KR101118460B1 - Cationic, Oxidized Polysaccharides in Conditioning Applications - Google Patents

Abstract

Cationic oxidized polysaccharides or derivatives thereof having an average molecular weight (Mw) having a lower limit of 50,000 and an upper limit of 1,000,000 and an aldehyde functional group content of at least 0.001 meq / g are used in personal care and household care compositions. The cationic oxidized polysaccharides are prepared in a continuous or batch process using hydrolysing, oxidizing or combinations of hydrolysing and oxidizing agents. Personal care or household care compositions are prepared by adding a cationic oxidized polysaccharide to a personal care or household composition containing at least one active ingredient in addition to the cationic oxidized polysaccharide of the present invention.

Description

Cationic Oxidized Polysaccharides in Conditioning Applications

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

Cationic polysaccharides and other polymers have been widely used in personal care and household products to perform the functions of the final product, from thickening to conditioning of the substrate. Depending on the use, the substrate may be skin, hair or textile material.

Cationic polysaccharides are used in hair hygiene products to provide conditioning to hair. In skin care products, these same polymers can provide conditioning effects to the skin. When incorporated into detergents and fabric softening compositions, these same polymers can provide the fabric with conditioning, softening, anti-pilling, color retention and antistatic properties.

Hair conditioning agents perform their function in the cuticle, or the sheath of the keratinized scale of the hair fiber surface. The skins of the cuticles are arranged in such a way as to overlap the shingles of the roof. The cell structure of the cuticle is composed of the outer layer A layer and the inner layer B layer. The transparent outer A layer of sulfur-containing protein protects the hair from chemical, physical and environmental damage. As a result, the condition of the cuticle determines the condition of the hair, and the hair-conditioning product is directed to the strengthening and recovery of the cuticle shaft layer. Undamaged cuticles make hair strength, gloss, smoothness, smoothness and care possible. (Conditioning Agents for Hair & Skin, Ed.R. Schueller and P. Romanowski, Marcel Dekker, Inc., NY, N.Y., 1999.)

Wet and dry combability measurements are typical test methods used to measure conditioning performance in shampoo and conditioner applications. Commercially available cationic conditioning polymers have been reported to reduce the wet combing force experienced when combing wet hair by 30% to 50% compared to shampoos that do not contain the polymer.

Conventionally, only high molecular weight cationic polymers have been used in cleaning products, and it has been suggested that only high molecular weight cationic polymers can deliver the conditioning effects required in cleaning systems (V. Andre ', R. Norenberg, J. Rieger, P. Hoessel, Proceedings, XXIst IFSCC International Congress 2000, Berlin, p. 189-199). However, commercially available high molecular weight cationic guar conditioning polymers have disadvantages such as incompatibility with surfactant systems used in shampoos, body washes, conditioners, skin care, sun care, laundry products and the like. In addition, they also contribute to the final product viscosity, which may be 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 their backbones for treating keratin materials. The composition is used in aqueous systems of cosmetics and fragrances and / or products containing antibacterial agents such as shampoos, topical sprays, dental care products.

US Pat. No. 5,756,720 describes a process for preparing polygalactomannan compositions having nonionic and cationic groups attached to the backbone. The patent describes the achievement of high optical transparency in cleaning surfactant compositions with the composition. However, the hydroxypropyl cationic polygalactomannan of the composition is known to lack conditioning performance as described in WO 99/36054.

U. S. Patent No. 5,489, 674 describes a process for preparing polygalactomannan gum and polygalactomannan gum compositions prepared by certain methods, including aqueous alcohol processes. The product is described to impart 85 to 100% transmittance with 0.5 parts of polymer per 100 parts of aqueous solution at wavelengths between 500-600 nm. The use of such materials in personal hygiene applications is disclosed.

Japanese Patent Application No. Hei 10 [1998] -36043 discloses a cosmetic composition using a polygalactomannan degradation product having a molecular weight distribution in the range of 4,500 to 35,000 of at least 80% for use in hair and skin care products.

U.S. Pat.Nos. 5,480,984 and 6,054,511 disclose aqueous, high solids low viscosity polysaccharide compositions and polysaccharides with hydrogen peroxide oxidants to react between about 20% to about 50% solids and a viscosity of less than 9500 mPa.s at 25 ° C. A method for producing the composition is disclosed by preparing a product having Cellulose ethers, guar and guar derivatives are disclosed as polysaccharides with a wide range of uses such as cosmetics.

US patent application Ser. No. 20030199403 A1 discloses a shampoo composition consisting of a detergent for detergent, 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.

Cationic HECs, such as Ucare Polymer JR400 ^™ with high cation substitutions, have been mentioned by the manufacturer to cause "buildup" problems after repeated use. One manufacturer recommends the use of cationic HECs with lower cation substitution levels to eliminate accumulation problems ("Cationic Conditioners that Revitalize Hair and Skin", Amerchol Product Literature, WSP801, July, 1998). Accumulation is defined by the manufacturer as a bond to the substrate of the polymer, which makes the polymer more difficult to remove from the substrate in subsequent cleaning treatments.

There is still a need in the market for cationic conditioning polymers that have wide surfactant compatibility and are capable of dispensing personal hygiene and household compositions with good conditioning performance. The present invention meets this need by providing cationic conditioning polymers that not only have broad surfactant compatibility with good conditioning performance, but are also economical in formulating compositions in which transparency is not necessarily a problem.

Brief summary of the invention

The present invention relates to a personal care and household composition comprising at least one cationic oxidized polysaccharide or derivative thereof having a weight average molecular weight (Mw) having a lower limit of 50,000 and an upper limit of 1,000,000 and an aldehyde functional group of at least 0.001 meq / g. It is about.

The cationic oxidized polysaccharide or derivative thereof preferably has a Brookfield viscosity lower limit of 30 cps and an upper limit of 20,000 cps at 10 wt% polysaccharide solids using spindle 4 at 25 ° C., 30 rpm, provided that the polysaccharide When the viscosity of is higher than 20,000 cps, the Brookfield viscosity is measured at 10% by weight solids using spindle 4 at 25 ° C., 0.3 rpm and has a lower limit of 20,000 cps and an upper limit of 2,000,000. The viscosity range is particularly preferred for cationic oxidized polygalactomannans.

The present invention also relates to a method of making a personal care or household composition comprising adding a cationic oxidized polysaccharide to a personal care or household composition containing at least one active ingredient in addition to the cationic oxidized polysaccharide of the present invention. will be.

According to the invention, the cationic oxidized polysaccharides of the present invention are shampoos, combined shampoos (i.e., to clean and condition hair), three-functional shampoos (i.e. clean, condition and style), conditioners, shower gels It can deliver the conditioning or gloss effect required for cleaning products such as liquid soaps, body washes, styling products, shaving gels / creams, body cleansers and soaps. The polymers of the present invention deliver such properties to hair when they are incorporated into a wide range of cleaning shampoo surfactant systems that require conditioning or glossing properties that result in a reduction in combing power upon good wetting and drying. The polymers of the present invention also deliver conditioning or gloss properties that give the skin a softer feel when incorporated into skin care, sun care, body washes, body cleansers and soaps.

Similar conditioning or gloss effects are expected for surfactant-based household cleaning product compositions that require conditioning performance, such as dish detergents, laundry detergents, fabric softeners and antistatic products. Conditioning in fabric softeners and laundry detergents means giving the fabric a softer feel, agglomeration-proof, color retention and eliminating static action.

Cationic functional groups of polysaccharides or derivatized polysaccharides can be added to the backbone by known methods. For example, the polysaccharide material may be used at a sufficient time and at a sufficient temperature for tertiary amino or quaternary ammonium alkylating agents such as 2-dialkylaminoethyl chloride and 3-chloro-2-hydroxypropyltrimethylammonium chloride and 2,3-epoxy. React with quaternary ammonium compounds such as propyltrimethylammonium chloride. Preferred examples are glycidyltrialkylammonium salts, and glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltripropylammonium chloride, glycidylethyldimethylammonium chloride, glycidyldiethylmethylammonium chloride 3-halo-2-hydroxypropyltrialkylammonium salts such as, and their corresponding bromide and iodide; 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, 3-chloro-2-hydroxypropyltripropylammonium chloride, 3-chloro-2-hydroxypropyl Ethyldimethylammonium chloride, and their corresponding bromide and iodide; And quaternary ammonium compounds such as halides of imidazoline ring containing compounds.

The cationic polysaccharide is also a nonionic substituent, ie hydroxyalkyl (e.g., hydroxyethyl, hydroxypropyl, hydroxybutyl) or carboxymethyl, in which the alkyl represents a straight or branched chain hydrocarbon moiety having from 1 to 30 carbon atoms. It may optionally contain other substituents such as anionic substituents such as groups. These optional substituents may be used to obtain (1) alkylene oxides (e.g., ethylene oxide, propylene oxide, butylene oxide), or (2) carboxymethyl groups for obtaining hydroxyethyl groups, hydroxypropyl groups or hydroxybutyl groups. To the polysaccharide polymer by reaction with a reagent such as chloromethyl acetic acid. Methods of preparing derivatized polygalactomannan are known in the art.

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

According to the present invention, cationic oxidized polysaccharides used to prepare personal care or household compositions having good conditioning properties include oxidants alone or biochemical reagents that reduce molecular weight and / or introduce oxidized functional groups. It is preferably prepared by using in combination with other reagents. In order to obtain the results of the titration, it is necessary to include only the oxidation step in the process or otherwise together with other reagents.

Oxidizers include any reagent that introduces oxygen atoms into the polymer structure. Some oxidants may act to reduce the molecular weight of the polymer. Examples of such bifunctional oxidants are peroxides, peracids, persulfates, permanganates, perchlorates, hypochlorites and oxygen. An example of a biochemical oxidant that does not reduce the molecular weight is oxidase. Particular examples of oxidases useful in the present invention are galactose oxidases, and other biochemical oxidants known to those skilled in the art.

The introduction of oxidants into the process for the production of the products of the present invention results in larger cationic polymers prepared using oxidants in a wider range of surfactant systems commonly used in personal care and household compositions compared to cationic polymers not treated with oxidants. It has been found to be useful in that it has solubility.

As mentioned above, the introduction of oxidants into the process for the preparation of the products used to make the personal care and household compositions of the present invention introduces aldehyde groups into the polymer composition. The polymer has been found to contain at least 0.001 milliequivalents (meq / g) of aldehyde per gram of polysaccharide. The upper limit of the aldehyde content is about 1.0 meq / g.

According to the present invention, cationic oxidized polysaccharides or derivatives thereof generally have a cationic degree of substitution (DS) having a lower limit of about 0.001 and an upper limit of about 3.0. Preferably the lower limit of the cation DS is 0.01 and more preferably 0.05. Preferably the upper limit of the cation DS is 2.0, more preferably 1.0, even more preferably 0.25. Cationic oxidized polysaccharides or derivatives thereof of the present invention generally have a weight average molecular weight (Mw) having a lower limit of about 50,000 and an upper limit of about 1,000,000. Preferably, the lower limit of 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 hygiene active ingredient should provide some benefit to the user's body. Personal care products include hair care, skin care, sun care and oral care products. Examples of materials that may be suitably included in the personal care product according to the present invention include, but are not limited to:

1) a deodorant flavor that can reduce the odor of the body as well as provide a flavor and aroma response that gives rise to an olfactory response in the form of aroma;

2) skin refreshing agents such as menthol, menthyl acetate, menthyl pyrrolidone carboxylate N-ethyl-p-mentan-3-carboxamide and other derivatives of menthol, which cause tactile reactions in the form of cool sensations on the skin ( coolant);

3) emollients such as isopropyl myristate, silicone materials, mineral oils and vegetable oils, which cause tactile reactions in the form of increasing skin smoothness;

4) deodorants other than flavors, which function on the surface of the skin, in particular to reduce or eliminate the level of microbial flock leading to the manifestation of body malodor;

5) antiperspirant actives that function to reduce or eliminate the appearance of sweat on the skin surface;

6) moisturizers to maintain skin moisture by applying moisture or preventing evaporation from the skin;

7) cleaning agents that remove dirt and oil from the skin;

8) Sunscreen active ingredients that protect skin and hair from UV and other harmful rays from the sun. According to the invention the therapeutically effective amount will usually be from 0.01 to 10%, preferably 0.1 to 5% by weight of the composition;

9) Condition hair, rinse hair, entangle hair, styling, volumening and varnishing, anti-dandruff, hair growth promoter, hair dye and pigment, hair fragrance, hair relaxer, hair bleach, hair moisturizer, hair oil Hair treatments that act as treatments and anti-friction agents;

10) oral hygiene such as toothpaste and mouthwash, which cleans, whitens, deodorizes and protects teeth and gums;

11) denture adhesives that provide adhesive properties to dentures;

12) shaving products such as creams, gels and lotions and razor blade lubrication strips;

13) tissue products such as moisturizing or cleaning tissues;

14) beauty aids such as foundation powders, lipsticks and eye cosmetic products; And

15) textile products such as moisturizing and / or cleaning wipes, and diapers;

16) Nail care products such as nail polish.

