sufficient for 1,000 g of water.

The fabric which is obtained has a Bordeaux red coloring with a light fastness of 3. The control fabric dyed under the same conditions, but without the presence of nitrobenzene has a light fastness of only 2.

The improvement in light fastness remains after washings and dry cleanings.

Example 3 A fabric identical with that of Example 1 is dyed under the same conditions as Example 1, except the dye bath contains: I

7.5 g of methyl-bis(N-nitrophenyl) phosphine oxide,

2.5 g of a basic dye red Cl 48 020,

20 g of benzaldehyde as carrier,

1 g of formic acid,

amount sufficient for 1,000 g of water.

The fabric obtained has a Bordeaux red coloring and a light fastness of 3-4. A control fabrc dyed under the same conditions but without vthe presence of methylbis(N-nitrophenyl) phosphine oxide has a light fastness of only 2. I r

Improvement of the light fastness remains after washings and dry cleanings.

Example 4 A fabric identical with that described in Example 1 is dyed under the same conditions as Example 1. except the dye bath contains:

5 g of l-methyl 2-amino 4-nitrobenzene,

2.5 g of a basic dye blue Cl 42 140,

20 g of benzaldehyde as carrier,

1 g of formic acid, 7

amount sufficient for 1,000 g of water.

The fabric obtained has a rather dark blue-green coloring, and a light fastness giving the results indicated in Table l. The table also has a comparison with a control fabric dyed under the same conditions but without the presence of l-methyl 2-amino 4-nitrobenzene and that of an identical fabric dyedv under the same conditions but by replacing l-methyl 2-amino 4-nitrobenzene with the same amount of 2-hydroxy 3,5-methyl-phenylbenzotriazole (standard ultraviolet ray absql'hcfli w Table 1 Control With 2-hydroxy With l-methyl 3,5-methylphenyl Z-amino benzotriazole 4-nitrobenzene Light fastness 4 4-5 6-7 Example 5 A fabric identical with that described in Example 1 is dyed under the same conditions, except the dye bath contains:

5 g of l-methyl 2-amino 4-nitrobenzene,

2.5 g of a dispersed dye orange Cl 11 005,

20 g of benzaldehyde as carrier,

amount sufficient for 1,000 g of water.

The fabric which is obtained has a rather dark orange coloring and a light fastness of 4. In comparison, the light fastness of a control fabric dyed under the same conditions, but without the presence of b l-methyl 2- amino 4-nitrobenzene, is only 2.

The improvement in the light fastness lasts after washings and dry cleanings.

Example without the presence of a-nitronaphthalene ,'is only 2.

Improvement of the light fastness lasts after washings and dry cleanings.

. Example 7 Flock, having a count per strand is 2.2 dtex (2 den) and a section length of 51 mm, of an aromatic polyamide obtained by the reaction of 50 moles of metaphenylene diamine and 50 moles of isophthalic acid chloride, is dyed under thesame conditions as in Example 1, except the dye bath contains:

g of l-methyl 2-amino 4-nitrobenzene,

2.5g of a basic dye blue Cl 51 005,

g of benzaldehyde as carrier,

1 g of formic acid,

sufficient amount for 1,000 g of water. a

The fabric which is obtained has a blue coloring an a light fastness of 3. In comparison, the light fastness of a control fabric dyed under the same conditions, but without l-methyl 2-amino 4-nitrobenzene, is only 2.

it can be seen from the foregoing that through the process of the present invention a considerable improvement is created with respect to the dyeing or printing of textile'articles composed at least in part of l a thermostable synthetic polymer. As clearly illustrated from the foregoing, the textile articles dyed or printed in accordance with the present invention show improved light fastness without deterioration of any advantageous properties. a

. marily with respect to the foregoing exemplification, it

is to be understood that the present invention is in no way to be deemed as limited thereto but, rather, must be construed as broadly as all and any equivalents thereof.

