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Publication numberUS2961347 A
Publication typeGrant
Publication dateNov 22, 1960
Filing dateNov 13, 1957
Priority dateNov 13, 1957
Publication numberUS 2961347 A, US 2961347A, US-A-2961347, US2961347 A, US2961347A
InventorsFloyd John D
Original AssigneeHercules Powder Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for preventing shrinkage and felting of wool
US 2961347 A
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Description  (OCR text may contain errors)

United States tent O PROCESS FOR PREVENTING SHRINKAGE AND FELTING OF WOOL John D. Floyd, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware This application relates to a process for preventing shrinkage and felting of wool.

It is well known in the textile trade that both woven and knitted woolen fabrics shrink excessively on laundering. This shrinkage varies with the type of weave in the fabric and, in some cases, may run as high as 60% of the original dimensions. Woolen fabrics shrink by two methods; by the so-called relaxation or consolidation phenomenon, and by felting. The former is due to the relaxation of tensions introduced during the knitting or weaving operation and is common to all hydrophilic fibets. The latter is due to the unique physical and mechanical properties of the wool fiber. The physical property which brings about felting is the scaled surface of the fiber which givesit a low coefiicient of friction in one direction. This means that when a fabric is subjected to mechanical action, the individual fibers migrate in one direction making for a more dense structure, thereby reducing the linear dimensions. This dense structure is consolidated by the higher resilience of the fibers which is related to their curling or spiraling tendency.

Various treatments such as chlorination treatments, oxidative treatments, alkali treatments and resin treatments have been used to reduce the felting shrinkage of wool. None of these treatments, however, has been entirely satisfactory. Thus, chlorination treatments require close control of conditions to prevent general loss of desirable wool-like character of the fabric made therefrom and reduction of wear qualities. Moreover, chlorination treatments generally result in weakening the fabric and also impart a harsh feel thereto. Oxidative treatments as with peroxy compounds and permanganate, are likewise diflicult to carry out in a manner such as to achieve adequate resistance to shrinkage without undue fiber damage. Alkali treatments, as with caustic or potash from dry solvents are disadvantageous from the cost standpoint due to the necessity for solvent-recovery systems and other special equipment. 'Resin treatments, such as with methylated methylolmelamine and methylated nylon, cause a loss in the subjective properties of the fabric. Such treatments, moreover, require a high-temperature cure and a high add-on level to obtain acceptable shrink resistance. This high additive level causes more or less permanent fabric stiffening and, in addition, increases the cost.

The principal object of the present invention is the provision of an improved process for preventing shrinkage and felting of wool.

Another object of the invention is the provision of a durable treatment to prevent shrinkage in woolen fabrics without detriment to the desirable physical properties of the fabrics.

A further object of the invention is the provision of a process for making a shrink-resistant wool fabric without the use of oxidizing, reducing, strongly acid or strongly basic chemicals, all of which are detrimental to the physical properties of the fabric.

ice

In accordance with the invention, the above and other objects are accomplished by treating a wool fabric with certain water-soluble cationic thermosetting polyamideepichlorohydrin resins to be described more fully hereinafter. It has been found that treatment with suchresins is highly effective for the dimensional stabilization of woolen fabrics. The treatment, moreover, does not add harshness or stiffness to the fabric and does not significantly yellow or otherwise change the color of the fabric. a

In carrying out the process of the invention, an aqueous solution of the cationic resin is applied to the fabric in any suitable manner as by dipping, spraying, padding or the like. Any desired or convenient concentration of the aqueous resin solution may be utilized for such ap: plication; however, it has been found that concentrations from about 1% to about 10% are quite satisfactory and these, therefore, are preferred. 'The concentration and time of treatment should be such that the fabric absorbs from about 0.5% to about 10% by weight, based on the dry weight of fabric, of the cationic resin. j Less than 0.5% will not produce the desired resistance to shrinkage and felting, and more than 10% offers no particular advantage and, hence, will normally not be used.

After treatment with the cationic resin, the fabric is dried preferably at about C. for about 5 minutes in an air-circulating oven. The oven temperature is then raised to about C. and the treated fabric given a 5-minute cure at this temperature. This short, low-temperature cure cycle can easily be handled by ordinary textile processing equipment. While the described temperatures and times are quite advantageous, it will be appreciated that the invention is not limited thereto and that drying and curing may be effected at higher-or lower temperatures, i.e., fromabout. 40 C. to about C. with a corresponding decrease or increase inthe duration of treatment.

A particular advantage of the invention is that the treatment may be carried out, under acid, neutral or alkaline conditions, i.e., at pHs from about 3 to about 10. The preferred pH range is from about 5 to about 8. i 1

The cationic thermosetting polyamide-epichlorohydrin resins contemplated for use herein comprise a watersoluble polymeric reaction product of epichlorohydrin and a polyamide derived from a polyalkylene polyamine and a C C saturated aliphatic dicarboxylic acid. It has .been found that resins of this type are uniquely effective for preventing shrinkage of wool fabrics without adversely affecting other desirable physical properties of the fabric.