According to the invention, household hygiene active ingredients should provide some benefit to the user. Examples of materials that may be suitable in accordance with the present invention include, but are not limited to:

1) Deodorant flavors that can reduce the odor as well as provide flavors and aroma reactions that cause olfactory reactions in the form of aromas;

2) insect repellents that function to defend the insects from certain areas or skin attacks;

3) bubble generating agents such as surfactants that produce bubbles or bubbles;

4) pet deodorants, such as pyrethrin, which reduce pet odor;

5) pet shampoos and active ingredients which, when removed from the skin and hair surface, function to remove foreign substances and bacteria and condition the skin and hair;

6) industrial grade soaps, shower gels and liquid soap active ingredients which remove bacteria, dirt, oils and oils from the skin, sanitize the skin and condition the skin;

7) all-purpose cleaners to remove oil, grease, germs from the surface in areas such as kitchens, toilets and public facilities;

8) disinfectant components that kill or inhibit growth of bacteria in the home or public facilities;

9) carpet and furniture cleaning active ingredients that dislodge and remove dirt and debris from the surface and also deliver softness and fragrance;

10) laundry softener active ingredients that reduce static electricity and soften the feel of the fabric;

11) When cleaning detergent ingredients to remove oil, grease, stains and kill germs;

12) dishwashing detergents to remove stains, food and germs;

13) toilet bowl cleaner that removes stains, kills bacteria and removes odors;

14) laundry pre-staining active ingredients to help remove stains from clothing;

15) fabric sizing agents that improve the appearance of the fabric;

17) Vehicle cleaning active ingredients that remove dirt, fats and the like from vehicles and equipment:

18) lubricants to reduce friction between parts; And

19) Textile products, such as dust removal or sanitizing wipes.

The above list of personal care and household active ingredients is merely an example and is not a complete list of active ingredients that can be used. Other components used in this kind of product are known in the industry. In addition to the components commonly used, the compositions according to the invention may optionally contain colorants, preservatives, antioxidants, nutritional supplements, alpha or beta hydroxy acids, activity enhancers, emulsifiers, functional polymers, viscosity agents (salts, ie NaCl, NH ₄ Cl & KCl, water soluble polymers, ie hydroxyethylcellulose, and fatty alcohols, ie cetyl alcohol; such as water-swellable materials such as clay and silica, alcohols, fats or fatty compounds having 1 to 6 carbons (ie , Fatty amides and fatty acid esters and fatty alcohols polyethylene glycol ethers), antibacterial compounds, zinc pyrithione, silicone materials, hydrocarbon polymers, emollients, oils, surfactants, pharmaceuticals, flavoring agents, fragrances, suspending agents (ie, xanthan gum , Carbomers, clays and silicas), and mixtures thereof.

According to the invention, examples of functional polymers that can be used in combination with the cationic oxidized polysaccharides or derivatives thereof of the invention are acrylic acid homopolymers such as Carbopol ^(R) products and anionic and amphoteric acrylic acid aerials. Water-soluble polymers such as copolymers, vinylpyrrolidone homopolymers and cationic vinylpyrrolidone copolymers; Nonionic, cationic, such as hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, cationic hydroxyethyl cellulose, cationic carboxymethyl hydroxyethyl cellulose and cationic hydroxypropyl cellulose, Anionic and amphoteric cellulosic polymers; clay; Acrylamide homopolymers and other polymers referred to as cationic, amphoteric and hydrophobic acrylamide copolymers, polyethylene glycol polymers and copolymers, hydrophobic polyethers, hydrophobic polyetheracetals, hydrophobically modified polyetherurethanes and related polymers, Hydrophobic cellulose polymer, polyethylene oxide propylene oxide copolymer, and xanthan, chitosan, carboxymethyl guar, alginate, hydroxypropyl guar, carboxymethyl guar hydroxypropyltrimethylammonium chloride, guar hydroxypropyltrimethylammonium chloride, hydroxy Nonionic, anionic, hydrophobic, amphoteric and cationic polysaccharides such as propyl guar hydroxypropyltrimethylammonium chloride.

According to the invention, the silicone material which can be used can be in particular polyorganosiloxanes which are insoluble in the composition and can be used in the form of polymers, oligomers, oils, waxes, resins or gums.

Organopolysiloxanes are defined in more detail in Walter Noll, "Chemistry and Technology of Silicones" (1968) Academic Press. These may be volatile or nonvolatile.

When volatile, the silicone is more particularly selected from those having a boiling point between 60 ° C. and 260 ° C., and even more particularly the following.

(i) cyclic silicon containing 3 to 7, preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane, unions sold under the trade name "Silbione 70045 V2" by, for example, "volatile silicone 7207" by Union Carbide or by Rhone-Poulenc. Decamethyl-cyclopentasiloxane, marketed under the trade name "volatile silicon 7158" by carbide and "Silbion 70045 V 5" by Long-Flan, and mixtures thereof.

A mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and octamethylcyclotetrasiloxane and oxy-1,1'-bis (2,2,2 ', 2', 3,3'- Mention may also be made of mixtures of cyclic silicones and organosilicon compounds, such as mixtures of hexatrimethylsilyloxy) neopentane.

(ii) straight-chain volatile silicones having from 2 to 9 silicon atoms and having a viscosity at 25 ° C. of up to 5 × 10 ⁻⁶ m ² / s. An example is in particular decamethyltetrasiloxane sold under the trade name "SH 200" by Toray Silicone company. Silicones belonging to this class are described in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, "Volatile Silicone Fluids for Cosmetics".

Nonvolatile silicones, more particularly polyarylsiloxanes, polyalkylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanes modified with organic functional groups, and mixtures thereof, are preferably used.

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

Examples of such silicone polymers and resins are as follows:

Polydimethylsiloxane,

Polydimethylsiloxane / methylvinylsiloxane gum,

Polydimethylsiloxane / diphenylmethylsiloxane,

Polydimethylsiloxane / phenylmethylsiloxane, and

Polydimethylsiloxane / diphenylsiloxanemethylvinylsiloxane.

More particularly usable products according to the invention are mixtures as follows:

(a) cyclic polydimethyl, such as product Q2 1401, sold from Dow Corning Company by Dow Corning Company and (from the hydroxylated polydimethylsiloxane (called dimethiconol according to the CTFA nomenclature); Mixtures formed from siloxanes (called cyclomethicone according to the nomenclature of the CTFA Dictionary);

(b) Product from General Electric Company A mixture formed from cyclic silicone such as SF 1214 silicone fluid and polydimethylsiloxane, which is dissolved in SF 1202 silicone fluid oil corresponding to decamethylcyclopentasiloxane. SF 30 gum corresponding to dimethicone having a number-average molecular weight of 500,000); And

(c) a mixture formed of two PDMS of different viscosities, more particularly a mixture formed of PDMS gum and PDMS oil, for example the product SF 1236 from General Electric. The product preferably comprises 15% SE 30 gum and Contains 85% SF 96 oil.

For a more detailed understanding of the invention, reference may be made to the following examples, which are intended to further illustrate the invention and should not be taken in a limiting sense. All parts and percentages are by weight unless otherwise indicated.

I. Use of chemical oxidants-(4-step standard decomposition method)

matter:

Cationic Polygalactomannans (Guar Hydroxypropyltrimonium Chloride)-Hercules, Incorporated

CAS # 65497-29-2

Fumaric acid, P.A. -Acros / Fisher Scientific,

CAS # 110-17-8

Dow Corning 200 ^(R) Fluid, 50 CST. -Silicone Oil-Neslab Oil-Bath

CAS # 63448-62-9

Kathon ^(R) CG stabilized biocides / preservatives-Rohm and Haas Co

CAS # mixture, see MSDS

Hydrogen peroxide, 30%-JTBaker-CAS # 7722-84-1

EM Quant Peroxide Test Strips from EM Science.

Cationic Polygalactomannan Depolymerization

First stage
Charge 2nd step
Charge 3rd step
Charge 4th step
Charge Final gun
Charge Deionized water 2400.0 Quantity to be 2500 Quantity to be 2500 Quantity to be 2500 2097.5 Hydrogen peroxide, 1.0% 37.5 37.5 37.5 37.5 150.0 Cationic Polygalactomannan Added 2.0% Fumaric Acid 62.5 62.5 62.5 62.5 250.0 2500.0 2500.0 2500.0 2500.0 2497.5 Caton CG 2.5 system 2500.0 2500.0 2500.0 2500.0 2500.0 Note: In this composition, hydrogen peroxide is used at 1.0% H ₂ O ₂ 60 (parts by weight) pbw per 100 pbw polygalactomannan.

Experimental Process:

The deionized water of the first stage was weighed and placed in a beaker and the beaker was suspended in a bath using a chain clamp. The Capramo Stirrer Model BDC-3030 was assembled with the Capramo "U" -shaped 4 "(Anchor) paddle and digital alarm thermometer probe in batch.The beaker was covered with a Saran film to minimize moisture loss. The water was heated to 85-90 ° C. with stirring at about 50 rpm in an oil bath adjusted to 95 ° C. The temperature of the oil bath was adjusted as necessary to maintain the batch temperature at 85 to 90 ° C. An additional Caphramo Mixer Model RZR-1 with a slow 2 "propeller blade was used in the oil bath to improve.

If volume was allowed, the stirrer speed was increased to about 100 rpm and a quarter of the total peroxide load was applied to the beaker by injecting the peroxide through the saran cover using a properly sized weighed hypodermic syringe. . The contents of the beaker were left to mix for about 5 minutes. The cover on the beaker was then removed and very slowly sprinkled into the beaker mixing 1/4 of the total load of cationic polygalactomannan. The stirring speed of the stirrer was adjusted to maintain an appropriate vortex speed. In particular, some lumps may appear during the first polygalactomannan addition; Small chunks will dissolve with increasing viscosity. The cover was replaced and mixing continued at a temperature of 85-90 ° C. until the viscosity was reduced enough to allow the next polymer addition.

The addition of the peroxide and the polymer was repeated four times in total until the total loading of H ₂ O ₂ and polygalactomannan was added, allowing time for the polymer to dissolve and decrease in viscosity before the next additional addition. If necessary, the beaker's water level was adjusted at each time interval for moisture loss. After the last addition, mixing was continued for 1 hour, then the amount of residual peroxide was checked using an EM quant peroxide test strip. The mixture was stopped and a small hole was made in the pores where the sensing area of the test sheet 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 with the score on the container. The reaction was continued until the H ₂ O ₂ level was below 50 ppm. Note: The detection area of the test strip will probably be dark brown due to the high levels of peroxide present. In such a case, a small sample of the solution (about 5 g) is carefully extracted and diluted with a certain amount of room temperature deionized water to allow reading on the test strip within the detection range.

The heat of the oil bath was turned off and the oil was diverted through a Neslab FTC-350 chiller. When the oil had cooled sufficiently, the beaker was carefully removed from the oil bath (slip with silicone oil) and the total weight of the batch was measured. The amount of make-up moisture required was determined and the substrate moisture was premixed with 1.0% Germaben II product and the water / germaben II mixture was added with manual stirring. If the solution was extremely viscous, the beaker was returned to the oil bath and a stabilizing biocide and substrate moisture were added with mechanical stirring. The contents of the beakers were filled into appropriate containers for storage, pH stability tests, Brookfield viscosity, and required analysis when warmed.

Combing test

Wet comb and dry comb measurements were performed on an Instron instrument using a slightly bleached European tress wound with a mild anionic surfactant-based shampoo or a nonionic surfactant shampoo.

The percentage of reduction of wet comb and dry comb energy is defined as shown in equation (1) below. The energy needed to empty the tress after winding with a shampoo containing the cationic polymer was subtracted from the energy needed to comb the tress wound twice with a 4.5 wt% sodium lauryl sulfate (SLS) solution. This remainder was then divided by the energy needed to comb the tress washed with SLS solution. The value was multiplied by 100 and called the percentage reduction in combing force. The percentage reduction was typically positive when the cationic conditioning polymers condition the hair.

[Energy (without polymer) (gf-mm)-energy (with polymer)] / energy (without polymer)] x 100 = percent reduction in combing energy

Example  One

The standard decomposition method mentioned above was used. About 935 g of water was placed in a 1500 ml beaker and placed in an oil bath adjusted to about 120 ° C. The beaker was then heated to and maintained at a temperature of about 85-95 ° C. in an oil bath. Two 2 "propeller blade mixers were inserted into the beaker and a small amount of N-Hance ^(R ) 3205 cationic guar product (Hercules Incorporated, Wilmington, DE) was added with stirring. Next, a small amount of peroxide Was added to the beaker while mixing was continued, if the viscosity of the mixture was increased, mixing was continued at 85-95 ° C. until the viscosity was sufficiently low for the next amount of polymer and peroxide addition. Three additional portions of the polymer and peroxide were repeated until complete, a portion of the water was evaporated during the further addition of the polymer and the peroxide, therefore, at the end of the addition, the level of water was adjusted for water loss. The amount was periodically checked in the beaker using a test strip and reacted until less than 50 ppm of peroxide remained. It was., Turn off the oil-bath cooled the beaker to ambient temperature. The germanium Ben ^(R) II stabilizing biocide / preservative (ISP Incorporated, Wayne, NJ) were added to a beaker.

Table 1 below (Experiments A to F) describes the components for the above experiments.