What is claimed is:

l. In a process of dyeing or printing a textile article composed of an aromatic polyamide and polyamideimide polymer wherein said aromatic polyamide and polyamide-imide polymer is contacted with a dyeing or printing solution containing a pro-formed dye, the improvement wherein said dyeing or printing solution contains, as an adjuvant, in an amount sufficient to provide improved light fastness to said textile article, an ultraviolet light absorbing nitro aromatic compound which is not used as a dye selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.

2. The process of claim 1 wherein said aromatic polyamide and polyamide-imide polymer is selected from aromatic polyamides and polyamide-imides having a heat resistance of 350 500C. 7

3. The process of claim 1 wherein said nitro aromatic compound is present in said dyeing orprinting solution in an amount such that the dyed or printed textile article contains 1 e 5 percent of said nitro aromatic compound based on the weight of the textile material.

4. The process of claim 1 wherein said nitro aromatic compound is present in said dyeing or printing solution in an amount such that the dyed or printed textile arti-v cle contains 1.5 3 percent of said nitro aromatic compound based on the weight of the textile material.

5. The process of claim 1 wherein said nitro aromatic compound is a nitro aromatic hydrocarbon.

6. The process of claim 5 wherein said nitro aromatic hydrocarbon is nitrobenzene.

7. The process of claim 5 wherein said nitro aromatic hydrocarbon is a-nitronaphthalene.

8. The process of claim 1 wherein said nitro aromatic compound is a nitro aromatic amine.

1 9. The process of claim 8 wherein said nitro aromatic amine is l-methyl-2-amino-4-nitrobenzene.

10. The process of claim 1 wherein said nitro aromatic compound is a nitro aromatic phosphine oxide.

11. The process of claim 10 wherein said nitro aromatic phosphine oxide is methyl-bis,N-nitro- EIJQIllElE RhlP? x d 12. The process of claim l wherein said textile ar'ticles are dyed at a temperature of C.

13. A textile article composed at least in part of an aromatic polyamide and polyamide-imide synthetic polymer, said textile article having improved light fastness associated with the presence in said textile article of 1-5 percent by weight of a nitro aromatic compound whichis not used as a dye selected from nitro aromatic hydrocarbons, nitro aromatic t amines and nitro aromatic phosphine oxides.

14. The textile article of claim 13 wherein said nitro aromatic compound is selectedfrom nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.

15. The textile article of claim 13 wherein said nitro aromatic compound is a nitro aromatic hydrocarbon.

16. The textile article of claim 15 wherein said nitro aromatic hydrocarbon is nitrobenzene.

17. The textile article of claim 16 wherein said nitro aromatic hydrocarbon is a-nitronaphthalene.

18. The textile article of claim 13 wherein said nitro aromatic compound is a nitro aromatic amine.

19. The textile article of claim 18 wherein said nitro aromatic amine is l-methyl-2-amino-4-nitrobenzene.

20. The textile article of claim 13 wherein said nitro aromatic compound is a nitro aromatic phosphine oxide.

21. The textile article of claim 20 wherein said nitro aromatic phosphine oxide is methyl-bis,N-nitrophenyl)phosphine oxide.

UNKTE'D STL-JEEH EATEN'E OFFECE CQRWEQTKUN Apfil 9, 1974 Patent No. 3,802,841 Dated Inventor Jean-Baptiste RQBIN is certified that error agpear's in the above-identified patent and that said Letters Pa..et1t are hereby corrected as shown below:

in the Heading, insert patentees claim for priority as follows: Claims priority, application Fran ce, June 14, 1971 Signed and sealed this 10th day of September 1974.

