JP4933251B2 - Cationic oxidized polysaccharides for conditioning applications - Google Patents

Abstract

A cationic, oxidized polysaccharide or derivative thereof that has a mean average molecular weight (Mw) having a lower limit of 50,000 and an upper limit of 1,000,000 and an aldehyde functionality content of at least 0.001meq/gram is used in personal care and household care compositions. This cationic, oxidized polysaccharide is prepared in continuous or batch processes using hydrolytic reagents, oxidizing reagents, or combination of hydrolytic reagents and oxidizing reagents. Personal care or household care compositions are prepared by adding the cationic, oxidized polysaccharide to a personal care or household composition containing at least one active ingredient other than the cationic, oxidized polysaccharide of this invention.

Description

Field of Invention

The present invention relates to the use of cationic oxidized polysaccharide compositions in personal care and household compositions.

Background of the Invention Cationic polysaccharides and other polymers are widely used in personal care and household products to perform functions ranging from thickening of substrates to conditioning in end products. Depending on the application, the substrate can be skin, hair, or textile material.

  In hair care products, cationic polysaccharides are used to provide conditioning to the hair. Similar polymers can provide a conditioning effect to the skin in skin care products. When such a polymer is included in a detergent or fabric soft finish formulation, it can impart conditioning, soft finish, anti-pilling, dye retention and antistatic properties to the fabric.

  Hair conditioning agents function in a cuticle or outer coat of keratinized flakes on the fiber surface of the hair. Cuticle flakes are arranged in an overlapping manner like a roofing board. The cell structure of the cuticle is composed of an A layer (outer cuticle) and a B layer (inner cuticle). A clear outer A layer of sulfur-containing protein protects the hair from chemical, physical and environmental damage. Thus, the state of the cuticle is an indicator of the state of the hair, and hair conditioning products are aimed at strengthening and restoring the cuticle shaft layer. A complete cuticle provides hair strength, shine, softness, smoothness and ease of handling. (Conditioning Agents for Hair & Skin, edited by R. Schueller and P. Romanowski, Marcel Dekker, Inc., New York, NY, 1999).

  Combability measurement in wet and dry conditions is a typical test method used to measure conditioning performance in shampoo and conditioner applications. Commercially available cationic conditioning polymers have been reported to reduce the wet combing force produced when combing wet hair by 30% to 50% compared to shampoos that do not contain the polymer.

  Conventionally, cleansing products have exclusively used high molecular weight cationic polymers, and it has been suggested that only high molecular weight cationic polymers can provide the conditioning effect required for cleansing systems (V. Andre, R. Norenberg, J. Rieger, P. Hoessel, Proceedings, 21st IFSCC International Conference Bulletin (2000, Berlin), pages 189-199). However, high molecular weight cationic guar conditioning polymers available on the market have drawbacks, such as incompatibility with surfactant systems used in shampoos, body detergents, conditioners, skin care, sun care, laundry products, etc. is there. In addition, the polymer contributes to the viscosity of the final product, which is often undesirable. High molecular weight cationic guar polymers are also known to be difficult to disperse and dissolve in aqueous solutions.

  US Pat. No. 6,210,689 (B1) discloses the use of amphoteric guar gum compositions containing cationic and anionic groups attached to the backbone for treating keratin materials. This composition is used in aqueous systems for cosmetics such as shampoos, topical sprays, dental care products, and products containing fragrances and / or antibacterial agents.

  US Pat. No. 5,756,720 describes a process for making a polygalactomannan composition having nonionic and cationic groups attached to the backbone. This patent explains that high optical clarity has been achieved in cleansing surfactant formulations containing this composition. However, the hydroxypropyl cationic polygalactomannan of this composition has been found to be deficient in conditioning performance, as described in WO 99/36054.

  US Pat. No. 5,489,674 describes a process for making polygalactomannan gum and polygalactomannan gum compositions made by a special process involving the processing of hydroalcoholics. This product is described as having a transmittance of 85-100% at a wavelength of 500-600 nm in 0.5 parts of polymer in 100 parts of aqueous solution. The use of this material in personal care applications is disclosed.

  Japanese Patent Application No. 10 [1998] -36403 used a polygalactomannan degradation product in which more than 80% of the molecular weight distribution is in the range of 4,500-35,000 for use in hair and skin care products. A cosmetic composition is disclosed.

  U.S. Pat. Nos. 5,480,984 and 6,054,511 disclose aqueous, high solids, low viscosity polysaccharide compositions and reacting polysaccharides with hydrogen peroxide (oxidant) at 25 ° C. The solid content is about 20% to about 50% and the viscosity is 9500 mPa.s. Disclosed is a method for making the composition by producing a product of less than s. Cellulose ethers, guar and guar derivatives are disclosed as polysaccharides having a wide variety of uses, for example in cosmetics.

  U.S. Patent Application No. 2003030199403 (A1) discloses a shampoo composition comprising a detergent having a cleaning effect, a cationic guar derivative and an aqueous carrier. The cationic guar derivative has a charge density of about 1.25 meq / g to about 7 meq / g and a molecular weight of about 10,000 to about 10,000,000.

Highly cationically substituted cationic HECs, such as Ucare Polymer JR400 ^™ , have been cited by manufacturers as causing “build-up” problems after repeated specifications. One manufacturer recommends the use of cationic HECs with lower cation substitution levels to eliminate build-up problems (“Cationic Conditioners that Revitalize Hair and Skin”, Amerchol Product Literature, WSP 801, 1998 7). Moon). According to this manufacturer, buildup is defined as the polymer binding to the substrate, which makes it difficult for the polymer to separate from the substrate in subsequent cleansing processes.

  There remains a need in the market for cationic conditioning polymers that are compatible with a wide range of surfactants and can provide personal care and household formulations with excellent conditioning performance. The present invention provides a cationic conditioning polymer that not only has excellent conditioning performance with compatibility with a wide range of surfactants, but is economical to formulate into compositions where transparency is not necessarily important. By providing it meets this need.

BRIEF SUMMARY OF THE INVENTION The present invention, the lower limit of 50,000 and have a weight average molecular weight upper limit 1,000,000 (Mw), having at least 0.001 meq / g level of aldehyde functional groups, It relates to personal care and household compositions comprising at least one cationic oxidized polysaccharide or derivatives thereof.

  The Brookfield viscosity of the cationic oxidized polysaccharides or derivatives thereof is preferably 10% by weight of polysaccharide solids at 25 ° C., lower limit 30 cps, and upper limit 20,000 cps when spindle 4 is used at 30 rpm. However, if the polysaccharide has a viscosity greater than 20,000 cps, the Brookfield viscosity is 10 wt% solids using a spindle 4 at 0.3 rpm, 25 ° C., and a lower limit of 20,000 cps. And an upper limit of 2,000,000. This viscosity range is particularly preferred for cationic oxidized polygalactomannans.

  The present invention further relates to a method for producing a personal care or household composition, wherein the method comprises a cationic oxidized polysaccharide comprising at least one active ingredient other than the cationic oxidized polysaccharide of the present invention. Adding to the composition for use.

DETAILED DESCRIPTION OF THE INVENTION Surprisingly, according to the present invention, the cationic oxidized polysaccharide of the present invention is a cleansing product such as a shampoo, one shampoo having two functions (ie hair cleansing and conditioning). Shampoo with three functions in one (ie, clean, condition, hair styling), conditioner, shower gel, liquid soap, body detergent, hair styling product, shaving gel / cream, body cleaner, and It has been found that a desired conditioning effect or lubricating effect can be imparted to the soap bar. When the polymers of the present invention are included in various cleansing shampoo surfactant systems that require conditioning or lubricating properties that reduce wet and dry combing forces well, such properties are imparted to the hair. Also, when the polymers of the present invention are included in skin care, sun care, body detergents, body cleaners and bar soaps, they impart a softer feel conditioning or lubricating property to the skin.

  Similar conditioning or lubricating effects are expected in surfactant-based household cleansing product formulations that require conditioning performance, such as dishwashing detergents, laundry detergents, fabric softeners, and antistatic products Is done. Conditioning in fabric softeners and laundry detergents means providing the fabric with a softer feel, anti-pilling, pigment retention, and eliminating electrostatic effects.

  The cationic functional group of the polysaccharide or derivatized polysaccharide can be added to the main chain by a known method. For example, polysaccharide materials and tertiary amino or quaternary ammonium alkylating reagents such as 2-dialkylaminoethyl chloride, and quaternary ammonium compounds such as 3-chloro-2-hydroxypropyltrimethylammonium chloride, and 2,3-epoxy-propyltrimethylammonium chloride may be reacted at a sufficient temperature for a sufficient time. Preferred examples include glycidyl trialkyl ammonium salts and 3-halo-2-hydroxypropyl trialkyl ammonium salts such as glycidyl trimethyl ammonium chloride, glycidyl triethyl ammonium chloride, glycidyl tripropyl ammonium chloride, glycidyl ethyl dimethyl ammonium. Chloride, glycidyl diethylmethylammonium chloride and their corresponding bromides and iodides; 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, 3-chloro 2-hydroxypropyltripropylammonium chloride, 3-chloro-2-hydroxypropylethyldimethylammonium chloride, and Bromides and iodides response; and quaternary ammonium compounds such as halides of imidazoline ring containing compounds.

  Cationic polysaccharides may also contain other substituents, such as non-ionic substituents (ie, hydroxyalkyl), where alkyl is a straight chain having 1 to 30 carbon atoms or Indicates a branched hydrocarbon component (eg, hydroxyethyl, hydroxypropyl, hydroxybutyl), and an anionic substituent (eg, carboxymethyl group) is optional. These optional substituents are linked to the polysaccharide polymer by reacting with a reagent, which comprises, for example, (1) an alkylene oxide (eg, to obtain a hydroxyethyl, hydroxypropyl, or hydroxybutyl group) Ethylene oxide, propylene oxide, butylene oxide) or (2) chloromethylacetic acid to obtain a carboxymethyl group. Processes for producing derivatized polygalactomannans are well known in the art.

  Polysaccharides can be oxidized by several known reagents and methods such as (1) biochemical oxidants (eg galactose oxidase), (2) chemical oxidants (eg hydrogen peroxide), (3) Physical methods using high speed agitation and shearing machines, (4) thermal methods, and (5) mixtures of these reagents and methods.

  According to the present invention, the cationic oxidized polysaccharide used to produce a personal care or household composition having excellent conditioning properties is preferably produced using an oxidizing reagent alone or has a molecular weight. And / or in combination with other reagents such as biochemical reagents that introduce oxidized functional groups. In order to achieve optimal results, it is necessary that the process include an oxidation step by itself or with other reagents.

  Oxidizing agents include any reagent that allows oxygen atoms to be incorporated into the polymer structure. Some oxidizing reagents may also act to reduce the molecular weight of the polymer. Examples of these dual function oxidants are peroxides, peracids, persulfates, permanganates, perchlorates, hypochlorites, and oxygen. An example of a biochemical oxidant that does not reduce molecular weight is oxidase. Particular examples of oxidases useful in the present invention are galactose oxidase and other biochemical oxidants known to those skilled in the art.

  Cationic polymers made using oxidants are superior to cationic polymers not treated with oxidants in a wide variety of surfactant systems commonly used in personal care and household compositions. In view of its high solubility, it has been found useful to incorporate an oxidant into the process for producing the product of the present invention.