Degradation of Cationic Guar Polymer A B C D E F Deionized water 935.07 947.36 960.00 965.15 967.74 970.35 N-Hands 3205 25.97 26.32 26.67 26.81 26.88 26.95 Hydrogen Peroxide-6.0% 38.96 26.32 13.33 8.04 5.38 2.70 1000.00 1000.00 1000.00 1000.00 1000.00 1000.00 N-Hands 3205 25.97 26.32 26.67 26.81 26.88 26.95 Hydrogen peroxide-6.0% 38.96 26.32 13.33 8.04 5.38 2.70 N-Hands 3205 25.97 26.32 26.67 26.81 26.88 26.95 Hydrogen peroxide-6.0% 38.96 26.32 13.33 8.04 5.38 2.70 N-Hands 3205 25.97 26.32 26.67 26.81 26.88 26.95 Hydrogen peroxide-6.0% 38.96 26.32 13.33 8.04 5.38 2.70 Germanmaven II 10.00 10.00 10.00 10.00 10.00 10.00 1204.79 1167.92 1130.00 1114.55 1106.78 1098.95

Example  2

The procedure described in Example 1 was repeated for Experiments G, H and I, except that the oil bath temperature was adjusted to maintain the sample temperature at about 85-90 ° C. and 1.0% hydrogen peroxide solution was used instead of 6.0% solution. In addition, the order of addition of the polymer and the peroxide was reversed to add the peroxide first and then add the polymer further. Table 2 below describes the components of Experiments G, H and I.

Example  3

In the experiments below (Table 2 Experiments J, K and L), the procedure used in Example 2 above was used except that N-hands ^(R) 3215 product (including fumaric acid) was used instead of N-hands ^(R) 3205 polymer. It was.

Degradation of Cationic Guar Polymer G H I J K L Deionized water 957.44 963.59 969.83 957.44 963.59 969.83 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 N-hands 3215,
Contains fumaric acid 26.60 26.77 26.94 1000.00 1000.00 1000.00 1000.00 1000.00 1000.00 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 N-hands 3215,
Contains fumaric acid 26.60 26.77 26.94 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 N-hands 3215,
Contains fumaric acid 26.60 26.77 26.94 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 N-hands 3215,
Contains fumaric acid 26.60 26.77 26.94 Germanmaven II 10.00 10.00 10.00 10.00 10.00 10.00 1111.08 1092.46 1073.57 1111.08 1092.46 1073.57

Example  4

(a) For the experiment M, was used to reconstruct O ^{(Jaguar (R)) C-} 13-S cationic guar product (Rhodia Incorporated, Cranberry, NJ) , the case of (b) Experiment N is reconstituted ah ^(R) c-162 was used as a cationic hydroxypropyl guar product (Rhodia Incorporated, Cranberry, NJ) , (c) O experiment cases, the thermal decomposition only non-peroxide haenseu N- ^(R) 3215 cationic guar product (Hercules Incorporated, Wilmington, DE), the same procedure as used in Example 3 was repeated in Example 4 for Experimental M, N and O series and shown in Table 3.

Experiment O was extremely viscous after the first polymer addition. The second and third polymer additions were cut in half, but the viscosity remained extremely high. Manufacturing was stopped; No germanma ^(R) II preservative was added. This example showed that pyrolysis without hydrogen peroxide proceeds very slowly.

Degradation of Cationic Guar Polymer M N O Deionized water 963.59 963.59 972.97 Hydrogen Peroxide-1.0% 9.64 9.64 ---- Jaguar C-13-S 26.77 ---- ---- Jaguar C-162 ---- 26.77 N-Hands 3215 27.03 Hydrogen Peroxide-1.0% 9.64 9.634 ---- Jaguar C-13-S 26.77 ---- ---- Jaguar C-162 ---- 26.77 N-Hands 3215 ^* 13.52 Hydrogen Peroxide-1.0% 9.64 9.64 ---- Jaguar C-13-S 26.77 ---- ---- Jaguar C-162 ---- 26.77 N-Hands 3215 ^* 13.52 Hydrogen Peroxide-1.0% 9.64 9.64 ---- Jaguar C-13-S 26.77 ---- ---- Jaguar C-162 ---- 26.77 ---- Germanmaven II 10.00 10.00 ---- 1092.46 1092.46 972.97

Example  5

The same formulation and procedure as used in Example 2 was also reported in Table 4 using Experiment 5 for Experiments P, Q and R.

Degradation of Cationic Guar Polymer P Q R Deionized water 957.44 963.59 969.83 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 1000.00 1000.00 1000.00 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 Hydrogen Peroxide-1.0% 15.96 9.64 3.23 N-Hands 3205 26.60 26.77 26.94 Germanmaven II 10.00 10.00 10.00 1111.08 1092.46 1073.57

Example  6

The same procedure as used for Experiments J, K and L in Example 3 was reported in Tables 5a and 5b using the Experiments S, T, U, V, W and X of Example 6. For experiments X and Y, tap water concentrations were expressed in gallons and all other material concentrations were expressed in pounds. For experiments W and X, a cationic guar split wetted with N-hands 3215 water was used instead of N-hands 3215 cationic guar powder, and hydrochloric acid was used instead of fumaric acid to neutralize the cationic guar split to pH 6.5. Sodium metabisulfite was added at the end of the reaction to decompose the residual peroxide. The product of Experiment X was further treated with sodium hydroxide at pH 8 for 30 minutes and then neutralized with dilute hydrochloric acid. The product from Experiment V had an aldehyde content of 0.035 meq / g and a Mw of 61,000. The product from Experiment U had a molecular weight of 50,400. For Experiment Y, all hydrogen peroxide and malic acid were added after the reactor was heated to 90 ° C. The N-hands cationic guar was added to the reactor as a slurry of 20% solids. The reaction pH was maintained at 6 and sodium metabisulfite was added to decompose the residual hydrogen peroxide at the end of the reaction. The product of Experiment Y was adjusted to pH 7 and further treated with nitrogen sparging, and then the pH was brought to about 6 by addition of preservative and additional acid.

For Experiment Z, the same procedure as in Experiment V was repeated using high molecular weight cationic guar precursor 2 (cation DS 0.5) combined with fumaric acid. Experiments AA and AB were reacted in a one step reaction at 90 ° C. using high molecular weight cationic guar precursor 3 (999,145 Daltons, cation DS 0.9) at which temperature hydrogen peroxide was added to water followed by cationic guar. Sodium metabisulfite was added to decompose excess peroxide.

N-Hands 3000 product with cation DS 0.06 was depolymerized using the following steps. 918.5 grams of water was heated to about 95 ° C. Then 31.5 g of 1.0% hydrogen peroxide were added followed by 50 g of N-Hands ^(R) 3000 product. Stir for 30 minutes. Next, 15.75 g of 1.0% peroxide was added. After stirring for 90 minutes, 0.21 g sodium metabisulfite was added and cooled with mixing. The solution was stored with 0.5% phenoxetol ^(R) and 0.18% nifacept ^(R) sodium preservative. Both preservatives are available from Clariant Corporation. The sample had an aldehyde of 15 ppm (0.009 meq / g) and a molecular weight of 298,000 Daltons as measured by EM Science Aldehyde Test Kit 10036-1.

Example  7

The procedure of Example 6, Experiment W was repeated using cationic hydroxyethylcellulose (Celquat ^(R) SC-240 and Ucare ^(R) polymer JR-400) as cationic polysaccharides instead of cationic guar. These examples are shown in Table 6. The pH value was maintained between 5 and 5.5 with 10% sodium hydroxide. Sodium metabisulfite was added to decompose excess hydrogen peroxide at the end of the reaction. BHT and Catone ^(R) CG preservatives were added to preserve the product. In Table 6 the Mw values for the products from Experimental AD, AE and AF were 90,000, 179,000 and 46,500. The procedure for Experimental AF used product from Experimental AD and only one hydrogen peroxide addition.

Degradation of Cationic Hydroxyethyl Cellulose Polymers AD AE AF Deionized water 1173 1172 Hydrogen peroxide-30.0% 4.33 2.16 ---- Celquat SC-240 38.6 ---- ---- Polymer JR-400 ---- 31 Product of Experiment A 100 Hydrogen peroxide-30.0% 4.33 2.16 0.5 CellQuart SC-240 38.6 ---- ---- Polymer JR-400 ---- 31 Hydrogen peroxide-30.0% 4.33 2.16 ---- CellQuart SC-240 38.6 ---- ---- Polymer JR-400 ---- 31 Hydrogen peroxide-30.0% 4.33 2.16 ---- CellQuart SC-240 38.6 ---- ---- Polymer JR-400 ---- 31 BHT 1.95 1.95 Caton CG 1.3 1.3 ---- 1347.97 1307.9 Mw measured by SEC 90,000 179,000 46,500

Example  8a

Chemical methods that use oxidants Combined  Biochemical methods

A product having a 10% total solids, molecular weight (Mw) of 45,000 to 65,000 Daltons, was prepared using the following method. The product produced also had an aldehyde functional group on 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) When the pH was adjusted below 9.0 with acid, but before reaching pH 7.5, 300 mg of mannase (product of ChemGen Corp., Rockville, MD) was added to the cationic guar split slurry. After 30 minutes at basic pH of 9.0 to 8.0, the pH was further reduced to 5.0 to 5.5 with acid.

4) Once the cationic guar split slurry is fully hydrated and the suspension like thick apple sauce starts to dilute, 13.6 g of 30% H ₂ O ₂ (4,000 ppm or 0.40% in guar suspension) is added to the cationic guar split suspension. Was added.

5) The temperature was raised to 90 ° C.

6) Once the in-process viscosity of the suspension has been reduced to 230 to 280 cps, the heating of the reactor is stopped and 0.1 to 0.5 g of sodium metabisulfite is measured by test strip EM quant ^(R) peroxide test. Bar residual H ₂ O ₂ was removed immediately.

7) H ₂ O ₂ using the test strip The level was checked to be zero.

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

Example  8b

Chemical methods that use oxidants Combined  Biochemical methods

By enzymatic degradation followed by peroxide decomposition High molecular weight  Precursor 3 Cationic  Preparation of Lower Molecular Weight Liquid Polymers from Guar

Experiment 8b (1)

933 g of water were heated to about 50-55 ° C. In a separate container 0.05 g of the mannase enzyme was premixed with water. The premix was added to the heated water while mixing. Next, 56.5 g of a high molecular weight, 999,145 Dalton precursor 3 polymer with a cation DS of about 0.9 was added while mixing. The polymer slurry temperature was raised to about 90 ° C. over about 90 minutes.

Then 2.22 g of 1.0% H ₂ O ₂ were added and mixed for 45 minutes. Then 0.19 g sodium metabisulfite was added and cooled. 10 g of lowmaben ^(R) II preservative and substrate moisture were added to obtain a batch size of 1000 g. The polymer molecular weight was 963759 Dalton.

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 the mannase enzyme was premixed with water. The premix was added to the heated water while mixing. Next, 56.5 g of a high molecular weight, 999,145 Dalton precursor 3 polymer with a cation DS of about 0.9 was added while mixing. The pH of the slurry was about 8.2. The slurry pH 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 the polymer was about 862,000 Daltons. The samples were tested for aldehyde levels using M quant formaldehyde test strips available from EM Science, Gibbstown, NJ. The polymer sample had 0 ppm formaldehyde. The polymer solution was then warmed to about 90 ° C. and 4.44 g of 1.0% peroxide solution was added. The reaction was stopped with 0.2 g 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 meta metabisulfite was added and cooled. The solution was stored with 0.5% phenoxetol ^(R) and 0.18% nifacept ^(R) sodium preservative. Both preservatives are available from Clariant. The sample had 10 ppm of aldehyde per strip test. The sample had a weight average molecular weight of 293,000 Daltons.

Example  8c

Chemical methods that use oxidants Combined  Biochemical methods

N- by peroxide decomposition and subsequent enzymatic degradation Hands ^(R)  3000 cationic From guar  Preparation of Lower Molecular Weight Liquid Polymers

The N-Hands 3000 polymer used in this example had a cationic DS of about 0.06 and a weight average molecular weight of 923,655 Daltons. 929 g of water were heated to about 90 ° C. in a silicone oil bath. 10.5 g of 1.0% active H ₂ O ₂ was added to the heated water. Next, 50 g of N-Hands ^(R) 3000 polymer was added to the water-peroxide mixture and held at 80-90 ° C. for about 110 minutes. 0.19 g of sodium metabisulfite was added and further mixed for 10 minutes and then cooled. The pH was adjusted to 6.5 using hydrochloric acid. 10 g of Lowmaven ^(R) II preservative and substrate moisture were added to adjust the total batch size to 1000 g and mix. This produced a 1000 gram batch with 5% polymer. The final product had a weight average molecular weight of 418,000 Daltons.

815 g of the peroxide decomposed polymer solution sample were heated to about 50-55 ° C. In a separate container 0.05 g of the mannase enzyme was premixed with water. The premix was added to the polymer solution while mixing. The polymer solution temperature was raised to about 92 ° C. over about 70 minutes. Samples were removed from the oil bath and allowed to cool while mixing. 8 g of lowmaben ^(R) II preservative and substrate moisture were added to give a batch size of 815 g. The weight average molecular weight of the polymer was 131,308 Daltons.