MCCOY 1 GIBSON, I C. MARSHALL DANN v Attesting Officer v Commissioner of Patents L a a. zovmwsnr PRINTamG omcr: wa 0-

Claims (20)

  1. 2. The process of claim 1 wherein said aromatic polyamide and polyamide-imide polymer is selected from aromatic polyamides and polyamide-imides having a heat resistance of 350 - 500*C.
  2. 3. The process of claim 1 wherein said nitro aromatic compound is present in said dyeing or printing solution in an amount such that the dyed or printed textile article contains 1 - 5 percent of said nitro aromatic compound based on the weight of the textile material.
  3. 4. The process of claim 1 wherein said nitro aromatic compound is present in said dyeing or printing solution in an amount such that the dyed or printed textile article contains 1.5 - 3 percent of said nitro aromatic compound based on the weight of the textile material.
  4. 5. The process of claim 1 wherein said nitro aromatic compound is a nitro aromatic hydrocarbon.
  5. 6. The process of claim 5 wherein said nitro aromatic hydrocarbon is nitrobenzene.
  6. 7. The process of claim 5 wherein said nitro aromatic hydrocarbon is Alpha -nitronaphthalene.
  7. 8. The process of claim 1 wherein said nitro aromatic compound is a nitro aromatic amine.
  8. 9. The process of claim 8 wherein said nitro aromatic amine is 1-methyl-2-amino-4-nitrobenzene.
  9. 10. The process of claim 1 wherein said nitro aromatic compound is a nitro aromatic phosphine oxide.
  10. 11. The process of claim 10 wherein said nitro aromatic phosphine oxide is methyl-bis(N-nitrophenyl)phosphine oxide.
  11. 12. The process of claim 1 wherein said textile articles are dyed at a temperature of 105 - 140*C.
  12. 13. A textile article composed at least in part of an aromatic polyamide and polyamide-imide synthetic polymer, said textile articLe having improved light fastness associated with the presence in said textile article of 1-5 percent by weight of a nitro aromatic compound which is not used as a dye selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.
  13. 14. The textile article of claim 13 wherein said nitro aromatic compound is selected from nitro aromatic hydrocarbons, nitro aromatic amines and nitro aromatic phosphine oxides.
  14. 15. The textile article of claim 13 wherein said nitro aromatic compound is a nitro aromatic hydrocarbon.
  15. 16. The textile article of claim 15 wherein said nitro aromatic hydrocarbon is nitrobenzene.
  16. 17. The textile article of claim 16 wherein said nitro aromatic hydrocarbon is Alpha -nitronaphthalene.
  17. 18. The textile article of claim 13 wherein said nitro aromatic compound is a nitro aromatic amine.
  18. 19. The textile article of claim 18 wherein said nitro aromatic amine is 1-methyl-2-amino-4-nitrobenzene.
  19. 20. The textile article of claim 13 wherein said nitro aromatic compound is a nitro aromatic phosphine oxide.
  20. 21. The textile article of claim 20 wherein said nitro aromatic phosphine oxide is methyl-bis(N-nitrophenyl)phosphine oxide.
US3802841A 1971-06-14 1972-06-14 Nitro aromatic hydrocarbon,amino nitro aromatic & nitro aromatic phosphine oxides on aromatic polyamide-imide as light fading inhibitors for dyes thereon Expired - Lifetime US3802841A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FR7121770A FR2141556B1 (en) 1971-06-14 1971-06-14
US3802841A US3802841A (en) 1971-06-14 1972-06-14 Nitro aromatic hydrocarbon,amino nitro aromatic & nitro aromatic phosphine oxides on aromatic polyamide-imide as light fading inhibitors for dyes thereon

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
FR7121770A FR2141556B1 (en) 1971-06-14 1971-06-14
NL7208000A NL7208000A (en) 1971-06-14 1972-06-12
LU65501A1 LU65501A1 (en) 1971-06-14 1972-06-13
BE784808A BE784808A (en) 1971-06-14 1972-06-13 New process for dyeing or printing articles textilesen synthetic polymers thermostable
GB2764372A GB1364000A (en) 1971-06-14 1972-06-13 Process for dyeing or printing textile articles
DE19722229046 DE2229046A1 (en) 1971-06-14 1972-06-14
US3802841A US3802841A (en) 1971-06-14 1972-06-14 Nitro aromatic hydrocarbon,amino nitro aromatic & nitro aromatic phosphine oxides on aromatic polyamide-imide as light fading inhibitors for dyes thereon