  As noted above, aldehyde groups are introduced into the polymer composition by incorporating an oxidant into the process to produce a product used to produce the personal care and household compositions of the present invention. These polymers were found to contain at least 0.001 milliequivalent (aldehyde) / gram (polysaccharide) (milliequivalent / g). The upper limit of aldehyde content is about 1.0 meq / g.

  According to the present invention, the cationic oxidized polysaccharides or derivatives thereof generally have a cationic degree of substitution (DS) with a lower limit of about 0.001 and an upper limit of about 3.0. The lower limit of the cationic DS is preferably 0.01, more preferably 0.05. The upper limit of the cationic DS is preferably 2.0, more preferably 1.0, and even more preferably 0.25. The cationic oxidized polysaccharides or derivatives thereof of the present invention generally have a weight average molecular weight (Mw) with a lower limit of about 50,000 and an upper limit of about 1,000,000. Preferably, the lower limit for Mw is about 75,000, more preferably about 100,000. The upper limit of Mw is preferably about 600,000, more preferably about 300,000, and even more preferably about 150,000.

According to the present invention, the personal care active ingredient must provide several benefits to the user's body. Personal care products include hair care, skin care, sun care, and oral care products. Examples of substances that can be suitably included in the personal care product according to the present invention include, but are not limited to:
1) Perfume; can cause olfactory reactions in the form of fragrances and deodorant fragrances, in addition to providing a response to scents, can reduce body malodor;
2) Skin coolants, such as menthol, menthyl acetate, menthyl pyrrolidone carboxylate N-ethyl-p-menthane-3-carboxamide, and other menthol derivatives; cause a tactile reaction in the form of a cooling sensation in the skin;
3) emollients such as isopropyl myristate, silicone materials, mineral and vegetable oils; cause tactile reactions in a form that increases the lubricity of the skin;
4) Deodorant other than perfume; its function is to reduce or eliminate the level of microflora on the skin surface, especially the microflora involved in the generation of malodor in the body. Also, deodorant precursors other than fragrances can be used;
5) Antiperspirant active; its function is to reduce or eliminate sweating on the skin surface;
6) moisturizer; keeps the skin moist by either adding moisture to the skin or preventing evaporation of moisture from the skin;
7) Cleansing agent; removes dirt and oil from the skin;
8) Sunscreen active ingredient; protects skin and hair from harmful rays from the sun such as UV. According to the present invention, a therapeutically effective amount is normally expected to be 0.01 to 10%, preferably 0.1 to 5% by weight of the composition;
9) Hair treatment agent: Conditioning hair, cleansing hair, untangling hair, hair styling agent, volumetric and gloss-enhancing agent, anti-dandruff agent, hair growth promoter, hair dye and pigment, hair Acts as a fragrance, hair relaxer, hair bleach, hair moisturizer, hair oil treatment and anti-curling agent;
10) Oral care agents such as dentifrices and mouthwashes; clean, whiten, deodorize and protect teeth and gums;
11) Denture adhesives; provide adhesive properties to dentures;
12) Sheets for lubricating shaving products, such as creams, gels and lotions, and razor blades;
13) Tissue paper products such as moisturizing or cleansing tissue;
14) Cosmetics such as foundation powders, lipsticks and eye care; and
15) Textile products such as moisturizing and / or cleansing wipes and diapers;
16) Nail care products such as nail polish.

According to the present invention, the home care active ingredient must provide several benefits to the user. Examples of substances that can be appropriately included in the present invention include, but are not limited to:
1) Perfume; in addition to causing an olfactory reaction in the form of fragrance and deodorant fragrance and providing a response to the scent, it can reduce malodors;
2) insect repellent; its function is to keep insects out of specific areas or from attacking the skin;
3) A foam-forming agent, such as a surfactant that produces foam or foam;
4) Pet deodorants such as pyrethrins that reduce pet odor;
5) Pet shampoo and active substances; its function is to remove dirt, foreign matter and microorganisms from the skin and hair surfaces and to condition the skin and hair;
6) Industrial grade solid, shower gel and liquid soap actives; remove microorganisms, dirt, grease and oil from the skin, make the skin hygienic and condition the skin;
7) Multipurpose cleaning agent; removes dirt, oil, grease and microorganisms from the surface of areas such as kitchens, bathrooms and public facilities;
8) Disinfecting ingredients; kill or prevent the growth of microorganisms at home or public facilities;
9) Cleaning actives for rugs and upholstery materials; removes dirt and foreign matter from the surface and removes them, and gives a soft finish and fragrance;
10) Laundry softener active substance; reduces static electricity and softens the feel of the fabric;
11) Laundry cleaning ingredients; removes dirt, oil, grease, stains and kills microorganisms;
12) Dishwashing detergent; removes stains, food and microorganisms;
13) Toilet bowl cleaning agent; removes stains, kills microorganisms and deodorizes;
14) Laundry pre-spot active agent; promotes removal of stains from clothing;
15) sizing agent for textiles; improving the appearance of the textiles;
17) Vehicle cleaning activator; removes dirt, grease, etc. from vehicles and equipment;
18) lubricants; reduce friction between parts; and
19) Textile products, such as wipes for dust collection or wipes for disinfection.

The above list of personal care and household active ingredients is only an example and is not a complete list of active ingredients that can be used. Other ingredients used in these types of products are well known in the art. In addition to the above-described components used conventionally, the composition according to the present invention may also optionally include, but are not limited to, colorants, preservatives, antioxidants, nutritional supplements, alpha or beta hydroxy acids, activity enhancers, Emulsifiers, functional polymers, thickeners (eg salts, ie NaCl, NH ₄ Cl and KCl, water soluble polymers, ie hydroxyethyl cellulose, and aliphatic alcohols, ie cetyl alcohol; water swellable materials, eg clay and silica) , Alcohols having 1 to 6 carbons, fats or aliphatic compounds (ie fatty amides and fatty acid esters and aliphatic alcohol polyethylene glycol ethers), antibacterial compounds, zinc pyrithione, silicone materials, hydrocarbon polymers, skin Softener, oil, surfactant , Pharmaceuticals, flavors, fragrances, suspending agents (i.e. xanthan gum, carbomer, clay, and silica) components such as, and mixtures thereof.

  In accordance with the present invention, examples of functional polymers that can be used in blends with the cationic oxidized polysaccharides or derivatives thereof of the present invention include water-soluble polymers such as Carbopol (R) products. Acrylic acid homopolymers and anionic and amphoteric acrylic copolymers, vinylpyrrolidone homopolymers, and cationic vinylpyrrolidone copolymers; nonionic, cationic, anionic and amphoteric cellulose-based polymers such as hydroxyethylcellulose, hydroxypropylcellulose, Carboxymethylcellulose, hydroxypropylmethylcellulose, cationic hydroxyethylcellulose, cationic carboxymethylhydroxyethylcellulose, and cationic hydroxypropylene Cellulose; Clay; Acrylamide homopolymers and cationic, amphoteric and hydrophobic acrylamide copolymers, polyethylene glycol polymers and copolymers, hydrophobic polyethers, hydrophobic polyether acetals, hydrophobically modified polyether urethanes and other polymers (associations) Hydrophobic polymers, polyethylene oxide-propylene oxide copolymers, and nonionic, anionic, hydrophobic, amphoteric and cationic polysaccharides such as xanthan, chitosan, carboxymethyl guar, alginate, Hydroxypropyl guar, carboxymethyl guar hydroxypropyltrimethylammonium chloride, guar hydroxypropyltrimethylammonium salt Things, hydroxypropyl guar hydroxypropyl trimethyl ammonium chloride and the like.

  According to the invention, silicone materials that can be used include, in particular, polyorganosiloxanes that are insoluble in the composition, which can be in the form of polymers, oligomers, oils, waxes, resins or rubbers. It is.

  Organopolysiloxanes are defined in more detail in Walter Noll's “Chemistry and Technology of Silicones” (1968) Academic Press. These may be volatile or non-volatile.

If volatile, the silicone is more particularly selected from those having a boiling point of 60 ° C to 260 ° C, and even more particularly selected from:
(I) Cyclic silicone containing 3-7, preferably 4-5 silicon atoms. These are, for example, in particular octamethylcyclotetrasiloxane sold under the name “Volatile Silicone 7207” by Union Carbide, or “Silbione 70045V2 from Rhone-Poulenc”. Octamethylcyclotetrasiloxane sold under the name "Decamethyl-cyclopentasiloxane sold under the name" Volatile Silicone 7158 "from Union Carbide, and Decamethyl sold under the name" Sylbione 70045V5 "from Rhone-Poulenc -Cyclopentasiloxane and mixtures thereof.

Also, a mixture of a cyclic silicone and an organosilicone compound, for example, a mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50), and octamethylcyclotetrasiloxane and oxy-1,1′-bis ( Also included are mixtures with 2,2,2 ′, 2 ′, 3,3′-hexatrimethylsilyloxy) neopentane;
(Ii) A linear volatile silicone having ² to 9 silicon atoms and having a viscosity of less than or equal to 5 × 10 ⁻⁶ m ² / s at 25 ° C. An example is decamethyltetrasiloxane sold under the name “SH 200” by Toray Silicone company. Silicones belonging to this category are also described in an article published in Cosmetics and Toiletries, Vol. 91, Jan., 76, pp. 27-32, Todd & Byers “Volatile Silicone Fluids for Cosmetics”.

  Preferably, non-volatile silicones, more particularly polyarylsiloxanes, polyalkylsiloxanes, polyalkylarylsiloxanes, silicone rubbers and resins, polyorganosiloxanes modified with organofunctional groups, and mixtures thereof are used.

  According to the invention, usable silicone polymers and resins are in particular polydiorganosiloxanes having a high number average molecular weight of 200,000 to 1,000,000, used alone or as a mixture in a solvent. It is done. The solvent can be selected from volatile silicones, polydimethylsiloxane (PDMS) oil, polyphenylmethylsiloxane (PPMS) oil, isoparaffin, polyisobutylene, methylene chloride, pentane, dodecane and tridecane, or mixtures thereof.

Examples of these silicone polymers and resins are as follows:
Polydimethylsiloxane,
Polydimethylsiloxane / methylvinylsiloxane rubber,
Polydimethylsiloxane / diphenylmethylsiloxane,
Polydimethylsiloxane / phenylmethylsiloxane, and
Polydimethylsiloxane / diphenylsiloxane methylvinylsiloxane.

Products that can be used more specifically in the present invention are the following mixtures:
(A) a mixture formed from a polydimethylsiloxane hydroxylated at the chain end (referred to as dimethiconol according to the CTFA dictionary nomenclature), and a cyclic polydimethylsiloxane (cyclomethicone according to the CTFA dictionary nomenclature) For example, product Q21401 sold by Dow Corning Company;
(B) Mixtures formed from polydimethylsiloxane rubber with cyclic silicones, for example the product SF1214 silicone fluid sold by General Electric Company; this product is SF30 rubber and has a number average molecular weight Equivalent to 500,000 dimethicone and soluble in SF1202 silicone fluid oil (corresponding to decamethylcyclopentasiloxane); and
(C) A mixture formed from two PDMS with different viscosities, more particularly PDMS rubber, and PDMS oil (eg, product SF1236 from General Electric). This product preferably contains 15% SE30 rubber and 85% SF96 oil.

  In order to understand the present invention in more detail, reference may be made to the following examples, which are intended to further illustrate the invention and are not to be construed in a limiting sense. All parts and percentages are based on weight unless otherwise specified.