Example  8d

Biochemical method without oxidant

By enzymatic digestion High molecular weight Cationic  Guar from  Preparation of Lower Molecular Weight Liquid Polymers

The process of Example 1-3 of Example 8a was repeated. Once the desired viscosity was reached, the temperature was raised to 90 ° C. to denature the enzyme and stop the reaction. The mixture was allowed to cool to ambient temperature and 0.1% Caton 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 measured by indirect iodine titration.

Example  9

Biochemical oxidation and Combined  Biochemical methods

A product of 10% total solids with Mw of 40,000 was prepared. The product had an aldehyde group on low molecular weight cationic guar. The experimental procedure was as follows:

1) 700 g of tap water at 25 ° C. was placed in a glass reactor equipped with an overhead mixer.

2) 282 g of washed wet cationic guar split with about 60-65% moisture was added to the reactor to form a suspension while 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 of mannase was added to the guar split suspension.

5) The suspension was then sparged with 0.1-0.3 volumes of air per minute per suspension volume.

6) Next, 6,000 international units of galactose oxidase (Hercules Incorporated, Wilmington Delaware), 60,000 international units of catalase (NovoZymes, Franklintwon, North Carolina's Terminox Ultra 50L product), and 1,500 units of peroxidase (NS51004, also NovoZymes) Product) was added to the suspension.

7) The reaction was continued for 1 to 3 hours depending on the desired molecular weight and the degree of oxidation 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 maintained for 30 minutes to deactivate the enzyme.

9) 1 g of Caton CG (0.1%) solution was added to the final product as a preservative.

The aldehyde content of the sample was 0.4 meq / g as measured by the change in galactose / mannose ratio.

Example  10-15

Conditioning shampoo Example : Of the present invention in a conditioning shampoo Cationic  Performance of Oxidized Polysaccharides

In the shampoo composition, a conditioning agent, cationic guar or cationic hydroxyethylcellulose was added to improve the entanglement of both wet and dry hair as indicated by the decrease in energy for combing wet and dry hair. . In the results of Table 7, Examples 11, 12, and 14 show that the cationic oxidized guar and cationic oxidized hydroxyethylcellulose materials of the present invention are wetted and compared with the shampoos that do not contain the polymer of Example 10. Improves untangling of both dry hair. In Examples 11 and 12, shampoos prepared using low and medium molecular weight cationic oxidized guar prepared according to the method as described in Experiment U of Tables 5a and 5b were prepared for bleached medium brown European hair. Wet comb energy reductions of 62% and 51%, respectively, and dry comb energy reductions of 35% and 22%, respectively. The wet and dry comb energy reduction achieved by the polymers of the present invention is equivalent to or better than the corresponding performance of the high molecular weight cationic guar of Comparative Example 13. The wet and dry comb energy reductions of the polymers of the present invention in Examples 11 and 12 were also improved over the performance of the shampoos that did not contain the polymer of Example 10, which was 9% and 7%, respectively. Example 14 is wetted better than the polymer of the invention derived from cationic hydroxyethylcellulose polymer prepared according to the method described in Example 7, Experiment AF of Table 6, also containing no polymer of Control Example 10 And dry combing performance.

Example 15 is included as a comparative example for low molecular weight cationic guar prepared by biochemical degradation without oxidant treatment as described in Example 8d. The polymer provided improved wet and dry combing performance compared to the polymer free control example of Example 10, but the shampoo showed sedimentation over time.

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

Phase 1 water was heated to 80-90 ° C. in a vessel and HPMC was added while mixing. Cationic oxidized polysaccharides were added at about 60-65 ° C. while mixing with the heated water. The mixture was allowed to cool to 25-35 ° C. while mixing. Citric acid was added to the cooled mixture to lower the pH to 5.00-6.00. The mixture was then stirred until dissolved for about 1 hour.

Phase 2 Rhodapex ES STD product was weighed into a separate tar beaker. Phase 1 was added to phase 2 with mixing.

The pH was adjusted back to 5.0-5.5 with citric acid.

The mixture was stirred for 30-60 minutes until homogeneous.

Phase 3 Amposol CA product was added to the combined phases 1 and 2 with mixing and stirred for 5 minutes after the mixing was complete.

Mixing was continued until homogeneous.

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 checked and the pH was adjusted again between 5.0 and 5.5 if necessary. The shampoo was mixed for 15 minutes if adjusted.

ingredient Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Deionized water 48.5 48.5 48.5 48.5 48.5 48.5 HPMC60SH4000 0.5 0.5 0.5 0.5 0.0 0.0 N-Hands ^(R) 3215 0.0 0.0 0.0 0.5 0.0 0.0 Cationic Guar of the Invention 0.0 0.5 0.5 0.0 0.0 0.0 Cationic hydroxyethyl cellulose of the present invention 0.0 0.0 0.0 0.0 0.2 0.0 Cationic Guar of Example 8D 0.0 0.0 0.0 0.0 0.0 0.5 Amphosol ^(R ) CA 12 12 12 12 12 12 Rhodapex ^(R ) ES STD 35 35 35 35 35 35 10 wt% sodium chloride 4 4 4 4 4 4 Glidant ^(R) 0.5 0.5 0.5 0.5 0.5 0.5 Citric Acid (5%) pH adjustment pH adjustment pH adjustment pH adjustment pH adjustment pH adjustment water Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 system 100 100 100 100 100 100 shampoo Exterior Muddy Very turbid, a little gel Mist,
A little gel Translucent Transparency Very turbid, sedimentation pH 5.4 5.5 5.3 5.6 5.41 5.41 Reduction of wet combing energy (%) -9 62 51 52 45 51 Reduction of Dry Comb Energy (%) 7 35 22 28 16 8 Mw - 50200 197000 1200000 45,600 67200 Cationic DS - 0.18 0.18 0.18 0.3 0.18

(1) amposol CA, 30% activity (Stepan Chemicals, Chicago, IL)

(2) Rodapex ES STD, 30% active (Rhodia Incorporated, Cranberry, N.J.)

(3) Glidant ^TM 55% activity (Lonza, Fair Lawn, NJ)

(4) hydroxypropylmethylcellulose-HPMC60SH4000 (Shin Etsu, Tokyo, Japan).

Example  16-20

polymer MW Effect on Composition Viscosity of

In the shampoo composition, a conditioning agent, cationic guar was added to improve the entanglement of both wet and dry hair. Commercially available cationic guar has a significant effect on the viscosity of shampoo products and can therefore only be used at very low levels. In Examples 16-20 of Table 8, the shampoo 1) contains no cationic guar, 2) has a commercially available N-Hands ^(R) 3215 cationic guar of 0.2 to 1.5%, and 3) 1.5% of Prepared with cationic oxidized guar product according to the invention.

Shampoo Preparation: The vessel containing water was warmed to 70 ° C. by placing it in a 70 ° C. water bath. Benecel ^(R) products were sprinkled with mixing to the heated water. A commercially available N-Hands ^(R) 3215 product or polymer of the invention was then added to the vessel with mixing. The solution formed was cooled to about 40 ° C. while mixing. The remaining ingredients of the shampoo were added to the containers in the order listed. The shampoo pH was adjusted to about pH 5.5. Cool to room temperature while mixing shampoo.

The product of the invention used in Examples 17 and 19 of Table 8 was an aqueous solution having a weight average molecular weight of about 10% solids and about 42,000 Daltons prepared according to the procedure used in Experiment Y of Tables 5a and 5b. In comparison, a commercially available N-Hands ^(R) 3215 product is a dry polymer having a molecular weight of about 1 million. Because of its high molecular weight, the product has a significant impact on the viscosity of the conditioning shampoo. In Table 8, Example 16 shampoos were prepared without the conditioning agent. It had a Brookfield viscosity of about 3540 cps. In Example 18, the same shampoo prepared using the 1.5% N-Hands 3215 product had a Brookfield LVT viscosity of 193,000 cps. At such high viscosities it is not only difficult for a manufacturer to fill the composition into a shampoo bottle, but also very difficult to dispense by the consumer. Most of the commercially available shampoos have a viscosity of less than 10,000 cps. Even in the 0.2% N-Hands ^(R) 3215 product of Example 20, the shampoo viscosity was 13,600 cps. However, the product of the present invention (Example 17) was used with 1.5% activity and kept the shampoo viscosity 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 12 rpm, 25 ° C. using a Brookfield viscometer model LVT.

The conditioning shampoo was tested for its combing performance against mildly bleached European virgin hair. A 12-inch tress with a weight of about 5 g was used. In this study, the reduction of combing energy was measured. Reduction of combing energy is an indirect measure of the conditioning performance of the polymer. As shown in Example 16, when no conditioning polymer is used in the shampoo, it requires more force to comb the hair. Negative combing energy means higher power or energy is needed to tangle the hair and comb the hair. At the polymer level of 0.2%, the inventive polymers (Examples 19, Table 8) and commercially available polymers (Examples 20, Table 8) provide approximately the same reductions in wet comb energy, 15.8% and 17.1%, respectively. It was. However, the polymer of the present invention (Example 17) at the 1.5% polymer level was 53.7%, providing a significantly higher reduction in wet combing. Shampoo with a 1.5% commercial N-Hands ^(R) 3215 product was not tested because it had a viscosity significantly outside the shampoo viscosity range (Example 18).

ingredient Example 16 Example 17 Example 18 Example 19 Example 20A Example 20B Deionized water 51.6 51.6 51.6 51.6 51.6 51.6 Venecel ^(R) MP943 0.6 0.6 0.6 0.6 0.6 0.6 N-Hands ^(R) 3215 0.0 0.0 1.5 0.0 0.2 0.5 Cationic Guar of Tables 5a and 5b, Experiment Y of the Invention 0.0 13.64
(1.5% active) 0.0 1.82
(0.2% active) 0.0 0.0 Stepanol ^(R ) AM 27.5 27.5 27.5 27.5 27.5 27.5 Miranol ^(R ) C2M 6.9 6.9 6.9 6.9 6.9 6.9 Steol CS330 11.4 11.4 11.4 11.4 11.4 11.4 Germanmaben ^(R) II 0.5 0.5 0.5 0.5 0.5 0.5 Citric Acid (5%) pH adjustment pH adjustment pH adjustment pH adjustment pH adjustment pH adjustment water Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 system 100 100 100 100 100 100 shampoo Viscosity 3540 9180 193800 8300 13600 23250 pH 5.4 5.5 5.3 5.6 5.41 5.5 % T 600 nm Reduction of wet combing energy (%) -1.1 53.7 Not tested 15.8 17.1 Reduction of Dry Comb Energy (%) -28.0 7.4 Not tested 33.4 9.2 Mw - 42030 1087074 42030 1087074 1087074 Cationic DS - 0.23 0.26 0.23 0.26 0.26

(1) Venecel ^(R) MP943 Hydroxypropylmethylcellulose Aqualon (Aqualon, Wilmington, DE) (2) N-Hands ^(R) 3215 Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (3) Cationic Guar of the Invention (11.0% Activity) Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (4) stepanol ^(R) AM Ammonium Lauryl Sulfate Stepan Co. Northfield, Il (5) Miranol ^(R) C2M Conc. NP Disodium coco ampo diacetate Stefan (Northfield, Il) (6) steol ^(R) CS 330 Sodium laureth sulfate Stefan (Northfield, Il) (7) Germanmaben ^(R) II antiseptic ISP (Wayne, NJ)

Example  21-32

Does not affect the viscosity of the shampoo Without higher  Improved Performance Expression at Polymer Concentration

In Table 9, the effect of the polymer concentration of the present invention on the wet combing performance of the shampoo is shown. The higher the reduction in the wet combing energy of the hair, the greater the conditioning effect imparted by the conditioning polymer. Based on the wet combing data of Examples 21-25, at least 0.8% active polymer is required for maximum wet combing performance. Using commercially available high molecular weight cationic guar, such as the N-Hands ^(R) 3215 product, the sampu viscosity was 13,600 cps at the 0.2% polymer level (Example 20A in Table 8), which was 23,250 cps at the 0.5% polymer level. (Example 20B of Table 8). All of the above viscosities are believed to be at the boundaries of the preferred viscosity range for commercial shampoos, as seen in Examples 26-30 of Table 10. However, when using the polymer of the present invention, the shampoo viscosity was less than 10,000 cps even at the polymer level as high as 1.5% (Example 17 in Table 8 and Example 25 in Table 9). The viscosity comparisons for the shampoos of Examples 31 and 32 of Table 11 also show the effect of the polymers of the invention on conditioning performance on hair without affecting shampoo viscosity, even for guar with higher cation DS. . The polymer of Example 32 was prepared according to the procedure of Example 6, Experiment Z, in Tables 5A and 5B. Shampoos were prepared using the procedures described for the shampoos in Table 8. The shampoo viscosity was about 11,000 cps with 1.5% of the inventive polymer in Example 32 and compared to 32,000 cps for the high molecular weight polymer of Example 31. In Example 32 the polymer of the present invention had slightly better wet combing performance.