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DE (1) DE2229046A1 (en)
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GB (1) GB1364000A (en)
LU (1) LU65501A1 (en)
NL (1) NL7208000A (en)

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FR2406021A1 (en) * 1977-10-11 1979-05-11 Du Pont Dyeing aromatic polyamide fibers of high strength and high modulus
FR2844710A1 (en) * 2002-09-20 2004-03-26 Oreal Cosmetic composition, preferably for make-up of keratin fibers, especially mascara, containing rigid, rectilinear fibers, preferably of polyimide-amide, to give accurate, natural-looking extension effect
US20040071648A1 (en) * 2001-01-08 2004-04-15 Marie-Laure Delacour Cosmetic composition having a pasty to pulverulent texture and the cosmetic use thereof
US20040091447A1 (en) * 2002-09-06 2004-05-13 Societe L'oreal. S.A. Charging/separating cosmetic makeup compositions for keratin fibers
US20040096473A1 (en) * 2002-09-20 2004-05-20 L'oreal Cosmetic composition comprising fibres
US20040120920A1 (en) * 2002-09-26 2004-06-24 Bertrand Lion Novel block polymers and cosmetic compositions and processes comprising them
US20040137020A1 (en) * 2002-09-06 2004-07-15 De La Poterie Valerie Composition for coating keratin fibres comprising a tacky wax
US20040137021A1 (en) * 2002-09-06 2004-07-15 De La Poterie Valerie Cosmetic composition comprising a tacky wax
US20040142831A1 (en) * 2002-09-20 2004-07-22 Nathalie Jager Lezer Cosmetic composition comprising rigid fibres and at least one compound chosen from film-forming polymers and waxes
US20040191200A1 (en) * 2002-12-20 2004-09-30 Lezer Nathalie Jager Composition for coating keratin fibres having a threading nature
US20040197297A1 (en) * 2002-09-06 2004-10-07 Societe L'oreal, S.A. Charging/separating cosmetic makeup compositions for keratin fibers
US20050005002A1 (en) * 2003-07-02 2005-01-06 International Business Machines Corporation Administering device with domain state objects
US20050095213A1 (en) * 2003-09-26 2005-05-05 Xavier Blin Two-coat cosmetic product, cosmetic process of using thereof and makeup kit containing this product
US20050106197A1 (en) * 2003-09-26 2005-05-19 Xavier Blin Cosmetic composition comprising a block polymer and a non-volatile silicone oil
US20050169950A1 (en) * 2002-01-08 2005-08-04 Marie-Laure Delacour Solid cosmetic composition comprising fibers
US20050175562A1 (en) * 2004-01-05 2005-08-11 Anke Hadasch Skin makeup composition
US20050175650A1 (en) * 2003-07-08 2005-08-11 Anke Hadasch Composition comprising an elastomeric organopolysiloxane and additional particles
US20050191259A1 (en) * 2004-02-13 2005-09-01 Sue Feng Composition for coating keratin fibers, comprising at least one tacky microcrystalline wax and fibers
US20050215679A1 (en) * 2004-02-13 2005-09-29 De La Poterie Valerie Composition for coating keratin fibers, comprising at least one tacky wax and fibers
US20050220731A1 (en) * 2004-03-23 2005-10-06 Philippe Ilekti Nail varnish composition comprising at least one polymer and at least one plasticizer
US20050260151A1 (en) * 2002-09-06 2005-11-24 Societe L'oreal, S.A. Charging/separating cosmetic makeup compositions for keratin fibers
US20060093568A1 (en) * 2002-09-26 2006-05-04 Xavier Blin Composition comprising a block polymer and a film-forming agent
US20060099231A1 (en) * 2002-09-06 2006-05-11 De La Poterie Valerie Make-up composition for keratin fibres such as eyelashes
US20060104936A1 (en) * 2002-09-06 2006-05-18 Societe L'oreal Charging/separating cosmetic makeup compositions for keratin fibers
US20060134038A1 (en) * 2002-09-06 2006-06-22 De La Poterie Valerie Make-up composition for keratin fibres such as eyelashes