Example
I. Use of Chemical Oxidizing Reagents-(4-step standard decomposition method)
Material :
Cationic polygalactomannan (guarhydroxypropyltrimonium chloride) -Hercules, Incorporated, CAS # 65497-29-2
Fumaric acid, P.I. A-Across / Fisher Scientific, CAS # 110-17-8
Dow Corning 200 (R) Fluid, 50 CST. -Silicone oil-for Neslab oil bath, CAS # 63448-62-9
Katon (R) CG Stabilizing biocide / preservative-see Rohm and Haas Co, CAS # mixture, MSDS Hydrogen peroxide, 30%-JT Baker-CAS # 7722- 84-1
EM Quant peroxide test strip, manufactured by EM Science.

Procedure ;
The deionized water in the first step was weighed and charged into a beaker, and the beaker was suspended in the bath using a chain clamp. A Caframo stealer model BDC-3030 was fitted with a Kaframo “U” type 4 ”(anchor) paddle, and a digital alarm thermometer probe was attached during the batch. The beaker was covered with saran film and moisture Water was heated to 85-90 ° C. with stirring at −50 rpm in an oil bath set at −95 ° C. The bath temperature maintains the batch temperature at 85-90 ° C. To facilitate oil circulation in the bath, an additional Kaframo mixer model RZR-1 with 2 "propeller blades was used at low speed.

  Increase the steeler speed to ~ 100 rpm as far as the volume allows, and use one-fourth of the total peroxide charge to penetrate the Saran wrap using a suitably sized hypodermic syringe. Added to the beaker by injecting peroxide. The contents of the beaker were mixed for ~ 5 minutes. The beaker cover was then removed very slowly and transferred to the beaker with mixing a quarter of the total charge of cationic polygalactomannan. The stirring speed of the steeler was adjusted so that a sufficient vortex speed was maintained. In particular, when the polygalactomannan is added for the first time, some lumps may be formed, but if the lumps are small, they can be dissolved as the viscosity increases. The cover was removed and mixing continued at a temperature of 85-90 ° C. until the viscosity was reduced to the extent that the next polymer addition was possible.

Considering the time it takes for the polymer to dissolve and the viscosity to decrease before the next further addition, the peroxide and polymer additions are repeated a total of four times to achieve a total charge of H ₂ O ₂ and polygalactomannan. Added. As needed, the amount of water in the beaker was adjusted by the amount of water lost at each interval. Mixing continued for 1 hour after the last addition and then the amount of residual peroxide was examined using an EM Quant Peroxide Test Strip. The mixer was turned off and a small hole was made in Saran where the sensing area of the test strip was immersed in the solution for 1 second. Excess material was shaken off the test strip and after 15 seconds, the color of the sensing area of the test strip was compared to the scale on the container. The reaction was continued until the amount of H ₂ O ₂ was <50 ppm. Note: The sensing area of the test strip is expected to turn dark brown when a large amount of peroxide is present. In this case, a small sample of the solution (~ 5 g) is carefully extracted and diluted with an amount of room temperature deionized water sufficient to allow reading of the test strip with that range of detection.

  The bath was turned off and the oil was moved separately through a Neslab FTC-350 cooler. When the oil had cooled sufficiently, the beaker was carefully removed from the bath (made slippery with silicone oil) and the net weight of the batch was measured. The amount of water required to make up was determined, the water to make up was premixed with 1.0% Germaben II product, and the water / Gamaben II mixture was added with manual stirring. When the solution became very viscous, the beaker was returned to the bath and stabilized biocide and water supplemented with mechanical agitation were added. In order to maintain stability for testing pH, Brookfield viscosity and analysis as needed, the contents of the beaker were sealed in a suitable container while warm.

Combing test Wet comb and dry comb measurements were taken with Instron instruments, mildly decolorized Europeans shampooed with medium anionic surfactant-based shampoos or nonionic surfactant shampoos This was done using a single strand of hair.

  The percent reduction in wet comb and dry comb energy is defined as shown in equation (1). After shampooing with a shampoo containing a cationic polymer, the energy required to comb the hair strands is necessary to comb the hair strands shampooed twice with 4.5 wt% sodium lauryl sulfate (SLS) solution. Subtracted from energy. The remainder of the draw was then divided by the energy required to comb the hair strand washed with the SLS solution. The value was multiplied by 100 to give the percent reduction in combing force. When the cationic conditioning polymer is conditioning the hair, the percent reduction is usually a positive number.

  (1) [Energy (without polymer) (gf-mm) −Energy (with polymer)] / Energy (without polymer)] × 100 = Percent decrease in combing energy

Example 1
The standard decomposition method described above was used. About 935 g of water was charged into a 1500 ml beaker and placed in an oil bath set at a temperature of about 120 ° C. The beaker was then heated to a temperature of about 85-95 ° C. in an oil bath and maintained at this temperature. A double 2 "propeller blade mixer was inserted into the beaker and a small amount of N-Hance (R) 3205 cationic guar product (Hercules, Wilmington, Del.) Was added with stirring. A small amount of peroxide was added to the beaker with continued mixing and mixed at 85-95 ° C. until the viscosity of the mixture was high enough to add the next amount of polymer and peroxide. The polymer and peroxide additions were repeated three times to complete the addition of the total amount of polymer and peroxide, and some water evaporated during the addition of this further polymer and peroxide. At the end of the addition, the amount of water was adjusted by the amount of water lost, and the amount of residual peroxide was checked periodically using a test strip in a beaker, and the remaining amount of peroxide was 50 p. The reaction was continued until less than m.The oil bath was then closed and the beaker was cooled to ambient temperature.Gamaben® II stabilized biocide / preservative (ISP Incorporated, Wayne, NJ) State) was added to the beaker.

  Table 1 below (Experiments A to F) shows the components for this experiment.

Example 2
Experiments G, H and I followed the procedure described in Example 1 above (however, the oil bath temperature was adjusted so that the sample temperature was maintained at about 85-90 ° C., and 1.0% excess). Except that hydrogen oxide solution was used instead of 6.0% solution). Also, the order of addition of polymer and peroxide was reversed, the peroxide was added first, and then the polymer was added. The components of Experiments G, H and I are described in Table 2 below.

Example 3
In the following experiments (Table 2; Experiments J, K and L), the procedure used in Example 2 above was used, except that instead of N-Hance (R) 3205 polymer, N-Hance (R ) Except for using 3215 products (containing fumaric acid).

Example 4
In this series of experiments M, N and O in Example 4, the same procedure was used as in Example 3 (shown in Table 3), but note that: (a) For Experiment M, Jaguar (R) C-13-S Cationic Guar product (Rhodia Incorporated, Cranberry, NJ) was used. (B) For Experiment N, Jaguar (R ) C-162 cationic hydroxypropyl guar product (Rhodia, Cranberry, NJ) was used, and (c) for Experiment O, N-Hans (R) 3215 cationic decomposed only by heating Except that Guar products (Hercules, Wilmington, Delaware) were used and peroxide was not used .

  In Experiment O, it became very viscous after the first polymer addition. The second and third polymer additions were reduced in half, but the viscosity remained very high. Production was discontinued and no garmaben preservative was added. This example shows that thermal decomposition in the absence of hydrogen peroxide proceeds very slowly.

Example 5
In Experiments P, Q and R of this Example 5, the same formulation and procedure used in Example 2 was used (shown in Table 4).

Example 6
In this Example 6 experiments S, T, U, V, W and X, the same procedure used in the series of experiments J, K and L of Example 3 was used (shown in Table 5). In Experiments X and Y, tap water concentrations are in gallons and all material concentrations are in pounds. In experiments W and X, instead of N-Hans 3215 cationic guar powder, a split of cationic guar wetted with aqueous N-Hans 3215 solution was used to neutralize the split of cationic guar to pH 6.5. Hydrochloric acid was used in place of fumaric acid. At the end of the reaction, sodium metabisulfite was added to decompose the remaining peroxide. The product of Experiment X was further treated with sodium hydroxide at pH 8 for 30 minutes, followed by neutralization with dilute hydrochloric acid. The product from Experiment V had an aldehyde content of 0.035 meq / gram, Mw of 61,000. The product from experiment U had a molecular weight of 50,400. For experiment Y, all the hydrogen peroxide and malic acid were added after the reactor was heated to 90 ° C. N-hans cationic guar was added to the reactor as a 20% solids slurry. The pH of the reaction was maintained at 6 and sodium metabisulfite was added at the end of the reaction to decompose the remaining hydrogen peroxide. After adjusting to pH 7, the product of Experiment Y was further treated with a nitrogen sparge, followed by the addition of preservative and additional acid to bring the pH to about 6.

  In Experiment Z, the same procedure as in Experiment V was followed using a high molecular weight cationic guar precursor 2 (cationic DS of 0.5) blended with fumaric acid. In Experiments AA and AB, a high-molecular-weight cationic guar prequeuer 3 (999,145 daltons, cationic DS is 0.9) was reacted in a one-step reaction at 90 ° C. and peroxidized at that temperature. Hydrogen was added to water followed by cationic guar. Sodium metabisulfite was added to decompose excess hydrogen peroxide.

  An N-Hance 3000 product with a cationic DS of 0.06 was depolymerized using the following steps. 918,5 grams of water was heated to about 95 ° C. Next, 31.5 grams of 1.0% hydrogen peroxide was added, followed by 50 grams of N-Hance (R) 3000 product. Stir for 30 minutes. Next, 15.75 g of 1.0% peroxide was added. Stir for 90 minutes, then add 0.21 g of sodium metabisulfite and cool with mixing. This solution was stored with 0.5% phenoxyethanol (R) and 0.18% Nipassept (R) sodium preservative. Both preservatives are available from Clariant Corporation. This sample contains 15 ppm (0.009 meq / g) of aldehyde (measured with EM Science's Aldehyde Test Kit 10031-1) and has a molecular weight of 298,000 Daltons.

Example 7
Experiment of Example 6 using cationic hydroxyethyl cellulose (Celquat (R) SC-240 and U-Care (R) polymer JR-400) instead of cationic guar as the cationic polysaccharide The W procedure was repeated. These examples are shown in Table 6. The pH value was maintained between 5 and 5.5 using 10% sodium hydroxide. At the end of the reaction, sodium metabisulfite was added to decompose excess hydrogen peroxide. To preserve the product, BHT and Katon® CG preservative were added. The Mw values for the products from experiments AD, AE and AF listed in Table 6 were 90,000, 179,000, and 46,500. The experimental AF procedure used the product from experimental AD and hydrogen peroxide was added only once.

Example 8
A biochemical process combined with a chemical process using an oxidizing reagent A product with a total solids content of 10% and a molecular weight (Mw) of 45,000-65,000 daltons was produced using the following process. The product produced also contained aldehyde functionality in a low molecular weight cationic guar.

  1) 700 g of tap water was heated to 50 ° C. in a glass reactor equipped with an overhead mixer.

  2) 282 g of washed wet cationic guar split was added to water to form a slurry.

  3) Once the pH was adjusted with acid to less than 9.0 but before reaching pH 7.5, 300 mg of mannanase (ChemGen, Rockville, Md.) Was added to the slurry of the cationic guar split. After 30 minutes at basic pH 9.0-8.0, the pH was gradually reduced with acid to pH 5.0-5.5.

4) Once the cationic guar split slurry is fully hydrated and the thick applesauce suspension begins to thin, 13.6 g of 30% H ₂ O ₂ (4,000 ppm in guar suspension or 0.40%) was added to the suspension of the cationic guar split.

  5) The temperature was raised to 90 ° C.