The results show that the polymers of the present invention allow the manufacturer to add special conditioning without substantially increasing the shampoo viscosity.

ingredient Example 21 Example 22 Example 23 Example 24 Example 25 Deionized water 51.3 48.6 45.8 44.0 39.5 Venecel ^(R) 943 0.6 0.6 0.6 0.6 0.6 N-Hands ^(R) 3215 0.0 0.0 0.0 0.0 0.0 Cationic Guar of Tables 5a and 5b, Experiment Y of the Invention 1.82
(0.2% active) 4.55
(0.5% active) 7.27
(0.8% active) 9.10
(1.0% active) 13.64
(1.5% active) Stefanol ^(R) AM 27.5 27.5 27.5 27.5 27.5 Miranole C2M 6.9 6.9 6.9 6.9 6.9 Steol ^(R) CS330 11.4 11.4 11.4 11.4 11.4 Germanmaben ^(R) II 0.5 0.5 0.5 0.5 0.5 Citric Acid (5%) pH adjustment pH adjustment pH adjustment pH adjustment pH adjustment water Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 system 100 100 100 100 100 shampoo Viscosity (cps) 8300 9450 7600 6250 7700 pH 5.6 5.4 5.7 5.5 5.4 % T600nm 83.8 71.6 62 57.7 43.5 Reduction of wet combing energy (%) 15.8 33.6 45.5 39.7 40.9 Reduction of Dry Comb Energy (%) 33.4 14.9 25.3 11.7 5.8 Mw 42030 42030 42030 42030 42030 Cationic DS 0.23 0.23 0.23 0.23 0.23

ingredient Example 26 Example 27 Example 28 Example 29 Example 30 Clarol ^(R) Herbal Essences ^(R) Shampoo Pantin ^(R) Pro-V ^(R) Shampoo Pantin ^(R) Pro-V ^(R) Shampoo and Conditioner Fines Plus ^(R) Silk Protein Johnson's ^(R) Baby Shampoo Anti-Tangle Prescription Brookfield LVT Viscosity at 12 rpm 7630 cps 7250 cps 12300 cps 2080 cps 1740 cps

ingredient Example 31 Example 32 Deionized water 51.6 25.17 Venecel ^(R) 943 0.6 0.6 Precursor 1 1.5 0.0 Inventive Tables 5a and 5b, Cationic Guar of Experimental AA Polymers 0.0 27.93
(1.5% active) Stefanol ^(R) AM 27.5 27.5 Miranol ^(R) C2M 6.9 6.9 Steol ^(R) CS330 11.4 11.4 Germanmaben ^(R) II 0.5 0.5 Citric Acid (5%) pH adjustment pH adjustment water Quantity to be 100 Quantity to be 100 system 100 100 shampoo Viscosity (cps) 32500 11250 pH 5.3 5.2 polymer Mw 1,200,000 27,900 Cationic DS 0.48 0.52 Reduction of wet combing energy (%) 17.1 24.4

(1) Venecel ^(R) MP943 Hydroxypropylmethylcellulose Aquaron (Wilm.DE) (2) precursor 1 Guar hydroxypropyl trimonium chloride Aquaron (Wilm.DE) (3) Experimental AA Polymer of the Invention (5.4% Activity) Guar hydroxypropyl trimonium chloride Aquaron (Wilm.DE) (4) stepanol ^(R) AM Ammonium Lauryl Sulfate Stefan (Northfield, IL) (5) Miranol ^(R) C2M Conc. NP Disodium coco ampo diacetate Stefan (Northfield, IL) (6) steol ^(R) CS 330 Sodium laureth sulfate Stefan (Northfield, IL) (7) Germanmaben ^(R) II antiseptic ISP (Wayne, NJ)

Swallows were prepared using the procedure described in Table 8. All viscosities were measured at 12 rpm, 25 ° C. using a Brookfield viscometer model LVT.

Example  33-37

Shower Gels: Comparative Effect of Increasing Polymer Concentration on Shower Gel Viscosity and Inventive Polymers vs. Commercial Cationic  Guar of  If foam stability

In Table 12 the conditioning shower gel was prepared by first dispersing the Venecel ^(R) MP943 product in water. Next N-Hands ^(R) 3196 product or cationic polymer of the present invention was added. The remaining ingredients of the next shower gel were added in the order listed with good mixing between each order of addition. Once all the ingredients were well mixed, the citric acid was used to lower the shower gel pH to 5.0-6.0. All viscosities were measured at 12 rpm, 25 ° C. using a Brookfield LVT viscometer.

Again, commercially available N-Hands ^(R) 3196 polymer in the shower gel could not be added at 1.5% without a very significant increase in viscosity as in Table 12, Example 34. The viscosity of the conditioning shower gel using the commercial N-Hands 3196 polymer was 42,700 at 12 rpm compared to the polymer-free shower gel with a viscosity of only 460 cps of Example 33. Using the polymer of the invention at a concentration of 1.5%, the viscosity was only 3,380 cps in Example 35. Examples 36, 37, and 34 show the effect of commercially available N-Hands ^(R) 3196 polymer on shower gel viscosity when compared to Example 33, which did not use a conditioning product polymer. Viscosity measurements were performed at 12 rpm, 25 ° C. using a Brookfield LVT viscometer.

Foam disappearance was measured using the method described below. Foam extinction time is an indirect measure of foam stability. Longer extinction times result in more stable and richer bubbles. Consumers recognize the more stable bubble positively. The foam disappearance time was more than doubled for the shower gel without the polymer of the present invention, the shower gel with the polymer of the present invention (Example 35) than that of Example 33. In Example 37 with 0.5% of commercially available N-Hands ^(R) 3196 cationic guar, almost the same viscosity was reached as with the polymer of the invention (Example 35), but the polymer of the invention foamed at least 20% higher Had stability.

Specification of foam test device / method

Foam Test: This method was used to measure the foam disappearance time of the diluted shower gel to determine the effect of the conditioning polymer on foam quality. Long extinction time results in rich and dense foam with good stability.

Device:

Wearing ( ^R) Blender Model # 7012 or 34BL97 or equivalent.

Funnels, preferably plastics; 6 "diameter, 7/8" ID neck, 5 1/4 "high, 2" horizontal wire from top. U.S.A. Standard test sieve NO. 20, 7 inch diameter. stopwatch.

Experimental Process:

1000 g of diluted shower gel solution was prepared in a beaker.

66.45 g of shower gel

Deionized Water 933.55 g

Total 1000.00 g

Next, 200 g of the diluted solution was weighed into an 8 ounce bottle. Three bottles containing 200 g of diluted shower gel were prepared. The bottle was placed in a water bath adjusted to 40 ° C. for 2 hours. The bottle was completely submerged. The foam disappearance test proceeded as follows. A total of three measurements were performed for each composition.

200 g of diluted shower gel was poured into a clean, dry wear ring blender glass container. With the lid closed, the shower gel was whipped at exactly the highest speed for exactly 1 minute to form bubbles. Immediately the foam was poured into a clean, dry funnel standing on a 20 mesh sieve on a beaker. The foam was poured from the blender for exactly 15 seconds. Attempts were made to obtain as much foam as possible without overflowing into the funnel. At 15 seconds, pouring of foam was stopped. The total time (including 15 seconds of pouring time) required for the foam to die out was recorded so that the wire was no longer covered by the foam or liquid. The test was performed in three replicates. The results are reported in seconds in Table 12.

references:

(1) Evaluation of the foaming Capacity in shampoos: Efficacy of various Experimental Methods by F.J. Domingo Campos, R. M. Druguet 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

Conditioning shower gel

(1) Venecel ^(R) MP943 Hydroxypropylmethylcellulose Aquaron (Wilm, DE) (2) N-Hands ^(R) 3196 Guar hydroxypropyl trimonium chloride Aquaron (Wilm, DE) (3) Cationic Guar of the Invention (5.6% Activity) Guar hydroxypropyl trimonium chloride Aquaron (Wilm, DE) (4) Stefan ^(R) Mild SL3 BA Disodium laureth sulfosuccinate Stefan (Northfield, IL) (5) Miranol ^(R) C2M Conc. NP Disodium coco ampo diacetate Stefan (Northfield, IL) (6) steol ^(R) CS 330 Sodium laureth sulfate Stefan (Northfield, IL) (7) phenonib ^(R) antiseptic Clariant (Clariant, Mt. Holly, NC) (8) Chrodanik ^(R) LS-3 Sodium Lauryl Sarcosinate Croda, Inc Parsippany, NJ (9) Propylene Glycol, USP EM Industries (Gibbstown, NJ) (10) Eufuran ^(R) PK3000 Cognis (amber, pa) (11) disodium EDTA VWR

In Example 35 of Table 12, the polymers of the present invention were prepared by methods similar to those described for Example 6, Experiment Z of Tables 5A and 5B, wherein N-hands 3205 cationic guar was precursor 2 cation It was used instead of St. Guar. The molecular weight of the final product was 550,000 Daltons, reduced from the molecular weight of 1,050,000 Daltons measured for the starting N-Hands 3205 cationic guar.

Example  38-42

Again, the commercially available cationic hydroxypropyl guar in the shower gel, Jaguar ^(R) C162 polymer, could not be added at 2.0% without significantly increasing the viscosity, as in Example 39 of Table 13. The viscosity of the conditioning shower gel with commercial Jaguar ^(R) C162 was 41,400 cps at 12 rpm compared to a shower gel that did not include the polymer having a viscosity of only 555 cps. When using the polymer of the present invention, the viscosity was only 3,320 cps in Example 40 with 2.0% active polymer. Viscosity measurements were performed at 12 rpm, 25 ° C. using a Brookfield LVT viscometer. Commercial Jaguar ^(R) C162 products were tested at 0.2% and 0.5% activity levels in Examples 41 and 42 as well. At the 0.5% level (Example 42), this reached the same viscosity as the composition with the 2.0% polymer of the invention in Example 40. Foam stability was measured using the method described above. For the Example 40 shower gel with the polymer of the present invention, the foaming time was more than twice the foaming time of the shower gel (Example 38) that did not include the polymer of the present invention. The longer the disappearance time, the more stable the foam.

The polymers of the invention described in Table 13, Example 40, replaced precursor 2 cationic guar with reguar ^(R) C162 cationic hydroxypropyl guar, for Example 6, Table 5a and Table 5b. It was prepared by a procedure similar to the one used. The product had a molecular weight of 555,532 Daltons and decreased from the starting molecular weight of 1,080,000 Daltons for the starting jaguar C162 cationic hydroxypropyl guar.

Inventive Polymers vs. Commercially Available Cationic  Hydroxypropyl guar of  Comparison of Effects on Shower Gel Viscosity and Foam Stability

ingredient Example 38 Example 39 Example 40 Example 41 Example 42 Deionized water 46.19 44.69 26.19 45.99 45.69 Venecel ^(R) 943 1.0 1.0 1.0 1.0 1.0 Jaguar ^(R) C162 0.0 2.00 0.0 0.2 0.5 Cationic Guar of the Invention from C162 0.0 0.0 20.00
(10.0% active) 0.00 0.00 Steol ^(R) CS330 23.06 23.06 23.06 23.06 23.06 Stefan ^(R) Mild SL3 BA 11.8 11.8 11.8 11.8 11.8 Miranol ^(R) C2M 6.0 6.0 6.0 6.0 6.0 Chrodanik ^(R) LS-30 7.25 7.25 7.25 7.25 7.25 Propylene glycol 2.0 2.0 2.0 2.0 2.0 Eufuran ^(R) PK3000 2.0 2.0 2.0 2.0 2.0 Disodium EDTA 0.1 0.1 0.1 0.1 0.1 Phenonib ^(R) 0.6 0.6 0.6 0.6 0.6 Citric Acid (5%) pH adjustment pH adjustment pH adjustment pH adjustment pH adjustment water Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 system 100 100 100 100 100 Shower gel Viscosity (cps) 555 41400 3320 1390 3180 pH 5.6 5.6 5.8 5.2 5.4 Bubble Vanish Time (sec) 53.7 seconds 94.7 seconds 92 sec polymer Mw 1080880 555532 1080880 1080880 Cationic DS 0.1 0.1 0.1 0.1

(1) Venecel ^(R) MP943 Hydroxypropylmethylcellulose Aquaron (Wilm., DE) (2) Jaguar ^(R) C162 Hydroxypropyl guar hydroxypropyl trimonium chloride Rhodia (3) cationic guar of the present invention (10% activity) Hydroxypropyl guar hydroxypropyl trimonium chloride Aquaron (Wilm., DE) (4) Stefan ^(R) Mild SL3 BA Disodium laureth sulfosuccinate Stefan (Northfield, Il) (5) Miranol ^(R) C2M Conc. NP Disodium coco ampodiacetate Stefan (Northfield, Il) (6) steol ^(R) CS 330 Sodium laureth sulfate Stefan (Northfield, Il) (7) phenonib ^(R) antiseptic Clariant (Mt.Holly, NC) (8) Chrodanik ^(R) LS-3 Sodium Lauryl Sarcosinate Croda, Inc, Parsippany, NJ (9) Propylene Glycol, USP M Industries, Gibbstown, NJ (10) Eufuran ^(R) PK3000 Cognis (Amber, PA) (11) disodium EDTA VWR

Example  43-47

High molecular weight Cationic  Effect of Polymer Concentration on Liquid Soap Viscosity and Foam Stability for Guar vs. Inventive Polymers Comparative example

Table 14 shows the effect of commercial N-Hands ^(R) 3198 cationic guar concentration on the viscosity of the liquid soap and its foam stability. Viscosity increased from 123 cps for 23% of commercially available N-Hands 3198 product (Example 46) for liquid soaps containing no polymer (Example 4). The liquid soap may be difficult to dispense at such high viscosity. The viscosity was only 315 cps with the inventive polymer (Example 47) in a 1.5% active composition. In order to maintain such a low viscosity, commercially available polymers could only be used at the 0.2% activity level (Example 44). However, liquid soaps at this level had poor foam stability. Foam stability was only about 30 seconds compared to about 71 seconds with the inventive polymer (Example 47).