US20070248765A1 (en) * 2006-04-20 2007-10-25 Rembert Joseph Truesdale Ultraviolet-resistant fabrics and methods for making them
WO2007133177A2 (en) 2006-04-20 2007-11-22 Southern Mills, Inc. Ultraviolet-resistant fabrics and methods for making them
US20080031837A1 (en) * 2006-07-27 2008-02-07 Celine Farcet Block polymers and their process of preparation
US20080153372A1 (en) * 2006-04-20 2008-06-26 Southern Mills Insect-Repellant Fabrics and Methods for Making Them
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US7854017B2 (en) 2005-12-16 2010-12-21 Southern Mills, Inc. Protective garments that provide thermal protection
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US8728451B2 (en) 2004-03-25 2014-05-20 L'oreal Styling composition comprising, in a predominantly aqueous medium, a pseudo-block polymer, processes employing same and uses thereof
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FR2406021A1 (en) * 1977-10-11 1979-05-11 Du Pont Dyeing aromatic polyamide fibers of high strength and high modulus
US20040071648A1 (en) * 2001-01-08 2004-04-15 Marie-Laure Delacour Cosmetic composition having a pasty to pulverulent texture and the cosmetic use thereof
US20050169950A1 (en) * 2002-01-08 2005-08-04 Marie-Laure Delacour Solid cosmetic composition comprising fibers
US20060099231A1 (en) * 2002-09-06 2006-05-11 De La Poterie Valerie Make-up composition for keratin fibres such as eyelashes
US20040091447A1 (en) * 2002-09-06 2004-05-13 Societe L'oreal. S.A. Charging/separating cosmetic makeup compositions for keratin fibers
US20060104936A1 (en) * 2002-09-06 2006-05-18 Societe L'oreal Charging/separating cosmetic makeup compositions for keratin fibers
US20060134038A1 (en) * 2002-09-06 2006-06-22 De La Poterie Valerie Make-up composition for keratin fibres such as eyelashes
US20050260151A1 (en) * 2002-09-06 2005-11-24 Societe L'oreal, S.A. Charging/separating cosmetic makeup compositions for keratin fibers
US20040137020A1 (en) * 2002-09-06 2004-07-15 De La Poterie Valerie Composition for coating keratin fibres comprising a tacky wax
US20040137021A1 (en) * 2002-09-06 2004-07-15 De La Poterie Valerie Cosmetic composition comprising a tacky wax
US7887788B2 (en) 2002-09-06 2011-02-15 L'oreal S.A. Cosmetic composition comprising a tacky wax
US7923002B2 (en) 2002-09-06 2011-04-12 L'oreal S.A. Composition for coating keratin fibres comprising a tacky wax
US20040197297A1 (en) * 2002-09-06 2004-10-07 Societe L'oreal, S.A. Charging/separating cosmetic makeup compositions for keratin fibers
US20100158962A1 (en) * 2002-09-06 2010-06-24 L'oreal S.A. Charging/separating cosmetic makeup compositions for keratin fibers
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FR2844710A1 (en) * 2002-09-20 2004-03-26 Oreal Cosmetic composition, preferably for make-up of keratin fibers, especially mascara, containing rigid, rectilinear fibers, preferably of polyimide-amide, to give accurate, natural-looking extension effect
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US20060128578A9 (en) * 2002-09-20 2006-06-15 Nathalie Jager Lezer Cosmetic composition comprising rigid fibres and at least one compound chosen from film-forming polymers and waxes
US20040096473A1 (en) * 2002-09-20 2004-05-20 L'oreal Cosmetic composition comprising fibres
US20040142831A1 (en) * 2002-09-20 2004-07-22 Nathalie Jager Lezer Cosmetic composition comprising rigid fibres and at least one compound chosen from film-forming polymers and waxes
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US20050065046A2 (en) * 2002-09-20 2005-03-24 L'oreal Cosmetic composition comprising rigid fibres and at least one compound chosen from film-forming polymers and waxes