6) When the in-process viscosity of the suspension has decreased to 230-280 cps, stop heating the reactor, add 0.1-0.5 g sodium metabisulfite and immediately test strip (EM Residual H ₂ O ₂ was removed as measured by Quant (R) peroxide test.

7) A test strip was used to confirm that the amount of H ₂ O ₂ was zero.

  8) 1 g of Katong CG (0.1%) solution was added to the final product as a preservative.

Example 8b
Biochemical process combined with chemical process using oxidizing reagent
Production of low molecular weight liquid polymer from high molecular weight pre-quecer 3 cationic guar by enzymatic degradation followed by peroxide degradation
Experiment 8b (1)
933 g of water was heated to about 50-55 ° C. In a separate container, 0.05 g of mannase enzyme and water were premixed. This premix was added to the heated water with mixing. Next, 56.5 grams of a high molecular weight 999,145 Dalton Precuser 3 polymer (cationic DS about 0.9) was added with mixing. The polymer slurry temperature was increased to about 90 ° C. over about 90 minutes.

Next, 2.22 g of 1.0% H ₂ O ₂ was added and mixed for 45 minutes. Next, 0.19 g of sodium metabisulfite was added and cooled. 10 g of Garmaben (R) II preservative and supplemental water were added to bring the batch size to 1000 g. The molecular weight of this polymer was 963759 daltons.

Experiment 8b (2)
In another experiment, 933 g of water was heated to about 45-55 ° C. In a separate container, 0.10 g of mannase enzyme and water were premixed. The premix was added to the heated water with mixing. Next, 56.5 grams of a high molecular weight 999,145 Dalton Prequeuer 3 polymer (cationic DS about 0.9) was added with mixing. The pH of the slurry was about 8.2. The pH of the slurry was lowered to about 6.1 with HCl. The slurry was mixed for about 50 minutes and a sample of the polymer solution was taken for analysis. The molecular weight of this polymer was about 862,000 daltons. The sample was tested for aldehyde content using an M quant formaldehyde test strip (available from EM Science, Gibbstown, NJ). The formaldehyde content of this polymer sample was 0 ppm. The polymer solution was then raised to about 90 ° C. and 4.44 grams of a 1.0% peroxide solution was added. The reaction was stopped with 0.2 g of sodium metabisulfite. Next, 17.6 g of 1.0% hydrogen peroxide solution was added and stirred at about 90 ° C. for about 60 minutes. Next, 0.34 g of sodium metabisulfite was added and cooled. This solution was stored using 0.5% phenoxyethanol (R) and 0.18% nipercept (R) sodium preservative. All of these preservatives are available from Clariant. The aldehyde content of this sample was 10 ppm for each test strip. This sample had a weight average molecular weight of 293,000 daltons.

Example 8c
Biochemical process combined with chemical process using oxidizing reagent
Production of low molecular weight liquid polymer from high molecular weight N-Hance (R) 3000 cationic guar by degradation with peroxide followed by enzymatic degradation The N-Hance 3000 polymer used in this example is about Cationic DS of 0.06, having a weight average molecular weight of 923,655 daltons. In a silicone oil bath, 929 g of water was heated to about 90 ° C. 10.5 grams of 1.0% active H ₂ O ₂ was added to the heated water. Next, 50 grams of N-Hans (R) 3000 polymer was added to the water and peroxide mixture and maintained at 80-90 ° C. for about 110 minutes. 0.19 grams of sodium metabisulfite was added and mixed for an additional 10 minutes and cooled. The pH was adjusted to 6.5 with hydrochloric acid. 10 grams of Garmaben® II preservative and water to make up were added and the total batch size was adjusted to 1000 g and mixed. This resulted in a 1000 gram batch containing 5% polymer. The weight average molecular weight of the final product was 418,000 daltons.

  A sample of polymer solution decomposed with 815 g of the above peroxide was heated to about 50-55 ° C. In a separate container, 0.05 g of mannase enzyme and water were premixed. This premix was added to the polymer solution with mixing. The temperature of the polymer solution was increased to about 92 ° C. over about 70 minutes. The sample was removed from the oil bath and allowed to cool while mixing. 8 g of Garmaben® II preservative and supplemental water were added to bring the batch size to 815 g. The weight average molecular weight of this polymer was 131,308 daltons.

Example 8d
Biochemical process without oxidizing reagents
Preparation of low molecular weight liquid polymer from high molecular weight cationic guar by enzymatic degradation The procedure in steps 1-3 of Example 8a was followed. When the desired viscosity was reached, the temperature was raised to 90 ° C. to denature the enzyme and stop the reaction. The mixture was cooled to ambient temperature and 0.1% Katong CG preservative was added to the reaction mixture. The weight average molecular weight of the product was 67,000 daltons. The sample contained no aldehyde content as determined by indirect iodine titration.

Example 9
A product with a total biochemical process solids combined with the biochemical oxidation process of 10% (Mw 40,000) was produced. This product had aldehyde groups in the low molecular weight cationic guar. The procedure is as follows:
1) 700 g of tap water at 25 ° C. was placed in a glass reactor equipped with an overhead mixer.

  2) A washed wet cationic guar split (282 g) containing about 60-65% moisture was added to the reactor to form a suspension with stirring with an overhead mixer.

  3) Carefully but quickly, fumaric acid was added to the reactor to adjust the pH to 6.5-7.5.

  4) 300 mg mannanase was added to the suspension of Guar splits.

  5) The suspension was then sprayed with air at 0.1-0.3 parts by volume of air per minute by volume of the suspension per minute.

  6) Next, 6,000 international units of galactose oxidase galactose oxidase (Hercules, Wilmington, Delaware), 60,000 international units of catalase (Terminox Ultra 50L product, Novozymes) (Franklin Town, NC) and 1,500 units of peroxidase (NS51004, also from Novozyme) were added to the above suspension.

  7) The reaction was continued for 1-3 hours depending on the desired molecular weight and oxidation level of the final product.

  8) At the end of the reaction, the pH was adjusted to 4.0, then the reactor was heated to 90 ° C. and held for 30 minutes to inactivate the enzyme.

  9) As a preservative, 1 g of Katong CG (0.1%) solution was added to the final product.

  The aldehyde content of this sample (measured by changing the ratio of galactose / mannose) is 0.4 meq / gram.

Examples 10-15
Conditioning Shampoo Examples: Performance of the Cationic Oxidized Polysaccharides of the Invention in Conditioning Shampoos To improve entanglement in both wet and dry hair, shampoo formulations may contain conditioning agents, cationic guar or cationic Hydroxyethylcellulose was added to demonstrate it by reducing the energy of combing wet and dry hair. The results in Examples 11, 12 and 14 of Table 7 show that the cationic oxidized guar and cationic oxidized hydroxyethyl cellulose material of the present invention were wet when compared to the shampoo without polymer in Example 10. It has been shown to improve tangles in both wet and dry hair. In Examples 11 and 12, shampoos made with low and medium molecular weight cationic oxide guars made according to the process described in Experiment U of Table 5 were used for decolored medium brown Europeans. In the hair, the wet comb energy was reduced by 62% and 51%, respectively, and the dry comb energy was reduced by 35% and 22%, respectively. The reduction in wet and dry comb energy achieved by the polymer of the present invention is equivalent to or better than that of the high molecular weight cationic guar in Comparative Example 13. The reduction in wet and dry comb energy of the inventive polymers in Examples 11 and 12 is also improved over the polymer-free shampoo performance in Example 10 (9% and 7%, respectively). In Example 14, the inventive polymer derived from the cationic hydroxyethyl cellulose polymer prepared according to the procedure described in Example 7, Experimental AF in Table 6, is also superior to the polymer-free control of Example 10. It has been demonstrated to impart high wet and dry combing performance.

  Example 15 is described as a comparative example for low molecular weight cationic guars produced by biochemical degradation without the use of oxidation treatment as described in Example 8d. Note that this polymer provides improved wet and dry comb performance over the polymer-free control example of Example 10; however, over time, this shampoo produced a precipitate.

  In Examples 10-14 of Table 7, conditioning shampoos were prepared using the following ingredients and procedures.

  Phase 1: Water was heated to 80-90 ° C. in a vessel and HPMC was added with mixing. At -60-65 ° C, the cationic oxidized polysaccharide was added with mixing in heated water. The mixture was cooled to 25-35 ° C. while mixing. Citric acid was added to the cooled mixture to reduce the pH to 5.00-6.00. The mixture was then stirred for about 1 hour until dissolved.

  Phase 2: The Rhodapex ES STD product was weighed into a separate tar-coated beaker. Phase 1 was added to Phase 2 with mixing. The pH was readjusted with citric acid to 5.0-5.5. The mixture was stirred for 30-60 minutes until uniform.

  Phase 3: Amfosol CA product was added to the combined Phases 1 and 2 with mixing and stirred for an additional 5 minutes after mixing was complete. Mixing continued until uniform.

  Phase 4: Sodium chloride solution (10 wt%) was added to Phase 3 and stirred for 5 minutes. Glydant product was added and mixed for 15 minutes. The pH value of the shampoo was examined and the pH was readjusted to 5.0-5.5 if necessary. When adjusted, the shampoo was mixed for 15 minutes.

(1) Amfosol CA, 30% active (Stepan Chemicals, Chicago, Illinois),
(2) Rhodapex ES STD, 30% activity (Rhodia, Cranberry, NJ))
(3) Glyant ^™ 55% active, (Lonza, Fairlawn, NJ),
(4) Hydroxypropylmethylcellulose-HPMC60SH4000 (Shin Etsu, Tokyo, Japan).

Examples 16-20
Effect of polymer molecular weight on the viscosity of the formulation To improve entanglement in both wet and dry hair, a conditioning agent, cationic guar, was added to the shampoo formulation. Cationic guar currently on the market has a significant effect on the viscosity of shampoo products and may only be used at very low levels. In Examples 16-20 of Table 8, 1) shampoo free of cationic guar, 2) shampoo containing 0.2% and 1.5% of commercially available N-Hance (R) 3215 cationic guar, and 3 ) A shampoo containing 1.5% of the cationic oxidized guar product of the present invention was made.

  Preparation of shampoo: A container containing water was heated to 70 ° C. by placing it in a 70 ° C. water bath. The Benecel® product was transferred to heated water with mixing. Next, the commercially available N-Hance (R) 3215 product or polymer of the present invention was added to the container with mixing. The resulting solution was cooled to about 40 ° C. with mixing. The remaining components of the shampoo were added to the container in the order listed. The pH of this shampoo was adjusted to about pH 5.5. The shampoo was cooled to room temperature with mixing.

  The inventive products used in Examples 17 and 19 of Table 8 were prepared according to the procedure used in Experiment Y of Table 5 and had a solids content of about 10% and a weight average molecular weight of about 42, 000 Dalton aqueous solution. In contrast, the commercially available N-Hance (R) 3215 product is a dry polymer with a molecular weight of about 1 million. Since this product has a high molecular weight, it has a significant effect on the viscosity of the conditioning shampoo. In Example 16 of Table 8, a shampoo containing no conditioning agent was prepared. This has a Brookfield viscosity of about 3,540 cps. In Example 18, a similar shampoo made with 1.5% N-Hance 3215 product has a Brookfield LVT viscosity of 193,000 cps. Such high viscosities are not only difficult for manufacturers to bottle shampoo, but also very difficult for consumers to dispense. Most commercial shampoos have a viscosity of less than 10,000 cps. Even with the 0.2% N-Hance® 3215 product in Example 20, the shampoo viscosity was 13,600 cps. However, when the product of the present invention (Example 17) was used at 1.5% activity, the shampoo viscosity was maintained at 9,180 cps. When the polymer of the present invention (Example 19) was used at 0.2%, the shampoo viscosity was 8,300 cps. All viscosities were measured at 25 rpm at 12 rpm using a Brookfield viscometer model LVT.

  Conditioning shampoos were tested for their combing performance on freshly depigmented European hair. A 12 inch hair strand weighing about 5 grams was used. In this study, a reduction in combing energy was measured. The reduction in combing energy is an indirect measure of the conditioning performance of the polymer. As shown in Example 16, more conditioning is required to comb the hair when the conditioning polymer is not used in the shampoo. Negative combing energy is an indicator of hair entanglement and requires more force or energy to comb the hair. At 0.2% polymer content, the inventive polymer (Example 19, Table 8) and the commercially available polymer (Example 20, Table 8) have approximately the same level of wet combing energy reduction (15. 8% and 17.1%). However, the inventive polymer (Example 17) showed a significantly higher wet combing reduction (53.7%) at 1.5% polymer content. A shampoo containing 1.5% commercial N-Hance (R) 3215 product was not tested because its viscosity deviated significantly from the shampoo viscosity range (Example 18).

Evidence that performance is improved without affecting shampoo viscosity at higher polymer concentrations Table 9 shows the effect of the concentration of the inventive polymer on the wet combing performance of the shampoo. If the decrease in the wet combing energy of the hair is large, the conditioning effect improved by the conditioning polymer is high. Based on the wet combing data in Examples 21-25, a polymer that is at least 0.8% active is desirable to obtain maximum wet combing performance . With a commercially available high molecular weight cationic guar (eg N-Hance® 3215 product), the viscosity of the shampoo is 13,600 cps at 0.2% polymer weight (Example 20A in Table 8), and , 23,250 cps with 0.5% polymer content (Example 20B in Table 8). Both of these viscosities are considered to be values at both ends of the desired viscosity range in a commercial shampoo as shown in Examples 26-30 of Table 10. However, in Example 17 in Table 8 and 25 in Table 9, when the polymer of the present invention was used, the viscosity of the shampoo was less than 10,000 cps even with a polymer amount of 1.5%. By comparing the shampoo viscosity in Examples 11 and 32 of Table 11, the polymers of the present invention have an effect on hair conditioning performance without affecting the shampoo viscosity, even for guar with higher cationic DS. It was further demonstrated to have. The polymer of Example 32 was made according to the procedure in Experiment Z of Example 5, Table 5. Shampoos were made using the procedure described in Table 8 for shampoos. The viscosity of the shampoo containing 1.5% inventive polymer (Example 32) was about 11,000 cps, compared to 32,000 cps for the high molecular weight polymer (Example 31). The polymer of the present invention in Example 32 had slightly better wet combing performance.

  These results demonstrate that the polymer of the present invention allows the manufacturer to provide further conditioning without significantly increasing the viscosity of the shampoo.

  Shampoos were made using the procedure described with respect to Table 8. All viscosities were measured at 25 rpm at 12 rpm using a Brookfield viscometer model LVT.

Examples 33-37
Shower gel: Comparison of the polymer of the present invention with commercially available cationic guar in the effect on shower gel viscosity and foam stability when the polymer concentration is increased First, disperse Benecel® MP943 product in water Thus, the conditioning shower gel shown in Table 12 was prepared. Next, N-Hance (R) 3196 product or the cationic polymer of the present invention was added. The remaining ingredients of the shower gel were then added in the order listed and mixed well for the time between each addition. When all ingredients were mixed well, the pH of the shower gel was lowered to 5.0-6.0 with citric acid. All viscosities were measured at 25 rpm and 12 rpm using a Brookfield LVT viscometer.

  Again, the commercially available N-Hance (R) 3196 polymer could not be added to the shower gel even at 1.5% without causing a very significant increase in viscosity (Example 34, Table 12). . The viscosity of the conditioning shower gel with the commercial N-Hance 3196 polymer was 42,700 cps at 12 rpm, whereas the viscosity of the shower gel without polymer (Example 33) was only 460 cps. When the polymer of the present invention was used at a concentration of 1.5%, the viscosity was only 3,380 cps (Example 35). Examples 36, 37 and 34 show the effect of commercially available N-Hance (R) 3196 polymer on shower gel viscosity compared to Example 33 which does not contain the conditioning product polymer. Viscosity measurements were made at 25 rpm and 12 rpm using a Brookfield LVT viscometer.

  Foam discharge was measured using the method described below. Foam discharge time is an indirect method of measuring foam stability. A longer discharge time indicates a more stable and dense foam. Consumers consider the more stable foam practical. The foam discharge time of the shower gel containing the polymer of the present invention (Example 35) was more than twice that of the shower gel containing no polymer of the present invention (Example 33). In Example 37, 0.5% commercially available N-Hance (R) 3196 cationic guar had almost the same viscosity as that containing the polymer of the present invention (Example 35), but the present invention. The stability of the polymer foam was higher than 20%.

Foam Test Equipment / Method Description Foam Test: This method was used to measure the discharge time of diluted shower gel foam and determine the effect of conditioning polymer on foam quality. Long drainage times indicate thick and dense bubbles with excellent stability.

Equipment :
(R) Blender model # 7012 or 34BL97 from Waring or equivalent. Funnel, preferably made of plastic; diameter 6 ″, ID neck 7/8 ″, height 5 and 1/4 ″, with horizontal wire at a distance of 2 ″ from the apex. US Standard Testing Sieve number 20, 7 inch diameter. Stopwatch.

Procedure :
A 1000 g diluted shower gel solution was prepared in a beaker.
66.45g of shower gel,
933.55 g of deionized water,
Total 1000.00g.

  The 200 gram diluted solution was then weighed in an 8 ounce jar. Three jars containing 200 grams of diluted shower gel were prepared. The jar was then placed in a water bath set at a temperature of 40 ° C. for 2 hours. The jar was completely immersed. A foam discharge test was performed as follows. A total of three measurements were made for each formulation.

  200 g of diluted shower gel was poured into a clean, dry Waring blender glass container. The shower gel was whisked at top speed for exactly 1 minute while covering to form a foam. Immediately, the foam was poured into a clean and dry funnel upright on a 20 mesh screen on a beaker. This foam was run from the blender for exactly 15 seconds. In order to avoid overflowing, as much foam as possible was poured into the funnel. Foam pouring was stopped in 15 seconds. The total time (including 15 seconds of pouring time) required to discharge the foam until the wire was no longer covered with foam or liquid was recorded. The test was performed three times. The results are shown in Table 12 in seconds.

References :
(1) Evaluation of the foaming Capacity in shampoos: Efficacy of various Experimental Methods by FJDomingo Campos, RMDruguet Tantina, Cosmetic & toiletries Page 121-130, Vol. 98, September 1983,
(2) The Lathering Potential of Surfactants-Simplified Approach to measurement by J. Roger Hart and Mark T. DeGeorge. J. Soc. Cosmet. Chem., 31, 223-236 September / October 1980.

  The polymer of the invention described in Example 35 of Table 12 was prepared in a manner similar to that described for Experiment Z in Table 5 of Example 6 except that the N-Hans 3205 cationic guar was replaced by the pre-queuer 2 cationic guar. Used in place of). The molecular weight of the final product was 550,000 daltons, down from the molecular weight of 1,050,000 daltons measured with the original N-Hans 3205 cationic guar.

Examples 38-42
Again, the commercial cationic hydroxypropyl guar, Jaguar® C162 polymer, even at 2.0%, could not be added to the shower gel without causing a very significant increase in viscosity (Examples). 39, Table 13). The viscosity of the conditioning shower gel with commercial Jaguar (R) C162 was 41,400 cps at 12 rpm, whereas the viscosity of the shower gel without polymer was only 555 cps. With the polymer of the present invention, the viscosity was only 3,320 cps with a 2.0% active polymer (Example 40). Viscosity measurements were made at 25 rpm and 12 rpm using a Brookfield LVT viscometer. Commercial Jaguar (R) C162 products were also tested at levels of 0.2% and 0.5% activity (Examples 41 and 42). This reached the same viscosity at the 0.5% level (Example 42) as the formulation containing 2.0% of the inventive polymer (Example 40). The foam stability was measured using the method described above. The foam discharge time of the shower gel (including the polymer of the present invention) in Example 40 was more than twice that of the shower gel (Example 38) not including the polymer of the present invention. The longer the discharge time, the more stable the foam.

  The polymer of the invention described in Example 40, Table 13, was prepared using a procedure similar to that used in Experiment Z of Example 6, Table 5, except that instead of the pre-queuer 2 cationic guar, Jaguar (R) C162 cationic hydroxypropyl guar was used). The molecular weight of the product was 555,532 daltons, reduced from the molecular weight of 1,080,000 daltons of the original Jaguar C162 cationic hydroxypropyl guar.

Examples 43-47
Comparative Example of the Effect of Polymer Concentration on Liquid Soap Viscosity and Foam Stability between High Molecular Weight Cationic Guar and the Polymer of the Invention Table 14 shows the commercial N-Hance (R) 3198 cationic guar concentration Shows the viscosity of liquid soap and its effect on foam stability. The viscosity increases from 123 cps for the liquid soap without polymer (Example 43) to 23,400 cps for the 1.5% commercial N-Hance 3198 product (Example 46). At such high viscosities, liquid soap dispensing becomes difficult. When the inventive polymer was included at 1.5% activity (Example 47), the viscosity of the formulation was only 315 cps. Commercially available polymers could only be used at 0.2% activity level to maintain such a low viscosity (Example 44). However, at this level, the stability of the liquid soap foam is poor. Foam stability was only about 30 seconds compared to about 71 seconds for the inventive polymer (Example 47).

Preparation of liquid soap Natrosol hydroxyethyl cellulose was dispersed in water with mixing. Next, cationic guar (commercially available N-Hance (R) 3198 or polymer of the present invention) was added with mixing. Ammonix (R) 4002, Biotage (R) AS40, and Emerest (R) ingredients were added in the order listed while mixing. This batch was mixed in an 80 ° C. water bath until the Emerest® component dissolved. The batch was then removed from the water bath and allowed to cool while mixing. The remaining ingredients were added while the batch was cooled to room temperature.

  The polymer of the present invention used in Example 47, Table 14, was made by a procedure similar to that used in Experiment 6, Example 5, Table 5 (N-Hance 3198 cationic guar was prepared as Precuser 2 Except for the replacement).

Examples 48-50
Comparative example demonstrating stability between a skin lotion containing the polymer of the present invention and a commercially available high molecular weight cationic guar
Skin lotion manufacturing method :
Part A: The water was weighed in an 8 ounce jar and then placed in an 80 ° C. water bath. Natrosol (R) was transferred with mixing. Next, N-Hance (R) 3215 or the polymer of the present invention was added, followed by glycerin.

  Part B: In a separate container, Emerest® 2400 was weighed and placed in an 80 ° C. water bath. The remaining ingredients of Part B were added in the order listed with mixing. Part A.

  Part A was slowly added to Part B with mixing. The temperature was maintained at 80 ° C.

  Part C: Part C was added to Part A / B. Mixing continued while cooling to 40 ° C. Next, the Garben (R) product was added and continued to cool while mixing. After 24 hours at 12 rpm and 25 ° C., the viscosity was measured using a Brookfield (R) LVT viscometer.