Preparation of Liquid Soap

Natrosol hydroxyethyl cellulose was dispersed in water with mixing. Then cationic guar (commercial N-Hands ^(R) 3198 or polymer of the invention) was added while mixing. Ammonix ^(R) 4002, Bioterge ^(R ) AS 40 and Emerest ^(R ) components were added in the order listed while mixing. The batch was mixed in an 80 ° C. water bath until the Emerest ^(R) 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.

ingredient Example 43 Example 44 Example 45 Example 46 Example 47 Deionized water 75.73 75.53 75.23 74.23 49.69 Natrosol ^(R) 250MR 0.80 0.80 0.80 0.80 0.80 N-Hands ^(R) 3198 0.0 0.20 0.50 1.50 0.0 Cationic Guar of the Invention 0.0 0.0 0.0 0.0 26.04
(5.76% active) Methyl paraben 0.25 0.25 0.25 0.25 0.25 Ammonix ^(R ) 4002 0.10 0.10 0.10 0.10 0.10 Bioterge ^(R ) AS-40 7.5 7.5 7.5 7.5 7.5 Emerest ^(R ) 2400 1.00 1.00 1.00 1.00 1.00 Chrodanik ^(R) LS-30 6.66 6.66 6.66 6.66 6.66 Amposol ^(R) CA 6.66 6.66 6.66 6.66 6.66 Propylene glycol 0.50 0.50 0.50 0.50 0.50 glycerin 0.50 0.50 0.50 0.50 0.50 Disodium EDTA 0.30 0.30 0.30 0.30 0.30 water Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 Quantity to be 100 system 100 100 100 100 100 Liquid soap Viscosity (cps) 123 443 2130 23450 315 pH 8.66 8.57 8.28 8.72 8.3 Bubble Vanish Time (sec) 20.3 seconds 30.3 seconds 71.3 seconds polymer 0.13 0.13 0.13 0.13 Mw 995,781 995,781 995,781 378,076 Cationic DS 0.13 0.13 0.13 0.13

(1) Venecel ^(R) MP943 Hydroxypropylmethylcellulose Aquaron (Wilmington, DE) (2) N-Hands ^(R) 3198 Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (3) Cationic Guar of the Invention (5.76% Activity) Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (4) methylparaben antiseptic Clariant (Mt.Holly, NC) (5) Ammonics ^(R) 4002 Stearalkonium chloride Stefan (Northfield, IL) (6) Biotudge ^(R) As-40 Na C14-C16 Olefin Sulfonate (40%) Stefan (Northfield, IL) (7) Emerset ^(R ) 2400 Glycol stearate Cognis (Amber, PA) (8) Chrodanik ^(R) LS-30 Sodium Lauryl Sarcosinate Crospanny, NJ (9) Propylene Glycol, USP EM Industries (Gibbstown, NJ) (10) Amposol ^(R) CA Cocamidopropyl Betaine (35% Active) Stefan (Northfield, IL) (11) disodium EDTA VWR 12 synthetic glycerin Spectrum Bulk Chemicals, New Brunswick, NJ

The polymer of the invention used in Example 47 of Table 14 was prepared by a similar procedure to that used for Example 6, Experiment Z of Tables 5A and 5B, replacing Precursor 2 with N-Hands 3198 cationic guar. Was prepared.

Example 48-50

Inventive Polymers vs. Commercial High molecular weight Cationic  Guar To  Containing skin  Indicating the stability of the lotion Comparative example

Skin lotion manufacturing method:

Part A: Water was weighed in an 8-ounce bottle and placed in an 80 ° C water bath. Natrosol ^(R) was sprinkled while mixing. Next, N-hands ^(R) 3215 or polymer of the invention was added followed by glycerin.

Part B: put it weighed Emma rest ^(R) 2400 in a separate vessel and placed in a water bath 80 ℃. The remaining ingredients of part B were added in the order listed while mixing. Part A.

Part A was slowly added to Part B while mixing. The temperature was kept at 80 ° C.

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

In Table 15, Example 50, the polymers of the invention were prepared as described in Example 6, Experiment Y of Tables 5A and 5B.

ingredient Example 48 Example 49 Example 50 Part A Deionized water 78.25 77.25 69.20 Natrosol ^(R) 250MR 0.50 0.50 0.50 N-Hands ^(R) 3215 0.0 1.0 0.0 Cationic Guar of the Invention 0.0 0.0 9.05 (11.05% active) glycerin 2.0 2.0 2.0 Part B Emerest ^(R ) 2400 2.75 2.75 2.75 Industrene ^(R ) 5016K 2.50 2.50 2.50 Drakeol ( ^R ) 7 2.00 2.00 2.00 Lipolan ^(R ) 98 0.50 0.50 0.50 Crodacol ^(R ) C-95 0.25 0.25 0.25 Part C Deionized water 10.00 10.00 10.00 Triethanolamine 0.50 0.50 0.50 Part D Germanmaben ^(R) II 0.75 0.75 0.75 water Quantity to be 100 Quantity to be 100 Quantity to be 100 system 100 100 100 Skin lotion Viscosity (cps) 1550 Phase separation 2800 pH 7.5 7.2 polymer Mw 1,087,074 42,030 Cationic DS

(1 ⁾ Natrosol ^(R) 250MR Hydroxyethyl cellulose Aquaron (Wilmington, DE) (2) N-Hands ^(R) 3215 Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (3) Cationic Guar of the Invention (11.05% Activity) Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (4) Industren ^(R) 5016K Stearic acid Whitco Co. Memphis TN (5) Drakeol ^(R) 7 Mineral oil Penreco, Karn City, PA (6) Emerest ^(R) 2400 Glycol stearate Cognis (Amber, PA) (7) Lipola ^(R) 98 LANNET-10 Acetate Lipo Chemicals, Inc., Patterson, NJ (8) Crodacol ^(R) C-95 Cetyl alcohol Croda Company (Parsipanny, NJ) (9) triethanolamine J.T. Baker, Phillipsburg, NJ (10) synthetic glycerin Spectrum Bulk Chemicals, New Brunswick, NJ (11) Germanmaben ^(R) II antiseptic ISP (Wayne, NJ)

In formulating lotions and creams, the stability of the final composition is the decisive purpose of the manufacturer. As shown in Example 49, the skin lotion emulsion with commercial N-Hands 3215 exhibited phase separation due to instability. The lotion emulsion without the polymer of the present invention in Example 48 had a viscosity of only about 1,500 cps and was flowing. The lotion emulsions with the polymers of the present invention not only were stable but also had a viscosity of about 2,800 cps and had better concentration when dispensed.

Example  51-53

Inventive polymer vs. High molecular weight Cationic  Guar To  Having improved formulation aesthetics Comparative example

Sunscreen  Product recipe:

Part A: Drakeol was weighed into an 8-ounce bottle. The bottle was then placed in a 70 ° C. water bath. The remaining ingredients of part A were added in the order listed while mixing. Mixing was continued at 70 ° C. for 30 minutes.

Part B: Water was weighed into a separate bottle and placed in a 70 ° C. water bath. Natrosol ^(R) polymer was added to the water while mixing. The remaining components of the next part B were added at 70 ° C. while mixing.

Part C: Premixed Part C. Part C was added to Part B once all components of Part B were dissolved. Once the mixture reached 70 ° C. Part B / C was added to Part A while mixing. Mixing was continued at 70 ° C. for 30 minutes.

Part D: The Part A / B / C mixture was removed from the water bath and allowed to cool to 50 ° C. while mixing. When the temperature reached 50 ° C. Germanaben II product was added. Mixing was continued until the sunscreen emulsion reached room temperature.

In Example 53 of Table 16, the polymer of the present invention was prepared by the method described in Example 6, Experiment U of Tables 5A and 5B, replacing N-Hands 3215 with N-Hands 3198.

ingredient Example 51 Example 52 Example 53 Part A Drakeol ^(R) 7 13.00 13.00 13.00 Arlamol ^(R ) E 6.00 6.00 6.00 Neo Heliopan ^(R ) AV 3.00 3.00 3.00 Ubinol ^(R) M40 0.0 0.0 9.05 Castor ^(R ) Wax 1.40 1.40 1.40 Crill-6 1.20 1.20 1.20 Arlatone ^(R ) T 1.00 1.00 1.00 Ozokerite ^(R ) 1.00 1.00 1.00 Dehymuls ^(R ) HRE7 0.50 0.50 0.50 Part B Deionized water 40.50 39.50 30.72 Natrosol ^(R ) 250HHR CS 0.50 0.50 0.50 N-Hands ^(R) 3198 0.00 1.00 0.00 Product of the invention 0.00 0.00 9.78 glycerin 3.00 3.00 3.00 Part C Deionized water 23.10 23.10 23.10 Magnesium sulfate 0.70 0.70 0.70 Part D Germanmaven II 0.1 0.1 0.1 Sunscreen Viscosity (cps) 4310 13250 5570 pH 6.3 5.9 6.0 polymer Mw 1,079,887 60,711 Cationic DS

(1) Natrosol ^(R) 250 HHR CS Hydroxyethyl cellulose Aquaron (Wilmington, DE) (2) N-Hands ^(R) 3198 Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (3) Cationic guar of the present invention (10.23% activity) Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (4) alamol ^(R) E PPG-15 Stearyl Ether Uniqema Americas, New Castle, DE (5) Drakeol ^(R) 7 Mineral oil Fenereco (Penereco, Karrn City, PA) (6) Neo Heliopan ^(R) HV Octyl methoxycinnamate Simrise, Totowa, NJ (7) Ubinol ^(R) M40 Benzophenone-3 BASF (Mount Olive, NJ) (8) castor wax Hydrogenated castor oil Frank B Ross (9) Alathon ^(R) T PPG-40 Sorbitan Peroleate Unichema Americas (New Castle, DE) (10) Ozokerite ^(R) Wax Wax Frank By Ross (11) Dehymals (R) HRE7 PEG-7 hydrogenated castor oil Cognis (Amber, PA) (12) Germanmaben ^(R) II antiseptic ISP (Wayne, NJ) (13) synthetic glycerin Spectrum Bulk Chemicals (New Brunswick, NJ) (14) magnesium sulfate Jetty Baker (Philipsburg, NJ)

When preparing sun care lotion, a creamy, glossy emulsion is preferred. It is also desirable to generate sufficient viscosity so that the lotion does not drip or flow, but not too viscous and difficult to spread. Sunscreen products made from commercially available cationic guar N-hands ^(R) 3198 (Example 52) were slightly granular and very viscous, as well as having an off-white color. The sunscreen product made from the product of the present invention (Example 52) not only had a comparable viscosity as compared to the sunscreen product without the conditioning polymer (Example 51), but was also glossy, white and stable as in Example 51. .

Example  54-62:

Inventive polymer vs. High molecular weight Cationic  Guar To  Laundry detergents and fabrics containing On softener  For improved stability and appearance Comparative example

In formulating liquid laundry detergents and fabric softeners, the stability of the composition and its appearance are important for delivering product performance. High viscosity compositions may not readily mix in the washing machine resulting in poor cleaning or fabric conditioning. The poor stability of the composition and the overall phase separation of the components also negatively affects performance.

The polymers of the invention described in Table 17 were prepared according to the method described in Example 6, Experiment Y of Table 6.

As shown in Table 17, Whisk, a product of Tide ^(R ) liquid laundry detergent and Unilever, Greenwich Connecticut, commercially available from Procter & Gamble Co., Cincinnati, Ohio. The liquid laundry detergent was post-added to the 0.2% activity level of the polymer of the present invention. 0.2% of commercially available N-Hands ^(R) 3215 cationic guar was post-added to the laundry detergent.

Example 54 55 56 Laundry Detergent Tide ^(R) , as received Tide ^(R) with 0.2% of the product of the invention Tide ^(R) with 0.2% N-Hands ^(R) 3215 Viscosity at 12 rpm 202 cps 214 cps 341 cps pH 8.0 7.9 7.8 evaluation Transparent blue Slightly turbid blue Cloudy and sedimentary % T at 600 nm Example 57 58 59 Laundry Detergent Whiskey ^(R) , as received Whiskey ^(R) with 0.2% of the product of the invention Above the disk ^(R) having a 0.2% N- haenseu ^(R) 3215 Viscosity at 12 rpm 100 cps 95 cps 260 cps pH 7.5 7.4 7.4 evaluation Turbid blue Turbid blue Opaque and settled % T at 600 nm Example 60 61 62 Fabric softener Downey ( ^R ) As Obtained Downey ^(R) with 0.2% product of the invention Downey ^(R) with 0.2% N-Hands ^(R) 3215 Viscosity at 12 rpm 120 cps 150 cps Gel-phase pH 3.2 3.5 3.6 evaluation opacity opacity opacity % T at 600 nm

The product of the present invention did not affect the viscosity of the original liquid laundry detergent and was also compatible (Examples 55 and 58). The N-Hands ^(R) 3215 product was found to be incompatible (Examples 56 and 59).

