|Publication number||US2961347 A|
|Publication date||Nov 22, 1960|
|Filing date||Nov 13, 1957|
|Priority date||Nov 13, 1957|
|Publication number||US 2961347 A, US 2961347A, US-A-2961347, US2961347 A, US2961347A|
|Inventors||Floyd John D|
|Original Assignee||Hercules Powder Co Ltd|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Referenced by (170), Classifications (7) |
|External Links: USPTO, USPTO Assignment, Espacenet|
Process for preventing shrinkage and felting of wool
US 2961347 A
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.
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.
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|US7220285||Apr 27, 2006||May 22, 2007||L'oreal S.A.||Pulverulent composition for bleaching human keratin fibers|
|US7220408||Nov 8, 2002||May 22, 2007||L'oreal, S.A.||Mixture of aminosilicone and thickener|
|US7223385||Nov 8, 2002||May 29, 2007||L'oreal S.A.||Cosmetic compositions containing a particular aminosilicone and a conditioner, and uses thereof|
|US7226486||Jan 15, 2004||Jun 5, 2007||L'oreal S.A||Ready-to-use bleaching compositions, preparation process and bleaching process|
|US7232561||Jun 2, 2003||Jun 19, 2007||L'oreal S.A.||Washing compositions comprising at least one amphiphilic block copolymer and at least one cationic or amphoteric polymer|
|US7250064||Apr 1, 2004||Jul 31, 2007||L'oreal S.A.||Using crosslinked acrylic polymer|
|US7258852||Sep 10, 2002||Aug 21, 2007||L'oreal S.A.||Cosmetic compositions containing a methacrylic acid copolymer and an oil, and uses thereof|
|US7261744||Dec 23, 2003||Aug 28, 2007||L'oreal S.A.||Method for dyeing or coloring human keratin materials with lightening effect using a composition comprising at least one fluorescent compound and at least one optical brightener|
|US7267696||Mar 25, 2004||Sep 11, 2007||L'oreal S.A.||Composition for dyeing keratinous fibers, comprising a hydroxycarboxylic acid or a salt, ready-to-use composition comprising it, implementation process and device|
|US7294152||Jan 7, 2005||Nov 13, 2007||L'oreal S.A.||Dyeing composition comprising at least one fluorindine compound for the dyeing of keratinic fibers, dyeing process comprising the composition and compound|
|US7303588||Mar 25, 2004||Dec 4, 2007||L'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|
|US7303589||Apr 1, 2004||Dec 4, 2007||L'oreal S.A.||Process for dyeing human keratin fibers, having a lightening effect, comprising at least one fluorescent compound and compositions of the same|
|US7323015||Oct 21, 2003||Jan 29, 2008||L'oreal S.A.||Dyeing human hair|
|US7326256||Dec 8, 2003||Feb 5, 2008||L'ORéAL S.A.||dyeing human hair; aqueous solution|
|US7329287||Dec 8, 2003||Feb 12, 2008||L'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|
|US7364594||Nov 22, 2001||Apr 29, 2008||L'oreal S.A.||E.g., a quaternized polyetherurethane copolymer and an acrylamide/ dimethyldiallylammonium chloride/acrylic acid terpolymer.|
|US7402180||Jul 11, 2006||Jul 22, 2008||L'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|
|US7429275||Dec 23, 2005||Sep 30, 2008||L'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|
|US7431740||Nov 22, 2001||Oct 7, 2008||L'oreal, S.A.||Oxidation dyeing composition for keratinous fibers comprising an associative polymer and a pearling agent|
|US7442214||Mar 31, 2006||Oct 28, 2008||L'oreal S.A.||Dye composition comprising at least one non-ionic associative polymer and process for dyeing keratin fibers using same|
|US7485289||Feb 15, 2007||Feb 3, 2009||L'oreal, S.A.||Cosmetic compositions containing a particular aminosilicone and a conditioner, and uses thereof|
|US7498022||Mar 28, 2003||Mar 3, 2009||L'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|
|US7504094||Feb 15, 2007||Mar 17, 2009||L'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|
|US7510705||Sep 21, 2006||Mar 31, 2009||L'oreal, S.A.||Process for permanently reshaping the hair using particular aminosilicones|
|US7550015||Mar 31, 2006||Jun 23, 2009||L'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|
|US7569078||Mar 31, 2006||Aug 4, 2009||L'oreal S.A.||Dye composition comprising at least one cellulose and process for dyeing keratin fibers using the dye composition|
|US7575605||Mar 31, 2006||Aug 18, 2009||L'oreal S.A.||Dye composition comprising at least one glycerol ester and a process for dyeing keratin fibers using the composition|
|US7578854||Mar 31, 2006||Aug 25, 2009||L'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|
|US7608115||Apr 30, 2004||Oct 27, 2009||L'oreal S.A.||Via applying direct dye, oxidation base, coupler, and oxidizing agent, then heating; oxidation color dyes; hair conditioners; cosmetics|
|US7651533||Mar 31, 2006||Jan 26, 2010||Oreal||Dye composition with a reduced content of starting materials, process for dyeing keratin fibers using the same and device therefor|
|US7708981||Mar 10, 2004||May 4, 2010||L'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|
|US7736631||Apr 1, 2004||Jun 15, 2010||L'oreal S.A.||Organic pigment colors and a modified polydimethylsiloxane homopolymer or copolymers for lightening hair or skin; multi-compartment kit for dyeing|
|US7771491||Dec 21, 2007||Aug 10, 2010||L'oreal S.A.||Hair dye; environmentally friendly, due to use of nonionic cellulose; good shampoo fastness|
|US7771492||Feb 23, 2009||Aug 10, 2010||L'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|
|US7799093||Oct 25, 2007||Sep 21, 2010||L'ORéAL S.A.||Coloring composition of keratinous fibers comprising at least one polysiloxane/polyurea block copolymer|
|US7867969||Oct 30, 2006||Jan 11, 2011||L'oreal S.A.||Composition for washing keratin materials comprising a magnesium salt anionic surfactant|
|US7914775||Nov 6, 2001||Mar 29, 2011||L'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|
|US7928087||Jan 11, 2002||Apr 19, 2011||L'oreal||provides 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|
|US7976831||Apr 4, 2005||Jul 12, 2011||L'oreal S.A.||Method for treating hair fibers|
|US7998464||Sep 28, 2006||Aug 16, 2011||L'oreal S.A.||Process for the photoprotective treatment of artificially dyed keratin fibers by application of a liquid water/steam mixture|
|US8349363||Nov 7, 2008||Jan 8, 2013||Kimberly-Clark Worldwide, Inc.||Temperature responsive delivery systems|
|US8557226||Jan 18, 2010||Oct 15, 2013||Isp Investments Inc.||Performance-boosting UV-absorbing compounds|
|US8586014||Oct 30, 2006||Nov 19, 2013||L'oreal||Composition for the care of keratin material and cosmetic treatment process using said composition|
|US8673272||Jul 22, 2010||Mar 18, 2014||Isp Investments Inc.||Ultraviolet-absorbing compounds|
|US8703109||Mar 28, 2008||Apr 22, 2014||L'oreal||Protection of keratinous fibers using ceramides and/or glycoceramides|
|US8784506||Oct 28, 2011||Jul 22, 2014||L'oreal||Dye composition having a low content of ammonia|
|DE2808841A1 *||Mar 1, 1978||Sep 7, 1978||Oreal||Haarkosmetisches mittel und haarbehandlungsverfahren|
|DE202013011676U1||Nov 8, 2013||Feb 14, 2014||L'oreal||Zusammensetzung, die eine Dicarbonylverbindung enthält|
|EP0723772A1||Jan 10, 1996||Jul 31, 1996||L'oreal||Reducing composition bared on a basic amino acid and a cationic polymer|
|EP2011473A1||Jun 26, 2008||Jan 7, 2009||L'Oreal||Anhydrous composition in paste form for bleaching keratinous fibres.|
|EP2065023A2||Nov 28, 2008||Jun 3, 2009||L'Oreal||Hairstyling composition comprising at least one (meth)acrylic copolymer and at least one pearlescent agent|
|EP2065024A2||Nov 28, 2008||Jun 3, 2009||L'Oreal||Hairstyling composition comprising (meth)acrylic copolymers and at least one oil|
|EP2072033A2||Sep 12, 2008||Jun 24, 2009||L'Oreal||Cosmetic 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|
|EP2198929A1||Dec 18, 2009||Jun 23, 2010||L'oreal||Hair dye or lightening composition comprising a fatty substance and a cationic polymer, and use thereof|
|EP2301630A2||Dec 18, 2009||Mar 30, 2011||L'Oréal||Oxidizing composition for the treatment of keratin fibres comprising a cationic polymer, a fatty amide and an anti-oxygen agent|
|EP2343040A2||Dec 17, 2010||Jul 13, 2011||L'Oréal||Cosmetic 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|
|WO2010070140A1||Dec 21, 2009||Jun 24, 2010||L'oreal||Antiperspirant 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|
|WO2011044859A1||Oct 16, 2009||Apr 21, 2011||Masarykova Univerzita||An apparatus and method for improving felting properties of animal fibres by plasma treatment|
|WO2011074140A1||Dec 18, 2009||Jun 23, 2011||L'oreal||Process for treating keratin fibers|
|WO2011107432A2||Feb 28, 2011||Sep 9, 2011||L'oreal||Composition comprising ellagic acid and a particular cationic surfactant, and cosmetic use thereof|
|WO2011107433A2||Feb 28, 2011||Sep 9, 2011||L'oreal||Cosmetic composition based on ellagic acid or a derivative thereof and a bacterial extract|
|WO2011107467A2||Mar 1, 2011||Sep 9, 2011||L'oreal||Cosmetic composition based on ellagic acid or a derivative thereof and on a particular mixture of surfactants|
|WO2011107468A2||Mar 1, 2011||Sep 9, 2011||L'oreal||Cosmetic antidandruff composition based on ellagic acid or a derivative thereof and a second, different active compound in a specific weight ratio|
|WO2011107469A1||Mar 1, 2011||Sep 9, 2011||L'oreal||Use of ellagic acid as an anti-dandruff agent|
|WO2012032055A1||Sep 6, 2011||Mar 15, 2012||L'oreal||Cosmetic composition comprising at least one cationic polymer and at least two cationic surfactants|
|WO2012032673A1||Sep 8, 2010||Mar 15, 2012||L'oreal||Cosmetic composition for keratin fibers|
|WO2012038536A2||Sep 23, 2011||Mar 29, 2012||L'oreal||Cosmetic composition comprising at least one hygroscopic salt, at least one aromatic polyol ether and at least one diol, and cosmetic treatment process|
|WO2012042019A2||Sep 30, 2011||Apr 5, 2012||L'oreal||Process for treating keratin fibres using at least one sulfureous reducing agent, at least one cationic polymer and at least one mercaptosiloxane.|
|WO2012049145A1||Oct 11, 2011||Apr 19, 2012||L'oreal||Cosmetic composition comprising a particular silicon derivative and one or more acrylic thickening polymers|
|WO2012055807A1||Oct 24, 2011||May 3, 2012||L'oreal||Cosmetic composition comprising a fatty-chain alkoxysilane and a cationic polymer|
|WO2012055812A1||Oct 24, 2011||May 3, 2012||L'oreal||Cosmetic composition comprising a fatty-chain alkoxysilane and an antidandruff agent.|
|WO2012059410A1||Oct 28, 2011||May 10, 2012||L'oreal||Dye composition having a low content of ammonia|
|WO2012072765A1||Dec 1, 2011||Jun 7, 2012||L'oreal||Cosmetic composition containing a non-amino silicone, a liquid fatty ester and an amino silicone, process and use|
|WO2012084863A1||Dec 19, 2011||Jun 28, 2012||L'oreal||Cosmetic composition comprising a zinc salt and 1,2-octanediol|
|WO2012084866A1||Dec 19, 2011||Jun 28, 2012||L'oreal||Composition comprising a non-nitrogenous zinc salt and a particular cationic surfactant|
|WO2012084867A1||Dec 19, 2011||Jun 28, 2012||L'oreal||Cosmetic composition comprising a zinc salt, a cationic polymer and a propellant|
|WO2012084901A1||Dec 20, 2011||Jun 28, 2012||L'oreal||Cosmetic composition comprising a zinc salt and a solid fatty ester|
|WO2012084903A1||Dec 20, 2011||Jun 28, 2012||L'oreal||Cosmetic composition comprising a particular zinc salt and an amino silicone|
|WO2012084904A1||Dec 20, 2011||Jun 28, 2012||L'oreal||Cosmetic composition comprising a particular zinc salt and a starch|
|WO2012137165A2||Apr 5, 2012||Oct 11, 2012||L'oreal||A hair treatment method|
|WO2012149617A1||May 4, 2011||Nov 8, 2012||L'oreal S.A.||Detergent cosmetic compositions comprising four surfactants, a cationic polymer and a silicone, and use thereof|
|WO2012163868A2||May 28, 2012||Dec 6, 2012||L'oreal||Composition comprising an alkoxysilane, a fatty ester and a silicone, and cosmetic use thereof|
|WO2012163869A2||May 28, 2012||Dec 6, 2012||L'oreal||Composition comprising an alkoxysilane and a modified starch, and cosmetic use thereof|
|WO2012164065A2||Jun 1, 2012||Dec 6, 2012||L'oreal||Process for treating straightened keratin fibres|
|WO2012171850A2||Jun 8, 2012||Dec 20, 2012||L'oreal||Cosmetic composition comprising an anionic surfactant, a nonionic or amphoteric surfactant and a solid fatty alcohol, and cosmetic treatment process|
|WO2013004773A2||Jul 5, 2012||Jan 10, 2013||L'oreal||Cosmetic 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|
|WO2013042274A1||Sep 22, 2011||Mar 28, 2013||L'oreal||Cosmetic cleansing composition|
|WO2013092608A2||Dec 18, 2012||Jun 27, 2013||L'oreal||Cosmetic composition comprising a hydrophobically modified cellulose, a sulfated or sulfonated anionic surfactant and a branched fatty alcohol|
|WO2013092722A1||Dec 19, 2012||Jun 27, 2013||L'oreal||Cosmetic composition comprising a hydrophobically modified cellulose and an anionic surfactant comprising one or more carboxylate group(s)|
|WO2013110653A1||Jan 23, 2013||Aug 1, 2013||L'oreal||Composition comprising at least one specific alkoxysilane polymer|
|WO2013144871A1||Mar 27, 2013||Oct 3, 2013||L'oreal||Cosmetic process for caring for and/or making up keratin materials|
|WO2014002290A1||Jun 29, 2012||Jan 3, 2014||L'oreal||Cosmetic composition for keratin fibers|
|WO2014020146A2||Aug 2, 2013||Feb 6, 2014||L'oreal||Dyeing composition comprising at least one fatty substance, at least one oxidizing agent and at least one non-ionic, anionic and amphoteric surfactant|
|WO2014020147A2||Aug 2, 2013||Feb 6, 2014||L'oreal||Dyeing 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|
|WO2014056962A2||Oct 9, 2013||Apr 17, 2014||L'oreal||Cosmetic composition comprising a bacterial lysate, a thickener and a particular surfactant system, and cosmetic treatment process|
|WO2014068795A1||Oct 31, 2012||May 8, 2014||L'oreal||Use of triazine derivatives for permanent deformation of keratin fibers|
|WO2014091111A2||Nov 27, 2013||Jun 19, 2014||L'oreal||Cosmetic composition comprising the association of nonionic and cationic surfactants, and cosmetic treatment method|
|WO2014091125A2||Dec 6, 2013||Jun 19, 2014||L'oreal||Cosmetic composition comprising a nonionic surfactant, a cationic surfactant, a liquid fatty ester and a particular silicone, and cosmetic treatment method|