US20060099164A1 (en) * 2002-09-26 2006-05-11 De La Poterie Valerie Composition for coating keratin fibres, comprising a high dry extract that contains a sequenched polymer
US20040120920A1 (en) * 2002-09-26 2004-06-24 Bertrand Lion Novel block polymers and cosmetic compositions and processes comprising them
US20060093568A1 (en) * 2002-09-26 2006-05-04 Xavier Blin Composition comprising a block polymer and a film-forming agent
US7803877B2 (en) 2002-09-26 2010-09-28 L'oreal S.A. Block polymers and cosmetic compositions and processes comprising them
US7875265B2 (en) 2002-09-26 2011-01-25 L'oreal Cosmetic composition comprising a sequenced polymer and a plasticizer
US9017704B2 (en) 2002-09-26 2015-04-28 L'oreal Composition comprising a block polymer and a film-forming agent
US20060115444A1 (en) * 2002-09-26 2006-06-01 Xavier Blin Glossy liquid composition comprising a sequenced polymer
US20060127334A1 (en) * 2002-09-26 2006-06-15 Veronique Ferrari Lipstick comprising a sequenced polymer
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US20060134051A1 (en) * 2002-09-26 2006-06-22 Xavier Blin Glossy non-transfer composition comprising a sequenced polymer
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US20060134044A1 (en) * 2002-09-26 2006-06-22 Xavier Blin Cosmetic composition comprising a sequenced polymer and a plasticizer
US20060147403A1 (en) * 2002-09-26 2006-07-06 L'oreal C.A. Non-transfer cosmetic composition comprising a sequenced polymer
US7915347B2 (en) 2002-09-26 2011-03-29 L'oreal S.A. Block polymers and cosmetic compositions and processes comprising them
US20080014158A1 (en) * 2002-09-26 2008-01-17 L'oreal Novel Block Polymers and Cosmetic Compositions and Processes Comprising Them
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US20040191200A1 (en) * 2002-12-20 2004-09-30 Lezer Nathalie Jager Composition for coating keratin fibres having a threading nature
US7993632B2 (en) 2002-12-20 2011-08-09 L'oreal S.A. Composition for coating keratin fibres having a threading nature
US20050005002A1 (en) * 2003-07-02 2005-01-06 International Business Machines Corporation Administering device with domain state objects
US20050175650A1 (en) * 2003-07-08 2005-08-11 Anke Hadasch Composition comprising an elastomeric organopolysiloxane and additional particles
US20050106197A1 (en) * 2003-09-26 2005-05-19 Xavier Blin Cosmetic composition comprising a block polymer and a non-volatile silicone oil
US20050095213A1 (en) * 2003-09-26 2005-05-05 Xavier Blin Two-coat cosmetic product, cosmetic process of using thereof and makeup kit containing this product
US8119110B2 (en) 2003-09-26 2012-02-21 L'oreal S.A. Cosmetic composition comprising a block polymer and a non-volatile silicone oil
US20050175562A1 (en) * 2004-01-05 2005-08-11 Anke Hadasch Skin makeup composition
US20050191259A1 (en) * 2004-02-13 2005-09-01 Sue Feng Composition for coating keratin fibers, comprising at least one tacky microcrystalline wax and fibers
US20050215679A1 (en) * 2004-02-13 2005-09-29 De La Poterie Valerie Composition for coating keratin fibers, comprising at least one tacky wax and fibers
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US20050220731A1 (en) * 2004-03-23 2005-10-06 Philippe Ilekti Nail varnish composition comprising at least one polymer and at least one plasticizer
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NL7208000A (en) 1972-12-18 application
GB1364000A (en) 1974-08-21 application
LU65501A1 (en) 1972-10-23 application
BE784808A1 (en) grant
FR2141556B1 (en) 1974-03-22 grant
FR2141556A1 (en) 1973-01-26 application
DE2229046A1 (en) 1972-12-21 application
BE784808A (en) 1972-12-13 grant

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