In the fabric softener the polymer of the present invention had no substantial effect on viscosity and was stable up to pH 3 to 3.5 (Example 61). In contrast, a commercially available N-Hands ^(R) 3215 polymer resulted in the gelation of the commercial fabric softener (Example 62) and made it unusable.

Example  63-69

High molecular weight Cationic  Guar on  Conditioning Polymers of the Invention Body wash  Showing an improved effect on viscosity Comparative example For polymers produced by the peroxide decomposition method and the combined biochemical-peroxide method

Body washes made with the inventive polymers in Examples 65 and 66 of Table 18 have a lower viscosity compared to the commercially available N-Hands ^(R) 3000 product of Example 64. In Example 65, the polymer was prepared by peroxide decomposition according to the procedure described for Example 6, Experimental AC of Tables 5A and 5B. In Example 66, the polymer was prepared by sequential peroxide treatment and enzymatic digestion as described in Example 8C.

The body wash of Table 19 prepared with the polymers of the present invention (Examples 68-69) had a much lower viscosity than the body wash prepared with Precursor 3 (Example 67). In fact, the wash made with precursor 3 was almost like a gel. The polymer of the present invention used in Example 68 was prepared by peroxide decomposition as described in Example 6, Experiments AA and AB of Tables 5A and 5B. The inventive polymer used in Example 69 was prepared by sequential enzymatic treatment followed by peroxide decomposition as described in Example 8B.

ingredient Example 63 Example 64 Example 65 Example 66 Deionized water 118.75 114.68 43.75 43.75 Rodapex ES-STD 87.5 87.5 87.5 87.5 N-Hands ^(R) 3000 0.0 4.072 0.0 0.0 Cationic Guar of the Invention (5% Activity) 0.0 0.0 75.0 75.0 Amposol ^(R) CA 30.0 30.0 30.0 30.0 Ninol ( ^R ) COMF 5.0 5.0 5.0 5.0 20% sodium chloride 6.0 6.0 6.0 6.0 Glidant ^(R) 1.25 1.25 1.25 1.25 Citric Acid (5%) pH adjustment pH adjustment pH adjustment pH adjustment water Quantity to be 250 Quantity to be 250 Quantity to be 250 Quantity to be 250 system 250 250 250 250 Shower gel Viscosity (cps) 9550 75000 27100 22230 pH 5.3 5.15 5.25 5.31 polymer Mw 923655 330717 131308 Cationic DS 0.06 0.06 0.06

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

(2) N-Hands ^(R) 3000 Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (3) Cationic Guar of the Invention (5.0% Activity) Guar hydroxypropyl trimonium chloride of Example 65 Aquaron (Wilmington, DE) (3) Cationic Guar of the Invention (5.0% Activity) Guar hydroxypropyl trimonium chloride of Example 66 Aquaron (Wilmington, DE) (4) Rodapex ^(R) ES-STD Sodium Lauret (3) Sulfate Rhodia (Cranberry, NJ) (5) Amfosol ^(R) CA Cocamidopropyl Betaine Stefan (Northfield, Il) (6) niol COMF Cocamide MEA Stefan (Northfield, Il) (7) Glidant ^(R) DMDM Hydantoin Lonza Corp (Fair Lawn, NJ) (8) citric acid Jetty Baker (Philipsburg, NJ)

ingredient Example 67 Example 68 Example 69 Deionized water 114.52 43.75 43.75 Rodapex ES-STD 87.5 87.5 87.5 N-Hands ^(R) 3000 4.235 0.0 0.0 Cationic Guar of the Invention (5% Activity) 0.0 75.0 75.0 Amposol ^(R) CA 30.0 30.0 30.0 Ninol ^(R) COMF 5.0 5.0 5.0 20% sodium chloride 6.0 6.0 6.0 Glidant ^(R) 1.25 1.25 1.25 Citric Acid (5%) pH adjustment pH adjustment pH adjustment water Quantity to be 250 Quantity to be 250 Quantity to be 250 system 250 250 250 Shower gel Viscosity (cps) Gel-phase 65200 35750 pH 5.4 5.3 5.4 polymer Mw 999145 719515 963759 Cationic DS 0.9 0.9 0.9

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

(2) precursor 3 Guar hydroxypropyl trimonium chloride Aquaron (Wilmington, DE) (3) Cationic Guar of the Invention (5.0% Activity) Guar hydroxypropyl trimonium chloride of Example 68 Aquaron (Wilmington, DE) (3) Cationic Guar of the Invention (5.0% Activity) Guar hydroxypropyl trimonium chloride of Example 69 Aquaron (Wilmington, DE) (4) Rodapex ^(R) ES-STD Sodium Lauret (3) Sulfate Rhodia (Cranberry, NJ) (5) Amfosol ^(R) CA Cocamidopropyl Betaine Stefan (Northfield, Il) (6) niol COMF Cocamide MEA Stefan (Northfield, Il) (7) Glidant ^(R) DMDM Hydration Fair Lawn, NJ (8) citric acid Jetty Baker (Philipsburg, NJ)

Table 20 Oxidative Group Content of Polymers of the Invention

The results in Table 20 show the differences in the compositions between the inventive materials prepared by the procedures of Examples 6, 7 or 8a, b, c and Example 8d and commercially available high molecular weight cationic polymers. Solutions of polymers were analyzed using specific methods for the detection of aldehyde groups (Analytical Biochemistry, 1983 , 134 , 499-504). The results from this test are shown as absorbance at 595 nm per gram of polymer by calorimeter test results in Table 20, or millimeter equivalents of aldehyde per gram of polymer.

As can be seen from the results in Table 20, the materials of the invention prepared by the procedure in Examples 6, 7 or 8a-c were prepared using the Purpald method [HB Hopps, Aldrichimica ACTA, 2000 , 33 (1), 28-30] produced a material with significant absorbance. The method is specific for aldehyde detection. A negligible absorbance was detected in the material according to the method prepared according to the procedure of Example 8d, or in the starting cationic guar or other commercially available cationic guar material.

The results show that a material prepared via a treatment comprising an oxidant, either as a single reaction treatment or in combination with a hydrolase treatment, will produce a low molecular weight material having a measurable amount of aldehyde groups on the polymer. Indirect iodine titration was used to quantify the aldehyde level of some samples, and a calibration equation was made to convert absorbance / gram to millequivalent aldehyde / gram. As measured by the method, the aldehyde group level in the material of the present invention is at least 0.001 meq / g. The correction equation is represented by the following equation (1). The meq / g aldehyde values shown in Table 20 were determined from equation (2) except for Examples 8-4, which were measured directly. For Example 9 of Tables 20 and 21, the aldehyde content was determined by sugar analysis of acid hydrolyzed guar products using HPLC to determine the galactose / mannose for the starting cationic guar precursor and the oxidized cationic guar product. The ratio was obtained. The aldehyde content of the oxidized cationic guar was 23%, corresponding to 0.41 mmol aldehyde / gram polymer.

Absorbance / gram = 445.52 (meq aldehyde / g) + 0.9953

Cationic  Oxidized Polygalactomannan  Aldehyde and Weight Average Molecular Weight Example Experimental Example Average Mw Absorbance / g polymer ¹ Aldehyde meq / g Example 6 Chemical Decomposition Using an Oxidizer 6-1 U 417,000 4.78 0.0085 6-2 U 119,000 5.65 0.01035 6-3 W 919,000 1.84 0.0019 6-4 W 434,000 4.12 0.007 6-5 W 292,000 3.85 0.00625 6-6 ² W 4.20 0.0072 Example 8a-c. Biochemical degradation method combined with oxidant 8a-1 63,000 5.88 0.0109 8a-2 52,800 8.6 0.0600 8a-3 36,100 13.64 0.02835 8a-4 38,800 13.01 0.0269 Example 8d. Biochemical method without oxidant 8d-1 55,000 0.16 0 8d-2 44,700 0.28 0 Example 9 Biochemical Methods Using Biochemical Oxidants 9 40,000 0.41 Commercial Cationic Polymers N-Hands 3215 1,200,000 1.4 ³ 0 N-Hands 3196 1,400,000 0.55 0 Jaguar C162 1,070,000 0 0 Jaguar Excel 1,200,000 0 0 E-Care Polymer JR400 500,000 0.78 0 Reagent Blank Test 0.09 0 Alrichimica ACTA, 2000, V33, No.1, p 28-30
2. Ammonium persulfate is used instead of hydrogen peroxide in the process.
3. Turbidity and haze in the sample give a value of 1.4-no purple light detected

Test strips coated with a perfold reagent (E-M Science) were also used to determine the aldehyde content in the samples prepared by the methods of Examples 6 and 8a-c. The results are shown in Table 21a and Table 21b together with the viscosity data and MW data for the products of the present invention. Combined, the results in Tables 20 and 21 show that the products of the present invention have an aldehyde content of at least 0.001 meq / g, and the Brookfield viscosity lower limit for the products of the present invention is 30 rpm, 25 ° C., 40 cps at spindle 4, and Brook The upper field viscosity upper limit is 2,000,000 cps at 0.3 rpm, 25 ° C., spindle 4.

Example  70

polymer Blend  Chemical oxidation method

Preparation of low molecular weight liquid cationic polysaccharides from high molecular weight cationic polysaccharide blends:

50 g of 0.06 cationic DS was combined with 50 g of cationic HEC (Dow Chemical, Polymer LR30M from Midland Michigan) and 1.25 g of fumaric acid. 816 g of water were heated to about 90 ° C. Next 75 g of 1.0% hydrogen peroxide were added. After mixing for about 30 minutes, 18.1 g of 1.0% hydrogen peroxide was added. 18.1 g of 1.0% hydrogen peroxide were added twice with mixing at intervals of about 30 minutes. Mix for about 90 minutes after addition of the last peroxide. Then 0.95 g of meta metabisulfite was added. The solution was stored with 0.5% phenoxetol and 0.18% nifacept sodium. Details regarding the inventive polymers of this experiment are provided in Tables 21a and 21b.

The above examples show that the polymers of the present invention can be prepared using blends of functional polymers.

Example  71

The following examples show that the low molecular weight cationic oxidized polysaccharides of the present invention can be incorporated into personal care products containing silicone materials, and the viscosity of the product obtained contains commercially available high molecular weight cationic polysaccharides. It shows a significant reduction compared to the viscosity of the silicone composition. The silicone material may be in the form of a polymer or oligomer of cyclosiloxane, straight chain siloxane, hydroxy terminal siloxane, honeycomb or graft siloxane structure with polyol, amino or other functional groups present in the siloxane structure.

Anionic shampoo compositions were used for these experiments consisting of the components of Table 22. The composition was prepared by mixing surfactant and water at 60 ° C. for 1 hour, cooling the mixture to 35 ° C. and then adding a silicone emulsion. The shampoo contained GE Silicones Emulsion SM555 with a silicone content of 0.5% by weight. The low molecular weight cationic guar from Example 6, Experiment Y of Tables 5a and 5b was introduced into the shampoo of Example 71-1, containing the high molecular weight commercially available cationic guar of Examples 71-2 through 71-5. Compared to shampoos and commercial shampoos of Examples 71-6. The viscosity of the shampoo was measured at 0.3 and 30 rpm using a Brookfield LVT viscometer, spindle 4 at room temperature.

Example 71 shampoo pH Viscosity / cps Viscosity / cps 25 ℃,
30 days Composition components Brand name Manufacturer 0.3 rpm 30 rpm Ammonium Lauryl Sulfate Stefanol AM Stefan (Northfield, Illinois) Ammonium Lauryl Ether Sulfate Steol CA-330 Stefan (Northfield, Illinois) Cocamidopropyl Betaine Amposol CA Stefan (Northfield, Illinois) Deionized water Dimethiconol Emulsion SM555 GE Silicones (Waterford, NY) Guar hydroxypropyltrimonium chloride 6 42,000 14,100 stability Hydroxypropyl Guar Hydroxypropyltrimonium Chloride 6.2 102,000 36,600 stability Guar hydroxypropyltrimonium chloride 6.1 136,000 44,050 stability Guar hydroxypropyltrimonium chloride 6 132,000 36,300 stability Guar hydroxypropyltrimonium chloride 6.1 198,000 43,200 stability Commercially available silicone shampoo with guahydroxypropyltrimonium chloride Helen Curtis 10,200 stability

The results in Table 22 show that the preferred shampoo viscosity is obtained using the polymer of the present invention, which does not exhibit phase separation. Shampoos prepared with high molecular weight commercial cationic polymers are undesirablely viscous and difficult to follow. Combinations of cationic oxidized polysaccharides and other water soluble polymers of the invention can also be incorporated into personal care compositions containing silicone polymers and oligomers to create stable systems.