In the preparation of these cationic thermosetting resins, the dicarboxylic acid is first reacted with the 'polyalkylene polyamine under conditions such as to produce a water-soluble polyamide containing the recurring groups where n and x are each 2 or more and R is the divalent hydrocarbon radical of the dicarboxylic acid. This wa ter-soluble polyamide is then reacted with epichlorohydrin to form the water-soluble cationic thermosetting resin.

tylene polyamines and so on may be employed of which the polyethylene polyamines represent an economically preferred class. More specifically, the polyalkylene polyamines contemplated fonuse mayberepresented as polyamine sbin which the nitrogen atoms are linked together by groups of the formula QQJlzr- Where n is a small integer greater than unity and'the number of such groups in the molecule ranges from two up to about eight. The nitrogen atoms may be attached to adjacentcarbon atoms in the group -C,,H or to carbon atoms furtheiapart, but not to the same carbon atom. This invention contemplates not .onlythe u se of such polyamines as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriarnine and the like, which can beobtained in reasonably pure form, but also mixtures and various crude polyarnine materials. For example, the mixture of polyethylene polyamines obtained by the reaction of ammonia and ethylene dichloride, refined only to the extent of removal of chlorides, water, excess ammonia and ethylenediamine, is a very satisfactory starting material. "The term polyalkylene polyamine" employed in the claims, therefore, refers to and includes any of the polyalkylene polyamines referred to above 01 to a mixture of such polyalkylene polyamines.

It is desirable, in some cases, to increase the spacing of secondary amino groups on the polyamide molecule in ordertochange the reactivity of the polyamide-epichlorohydrin complex. This can be accomplished by substituting a diamine such as ethylenediarnine, propylenediamine, hexamethylenediamine and the like for a portion of the polyalkylene polyamine. For this purpose, up to about 80% of the-polyalky-lene polyamine may be replaced by a molecularly equivalent amount of the diamine. Usually, a replacement of about 50% or less will serve the purpose.

The temperatures employed for carrying out the reaction between the dicarboxylic acid and the polyalkylene polyamine mayvary from about 110 C. to about 25.0? C. or higher at atmospheric pressure. For most purposes, however, temperatures between about 160 C. and 210 C. have been found satisfactory and are preferred. Where reduced pressures are employed, somewhat lower temperatures may be utilized. The time of reaction depends on the temperatures and pressures utilized and-will ordinarily vary from about /2 to 2 hours, although shorter or longer reaction times may be utilized depending on reaction conditions. In any event, the reaction is desirably continued to substantial com- Dltiflon for best results.

In carrying out the reaction, it is preferred to use an amount ,ofdicarboxylic acid 'sufitcient to react substantially, completely with the primary amine groups of the polyalkylene polyamine but insufficient to react with the secondary amine groups to any substantial extent. This will usually require a mole ratio of polyalkylene polyamine to dicarboxylic acid of from about 0.921 to about 1.2:1. However, mole ratios of from about 0.8:1 to about 1.4': 1.may eused with quite satisfactory results. Mole ratios outside of these ranges are generally unsatisfactory. Thus, mole ratios below about 0.8:1 result in a gelled product or one having a pronounced tendency to gel while mole ratios above 1.4:1 result in low molecular weight polyamides. Such products when reacted. with ,epichlorohydrin, do not produce resins having the desired efficiency for use herein.

In converting the polyamide, formed as above described, to a cationic thermosetting resin, it is reacted with, epichlorohydrin at a temperature from about 45 C. to about 100 -C. and preferably between about 45 C. and 70 .C. until the viscosity of a 20% solids solution at 25 C. has reached about C or higher on the Gardner-Holdt scale. This reaction is preferably carried out in aqueous solution to moderate the reaction. pH adjustment is usually not necessary. However, since the pH decreases during the polymerization phase of the .wash cycle.

4 action it may be desirable, in some cases, to add alkali to combine with at least some of the acid formed.

When the desired viscosity is reached, sufficient water is then added to adjust the solids content of the resin solution to the desired amount, i.e., about 10% more or less, the product cooled .to .about 25 C. and then stabilized by adding sufiicient acid to reduce the pH at least toabout 6 and preferably to about 5. Any suitable acid such as hydrochloric, sulfuric, nitric, formic, phosphoric and acetic acid may be used to stabilize the product. However, hydrochloric acid ispreferred.

In the polyamide-epichlorohydrin reaction, it is preferred to use sufficient epichlorohydrin to convert all secondary amine groupsto tertiary amine groups. However, more or less may be added to moderate or increase reaction rates. In general, satisfactory results may be obtained utilizing from about 0.5 moles to about 1.8 moles of epichlorohydrin for each secondary amine group of the polyamide. It is preferred to utilize from about 1.0 mole to about 1.5 moles for each secondary amine ere-1 29 he po ya ide- "The following examples willserve to illustrate the invention. .Inthese examples the cationic water-soluble thermosetting polyamide-epichlorohydrin resin utilized was prepared as follows: Two hundred twenty-five grams (2.18 moles) of ,diethylenctriamine and grams of water were placed in a 3-necked flask equipped with a mechanical stirrer, thermometer and condenser. To this was added 290 grams (2.0 moles) of adipic acid. After the acid had dissolved .in the amine, the solution was heatedto 185-200- C. and held there for 1% hour. Then vacuum from a water pump was applied to the flask during the period required for the contents of the flask to cool to C. following which 430 grams of H 0 was added. The polyamide solution contained 52.3% solids and had an acid number of 2.1.

To 60 grams of-this polyamide solution in a roundbottom flask was added 225 grams of H 0. This solution was heated to 50 C. and 12.5 grams of epichlorohydrin was added dropwise over a period of 11 minutes. The contents of the flask was then heated to 60-70" C. until it had attained a Gardner viscosity of E. Then grams of H 0 was added to the product, and it was cooled to 25 C. Eleven ml. of 3.7% HCl was then added to adjust the pH to 5.0. The product contained 9.0% solids and had a Gardner viscosity of C-D.

Example 1 A sample of scoured. carbonized and bleached wool flannel cloth was treated in the following manner with a 5% aqueous solution of the cationic thermosetting resin prepared as described above. The dry fabric was padded, double ends, through a room-temperature solution of the resin on a IO-inch laboratory padder. The wet pick-up was found to be 113% (5.6% resin solids based on the dry weight of the cloth). The treated fabric was air-dried and cured for 5 minutes at 150 C. after which it was washed for 45 minutes in a 130 F., 0.1% neutral soap wash. After air-drying, the total shrinkage of the fabric was 9.1%. This compared ,to 50% shrinkage for an untreated sample. It should be noted that these values represent total shrinkage, i.e., relaxation shrinkage plus felting shrinkage. The hand and color of the fabric after washing were not impaired by the foregoing treatment.

Example 2 The treated sample from Example 1 was given a second wash as described in Example 1, followed by /z-hour room temperature dry-cleaning cycle, followed by a third The additional shrinkage after these treatments was found to be nil.

Example 3 A sample of woolen ,fabric was treated as in Example ,1.

with a 5.1% aqueous solution of the cationic resin prepared as above described and cured for 5 minutes at 100 C. The wet pick-up was 100 (5.1% resin solids based on dry weight of the fabric). It was washed and dried as previously described. The total shrinkage was found to be 6.1%.

Example 4 A sample of woolen fabric was treated with a 3.13% aqueous solution of the cationic resin prepared as described above and treated as in Example 3. The wet pick-up was 100% (3.13% resin solids based on dry weight of the fabric). After washing, its total shrinkage was 3.1%. This sample was given four additional launderings. The increased shrinkage due to the extended laundering was 4.8%, or a total of 7.9% after five laundermgs.

The following example gives comparative results obtained with well-known resins used commercially for shrinkproofing wool fabrics. In this example, samples of woolen fabric similar to those treated in Examples 3 and 4 were treated with different commercial resins in accordance with the following procedure. The commercial resin was padded onto the fabric from a cold aqueous solution containing the ammonium sulfate catalyst (5% on resin solids). The fabric was dried 5 minutes and cured 5 minutes at 150 C. The results are shown in the following table.

What I claim and desire to protect by Letters Patent is:

1. A process of treating wool fabrics to prevent shrinkage thereof during washing which comprises treating the fabric with from about 0.5% to about 10% by weight, based on the weight of the fabric, of a cationic watersoluble thermosetting resin obtained by reacting a polyalkylene polyamine having two primary amine groups and at least one secondary amine group with a C -C saturated aliphatic dicarboxylic acid in a mole ratio of from about 0.8 to about 1.4 of the former to about 1.0 of the latter to form a long-chain polyamide having secondary amine groups, and then reacting the polyamide with epichlorohydrin in a mole ratio of epichlorohydrin to secondary amine groups of said polyamide of from about 0.5 :1 to about 1.821, and thereafter heating the treated fabric at a temperature from about C. to about 150 C. to cure the resin.

2. A process according to claim 1 wherein the cationic thermosetting resin is obtained by (1) reacting the C C saturated aliphatic dicarboxylic acid with the polyalkylene polyamine at a temperature from about 110 C. to about 250 C. to form the polyamide and (2) reacting the polyamide with epichlorohydrin at a temperature from about C. to about 100 C. to form the watersoluble cationic thermosetting resin.

3. A process according to claim 1 wherein the cationic thermosetting resin is obtained by (1) reacting a C -C saturated aliphatic dicarboxylic acid with the polyalkylene TABLE Shrinkproofing of wool fabric with commercial resins Curing Percent Concen- Conditions, Shrinkage Condition 01 Type of Resin tration, Catalyst min. at after 1-30 Fabric Weight 150 0. min. Neu- Percent tral Wash Melamine-formaldehyde Resin 6.45 Ammonium Sulfate--- 5 7.6 Harsh, sgifi, dis- CO 0T8 Mfithylated melamineformaldehyde Resin (Type 6.51 .do 5 13.7 Harsh and stiff- 130-. 4.21 do 5 29.5 Sllghtlystifl. Methylated melamineformaldehyde Resin (Type 3.29 -....do 5 31.3 Soft.

130-- 5.14 do a 16 Slightly stifl. Mzgthylated melamineformaldehyde Resin (Type 3. 53 do 5 19.1 Do.

Do. 6.07 .--.-do 5 12.2 Rather stiff.

It will be seen from the examples that woolen fabrics treated in accordance with the process of the invention are dimensionally stabilized through at least five one-halfhour wash cycles. A particular advantage of the invention is the fact that the treated fabric, after washing, is desirably soft, whereas commercial resins such as those illustrated in Example 5, lend a harsh, stiff hand to the fabric and/or provide substantially less dimensional stability in the fabric. The fact that the resins herein disclosed lend a durable soft hand to the fabric is unexpected since the resins themselves form rather brittle films.

Other advantages flowing from the use of the type of resin herein disclosed in comparison with commercial resins is that it is effective at low concentrations, cures independently of pH and at lower temperatures, ca. 100 0., requires no catalyst and does not significantly yellow or otherwise change the color of the fabric.

The term wool fabric as used herein includes any animal hair fabric such as sheep wool, mohair, cashmere,

camel hair, alpaca wool, vicuna wool, llama wool, cowhair and horsehair. The term also includes fabrics which are 100% animal hair and fabrics which are blends of animal hair with natural and/or synthetic fibers such as cotton, polyacrylonitrile fiber, polyterephthalate ester fibers, polyamide fibers and so on.

While specific embodiments of the invention have been illustrated and described herein, it will be understood that changes and variations may be made without departing from the scope of the invention as defined in the claims which follow.

polyamine at a temperature from about C. to about 210 C. to form the polyamide and (2) reacting the polyamide with epichlorohydrin at a temperature from about 45 C. to about 70 C. to form the water-soluble cationic thermosetting resin.

4. A wool fabric having improved resistance to shrinkage, said fabric containing from about 0.5% to about 10% by weight, based on the weight of the fabric, of a cured cationic thermosetting resin obtained by reacting a polyalkylene polyamine having two primary amine groups and at least one secondary amine group with a C -C saturated aliphatic dicarboxylic acid in a mole ratio of from about 0.8 to about 1.4 of the former to about 1.0 of the latter to form a long-chain polyamide having secondary amine groups, and then reacting the polyamide with epichlorohydrin in a mole ratio of epichlorohydrin to secondary amine groups of said polyamide of from about 0.5:1 to about 1.8:1.

References Cited in the file of this patent UNITED STATES PATENTS 2,468,086 Latham et al Apr. 26, 1949 2,595,935 Daniel et al May 6, 1952 2,696,448 Hammer et al Dec. 7, 1954 OTHER REFERENCES Ser. No, 323,512, Hagedorn (A.P.C.), published Apr. 20, 1943.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2468086 *Jun 21, 1948Apr 26, 1949Morton Chemical CompanyProcess of rendering anionic coating materials adherent to anionic bases
US2595935 *Aug 3, 1946May 6, 1952American Cyanamid CoWet strength paper and process for the production thereof
US2696448 *Mar 17, 1949Dec 7, 1954Ellis Foster CoShrinkproofed wool and method for producing same
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3125552 *Sep 21, 1960Mar 17, 1964 Epoxidized poly amides
US3224990 *Mar 11, 1963Dec 21, 1965Pacific Resins & Chemicals IncPreparing a water soluble cationic thermosetting resin by reacting a polyamide with epichlorohydrin and ammonium hydroxide
US3227671 *May 22, 1962Jan 4, 1966Hercules Powder Co LtdAqueous solution of formaldehyde and cationic thermosetting polyamide-epichlorohydrin resin and process of making same
US3239491 *Jan 26, 1962Mar 8, 1966Borden CoResin for wet strength paper
US3240761 *Jul 10, 1962Mar 15, 1966Hercules Powder Co LtdCationic thermosetting quaternized polyamide-epichlorohydrin resins and method of preparing same
US3352833 *Dec 31, 1963Nov 14, 1967Hercules IncAcid stabilization and base reactivation of water-soluble wet-strength resins
US3382096 *Apr 28, 1967May 7, 1968Hercules IncAntistatic composition, treatment of a hydrophobic material therewith, and the resulting material
US3526608 *Feb 13, 1968Sep 1, 1970Pfizer & Co CUse of polyamides derived from iminodiacetic acid and related compounds in improving the wet and dry strength of paper
US3657002 *Aug 5, 1969Apr 18, 1972Wyandotte Chemicals CorpShrinkproofing wool fabrics
US4240450 *Mar 14, 1978Dec 23, 1980L'orealHair conditioner of anionic polymers and cationic polymers
US4287110 *Sep 25, 1979Sep 1, 1981Sumitomo Chemical Company, LimitedProduction of aqueous solutions of cationic thermosetting resins
US4336835 *Apr 14, 1981Jun 29, 1982Sumitomo Chemical Company, LimitedPolyamide reacted with epichlorohydrin
US4488564 *Dec 18, 1981Dec 18, 1984L'orealOily composition intended for the treatment of keratin substances and the skin
US4719099 *Jun 27, 1985Jan 12, 1988L'orealAnionic and cationic
US4839415 *May 7, 1987Jun 13, 1989Akzo N.V.Polymerizing maleic anhydride with alpha-olefins; reacting copolymers with diamines; neutralization then quaternization with epichlorohydrin
US4842849 *Oct 30, 1987Jun 27, 1989L'orealComposition intended for the treatment of keratin fibres, based on a cationic polymer and an anionic polymer containing vinylsulphonic groups
US4842851 *Jun 2, 1987Jun 27, 1989L'orealPolyamino amides for protecting hair against atmospheric attack, and in particular against light, and process for protecting hair employing such polyaminoamides
US5009880 *Nov 4, 1987Apr 23, 1991L'orealMixture of an anionic and cationic polymer for shampoos, skin lotions, nail strengtheners and hair dyeing; improved fixing and anchoring; smoothness; gloss
US5262230 *Jun 1, 1990Nov 16, 1993Bayer AktiengesellschaftConstruction materials, molding materials, pile or knit fabric of glass fibers impregnated with resin
US5661118 *Apr 24, 1995Aug 26, 1997L'orealHair and skin washing and treatment compositions based on ceramide and/or glycoceramide and on polymers containing cationic groups
US5700456 *Apr 24, 1995Dec 23, 1997L'orealCompositions for the treatment and protection of hair, based on ceramide and/or glycoceramide and on polymers containing cationic groups
US5858023 *May 5, 1995Jan 12, 1999Precision Processes TextilesTreating cotton fibers, blends of wool and synthetic fibers or synthetic fibers with amine-modified polyether softener
US6153570 *Jun 6, 1997Nov 28, 2000L'oreal S.A.Mixture of cationic polymer and amine-containing silicone
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US6260556Jan 28, 2000Jul 17, 2001L'orealAnhydrous composition for bleaching keratin fibers
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US7294152Jan 7, 2005Nov 13, 2007L'oreal S.A.Dyeing composition comprising at least one fluorindine compound for the dyeing of keratinic fibers, dyeing process comprising the composition and compound
US7303588Mar 25, 2004Dec 4, 2007L'oreal S.A.Composition for dyeing keratinous fibers, comprising at least one polycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device
US7303589Apr 1, 2004Dec 4, 2007L'oreal S.A.Process for dyeing human keratin fibers, having a lightening effect, comprising at least one fluorescent compound and compositions of the same
US7323015Oct 21, 2003Jan 29, 2008L'oreal S.A.Dyeing human hair
US7326256Dec 8, 2003Feb 5, 2008L'ORéAL S.A.dyeing human hair; aqueous solution
US7329287Dec 8, 2003Feb 12, 2008L'oreal S.A.Oxidation dye composition for keratin fibers, comprising at least one oxidation dye, at least one associative polymer, at least one nonionic cellulose-based compound not comprising a C8-C30 fatty chain, and at least one cationic polymer with a charge density of greater than 1 meq/g and not comprising a C8-C30 fatty chain
US7364594Nov 22, 2001Apr 29, 2008L'oreal S.A.E.g., a quaternized polyetherurethane copolymer and an acrylamide/ dimethyldiallylammonium chloride/acrylic acid terpolymer.
US7402180Jul 11, 2006Jul 22, 2008L'ORéAL S.A.Composition for the oxidation dyeing of keratin fibres, comprising at least one fatty alcohol chosen from mono- and polyglycerolated fatty alcohols and a particular polyol
US7429275Dec 23, 2005Sep 30, 2008L'oreal S.A.Use of at least one compound chosen from porphyrin compounds and phthalocyanin compounds for dyeing human keratin materials, compositions comprising them, a dyeing process, and compounds therefor
US7431740Nov 22, 2001Oct 7, 2008L'oreal, S.A.Oxidation dyeing composition for keratinous fibers comprising an associative polymer and a pearling agent
US7442214Mar 31, 2006Oct 28, 2008L'oreal S.A.Dye composition comprising at least one non-ionic associative polymer and process for dyeing keratin fibers using same
US7485289Feb 15, 2007Feb 3, 2009L'oreal, S.A.Cosmetic compositions containing a particular aminosilicone and a conditioner, and uses thereof
US7498022Mar 28, 2003Mar 3, 2009L'oreal S.A.One amphiphilic polymer chosen from branched block copolymers comprising at least one nonionic unit derived from at least one monomer chosen from C1-20 alkyl (meth)acrylates, N-mono-(C2-12 alkyl)- meth)acrylamides and N,N-di-(C2-12
US7504094Feb 15, 2007Mar 17, 2009L'oreal, S.A.Hair conditioners; alkoxy-capped copolymer with dimethylsiloxy units and 3-(2-aminoethyl)aminopropyl)methyl- (or alkoxy-)siloxy units; for improving the lightness, softness, sheen and/or disentangling, and/or facilitating styling of hair
US7510705Sep 21, 2006Mar 31, 2009L'oreal, S.A.Process for permanently reshaping the hair using particular aminosilicones
US7550015Mar 31, 2006Jun 23, 2009L'oreal S.A.hair dyes comprising oxidation dye precursors and direct dyes, nonionic surfactants or anionic surfactants, hydroxyethylcellulose, cationic polymer; and one fatty substance; fatty acid esters of polyethylene glycol; multi-compartment kit for store the dyes
US7569078Mar 31, 2006Aug 4, 2009L'oreal S.A.Dye composition comprising at least one cellulose and process for dyeing keratin fibers using the dye composition
US7575605Mar 31, 2006Aug 18, 2009L'oreal S.A.Dye composition comprising at least one glycerol ester and a process for dyeing keratin fibers using the composition
US7578854Mar 31, 2006Aug 25, 2009L'oreal S.A.Applying to wet or dry keratin fibers a formulation containing oxidation dye precursor such as phenolamines, a direct dye ( azo dye, methine dye etc.), a fatty alchol, a fatty alcohol ester of polyglycerol, a oxyalkylenated or glycerolated nonionic surfactant, a cationic polymer
US7608115Apr 30, 2004Oct 27, 2009L'oreal S.A.Via applying direct dye, oxidation base, coupler, and oxidizing agent, then heating; oxidation color dyes; hair conditioners; cosmetics
US7651533Mar 31, 2006Jan 26, 2010OrealDye composition with a reduced content of starting materials, process for dyeing keratin fibers using the same and device therefor
US7708981Mar 10, 2004May 4, 2010L'oreal S.A.Cosmetic compositions comprising at least one crosslinked copolymer, at least one insoluble mineral particle and at least one polymer, and uses thereof
US7736631Apr 1, 2004Jun 15, 2010L'oreal S.A.Organic pigment colors and a modified polydimethylsiloxane homopolymer or copolymers for lightening hair or skin; multi-compartment kit for dyeing
US7771491Dec 21, 2007Aug 10, 2010L'oreal S.A.Hair dye; environmentally friendly, due to use of nonionic cellulose; good shampoo fastness
US7771492Feb 23, 2009Aug 10, 2010L'oreal S.A.Hair dyes; anionic thickener has hydrophilic olefinic unsaturated carboxylic acid and a C10-C30 alkyl unsaturated carboxylate; nonionic thickeners are celluloses modified by fatty chain or polyoxyethylenated polyurethanes; cationic thickener is quaternized cellulose with fatty acid chain; resists running
US7799093Oct 25, 2007Sep 21, 2010L'ORéAL S.A.Coloring composition of keratinous fibers comprising at least one polysiloxane/polyurea block copolymer
US7867969Oct 30, 2006Jan 11, 2011L'oreal S.A.Composition for washing keratin materials comprising a magnesium salt anionic surfactant
US7914775Nov 6, 2001Mar 29, 2011L'oreal S.A.Treating keratinous fibres, in particular human keratinous fibres such as hair, comprising in a physiologically acceptable medium, at least a protecting or conditioning agent, and further at least a cationic associative
US7928087Jan 11, 2002Apr 19, 2011L'orealprovides a flow texture to cosmetic compositions and are easily rinsed; Hair treated with the composition has a soft feel free of residue; used for washing and/or conditioning keratinous matter such as hair or skin
US7976831Apr 4, 2005Jul 12, 2011L'oreal S.A.Method for treating hair fibers
US7998464Sep 28, 2006Aug 16, 2011L'oreal S.A.Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture
US8349363Nov 7, 2008Jan 8, 2013Kimberly-Clark Worldwide, Inc.Temperature responsive delivery systems
US8557226Jan 18, 2010Oct 15, 2013Isp Investments Inc.Performance-boosting UV-absorbing compounds
US8586014Oct 30, 2006Nov 19, 2013L'orealComposition for the care of keratin material and cosmetic treatment process using said composition
US8673272Jul 22, 2010Mar 18, 2014Isp Investments Inc.Ultraviolet-absorbing compounds
US8703109Mar 28, 2008Apr 22, 2014L'orealProtection of keratinous fibers using ceramides and/or glycoceramides
US8784506Oct 28, 2011Jul 22, 2014L'orealDye composition having a low content of ammonia
DE2808841A1 *Mar 1, 1978Sep 7, 1978OrealHaarkosmetisches mittel und haarbehandlungsverfahren
DE202013011676U1Nov 8, 2013Feb 14, 2014L'orealZusammensetzung, die eine Dicarbonylverbindung enthält
EP0723772A1Jan 10, 1996Jul 31, 1996L'orealReducing composition bared on a basic amino acid and a cationic polymer
EP2011473A1Jun 26, 2008Jan 7, 2009L'OrealAnhydrous composition in paste form for bleaching keratinous fibres.
EP2065023A2Nov 28, 2008Jun 3, 2009L'OrealHairstyling composition comprising at least one (meth)acrylic copolymer and at least one pearlescent agent
EP2065024A2Nov 28, 2008Jun 3, 2009L'OrealHairstyling composition comprising (meth)acrylic copolymers and at least one oil
EP2072033A2Sep 12, 2008Jun 24, 2009L'OrealCosmetic composition comprising at least one specific cationic polymer and at least one fatty acid ester in C8-C24 and oxyethylenated sorbitan comprising 2 to 10 oxyethylene patterns, and cosmetic treatment method using said composition
EP2198929A1Dec 18, 2009Jun 23, 2010L'orealHair dye or lightening composition comprising a fatty substance and a cationic polymer, and use thereof
EP2301630A2Dec 18, 2009Mar 30, 2011L'OréalOxidizing composition for the treatment of keratin fibres comprising a cationic polymer, a fatty amide and an anti-oxygen agent
EP2343040A2Dec 17, 2010Jul 13, 2011L'OréalCosmetic composition containing at least one organic silicon compound, at least one anionic surface-active agent and at least one amine silicone as well as a method implementing said composition
WO2010070140A1Dec 21, 2009Jun 24, 2010L'orealAntiperspirant composition containing at least one complex formed by combining at least one anionic species and at least one cationic species, and process for treating human perspiration
WO2011044859A1Oct 16, 2009Apr 21, 2011Masarykova UniverzitaAn apparatus and method for improving felting properties of animal fibres by plasma treatment
WO2011074140A1Dec 18, 2009Jun 23, 2011L'orealProcess for treating keratin fibers
WO2011107432A2Feb 28, 2011Sep 9, 2011L'orealComposition comprising ellagic acid and a particular cationic surfactant, and cosmetic use thereof
WO2011107433A2Feb 28, 2011Sep 9, 2011L'orealCosmetic composition based on ellagic acid or a derivative thereof and a bacterial extract
WO2011107467A2Mar 1, 2011Sep 9, 2011L'orealCosmetic composition based on ellagic acid or a derivative thereof and on a particular mixture of surfactants
WO2011107468A2Mar 1, 2011Sep 9, 2011L'orealCosmetic antidandruff composition based on ellagic acid or a derivative thereof and a second, different active compound in a specific weight ratio
WO2011107469A1Mar 1, 2011Sep 9, 2011L'orealUse of ellagic acid as an anti-dandruff agent
WO2012032055A1Sep 6, 2011Mar 15, 2012L'orealCosmetic composition comprising at least one cationic polymer and at least two cationic surfactants
WO2012032673A1Sep 8, 2010Mar 15, 2012L'orealCosmetic composition for keratin fibers
WO2012038536A2Sep 23, 2011Mar 29, 2012L'orealCosmetic composition comprising at least one hygroscopic salt, at least one aromatic polyol ether and at least one diol, and cosmetic treatment process
WO2012042019A2Sep 30, 2011Apr 5, 2012L'orealProcess for treating keratin fibres using at least one sulfureous reducing agent, at least one cationic polymer and at least one mercaptosiloxane.
WO2012049145A1Oct 11, 2011Apr 19, 2012L'orealCosmetic composition comprising a particular silicon derivative and one or more acrylic thickening polymers
WO2012055807A1Oct 24, 2011May 3, 2012L'orealCosmetic composition comprising a fatty-chain alkoxysilane and a cationic polymer
WO2012055812A1Oct 24, 2011May 3, 2012L'orealCosmetic composition comprising a fatty-chain alkoxysilane and an antidandruff agent.
WO2012059410A1Oct 28, 2011May 10, 2012L'orealDye composition having a low content of ammonia
WO2012072765A1Dec 1, 2011Jun 7, 2012L'orealCosmetic composition containing a non-amino silicone, a liquid fatty ester and an amino silicone, process and use
WO2012084863A1Dec 19, 2011Jun 28, 2012L'orealCosmetic composition comprising a zinc salt and 1,2-octanediol
WO2012084866A1Dec 19, 2011Jun 28, 2012L'orealComposition comprising a non-nitrogenous zinc salt and a particular cationic surfactant
WO2012084867A1Dec 19, 2011Jun 28, 2012L'orealCosmetic composition comprising a zinc salt, a cationic polymer and a propellant
WO2012084901A1Dec 20, 2011Jun 28, 2012L'orealCosmetic composition comprising a zinc salt and a solid fatty ester
WO2012084903A1Dec 20, 2011Jun 28, 2012L'orealCosmetic composition comprising a particular zinc salt and an amino silicone
WO2012084904A1Dec 20, 2011Jun 28, 2012L'orealCosmetic composition comprising a particular zinc salt and a starch
WO2012137165A2Apr 5, 2012Oct 11, 2012L'orealA hair treatment method
WO2012149617A1May 4, 2011Nov 8, 2012L'oreal S.A.Detergent cosmetic compositions comprising four surfactants, a cationic polymer and a silicone, and use thereof
WO2012163868A2May 28, 2012Dec 6, 2012L'orealComposition comprising an alkoxysilane, a fatty ester and a silicone, and cosmetic use thereof
WO2012163869A2May 28, 2012Dec 6, 2012L'orealComposition comprising an alkoxysilane and a modified starch, and cosmetic use thereof
WO2012164065A2Jun 1, 2012Dec 6, 2012L'orealProcess for treating straightened keratin fibres
WO2012171850A2Jun 8, 2012Dec 20, 2012L'orealCosmetic composition comprising an anionic surfactant, a nonionic or amphoteric surfactant and a solid fatty alcohol, and cosmetic treatment process
WO2013004773A2Jul 5, 2012Jan 10, 2013L'orealCosmetic composition rich in fatty substances comprising a polyoxyalkylenated fatty alcohol ether and a direct dye and/or an oxidation dye, the dyeing method and the device
WO2013042274A1Sep 22, 2011Mar 28, 2013L'orealCosmetic cleansing composition
WO2013092608A2Dec 18, 2012Jun 27, 2013L'orealCosmetic composition comprising a hydrophobically modified cellulose, a sulfated or sulfonated anionic surfactant and a branched fatty alcohol
WO2013092722A1Dec 19, 2012Jun 27, 2013L'orealCosmetic composition comprising a hydrophobically modified cellulose and an anionic surfactant comprising one or more carboxylate group(s)
WO2013110653A1Jan 23, 2013Aug 1, 2013L'orealComposition comprising at least one specific alkoxysilane polymer
WO2013144871A1Mar 27, 2013Oct 3, 2013L'orealCosmetic process for caring for and/or making up keratin materials
WO2014002290A1Jun 29, 2012Jan 3, 2014L'orealCosmetic composition for keratin fibers
WO2014020146A2Aug 2, 2013Feb 6, 2014L'orealDyeing composition comprising at least one fatty substance, at least one oxidizing agent and at least one non-ionic, anionic and amphoteric surfactant
WO2014020147A2Aug 2, 2013Feb 6, 2014L'orealDyeing composition comprising a fatty substance, a non-ionic guar gum, an amphoteric surfactant and a non-ionic or anionic surfactant, and an oxidizing agent, dyeing process and suitable device
WO2014056962A2Oct 9, 2013Apr 17, 2014L'orealCosmetic composition comprising a bacterial lysate, a thickener and a particular surfactant system, and cosmetic treatment process
WO2014068795A1Oct 31, 2012May 8, 2014L'orealUse of triazine derivatives for permanent deformation of keratin fibers
WO2014091111A2Nov 27, 2013Jun 19, 2014L'orealCosmetic composition comprising the association of nonionic and cationic surfactants, and cosmetic treatment method
WO2014091125A2Dec 6, 2013Jun 19, 2014L'orealCosmetic composition comprising a nonionic surfactant, a cationic surfactant, a liquid fatty ester and a particular silicone, and cosmetic treatment method
Classifications
U.S. Classification442/106, 427/393.2, 525/430
International ClassificationD06M15/37, D06M15/59
Cooperative ClassificationD06M15/59
European ClassificationD06M15/59