  The inventive polymers in Example 50, Table 15 were made as described in Experiment Y in Example 6, Table 5.

  In lotion and cream formulations, the stability of the final formulation is an important goal for the producer. As shown in Example 49, a commercially available skin lotion emulsion containing N-Hance 3215 exhibited phase separation due to instability. The viscosity of the lotion emulsion without the polymer of the present invention (Example 48) is only about 1500 cps and is too soft. A lotion emulsion comprising the polymer of the present invention is not only stable, but also has a viscosity of about 2,800 cps and has a higher viscosity when dispensed.

Examples 51-53
Comparative example demonstrating the aesthetics of the improved formulation of the polymer of the present invention and high molecular weight cationic guar
How to make sunscreen :
Part A: Drakeol was weighed into an 8 ounce jar. The jar was then placed in a bath set at 70 ° C. The remaining ingredients of Part A were added in the order listed with mixing. Mixing continued at 70 ° C. for 30 minutes.

  Part B: Water was weighed into another jar and then placed in a 70 ° C. water bath. Natrosol® polymer was added to water with mixing. The remaining ingredients of Part B were then added with mixing at 70 ° C.

  Part C: Part C was premixed. When all the components of Part B were dissolved, Part C was added to Part B. Once 70 ° C. was reached with mixing, Part B / C was then added to Part A. Mixing continued at 70 ° C. for 30 minutes.

  Part D: The above Part A / B / C mixture was removed from the water bath and cooled to 50 ° C. with mixing. When the temperature reached 50 ° C., the Germaben II product was added. Mixing continued until the sunscreen emulsion was at room temperature.

  The inventive polymers in Example 53, Table 16 were made by the process described in Experiment U of Example 6, Table 5 (but N-Hance 3198 polymer was used in place of N-Hance 3215).

  When formulating sun care lotions, creamy glossy emulsions are desirable. It is also desirable to have sufficient viscosity so that the lotion does not sag or the consistency is not too soft, but it is not too thick and does not become difficult to spread. The sunscreen made with the commercial cationic guar N-Hance (R) 3198 (Example 52) was slightly rough and had an extremely high viscosity in addition to being off-white. The sunscreen made with the product of the present invention (Example 52) not only has a viscosity comparable to that of the sunscreen without the conditioning polymer (Example 51), but is also glossy, white and stable. (Example 51).

Examples 54-62 :
Comparative liquid demonstrating improved stability and consistency between laundry detergents and fabric softeners containing the polymers of the present invention and laundry detergents and fabric softeners containing high molecular weight cationic guar In blending laundry detergents and fabric softeners, the stability and consistency of the blend are important so that product performance can be imparted. High viscosity formulations are not easily mixed in a washing machine and may result in poor cleansing or fabric conditioning. Also, poor stability in the formulation and overall phase separation of the components negatively impact performance.

  The inventive polymers listed in Table 17 were prepared according to the process described for Example 6, Experiment Y in Table 5.

  As shown in Table 17, the polymer of the present invention is a Tide (R) liquid commercially available from Procter & Gamble Co., Cincinnati, Ohio at 0.2% activity level. The laundry detergent and Wisk liquid laundry detergent from Unilever, Greenwich, CT were added later. 0.2% of commercially available N-Hance (R) 3215 cationic guar was later added to these laundry detergents.

  The product of the present invention had no effect on the viscosity of the original liquid laundry detergent and was more compatible (Examples 55 and 58). The N-Hance (R) 3215 product was found not to be compatible (Examples 56 and 59).

  In the fabric softener, the polymer of the present invention had no significant effect on viscosity and was stable to pH 3-3.5 (Example 61). In contrast, the commercially available N-Hance (R) 3215 polymer gelled a commercially available fabric softener (Example 62), making it unsuitable for use.

Examples 63-69
Comparative examples demonstrating the improved effect of the polymers of the invention and high molecular weight cationic guar on the viscosity of conditioning body detergents: by peroxide decomposition processes and by biochemical and peroxide processes In the case of a polymer made by use in combination with a process The body detergent made with the inventive polymer described in Table 18 of Examples 65 and 66 is a commercially available N-Hance (R) 3000 product (Example 64) and It has a lower viscosity than that. In Example 65, a polymer was made by decomposition with peroxide according to the procedure described for Example 6, Experiment AC in Table 5. In Example 66, the polymer was made by a continuous treatment of peroxide followed by enzymatic degradation as described in Example 8C.

  The body detergents made with the inventive polymers listed in Table 19 (Examples 68-69) had a much lower viscosity compared to the body detergents made with Precutor 3 (Example 67). Actually, the detergent manufactured with the pre-queuer 3 was almost in a gel-like state. The polymer of the present invention used in Example 68 was made by decomposition with peroxide as described in Example 6, Experiments AA and AB in Table 5. The inventive polymer used in Example 69 was made by a continuous treatment of enzymes followed by degradation with peroxide as described in Example 8B.

  All viscosities were measured using a Brookfield LVT with a spindle rotation of 12 rpm for 2 minutes. Samples were conditioned at 25 ° C.

  All viscosities were measured using a Brookfield LVT with a spindle rotation of 12 rpm for 2 minutes. Samples were conditioned at 25 ° C.

Table 20: Oxidizing group content of polymers of the invention The results in Table 20 are for the materials of the invention prepared according to the procedure of Example 6, 7 or 8a, b, c and for the procedure of Example 8d. Figure 2 shows the compositional difference between the manufactured material of the present invention and a commercially available high molecular weight cationic, commercially available polymer. The polymer solution was analyzed using a specific method (Analytical Biochemistry, 1983, 134, 499-504) for aldehyde group detection. The results of these tests are shown as absorbance at 595 nm / gram (polymer) or as milliequivalents (aldehyde) / gram (polymer) depending on the colorimetric test results listed in Table 20.

  As shown by the results listed in Table 20, a material with significant absorbance was obtained from the material of the present invention produced by the procedure of Example 6, 7 or 8a-c (Purpald method [ H. B. Hopps, Aldrichichima ACTA, 2000, 33 (1), 28-30]). This method is specific for aldehyde detection. In this way, very little absorbance was detected in the material produced according to the procedure of Example 8d, or in the initial cationic guar or other commercially available cationic guar materials.

These results indicate that the material produced by the treatment containing the oxidant as a single reactive treatment or in combination with a hydrolase treatment has a low molecular weight, including a measurable amount of aldehyde groups in the polymer. Indicates to produce material. Indirect iodine titration was used to quantify the amount of aldehyde in several samples and create an equation that calibrates to convert absorbance / gram to milliequivalent (aldehyde) / gram. As determined by this method, the amount of aldehyde groups in the material of the present invention is at least 0.001 meq / g. The equation for calibration is shown in Equation 2. The milliequivalent / gram (aldehyde) values shown in Table 20 were determined from equation (2) except for Examples 8-4 (these were measured directly). In Example 9 in Tables 20 and 21, the aldehyde content was determined by analyzing the sugar of the acid-hydrolyzed guar product using HPLC to determine the initial cationic guar precursor and oxidized cationic guar production. The ratio of galactose / mannose to the product was obtained. The aldehyde content of the oxidized cationic guar was 23% (corresponding to 0.41 mmol (aldehyde) / gram (polymer)).

  (2) Absorbance / gram = 445.52 (milli equivalent (aldehyde) / g) +0.9953.

  Test strips coated with Pupard reagent (EM Science) were also used to measure the aldehyde content in the samples produced by the methods of Examples 6 and 8a-c. These results are shown in Table 21 along with viscosity and MW data for the products of the present invention. Taken together, the results in Tables 20 and 21 show that the product of the present invention has an aldehyde content of at least 0.001 meq / gram, and the lower limit of Brookfield viscosity for the product of the present invention is 30 rpm, 25C, The spindle 4 is 40 cps, and the upper limit of the Brookfield viscosity is 0.3 rpm, 25 C, and the spindle 4 is 2,000,000 cps.

Example 70
Chemical oxidation process for polymer blends
Production of low molecular weight liquid cationic polysaccharides from high molecular weight cationic polysaccharide blends :
50 g of 0.06 cationic DS was blended with 50 g of cationic HEC (Polymer LR30M, manufactured by Dow Chemical, Midland, Mich.) And 1.25 g of fumaric acid. 816 g of water was heated to about 90 ° C. Next, 75 g of 1.0% hydrogen peroxide was added. Mix for about 30 minutes and then add 18.1 g of 1.0% hydrogen peroxide. While mixing, 18.1 g of 1.0 hydrogen peroxide was further added twice at approximately 30 minute intervals. After the last peroxide was added, it was mixed for about 90 minutes. Next, 0.95 grams of sodium metabisulfite was added. This solution was stored with 0.5% phenoxyethanol and 0.18% sodium nipacept. Details regarding the inventive polymers of this experiment are shown in Table 21.

  This example demonstrates that the polymers of the present invention can be made using blends of functional polymers.

Example 71
The following examples show that low molecular weight cationically oxidized polysaccharides of the present invention can be included in personal care formulations containing silicone materials and the resulting product viscosity is commercially available It demonstrates that it is significantly reduced compared to the viscosity of silicone formulations containing high molecular weight commercial cationic polysaccharides. Silicone materials include cyclosiloxanes, linear siloxanes, hydroxy-terminated siloxanes, comb or graft siloxane polymer or oligomer forms that contain polyol, amino, or other functional groups in the siloxane structure. It is done.

  For these experiments, an anionic shampoo formulation comprised of the ingredients listed in Table 22 was used. Formulations were made by mixing surfactant and water at 60 C for 1 hour, cooling the mixture to 35 C, and adding the silicone emulsion. This shampoo contains GE silicone emulsion SM555 (silicone content 0.5% by weight). The low molecular weight cationic guar from Example 6, Table 5, Experiment Y was included in the shampoos of Examples 71-1 and the high molecular weight commercial cationic guar described in Examples 71-2 to 71-5. And a commercially available shampoo described in Example 71-6. The shampoo viscosity was measured at room temperature using a Brookfield LVT viscometer with spindles 4, 0.3 and 30 rpm.

  The results listed in Table 22 demonstrate that with the polymers of the present invention, the desired shampoo viscosity is obtained and that the shampoo does not exhibit phase separation. Shampoos containing commercially available high molecular weight cationic polymers are unnecessarily viscous and difficult to pour. Also, blends of the cationic oxidized polysaccharide of the present invention with other water soluble polymers can be included in personal care formulations including silicone polymers and oligomers to produce a stable system.

  The cationic oxidation of the present invention to improve the aesthetics (ie foaming), stability, conditioning oil (eg silicone) or other conditioning agent application to hair, skin and textile substrates and the degradation efficiency of the formulation Polysaccharides and other functional polymers such as chitosan, polyvinylpyrrolidone homopolymers and copolymers, acrylamide homopolymers and copolymers, high molecular weight cationic hydroxyethyl cellulose, high molecular weight cationic guar and hydrophobic polymers Binary and ternary blends with (or also known as associative polymers) can be designed. These blends also contain other ingredients such as antibacterial compounds, antidandruff compounds, conditioning agents, fragrances, sunscreen actives, emollients, moisturizers, pharmaceuticals such as anti-psoriatic agents, hair styling such as polyvinylpyrrolidone copolymers. It is also possible to improve the efficiency of applying adjuvants, sizing agents, etc. to the hair, skin and textile substrates. Some of the blends of the polymers of the present invention and water soluble functional polymers are shown in Example 72 and the viscosities of these blends are shown in Table 21. A wide variety of polymer blends including the polymers of the present invention can be made and this example is not exhaustive.

Example 72
This example demonstrates that the polymers of the present invention can be blended with other functional polymers. The viscosity of each blend is shown in Table 21.

5% dispersion of chitosan (Vanson Incorporated, Redmond, WA; 88% deacetylated, 1% viscosity: 660 cps), 2.1 grams of chitosan and 6% dispersion of fumaric acid Produced by mixing. Two blends were made using this dispersion:
72-1 :
25.3 grams of chitosan dispersion and 90.5 grams of Example 6, Experiment AC were mixed to produce a dispersion. The viscosity of this dispersion for 24 hours was measured with a Brookfield viscometer at 0.3 and 30 rpm at ambient temperature and found to be 14,000 and 2,220 cps, respectively.

72-2 :
11.4 grams of chitosan dispersion was mixed with 94.1 grams of Example 8B (molecular weight 964,000) to produce a dispersion. The viscosity of this dispersion for 24 hours was measured with a Brookfield viscometer at 0.3 and 30 rpm at ambient temperature and found to be 8,000 and 3,920 cps, respectively.

Although the invention has been described with reference to particular embodiments, it should be understood that the invention is not limited thereto and that many changes and modifications can be made without departing from the spirit and scope of the invention. .
[Aspect of the Invention]
[1]
A personal care or household care composition comprising at least one cationic oxidized polysaccharide or derivative thereof, the cationic oxidized polysaccharide or derivative thereof having a lower limit of 50,000 and an upper limit of 1,000. Said personal care comprising at least one cationic oxidized polysaccharide or derivative thereof having a weight average molecular weight of 1,000,000 and a content of aldehyde functional groups of at least 0.001 milliequivalent per gram of polysaccharide; Home care composition.
[2]
The at least one cationic oxidized polysaccharide or derivative thereof has a Brookfield viscosity at 25 ° C. of 10% by weight of the polysaccharide solids with a lower limit of 30 cps and an upper limit of 2,000,000 cps. A personal care or household care composition as described in 1.
[3]
2. The composition of 1, having a cationic substitution degree (DS) of about 0.001 as a lower limit and about 3.0 as an upper limit.
[4]
4. The composition according to 3, wherein the cationic substitution degree (DS) has a lower limit of 0.01.
[5]
4. The composition according to 3, wherein the cationic substitution degree (DS) has a lower limit value of 0.05.
[6]
4. The composition according to 3, wherein the cationic substitution degree (DS) has a lower limit of 0.1.
[7]
4. The composition of 3, wherein the cationic degree of substitution (DS) has an upper limit of about 2.0.
[8]
4. The composition of 3, wherein the cationic degree of substitution (DS) has an upper limit of about 1.0.
[9]
4. The composition of 3, wherein the cationic degree of substitution (DS) has an upper limit of about 0.5.
[10]
4. The composition of 3, wherein the cationic degree of substitution (DS) has an upper limit of about 0.25.
[11]
The derivative component in the cationically derivatized polysaccharide is selected from the group consisting of alkyl, hydroxyalkyl, alkylhydroxyalkyl, and carboxymethyl, wherein the alkyl is a carbon containing 1 to 22 carbons. 2. The composition according to 1, having a chain, wherein the hydroxyalkyl is selected from the group consisting of hydroxyethyl, hydroxypropyl, and hydroxybutyl.
[12]
2. The composition according to 1, wherein the polysaccharide is selected from the group consisting of cellulose, starch, dextran, and polygalactomannan.
[13]
13. The composition according to 12, wherein the polysaccharide is polygalactomannan and is either guar or locust bean or a derivative thereof.
[14]
The composition according to 12, wherein the polysaccharide is a cellulose type and is a cellulose ether derivative.
[15]
2. The composition according to 1, wherein the cationic component is selected from quaternary ammonium compounds.
[16]
The quaternary ammonium compound includes 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2,3-epoxy-propyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium bromide, 2,3-epoxy- Propyltrimethylammonium bromide; glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltripropylammonium chloride, glycidylethyldimethylammonium chloride, glycidyldiethylmethylammonium chloride, and their corresponding bromides and iodides; 3 -Chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, 3-chloro- -Selected from the group consisting of hydroxypropyltripropylammonium chloride, 3-chloro-2-hydroxypropylethyldimethylammonium chloride, and their corresponding bromides and iodides; and halides of imidazoline ring-containing compounds 15. The composition according to item 15.
[17]
2. The composition according to 1, wherein the lower limit of Mw is 50,000.
[18]
2. The composition according to 1, wherein the lower limit of Mw is 75,000.
[19]
2. The composition according to 1, wherein the lower limit of Mw is 100,000.
[20]
2. The composition according to 1, wherein the upper limit of Mw is 1,000,000.
[21]
2. The composition according to 1, wherein the upper limit of Mw is 600,000.
[22]
2. The composition according to 1, wherein the upper limit of Mw is 300,000.
[23]
2. The composition according to 1, wherein the upper limit of Mw is 150,000.
[24]
3. The composition according to 2, wherein the lower limit of the Brookfield viscosity at 30 rpm of the polysaccharide is 50 cps.
[25]
3. The composition according to 2, wherein the lower limit of the Brookfield viscosity at 30 rpm of the polysaccharide is 100 cps.
[26]
3. The composition according to 2, wherein the lower limit of the Brookfield viscosity at 30 rpm of the polysaccharide is 300 cps.
[27]
The composition according to 2, wherein the upper limit of the Brookfield viscosity at 30 rpm of the polysaccharide is 10,000 cps.
[28]
3. The composition according to 2, wherein the upper limit of the Brookfield viscosity at 30 rpm of the polysaccharide is 5,000 cps.
[29]
3. The composition according to 2, wherein the upper limit of the Brookfield viscosity at 30 rpm of the polysaccharide is 2,000 cps.
[30]
3. The composition according to 2, wherein the lower limit of the Brookfield viscosity at 0.3 rpm of the polysaccharide is 50,000 cps.
[31]
The composition according to 2, wherein the lower limit of the Brookfield viscosity at 0.3 rpm of the polysaccharide is 100,000 cps.
[32]
3. The composition according to 2, wherein the lower limit of the Brookfield viscosity at 0.3 rpm of the polysaccharide is 150,000 cps.
[33]
3. The composition according to 2, wherein the upper limit of the Brookfield viscosity at 0.3 rpm of the polysaccharide is 1,000,000 cps.
[34]
3. The composition according to 2, wherein the upper limit of the Brookfield viscosity at 0.3 rpm of the polysaccharide is 500,000 cps.
[35]
3. The composition according to 2, wherein the upper limit of the Brookfield viscosity at 0.3 rpm of the polysaccharide is 250,000 cps.
[36]
Colorants, preservatives, antioxidants, alpha or beta hydroxy acids, activity enhancers, emulsifiers, functional polymers, thickeners, alcohols, fatty or aliphatic compounds, antibacterial compounds, anti-dandruff agents, volumizers, electrostatic Ingredients selected from the group consisting of inhibitors, moisturizers, hair styling aids, zinc pyrithione, silicone materials, hydrocarbon polymers, emollients, oils, surfactants, suspending agents, sun care agents, and mixtures thereof The composition according to 1, further comprising:
[37]
The components include anionic, hydrophobically modified and amphoteric acrylic copolymers, vinyl pyrrolidone homopolymers and copolymers, cationic vinyl pyrrolidone copolymers, nonionic, cationic, anionic and amphoteric cellulose polymers, acrylamide homopolymers, Cationic, anionic, amphoteric and hydrophobic modified acrylamide copolymers, polyethylene glycol polymers and copolymers, hydrophobic modified polyethers, hydrophobic modified polyether acetals, hydrophobic modified polyether urethanes, associative polymers, hydrophobic Modified cellulose polymers, polyethylene oxide-propylene oxide copolymers, chitosan, clay, and nonionic, anionic, hydrophobic modified, amphoteric, cationic poly 36, a functional polymer selected from the group consisting of: chitosan, starch, alginate, konjac gum, clay, poloxamer (polyoxyethylene / polyoxypropylene block polymer), and mixtures thereof Composition.
[38]
The components are nonionic, cationic, anionic and amphoteric cellulose polymers, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydrophobically modified carboxymethylcellulose, cationic hydroxyethylcellulose, cationic hydrophobic Selected from the group consisting of hydrophobically modified hydroxyethylcellulose, hydrophobically modified hydroxyethylcellulose, hydrophobically modified hydroxypropylcellulose, cationic hydrophobically modified hydroxypropylcellulose, cationic carboxymethylhydroxyethylcellulose, and cationic hydroxypropylcellulose The composition according to 36, wherein
[39]
The components are nonionic, anionic, hydrophobically modified, amphoteric and cationic polygalactomannans, carboxymethyl guar, hydroxypropyl guar, hydrophobically modified guar, carboxymethyl guar hydroxypropyltrimethylammonium Chloride, guar hydroxypropyl trimethylammonium chloride, and hydroxypropyl guar hydroxypropyl trimethylammonium chloride, hydroxybutyl guar, hydroxybutyl guar hydroxypropyltrimethylammonium chloride, hydroxyethyl guar, hydroxyethyl guar 37. The composition according to 36, selected from the group consisting of hydroxypropyltrimethylammonium chloride and locust bean.
[40]
Said component is a thickener, NaCl, NH ₄ Cl, KCl, and fatty alcohol, fatty acid ester, fatty acid amide, aliphatic alcohol polyethylene glycol ether, sorbitol polyethylene glycol ether, polyethylene oxide fatty acid ester, monostearic acid From ethylene glycol or ethylene glycol distearate, cocamidopropyl betaine, clay, silica, cellulose polymers, xanthan, alginate, guar and guar derivatives, carrageenan, konjac powder, gelatin, dextrin, pectin, starch, and mixtures thereof 36. The composition according to 36, selected from the group consisting of:
[41]
The component is a silicone material and contains a polyol, amino, quaternary ammonium, or other functional group in the siloxane structure, cyclosiloxane, linear siloxane, comb or graft siloxane structure, and mixtures thereof 37. The composition according to 36, selected from the group consisting of:
[42]
Said components, optionally, an alkyl group of C ₆ -C _24, a substituted or unsubstituted amine group, a thiol group, alkoxylated group, a hydroxyl group, including acyloxyalkyl group, polyethyleneoxy, and / or, polypropylene oxy group 42. The composition according to 41, which is another functional group selected from the group consisting of:
[43]
42. The composition of 41, wherein the silicone material is selected from the group consisting of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, and mixtures thereof.
[44]
44. The composition according to 43, wherein the component is a polyalkylsiloxane selected from the group consisting of polydimethylsiloxane, polydimethylsiloxane chain end hydroxylated, and mixtures thereof.
[45]
37. The composition according to 36, wherein the component is an anionic, cationic, amphoteric or nonionic surfactant, or a mixture thereof.
[46]
A process for producing the cationic oxidized polysaccharide or a derivative thereof according to 1, wherein (a) at least one cationic polysaccharide or a cationically derivatized polysaccharide and the polysaccharide or a derivative thereof Reacting with at least one reagent that reduces the weight average molecular weight (Mw) of the above to an upper limit of 1,000,000 Daltons; and (b) recovering the cationic oxidized polysaccharide and Producing the oxidizable polysaccharide composition.
[47]
46. The cationic polysaccharide or cationically derivatized polysaccharide is treated with a reagent in an aqueous medium to produce an aqueous dispersion of the treated polysaccharide, producing the composition according to 1. The process described in
[48]
The reagent is an oxidizing reagent selected from the group consisting of peroxides, persulfates, permanganates, perchlorates, hypochlorites, oxygen, and biochemical oxidants; 46. Process according to 46.
[49]
47. The process according to 46, wherein the oxidizing reagent is hydrogen peroxide.
[50]
49. The process according to 48, wherein the oxidizing reagent is a biochemical oxidizing reagent and is an oxygenase.
[51]
51. The process according to 50, wherein the oxygenase is galactose oxidase.
[52]
49. The process according to 48, wherein the reagent further comprises a hydrolysis reagent.
[53]
53. The process according to 52, wherein the hydrolytic reagent is selected from the group consisting of hydrolytic enzymes.
[54]
54. The process according to 53, wherein the hydrolase is selected from the group consisting of hemicellulases.
[55]
55. The process according to 54, wherein the hemicellulase is mannanase.
[56]
53. The process according to 52, wherein the hydrolysis reagent is an organic acid or a mineral acid.
[57]
47. The process according to 46, wherein the cationic polysaccharide or cationically derivatized polysaccharide is a cellulose ether or a polygalactomannan.
[58]
58. The process of 57, wherein the cationic polysaccharide or cationically derivatized polysaccharide is a polygalactomannan selected from the group consisting of guar and guar derivatives.
[59]
The cationic polysaccharide or the cationically derivatized polysaccharide may be cationic hydroxyethyl cellulose (HEC), cationic hydrophobically modified hydroxyethyl cellulose (HMHEC), cationic hydroxypropyl methylcellulose (HPMC), cationic hydroxy A cellulose ether selected from the group consisting of propyl cellulose (HPC), cationic ethyl hydroxyethyl cellulose (EHEC), cationic methyl hydroxyethyl cellulose (MHEC), and cationic methyl cellulose (MC), and mixtures thereof. 58. The process according to 57.
[60]
47. The process of 46, further comprising the addition of sodium metabisulfite, sodium hydrogen sulfite, sodium hypochlorite, or sodium chlorite.
[61]
48. The process of 47, further comprising recovering the derivatized polysaccharide in a dry state from an aqueous solution.
[62]
59. The process according to 58, wherein the cationic polygalactomannan or cationically derivatized polygalactomannan is in the form of a powder, flour, or split.
[63]
A composition comprising the composition according to 1, for conditioning a surface selected from the group consisting of skin, hair, protein, polyester, cellulose, paper, and a textile substrate.
[64]
2. The composition of 1, which is a household care composition further comprising at least one other active household ingredient.
[65]
The active household ingredients include insect repellents, pet deodorants, pet shampoo actives, industrial grade solid and liquid soap actives, dishwashing soap actives, multipurpose cleaners, disinfectants, lawn and plant nutrition Replenishers, water treatment agents, cleaning actives for rugs and upholstery materials, laundry softeners active materials, laundry detergent actives, toilet cleaning agents, textile sizing agents, dust collectors, anti-redeposition agents, textiles 65. A home care composition according to 64, selected from the group consisting of a cleaning agent, a softener, an antistatic agent, and a lubricant.
[66]
Colorant, preservative, antioxidant, bleach, activity enhancer, emulsifier, functional polymer, thickener, alcohol, fat or aliphatic compound, oil, surfactant, fragrance, suspending agent, silicone The household care composition of 64, further comprising at least one additional ingredient selected from the group consisting of materials and mixtures thereof.
[67]
The composition of 1, which is a personal care composition further comprising at least one other active personal care ingredient.
[68]
The active personal care ingredients include perfumes, skin cooling agents, emollients, moisturizers, deodorants, antiperspirant active substances, moisturizers, cleansing agents, sunscreen active substances, hair treatment agents, oral care agents, dentures. 68. A personal care composition according to 67, selected from the group consisting of adhesives, shaving actives, cosmetics, and nail care actives.
[69]
68. The personal care composition according to 67, wherein the composition is a product selected from the group consisting of hair care, skin care, sun care, nail care, and oral care.
[70]
70. The product according to 69, wherein the product is a hair care product comprising a conditioning agent selected from the group consisting of silicone materials, hydrocarbon oils, panthenol and derivatives thereof, pantothenic acid and derivatives thereof, and mixtures thereof. Composition.
[71]
69. The product according to 69, wherein the product is a skin care product comprising a conditioning agent selected from the group consisting of silicone materials, hydrocarbon oils, panthenol and derivatives thereof, pantothenic acid and derivatives thereof, and mixtures thereof. Composition.
[72]
72. The composition according to 71, wherein the skin care product comprises an emollient selected from the group consisting of polyhydric alcohols and hydrocarbons.
[73]
70. The composition according to 69, wherein the product is a hair care product or a skin care product comprising the composition of the cationic oxidized polysaccharide or derivative thereof according to 1 in an amount of 99% by weight or less based on the total amount.
[74]
The composition is a colorant, preservative, antioxidant, alpha or beta hydroxy acid, activity enhancer, emulsifier, functional polymer, thickener, alcohol, fat or aliphatic compound, antibacterial compound, zinc pyrithione, silicone Group consisting of materials, anti-dandruff agents, hydrocarbon polymers, emollients, oils, surfactants, flavors, fragrances, pharmaceuticals, rejuvenating agents, suspending agents, stabilizing biocides, and mixtures thereof 68. The personal care composition of 67, further comprising at least one additional ingredient selected from.
[75]
2. The composition of 1, further comprising water in an amount of 1 to 99% by weight of the total amount of the composition.
[76]
Personal care comprising adding to the composition a cationic oxidized polysaccharide or a derivative thereof prepared as a component by treating the polysaccharide with an oxidizing reagent that introduces aldehyde functional groups and reduces molecular weight Or the manufacturing method of a household care composition.

Claims (13)

A personal care or household care composition comprising at least one cationic oxidized polysaccharide or derivative thereof, the cationic oxidized polysaccharide or derivative thereof having a lower limit of 50,000 and an upper limit of 1,000. has a weight average molecular weight of 000, have a content of polysaccharide per gram least 0.001 milliequivalents aldehyde functional groups, and in the polysaccharide solids 10 wt%, the lower limit at 25 ° C. 300 cps, and to have a Brookfield viscosity of upper 2,000,000 cps, comprising at least one cationic, oxidized polysaccharide or derivative thereof,
The personal care or household care composition is a shampoo, conditioner, shower gel, liquid soap, body detergent, hair styling product, shaving gel / cream, body cleaner, solid soap, skin care lotion, sun care lotion, dishwashing detergent. Selected from the group consisting of laundry detergents, fabric softeners, and antistatic products , and
Polysaccharide is selected from the polygalactomannan and cellulose and derivatives components hydroxyethyl, Ru is selected from the group consisting of Hiro de hydroxypropyl and hydroxybutyl,
Said personal care or household care composition. The composition of claim 1 having a cationic substitution degree (DS) of a lower limit of 0.001 and an upper limit of 3.0. The composition according to claim 1 , wherein the polysaccharide is polygalactomannan and is either guar or locust bean or a derivative thereof. The composition according to claim 1, wherein the cationic component is selected from quaternary ammonium compounds. Colorants, preservatives, antioxidants, alpha or beta hydroxy acids, activity enhancers, emulsifiers, functional polymers, thickeners, alcohols, fatty or aliphatic compounds, antibacterial compounds, anti-dandruff agents, volumizers, electrostatic Ingredients selected from the group consisting of inhibitors, moisturizers, hair styling aids, zinc pyrithione, silicone materials, hydrocarbon polymers, emollients, oils, surfactants, suspending agents, sun care agents, and mixtures thereof The composition of claim 1 further comprising: The components include anionic, hydrophobically modified and amphoteric acrylic copolymers, vinyl pyrrolidone homopolymers and copolymers, cationic vinyl pyrrolidone copolymers, nonionic, cationic, anionic and amphoteric cellulosic polymers, acrylamide homopolymers, Cationic, anionic, amphoteric and hydrophobic modified acrylamide copolymers, polyethylene glycol polymers and copolymers, hydrophobic modified polyethers, hydrophobic modified polyether acetals, hydrophobic modified polyether urethanes, associative polymers, hydrophobic modified cellulosic polymers, polyethylene oxide - propylene oxide copolymer, chitosan, clay, and nonionic, anionic, hydrophobically-modified, amphoteric, cationic multi S, chitosan, starch, alginate, konjac gum, clay, poloxamers (polyoxyethylene / polyoxypropylene block polymer) functional polymer selected from the group consisting of, and mixtures thereof, to claim 5 The composition as described. The components are nonionic, cationic, anionic and amphoteric cellulosic polymers, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydrophobically modified carboxymethylcellulose, cationic hydroxyethylcellulose, cationic hydrophobic Selected from the group consisting of hydrophobically modified hydroxyethylcellulose, hydrophobically modified hydroxyethylcellulose, hydrophobically modified hydroxypropylcellulose, cationic hydrophobically modified hydroxypropylcellulose, cationic carboxymethylhydroxyethylcellulose, and cationic hydroxypropylcellulose The composition according to claim 5 . The components are nonionic, anionic, hydrophobically modified, amphoteric and cationic polygalactomannans, carboxymethyl guar, hydroxypropyl guar, hydrophobically modified guar, carboxymethyl guar hydroxypropyltrimethylammonium Chloride, guar hydroxypropyl trimethylammonium chloride, and hydroxypropyl guar hydroxypropyl trimethylammonium chloride, hydroxybutyl guar, hydroxybutyl guar hydroxypropyltrimethylammonium chloride, hydroxyethyl guar, hydroxyethyl guar 6. The composition of claim 5 , selected from the group consisting of hydroxypropyltrimethylammonium chloride and locust bean. A method for producing the cationic oxidized polysaccharide or a derivative thereof according to claim 1, wherein (a) at least one cationic polysaccharide or a cationically derivatized polysaccharide and the polysaccharide or the same Reacting with at least one reagent that reduces the weight average molecular weight (Mw) of the derivative of the above to an upper limit of 1,000,000 daltons, and (b) recovering the cationic oxidized polysaccharide, The method comprising producing the cationic oxidized polysaccharide composition according to claim 1. The reagent is an oxidizing reagent selected from the group consisting of peroxides, persulfates, permanganates, perchlorates, hypochlorites, oxygen, and biochemical oxidants; The method of claim 9 . The composition of claim 1, which is a personal care composition further comprising at least one other active personal care ingredient. As one component, comprising adding a cationic, oxidized polysaccharide or derivative thereof which is prepared by treating a polysaccharide with an oxidizing reagent to reduce the molecular weight by introducing an aldehyde functional group in the composition, according to claim A method for producing a personal care or household care composition according to 1 . A personal care or household care composition comprising at least one cationic oxidized polysaccharide or derivative thereof, the cationic oxidized polysaccharide or derivative thereof having a lower limit of 50,000 and an upper limit of 1,000. At least one cationic oxidized polysaccharide or derivative thereof having a weight average molecular weight of 1,000,000 and a content of aldehyde functional groups of at least 0.001 milliequivalent per gram of polysaccharide;
  The personal care or household care composition is a shampoo, conditioner, shower gel, liquid soap, body detergent, hair styling product, shaving gel / cream, body cleaner, solid soap, skin care lotion, sun care lotion, dishwashing detergent. Selected from the group consisting of laundry detergents, fabric softeners, and antistatic products, and
  The polysaccharide is selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose and hydroxybutylcellulose;
Said personal care or household care composition.