Cationic oxidized polysaccharides of the invention, and other functional polymers such as chitosan, polyvinylpyrrolidone homopolymers and copolymers, acrylamide homopolymers and copolymers, high molecular weight cationic hydroxyethylcellulose, high molecular weight cations Sex guar, and hydrophobic polymers (also known as linking polymers) and combinations of two and three thereof may be applied to hair, skin, and textile substrates of compositional aesthetics (e.g. foaming), stability, conditioning oils such as silicone or other conditioning agents. It can be designed to improve delivery and attachment efficacy. The combinations also include antibacterial compounds, anti-dandruff compounds, conditioning agents, fragrances, sunscreen actives, skin softeners, moisturizers, drugs such as psoriasis prevention drugs, styling aids such as polyvinylpyrrolidone copolymers, sizing agents and other ingredients. It may also improve the efficacy of delivery to the hair, skin and fabric substrates of the skin. Specific blends of the inventive polymers and water soluble functional polymers are shown in Example 72, and the viscosity of the blends is shown in Tables 21a and 21b. Various polymer blends with the inventive polymers can be prepared, and the examples are not intended to be all inclusive.

Example  72

This example shows that the polymers of the present invention can be blended with other functional polymers. The viscosity of each compound is shown in Table 21a and Table 21b.

2.1 g of chitosan was mixed with a 6% dispersion of fumaric acid to prepare a 5% dispersion of chitosan (Vanson Incorporated, Redmond, Washington; 88% deacetylated, 1% viscosity: 660 cps). Two formulations were prepared using the dispersion.

72-1 25.3 g chitosan dispersion was mixed with 90.5 g Example 6, Experimental AC to prepare a dispersion. When the 24 hour viscosity of the dispersion was measured on a Brookfield viscometer at 0.3 and 30 rpm at ambient temperature, it was found to be 14,000 and 2,200 cps, respectively.

11.4 g of 72-2 chitosan dispersion was mixed with 94.1 g of Example 8B (MW 964,000) to obtain a dispersion. When the 24 hour viscosity of the dispersion was measured on a Brookfield viscometer at 0.3 and 30 rpm at ambient temperature, it was found to be 8,000 and 3,920 cps, respectively.

While the invention has been described in connection with specific embodiments, it should be understood that the invention is not limited thereto and that many variations and modifications are possible without departing from the spirit and scope of the invention.

Claims (76)

Having a weight average molecular weight having a lower limit of 100,000 and an upper limit of 1,000,000, Brookfield viscosity at 10 wt% solids with spindle 4 at 25 ° C., 0.3 rpm with a lower limit of 20,000 mPas [cps] and an upper limit of 2,000,000 mPas [cps], -Having an aldehyde functional content of at least 0.001 meq per gram, Obtained by oxidation with an oxidizing agent selected from the group consisting of peroxides, persulfates, permanganates, perchloric acid and hypochlorite, One or more cationic oxidized polysaccharides or derivatives thereof, The polysaccharide or derivatives thereof are polysaccharides or derivatives thereof selected from the group consisting of cellulose and polygalactomannan Personal hygiene or household hygiene composition. delete The composition of claim 1 having a cation substitution degree (DS) of a lower limit of 0.001 and an upper limit of 3.0. The method of claim 1, wherein the derivative moiety on the cationic derivatized polysaccharide is selected from the group consisting of alkyl, hydroxyalkyl, alkylhydroxyalkyl and carboxymethyl, wherein alkyl is a carbon containing 1 to 22 carbons. Having a chain and hydroxy alkyl is selected from the group consisting of hydroxyethyl, hydroxypropyl and hydroxybutyl. delete The composition of claim 1, wherein said polysaccharide or derivative thereof is polygalactomannan or a derivative thereof which is guar or locust bean. The composition according to claim 1, wherein the polysaccharide or a derivative thereof is a cellulose type which is a cellulose ether derivative. The composition of claim 1 wherein the cationic moiety on the cationic oxidized polysaccharide or derivative thereof is selected from quaternary ammonium compounds. The method of claim 8, wherein the quaternary ammonium compound is 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 these Corresponding bromide and iodide; 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, 3-chloro-2-hydroxypropyltripropylammonium chloride, 3-chloro-2-hydroxypropyl Ethyldimethylammonium chloride, and their corresponding bromide and iodide; And halides of imidazoline ring containing compounds. 2. A colorant, antiseptic, antioxidant, alpha or beta hydroxy acid, activity enhancer, emulsifier, functional polymer, viscosity agent, alcohol, fatty or fatty compound, antibacterial compound, anti-dandruff agent, volume agent, antistatic agent And an element selected from the group consisting of moisturizers, styling aids, zinc pyrithione, silicone materials, hydrocarbon polymers, emollients, oils, surfactants, suspending agents, sun care agents and mixtures thereof. 11. The method of claim 10 wherein the urea is anionic, hydrophobically modified, amphoteric, acrylic acid copolymer, vinylpyrrolidone homopolymer and copolymer, cationic vinylpyrrolidone copolymer, nonionic, cationic, anionic Amphoteric and amphoteric cellulosic polymers, acrylamide homopolymers, cationic, anionic, amphoteric and hydrophobically modified acrylamide copolymers, polyethylene glycol polymers and copolymers, hydrophobically modified polyethers, hydrophobically modified polys Etheracetals, hydrophobically modified polyetherurethanes, binding polymers, hydrophobically modified cellulose polymers, polyethylene oxide-propylene oxide copolymers, chitosan, clays and nonionics, anionic, hydrophobically modified amphoteric, cationic Polysaccharides, Chitosan, Starch, Alginate, Konjack Gum, Clay, Poloxamer (Poly Oxyethylene / polyoxypropylene block polymer), and mixtures thereof. The method of claim 10 wherein the urea is hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, hydrophobically modified carboxymethyl cellulose, cationic hydroxyethyl cellulose, cationic hydrophobically modified Hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, cationic hydrophobically modified hydroxypropyl cellulose, cationic carboxymethylhydroxyethyl cellulose, and cationic hydroxypropyl cellulose The composition is a nonionic, cationic, anionic and amphoteric cellulose polymer selected from the group consisting of. The method of claim 10 wherein the urea is carboxymethyl guar, hydroxypropyl guar, hydrophobically modified guar, carboxymethyl guar hydroxypropyltrimethylammonium chloride, guar hydroxypropyltrimethylammonium chloride, and hydroxypropyl guar hydroxypropyl Nonionic, anionic selected from the group consisting of trimethylammonium chloride, hydroxybutyl guar, hydroxybutyl guar hydroxypropyltrimethylammonium chloride, hydroxyethyl guar, hydroxyethyl guar hydroxypropyltrimethylammonium chloride, and locust bean Hydrophobically modified, amphoteric and cationic polygalactomannans. The method of claim 10 wherein the urea is NaCl, NH ₄ Cl, KCl, and fatty alcohols, fatty acid esters, fatty acid amides, fatty alcohol polyethylene glycol ethers, sorbitol polyethylene glycol ethers, polyethylene oxide fatty acid esters, ethylene glycol monostearates or diss. Selected from the group consisting of tearate, cocamidopropyl betaine, clay, silica, cellulosic polymer, xanthan, alginate, guar and guar derivatives, carrageenan, cornzac, gelatin, dextrin, pectin, starch and mixtures thereof The composition being a viscous agent. The silicone material of claim 10 wherein the element is a silicone material selected from the group consisting of cyclosiloxanes, linear siloxanes, honeycomb or graft siloxane structures having polyols, amino, quaternary ammonium or other functional groups in the siloxane structure, and mixtures thereof, Other functional groups are selected from the group consisting of polyethyleneoxy or polypropyleneoxy groups optionally containing C ₆ -C ₂₄ alkyl groups, amine groups, thiol groups, alkoxylated groups, hydroxyl groups, and acyloxyalkyl groups, or both Composition. delete The composition of claim 15 wherein said silicone material is selected from the group consisting of polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, and mixtures thereof. 18. The composition of claim 17, wherein said urea is polyalkylsiloxane selected from the group consisting of polydimethylsiloxane, polydimethylsiloxane hydroxylated at the chain end, and mixtures thereof. The composition of claim 10 wherein said element is an anionic, cationic, amphoteric, or nonionic surfactant or mixture thereof. (a) reacting one or more cationic polysaccharides or cationic derivatized polysaccharides with one or more reagents that reduce the weight average molecular weight (Mw) of the polysaccharide or derivative thereof to an upper limit of 1,000,000 Daltons, and (b) the cation Recovering the acid oxidized polysaccharide to prepare the cationic oxidized polysaccharide composition of claim 1, The reagent is an oxidizing agent selected from the group consisting of peroxide, persulfate, permanganate, perchlorate and hypochlorite, The polysaccharide or derivatives thereof are polysaccharides or derivatives thereof selected from the group consisting of cellulose and polygalactomannan A process for producing the cationic oxidized polysaccharide or derivative thereof of claim 1. The method of claim 20, wherein the composition of claim 1 is prepared by treating the cationic polysaccharide or cationic derivatized polysaccharide with an agent in an aqueous medium to produce an aqueous dispersion of the treated polysaccharide. delete 21. The method of claim 20, wherein said oxidant is hydrogen peroxide. delete delete 21. The method of claim 20, wherein said reagent further comprises a hydrolytic agent. 27. The method of claim 26, wherein said hydrolase is selected from the group consisting of hydrolases. The method of claim 27, wherein said hydrolase is selected from the group consisting of hemicellulase. The method of claim 28, wherein the hemicellulase is mannase. 27. The method of claim 26, wherein said hydrolysing agent is an organic or inorganic acid. The method of claim 20, wherein the cationic polysaccharide or cationic derivatized polysaccharide is cellulose ether or polygalactomannan. 32. The method of claim 31, wherein said cationic polysaccharide or cationic derivatized polysaccharide is a polygalactomannan selected from the group consisting of guar and guar derivatives. 32. The method of claim 31, wherein the cationic polysaccharide or cationic derivatized polysaccharide is cationic hydroxyethyl cellulose (HEC), cationic and hydrophobically modified hydroxyethyl cellulose (HMHEC), cationic hydroxypropylmethylcellulose (HPMC), cationic hydroxypropyl cellulose (HPC), cationic ethyl hydroxyethyl cellulose (EHEC), cationic methyl hydroxyethyl cellulose (MHEC), and cationic methyl cellulose (MC), and mixtures thereof A cellulose ether selected from the group consisting of: 21. The method of claim 20 further comprising adding sodium metabisulfite, sodium bisulfite, sodium hypochlorite or sodium chlorite. 22. The method of claim 21, further comprising recovering the derivatized polysaccharide from the aqueous dispersion in dry form. 33. The method of claim 32, wherein the cationic polygalactomannan or cationic derivatized polygalactomannan is in the form of a powder, fine powder or split. A composition for conditioning a surface selected from the group consisting of skin, hair, protein, polyester, cellulose, paper and textile substrates, comprising the composition of claim 1. The method according to claim 1, wherein the insect repellent, pet deodorant, pet shampoo active ingredient, industrial grade soap and liquid soap active ingredient, dish washing soap active ingredient, multipurpose cleaner, disinfectant, grass and plant feed, water treatment agent, Carpet and furniture cleaning active ingredient, laundry softener active ingredient, laundry detergent active ingredient, toilet bowl cleaner, fabric sizing agent, dust collector, anti-deposition agent, fabric cleaner, softener, antistatic agent and lubricant selected from the group consisting of Household hygiene composition further comprising the above active household ingredients. delete The composition of claim 38 wherein the composition is a colorant, preservative, antioxidant, bleach, activity enhancer, emulsifier, functional polymer, viscosity agent, alcohol, fatty or fatty compound, oil, surfactant, fragrance, suspending agent, silicone material and their Household hygiene composition further comprises at least one additional component selected from the group consisting of a mixture of a. 2. A fragrance, skin refreshing agent, emollient, moisturizer, deodorant, antiperspirant active ingredient, moisturizer, cleanser, sunscreen active ingredient, hair treatment agent, oral care agent, denture adhesive, shaving active ingredient, beauty aid And at least one active personal care ingredient selected from the group consisting of nail care active ingredients. delete 42. The personal hygiene composition of claim 41 wherein said composition is a product selected from the group consisting of hair care, skin care, sun care, nail care and oral care products. 44. The composition of claim 43, wherein said 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. 44. The composition of claim 43, wherein said 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. 46. The composition of claim 45, wherein said skin care product comprises an emollient selected from the group consisting of polyhydric alcohols and hydrocarbons. 44. The composition of claim 43, wherein said product is a hair care product or skin care product comprising up to 99% by weight, based on total composition, of the cationic oxidized polysaccharide or derivative thereof. 42. The method of claim 41 wherein the colorant, preservative, antioxidant, alpha or beta hydroxy acid, activity enhancer, emulsifier, functional polymer, viscosity agent, alcohol, fatty or fatty compound, antibacterial compound, zinc pyrithione, silicone material, antidandruff agent And at least one additional component selected from the group consisting of hydrocarbon polymers, emollients, oils, surfactants, flavorings, fragrances, drugs, refreshers, suspending agents, stabilizing biocides, and mixtures thereof. Personal hygiene composition. The composition of claim 1 further comprising water in an amount of 1 to 99% by weight of the total composition. Adding a cationic oxidized polysaccharide or a derivative thereof prepared by the method of claim 20 as a component to the composition, The polysaccharide or derivatives thereof are polysaccharides or derivatives thereof selected from the group consisting of cellulose and polygalactomannan Method of making a personal hygiene or household hygiene composition. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete