JP2020531533A - Soap compositions and treatments to relieve winter-related pruritus - Google Patents

Abstract

The disclosed techniques include a) a salt of at least one fatty acid, b) a crosslinked nonionic amphipathic emulsion polymer, c) water, and d) any surfactant different from a). It relates to a method of treating a pruritic skin condition caused by exposure to a low humidity environment, which comprises applying an object to the scalp and / or skin.

Description

The technique is caused by long-term exposure to low humidity conditions, including the application of a cleansing composition comprising at least one fatty acid soap and at least one crosslinked nonionic amphipathic polymer to the scalp and skin of a mammalian subject. Regarding how to relieve itching.

Many people suffer from a variety of skin conditions that result in dryness, discoloration, edema, pain, and general irritation. Some of these conditions are induced by topical cleansing products, including shampoos, body cleansers, and other personal care products that contain harsh detergency surfactants. These cleansing surfactants remove some of the protective lipids and / or secretions of the skin, which increases the permeability and sensitivity of the skin to locally applied chemicals that do not cause any particular irritation. In some cases. Typical symptoms of irritation include prurigo (prurigo). Prurigo can be defined as a sensation that causes the desire to scratch the area where the sensation occurs. Whatever the ultimate cause of prurigo, the sensations experienced are the same, causing the desire to scratch to suppress the sensations.

Environmental effects can also adversely affect the barrier function of the skin and cause irritation. The irritation results from or is exacerbated by extreme humidity, exposure to sunlight, unpleasant clothing. A very common condition caused by a low humidity environment is known as "winter prurigo", from very low humidity conditions in cold winter climates (especially with room heating), or from air conditioners in warm summer climates. Prolonged exposure to cold air results in itchy scalp and / or skin. When cold, dry air is artificially heated, it even acts as a dryer, acting almost like a sponge, "sucking up" water from the skin by promoting surface evaporation. Because water is the main "emollient" of the skin, dry skin can become rough, scaly, eventually red, inflamed, and prurigo. In severe cases, these changes will have a dermatitis appearance. Treatments for "winter pruritus" are as follows, which can exacerbate problems such as 1) increasing the relative humidity of the air, 2) excessive bathing and the use of cleansers containing harsh detergency surfactants. Reducing sexual factors, and 3) moisturizing the skin with moisturizers and / or emollients, including creams, lotions, or ointments.

Efforts have been made to reduce the use of body cleansers containing harsh synthetic surfactants by replacing the surfactants with liquid soaps derived from fatty acid salts. Liquid fatty acid soap compositions are known in the art. These soaps have been widely used for many years as effective, mild, versatile body cleansers. Fatty acid soaps are combined with countless different ingredients to obtain the desired cleaning effect and to obtain the necessary physical property parameters so that they can be easily stored and distributed in a convenient manner. It is compounded. Fatty acid soaps must have adequate rheological properties of sufficient viscosity to be fluid when dispensed from the product container but not run off the skin when applied to the body. In addition, today's consumers are increasingly demanding additional benefits that go beyond the basic cleansing effects provided by traditional soap products. By incorporating various auxiliary agents such as moisturizers, emollients, colorants, opalescent agents, fragrances, antioxidants, antibacterial agents, etc. into the formulation, the function and aesthetics of the product can be improved. Efforts to improve are ongoing. It is also becoming increasingly common to incorporate water-insoluble moieties such as microcapsules, beads, and pearl brighteners into soap compositions to enhance the delivery of active substances to the skin and the aesthetics of the product.

Synthetic rheology-modified polymers and synthetic surfactants have viscosity and visual phase uniformity over a period of time and over a wide range of temperatures in order to achieve the desired rheological profile and disperse a number of different components within the soap composition. Has been used in an attempt to obtain a composition that is stable with respect to. These parameters are especially for liquid compositions, where large amounts of water in the formulation make it more difficult to establish a stable composition, especially if a substantially water-insoluble adjunct is dispersed in the formulation. is important.

U.S. Patent Application Publication No. U.S. S. 2007/0213243 discloses a stable soap composition including: (a) crosslinked acrylic copolymer (INCI name: Acrylate copolymer), (b) fatty acid soap, (c) acid neutralizer, ( d) any surfactant, (e) any moisturizer, (f) any emollient, and (g) water. The composition is stabilized with an acrylic copolymer and then back-acidified with an acidifying agent to obtain a storage and phase-stable composition over a wide temperature range.

International Publication No. WO 2015/038601 is published in U.S.A. S. Bathing with a liquid soap composition thickened with a crosslinked acrylic copolymer (INCI name: Acrylate Copolymer) disclosed in 2007/0213243 alleviates the itching caused by long-term exposure to low humidity conditions. The method is disclosed.

U.S. S. Acrylate copolymers are disclosed in 2007/0213243 and WO2015 / 038601, the (meth) acrylic acid is prepared from _C 1 -C ₅ alkyl esters, and polyunsaturated crosslinking agent (meth) acrylic acid. The disclosed thickeners require neutralization with an acid neutralizer and any reverse acidification with an acidifying agent in order to increase the viscosity. Thus, the disclosed thickeners are pH dependent, meaning that the thickening mechanism depends on changes in the pH of the composition in which they are contained in order to increase the viscosity.

WO 2014/099573 discloses conventional crosslinked nonionic amphipathic polymers and their use as eye and / or skin irritation relievers in surfactant-containing compositions. These polymers alleviate skin and eye irritation caused by the harsh synthetic cleansing surfactants contained in personal care cleansing compositions. The disclosed amphipathic polymers provide adjusted yield stress properties, the ability to stably suspend insoluble materials, in cleansing formulations over a wide pH range. The disclosed polymers do not require base or acid neutralization to activate the thickening mechanism. In other words, the thickening mechanism is independent of pH.

WO 2015/095286 discloses an amphipathic crosslinker or a nonionic amphipathic polymer rheology modifier crosslinked with a mixture of an amphipathic crosslinker and a conventional crosslinker. The disclosed amphipathic polymers provide adjusted yield stress properties in surfactant-containing cleansing formulations over a wide pH range.

WO2014 / 099573 and WO2015 / 095286 disclose fatty acid salt soaps among the myriad of anionic surfactants useful in the disclosed surfactant-containing compositions, but winter pruritus. There is no recognition that irritation-induced pruritus can be treated or alleviated by a detergent combination of fatty acid soap (s) cross-linked nonionic amphipathic polymer and any synthetic surfactant (s).
Surprisingly, we found that a liquid cleanser containing fatty acid salt soap and a cross-linked nonionic amphipathic polymer caused itching caused by low environmental humidity, which is especially common in winter in the cold climate regions of the world. Found to mitigate the effects of.

U.S. Patent Application Publication No. 2007/0213243 International Publication No. 2015/038601 International Publication No. 2014/099573 International Publication No. 2015/095286

According to a general embodiment of the technique, a fatty acid salt soap base selected from at least one fatty acid salt, a crosslinked nonionic amphipathic emulsion polymer, and a normal bath to cleanse the scalp and skin. A liquid soap composition containing water utilized during the interval alleviates the development of winter itching caused by low environmental humidity.

According to another common embodiment of the technique, the cleansing soap comprises a soap base selected from at least one fatty acid salt, a crosslinked nonionic amphipathic emulsion polymer, water and anionic surfactants. Includes agents, amphipathic surfactants, and synthetic surfactants selected from mixtures thereof.

Yet another general embodiment of the technique provides a method for treating or alleviating pruritic skin conditions, comprising applying at least one composition to the scalp and / or skin, at least. One composition is
a) Soap containing at least one fatty acid salt and
b) A cross-linked nonionic amphipathic emulsion polymer.
i. At least one of about 35 wt% to about 55 wt%, and _C 1 -C ₅ hydroxyalkyl esters of (meth) acrylic acid,
ii. At least one of about 10 wt% to about 50 wt%, and _C 1 -C ₅ alkyl esters of (meth) acrylic acid,
iii. With at least one associative monomer and / or semi-hydrophobic monomer of about 0.1% to about 20% by weight (all monomer weight percent is based on the weight of the total monounsaturated monomer),
vi. Non-crosslinked prepared from about 0.01 to about 5 parts by weight of at least one polyunsaturated crosslinker monomer (based on 100 parts by weight of the monounsaturated monomer used to prepare the polymer). Ionic amphipathic emulsion polymer and
c) With water
d) Contain at least one surfactant, if desired.

According to yet another embodiment of the technique, the treatment or alleviation of pruritic skin conditions caused by long-term exposure to low relative humidity conditions, including the application of at least one composition to the scalp and / or skin. The method for at least one composition is provided.
a) Soap containing at least one fatty acid salt and
b) A cross-linked nonionic amphipathic emulsion polymer.
i. With about 40% to about 50% by weight, or about 42% to about 48% by weight, or about 44 to 46% by weight of 2-hydroxyethyl methacrylate,
ii. With about 10% to about 40% by weight, or about 12% to about 35% by weight, or about 15% to 25% by weight of ethyl acrylate,
iii. With about 10% to about 35% by weight, or about 12% to about 30% by weight, or about 15% to about 25% by weight of butyl acrylate,
iv. About 0.5% to about 18%, or about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or With associative monomers selected from 10% to about 15% by weight behenyl ethoxylated methacrylate (based on 100 parts by weight of the monovalent unsaturated monomer utilized in the preparation of the polymer),
v. About 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 to about 1, or about 1.5, 2 or 3 to With at least one polyvalent unsaturated cross-linking agent monomer selected from about 5 parts by weight of the polyvalent unsaturated amphipathic cross-linking monomer (based on 100 parts by weight of the monovalent unsaturated monomer used in the preparation of the polymer), Cross-linked nonionic amphipathic emulsion polymer prepared from
c) With water
d) Contain at least one surfactant, if desired.

According to yet another embodiment of the technique, the treatment or alleviation of pruritic skin conditions caused by long-term exposure to low relative humidity conditions, including the application of at least one composition to the scalp and / or skin. The method for at least one composition is provided.
a) Soap containing at least one fatty acid salt and
b) A cross-linked nonionic amphipathic emulsion polymer.
i. With about 44% by weight 2-hydroxyethyl methacrylate,
ii. With about 35% by weight ethyl acrylate,
iii. With about 15% by weight butyl acrylate,
iv. With about 6% by weight behenyl ethoxylated methacrylate (based on 100 parts by weight of the monounsaturated monomer used in the preparation of the polymer),
v. Prepared from about 0.5 to about 2 parts by weight of at least one polyunsaturated amphipathic crosslinker monomer (based on 100 parts by weight of the monounsaturated monomer used to prepare the polymer). Cross-linked non-ionic amphipathic emulsion polymer,
c) With water
d) Contain at least one surfactant, if desired.

According to yet another embodiment of the technique, the treatment or alleviation of pruritic skin conditions caused by long-term exposure to low relative humidity conditions, including the application of at least one composition to the scalp and / or skin. The method for at least one composition is provided.
a) Soap containing at least one fatty acid salt and
b) A cross-linked nonionic amphipathic emulsion polymer.
i. With about 45% by weight 2-hydroxyethyl methacrylate,
ii. With about 15% by weight ethyl acrylate,
iii. With about 25% by weight butyl acrylate,
iv. With about 15% by weight behenyl ethoxylated methacrylate (based on 100 parts by weight of the monounsaturated monomer used in the preparation of the polymer),
v. Prepared from about 0.5 to about 2 parts by weight of at least one polyunsaturated amphipathic crosslinker monomer (based on 100 parts by weight of the monounsaturated monomer used to prepare the polymer). Cross-linked non-ionic amphipathic emulsion polymer,
c) With water
d) Contain at least one surfactant, if desired.

According to yet another embodiment of the technique, the treatment or alleviation of pruritic skin conditions caused by long-term exposure to low relative humidity conditions, including the application of at least one composition to the scalp and / or skin. The method for at least one composition is provided.
a) Soap containing at least one fatty acid salt and
b) A cross-linked nonionic amphipathic emulsion polymer.
i. With about 45% by weight 2-hydroxyethyl methacrylate,
ii. With about 20.5% by weight ethyl acrylate,
iii. With about 27.5% by weight butyl acrylate,
iv. With about 7% by weight behenyl ethoxylated methacrylate (based on 100 parts by weight of the monounsaturated monomer used to prepare the polymer),
v. Prepared from about 0.1 to about 1 part by weight of at least one polyunsaturated amphipathic crosslinker monomer (based on 100 parts by weight of the monounsaturated monomer utilized to prepare the polymer). Cross-linked non-ionic amphipathic emulsion polymer,
c) With water
d) Contain at least one surfactant, if desired.

Certain embodiments of the techniques disclosed herein include a cleansing composition comprising at least one fatty acid salt soap, a crosslinked nonionic amphipathic emulsion polymer, water, and optionally at least one surfactant. Based on the surprising finding that things can relieve itching of the scalp and skin.

In particular, the soap-based cleansing compositions disclosed herein are effective treatments to relieve itching of the scalp and skin caused by long-term exposure to low humidity environments during normal bathing intervals. It has been discovered that it can be used.

As used herein and throughout the specification, the term "pruritus" or "pruritic" is a sensation that causes a desire or reflex to scratch.

The term "low relative humidity" (RH) as used herein and throughout the specification is 50% or less in one aspect, 45% or less in another aspect, 40% or less in yet another aspect, a further aspect. Means RH values of 35% or less, 30% or less in additional embodiments, 25%, 20%, 15%, 10%, 5% and 1% in additional embodiments.

"Relative humidity" is the actual amount of vapor (depending on vapor density or vapor pressure) present in the volume of air at a given temperature versus the maximum amount of vapor (saturated vapor) that may be present in the air at that temperature. Means the ratio (by density or saturated vapor pressure), expressed as a percentage, and can be calculated by the following equation:
RH = (actual steam density) / (saturated steam density) x 100
Or RH = (actual vapor pressure) / (saturated vapor pressure) x 100

"Long-term exposure to low relative humidity" means exposure to low humidity conditions for a time sufficient to develop pruritus.

As used herein and throughout the specification, "winter prurigo" is a prurigo condition caused by exposure to cold winter air and / or low humidity conditions.

"Cold winter air" means 20 ° C or lower in one embodiment, 15 ° C or lower in another embodiment, 10 ° C or lower in yet another embodiment, and 9 ° C, 8 ° C, 7 ° C, 6 ° C, 5 ° C in another aspect. It means a temperature of ℃, 4 ℃, 3 ℃, 2 ℃, 1 ℃, 0 ℃, -5 ℃, -10 ℃ and -15 ℃ or less.

As used herein, the prefix "(meth) acrylic" includes "acrylic" as well as "methacryl". For example, the term "(meth) acrylic acid" includes both acrylic acid and methacrylic acid.

As used herein, the term "nonionic" refers to polymers polymerized from monomers, monomeric compositions, or monomeric compositions that do not contain ionic or ionizable moieties ("nonionic"), and "substantially." Includes both "nonionic" monomers, monomer compositions, or polymers polymerized from monomeric compositions.

The ionizable moiety is any group that can be ionized by neutralizing with an acid or base.

The ionic or ionized moiety is any moiety that is neutralized by an acid or base.

“Substantially nonionic” means that the monomer, monomer composition, or polymer polymerized from the monomer composition is 15% by weight or less in one embodiment, 10% by weight or less in another aspect, and 5 in yet another aspect. By weight or less, 3% by weight or less in a further aspect, 1% by weight or less in a further aspect, 0.5% by weight or less in an additional aspect, 0.1% by weight or less in an additional aspect, and 0. It means that it contains an ionizable portion and / or an ionized portion of 05% by weight or less. Those skilled in the art will recognize that, depending on the commercial source, some nonionic monomers may contain residual amounts of monomers with ionic or ionizable properties. The amount of residual monomer in a nonionic monomer composition containing an ionic or ionizable moiety is 0, 0.05, 0.5, 1, 2, 3 based on the weight of a particular nonionic monomer. It can be in the range of 4, or 5-15 wt%.

The phrase "at least one" means one or more of a particular component, and thus includes individual components as well as mixtures / combinations of individually listed components.

The methods, polymers, components, and compositions of the present invention preferably include, consist of, or are essentially depictions of the components, elements, processes, and processes described herein. obtain. The techniques exemplified herein may be suitably performed in the absence of any element, component, or process not specifically disclosed herein.

Unless otherwise stated, all percentages, parts, and ratios expressed herein are based on the total weight of the composition of the soap cleansing composition.

When referring to a particular monomer (s) to be incorporated into a polymer of the disclosed technology, the monomer is incorporated into the polymer as a unit (s) (eg, repeating unit) derived from the particular monomer (s). Will be recognized.

As used herein, the term "personal care" refers to cosmetics, toiletries, medicated cosmetics, cosmetological aids, insect repellents, individuals that apply to the body, including human and animal skin, hair, scalp, and nails. Hygiene and cleansing products include, but are not limited to.

Here, and elsewhere in the specification and claims, individual numbers (including carbon atom numbers), or limits, combine to provide additional undisclosed and / or undescribed range. Can be formed.

The headings provided herein serve to illustrate, but do not limit the disclosed technology in any way or manner.

In addition to the ingredients mentioned above, the cleansing composition can include any other auxiliaries conventionally used in soaps. These include, for example, one or more emollients, one or more moisturizers, one or more preservatives, one or more viscosity modifiers, one or more skin conditioning agents, and one or more hair conditioning. Agents include one or more antibacterial agents, one or more antioxidants, one or more fragrances, one or more colorants, one or more chelating agents, and one or more insoluble materials. .. Any of these materials will be described in more detail below.

The selection and amount of the above ingredients will depend on the desired liquid soap final product of the present invention. For example, hand soaps, body soaps, shampoos, and cleansers can contain different ingredients as well as different amounts of the same ingredients. The selection and amount of ingredients in the formulation of the present invention will vary depending on the product and its function, as will be well known to those skilled in the art of formulation.

Overlapping weight ranges of the various ingredients that make up a cleansing soap composition are represented for various embodiments of the disclosed technique, but the sum of all ingredients in the liquid soap composition is 100% by weight. As such, it should be readily apparent that a particular amount of each component in the composition is selected from its disclosed range so that the desired amount of each component is adjusted.

Fatty Acid Salt Soap In one aspect of the disclosed technique, the soap composition comprises at least one fatty acid salt soap containing from about 8 to about 22 carbon atoms. In another aspect of the disclosed technique, the soap composition comprises at least one fatty acid salt soap containing about 10 to about 18 carbon atoms. In a further aspect of the disclosed technique, the soap composition comprises at least one fatty acid salt soap containing from about 12 to about 16 carbon atoms. The fatty acids utilized in soaps can be saturated and unsaturated and can be derived from synthetic sources as well as from the hydrolysis of fats and natural oils. Exemplary saturated fatty acids include octanic acid, decanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, nonadecanic acid, arachidic acid, behenic acid, and mixtures thereof. However, it is not limited to these. Exemplary unsaturated fatty acids include, but are not limited to, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and mixtures thereof. Fatty acids are animal fats such as tallow, lard, poultry fat, or coconut oil, red oil, palm kernel oil, palm oil, cottonseed oil, flaxseed oil, sunflower oil, olive oil, soybean oil, peanut oil, corn oil, benibana oil. Can be derived from plant sources such as sesame oil, rapeseed oil, canola oil, and mixtures thereof.

Soaps can be prepared by various well-known means, such as by direct base neutralization of fatty acids or mixtures thereof, or by saponification of their mixtures with suitable fats and vegetable oils or suitable bases. Exemplary bases include alkanolamines such as potassium hydroxide, potassium carbonate, sodium hydroxide, and triethanolamine. Generally, the fat or oil is heated until liquefied and a solution of the desired base is added to it. The soaps contained in the personal care compositions utilized by the methods of the disclosed techniques include natural fats and oils such as, for example, tallow or coconut oil or their equivalents, using procedures well known to those skilled in the art. It can be made by a classical kettle process or a modern continuous manufacturing process that is saponified with alkali metal hydroxides. Alternatively, the soap may contain advantageous fatty acids such as lauric acid (C ₁₂ ), myristic acid (C ₁₄ ), palmitic acid (C ₁₆ ), stearic acid (C ₁₈ ), isostearic acid (C ₁₈ ), and mixtures thereof. It can be prepared by direct neutralization with an alkali metal hydroxide or carbonate.

The amount of at least one fatty acid salt soap used in the soap composition of the present invention is from about 10% to about 35% by weight in one aspect and about 12% by weight in another, based on the total weight of the composition. It ranges from about 30% by weight, and in yet another aspect from about 15% to about 25% by weight, and from about 18% to about 20% by weight.

In one aspect of the disclosed technique, the fatty acid salt soap comprises a fatty acid salt and the fatty acid is selected from a mixture of lauric acid, myristic acid, and stearic acid. In another aspect, the fatty acid salt soap comprises a fatty acid salt and the fatty acid is selected from a mixture of lauric acid, myristic acid, and isostearic acid. In yet another embodiment, the fatty acid salt soap comprises a fatty acid salt and the fatty acid is selected from a mixture of lauric acid, myristic acid, and palmitic acid. In a further aspect, the fatty acid salt soap is an alkali metal fatty acid salt soap in which the fatty acid comprises a fatty acid salt selected from a mixture of lauric acid, myristic acid, palmitic acid and stearic acid. In another aspect of the technique, the fatty acid soap is a potassium salt of a fatty acid.

Amphiphile Polymer In one aspect of the disclosed technique, a crosslinked nonionic amphipathic polymer is polymerized from a monomeric component containing free radically polymerizable monovalent unsaturated. In one embodiment, disclosed embodiments useful crosslinking nonionic amphiphilic polymer technology, a) C ₁ -C ₅ hydroxyalkyl (meth) at least one monomer selected from acrylate, b) C ₁ ~ C _{5 At} least one monomer selected from alkyl (meth) acrylates, c) At least one monomer selected from associative monomers, semi-hydrophobic monomers and mixtures thereof, and d) At least one polyunsaturated Prepared from a monomer mixture containing crosslinked monomers.

In one embodiment, the crosslinked nonionic amphoteric polymers useful for practicing the disclosed techniques are a) at least one monomer selected from 2-hydroxyethyl methacrylate, b) ethyl acrylate, butyl acrylate, and these. Prepared from a monomer mixture containing at least one monomer selected from the mixture of, c) at least one monomer selected from the associative monomer and its mixture, d) an amphoteric cross-linking monomer, and e) an amphoteric additive. And the polymerizable monomer mixture containing the amphoteric additive is free of protective colloids and / or polymer stabilizers. In one embodiment, the monomer mixture is polymerized in a medium containing protective colloids, polymer tranquilizers and combinations thereof.

Hydroxy (C _{1 to} C ₅ ) alkyl (meth) acrylates can be structurally represented by the following equation:
In the formula, R ¹ is hydrogen or methyl, R ² is a divalent alkylene moiety containing 1 to 5 carbon atoms, the alkylene moiety being optionally one or more methyl groups. It may be replaced. Representative monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and mixtures thereof.

In one aspect, at least one of 35% to about 55% by weight, or about 40% to about 50% by weight, or about 42% to about 48% by weight, or about 44% to about 46% by weight. (meth) utilizing C ₁ -C ₅ hydroxyalkyl esters of acrylic acid (based on the total weight of monounsaturated monomers in the polymerization medium) to prepare a polymer.

(C _{1 to} C ₅ ) Alkyl (meth) acrylate can be structurally expressed by the following equation:
In the formula, R ¹ is hydrogen or methyl and R ³ is C _{1 to} C ₅ alkyl. Representative monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, and iso-butyl (meth) acrylate, and mixtures thereof. , Not limited to these.

In one aspect, about 10% to about 50% by weight, or about 12% to about 45% by weight, or about 15% to about 40% by weight, or about 20% to about 35% by weight, or about 25%. of at least 1 weight% to about 30 wt% to prepare a polymer using a (meth) (based on the total weight of monounsaturated monomers in the polymerization medium) C ₁ -C ₅ alkyl esters of acrylic acid.

The associative monomer of the disclosed technique imparts ethylenically unsaturated terminal group moiety (i), selective hydrophilicity and / or hydrophobicity to the produced polymer for addition polymerization with other monomers of the disclosed technique. It has a polyoxyalkylene intermediate section portion (iii) for the purpose of providing a hydrophobic end group portion (iii) for providing selective hydrophobicity to the polymer.

The portion (i) that supplies the ethylenically unsaturated terminal group can be a residue derived from an α, β-ethylenically unsaturated monocarboxylic acid. Alternatively, part (i) of the associative monomer is a residue derived from an allyl ether or vinyl ether, a nonionic as disclosed in US Reissue Patent Nos. 33,156 or US Pat. No. 5,294,692. It can be a vinyl-substituted urethane monomer or a vinyl-substituted urea reaction product as disclosed in US Pat. No. 5,011,978, the respective relevant disclosures of which are incorporated herein by reference. ..

Midsection portion (ii) _repeats the C 2 -C ₄ alkylene oxide units, in one embodiment of from about 2 to about 150, in another embodiment from about 10 to about 120, from about 15 to about 60 in a further aspect Polyoxyalkylene segment of. The intermediate section portion (ii) was arranged in a random or block sequence of ethylene oxide, propylene oxide and / or butylene oxide units, about 2 to about 150 in one embodiment and about 5 to about 120 in another. , And in a further embodiment, polyoxyethylene, polyoxypropylene, and polyoxybutylene segments containing about 10 to about 60 ethylene, propylene and / or butylene oxide units, and combinations thereof.

The hydrophobic end group moiety (iii) of the associative monomer is a hydrocarbon moiety belonging to one of the following hydrocarbon classes: C _{8 to} C ₃₀ linear alkyl, C _{8 to} C ₃₀ branched chain alkyl, C _{8 to} C ₃₀ carbocyclic alkyls, C _{2 to} C ₃₀ alkyl substituted phenyls, araalkyl substituted phenyls, and aryl substituted C _{2 to} C ₃₀ alkyl groups.

Non-limiting examples of suitable hydrophobic end group moieties (iii) of associative monomers are capryl (C ₈ ), isooctyl (branched chain C ₈ ), decyl (C ₁₀ ), lauryl (C ₁₂ ), myristyl (C ₁₂ ). C ₁₄ ), cetyl (C ₁₆ ), cetearyl (C _16- C ₁₈ ), stearyl (C ₁₈ ), isostearyl (branched chain C ₁₈ ), arachidyl (C ₂₀ ), behenyl (C ₂₂ ), lignoceryl (C ₂₄ ) ), Cerotyl (C ₂₆ ), Montanyl (C ₂₈ ), Melicyl (C ₃₀ ), etc., which are straight or branched chain alkyl groups having about 8 to about 30 carbon atoms.

Examples of straight and branched alkyl groups with about 8 to about 30 carbon atoms derived from natural sources are hydrogenated peanut oil, soybean oil and canola oil (all mainly C ₁₈ ), hydrogenated tallow. _(C 16 _{-C 18)} alkyl groups derived from such, as well as hydrogenated geraniol (branched _{C 10),} hydrogenated farnesol (branched _{C 15),} hydrogenated _{C 10,} such as hydrogenated phytol (branched _{C 20)} alkyl groups derived from -C ₃₀ terpenols, but not limited thereto.

Non-limiting examples of suitable C _{2 to} C ₃₀ alkyl substituted phenyl groups include octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, hexadecyl, octadecylphenyl, isooctylphenyl, sec-butylphenyl and the like.

Exemplary aryl-substituted _C 2 _{-C 40} alkyl group, styryl (e.g., 2-phenylethyl), distyryl (e.g., 2,4-diphenyl-butyl), tristyryl (e.g., 2,4,6-triphenyl-hexyl ), 4-Phenylbutyl, 2-methyl-2-phenylethyl, tristyrylphenolyl and the like, but are not limited thereto.

Suitable C _{8 to} C ₃₀ carbocyclic alkyl groups include sterols from animal sources such as cholesterol, lanosterol, 7-dehydrocholesterol, and plant source empty sterols such as phytosterols, stigmasterols, campesterols, etc. , And, for example, groups derived from sterols from yeast sources such as ergosterol, mycosterol, but not limited to these. Other carbocyclic alkyl hydrophobic end groups useful in the disclosed techniques include cyclooctyl, cyclododecyl, adamantyl, decahydronaphthyl, and, for example, pinene, hydrogenated retinol, camphor, isobornyl alcohols, etc. Groups derived from natural carbocyclic substances include, but are not limited to.

Useful associative monomers can be prepared by any method known in the art. For example, U.S. Pat. Nos. 4,421,902 to Chang et al., 4,384,096 to Sonnabend, 4,514,552 to Shay et al., 4,600 to Ruffner et al. , 761, No. 4,616,074 to Ruffner, No. 5,294,692 to Barron et al., No. 5,292,843 to Jenkins et al., No. 5,770 to Robinson. , 760, and No. 5,421,142 to Wilkerson, III et al. (These relevant disclosures are incorporated herein by reference).

In one aspect, exemplary associative monomers include those represented by the following formula:
In the formula, R ¹ is hydrogen or methyl, and A is -CH ₂ C (O) O-, -C (O) O-, -O-, -CH ₂ O-, -NHC (O) NH. -, -C (O) NH-, -Ar- (CE ₂ ) _z -NHC (O) O-, -Ar- (CE ₂ ) _z -NHC (O) NH-, or -CH ₂ CH ₂ NHC ( O)-, Ar is a divalent arylene (eg, phenylene), E is H or methyl, z is 0 or 1, k is an integer in the range of about 0 to about 30. m is 0 or 1, where m is 0 when k is 0, m is 1 when k is in the range 1 to about 30, and D represents a vinyl or allyl moiety, and ( R ^15- O) _n is a polyoxyalkylene moiety, which is a homopolymer, random copolymer, or block copolymer of C _{2 to} C ₄ oxyalkylene units, and R ¹⁵ is C ₂ H ₄ , C ₃ A divalent alkylene moiety selected from H ₆ , or C ₄ H ₈ , and combinations thereof, where n is an additional embodiment of about 2 to about 150 in one embodiment and about 10 to about 120 in another. in an integer ranging from about 15 to about 60, Y is ^{-R 15 O -, - R 15} NH -, - C (O) -, - C (O) NH -, - R 15 NHC (O) NH -Or -C (O) NHC (O)-, where R ¹⁶ is C _{8 to} C ₃₀ linear alkyl, C _{8 to} C ₃₀ branched chain alkyl, C _{8 to} C ₃₀ carbocyclic alkyl, C ₂ ~ C ₃₀ alkyl substituted phenyl, araalkyl substituted phenyl, and aryl substituted C _{2 to} C ₃₀ alkyl substituted or unsubstituted, and in the formula, the alkyl group, aryl group, phenyl group of R ¹⁶ is hydroxyl. It contains, if necessary, one or more substituents selected from the group consisting of groups, alkoxy groups, benzyl groups, phenylethyl groups, and halogen groups.

In one aspect, the hydrophobically modified associative monomer is an alkoxylated (meth) acrylate having a hydrophobic group containing 8 to 30 carbon atoms, represented by the following formula:
In the formula, R ¹ is hydrogen or methyl, R ¹⁵ is a divalent alkylene moiety selected independently of C ₂ H ₄ , C ₃ H ₆ and C ₄ H ₈ , and n is one. about 2 to about 150 in the embodiment, in one aspect, from about 5 to about 120, and further aspects, represents an integer in the range of from about 10 to about ^{60, (R} 15 -O) shall be arranged in random or block configuration R ¹⁶ can be C _{8 to} C ₃₀ linear alkyl, C _{8 to} C ₃₀ branched chain alkyl, C _{8 to} C ₃₀ carbocyclic alkyl, C _{2 to} C ₃₀ alkyl substituted phenyl, aryl substituted C ₂ to C. A substituted or unsubstituted alkyl selected from ₃₀ alkyls.

Typical associative monomers include lauryl polyethoxylated methacrylate (LEM), cetyl polyethoxylated methacrylate (CEM), cetearyl polyethoxylated methacrylate (CSEM), stearyl polyethoxylated (meth) acrylate, and arachidyl polyethoxy. Chemical (meth) acrylate, behenyl polyethoxylated methacrylate (BEM), cellotyl polyethoxylated (meth) acrylate, montanyl polyethoxylated (meth) acrylate, melicyl polyethoxylated (meth) acrylate, phenyl polyethoxylated (meth) Meta) acrylate, nonylphenyl polyethoxylated (meth) acrylate, ω-tristyrylphenyl polyoxyethylene methacrylate (here, the polyethoxylated portion of the monomer is about 2-150 ethylene oxide units in one embodiment, in another embodiment. Approximately 5 to about 120, yet another embodiment contains about 10 to about 60, a further embodiment contains 10 to 40, and yet another embodiment contains 15 to 30 ethylene oxide units), octyloxypolyethylene glycol (8). Examples thereof include polypropylene glycol (6) (meth) acrylate, phenoxypolyethylene glycol (6) polypropylene glycol (6) (meth) acrylate, and nonylphenoxypolyethylene glycol polypropylene glycol (meth) acrylate.

The semi-hydrophobic monomers of the disclosed technique are structurally similar to the associative monomers described above, but have a substantially non-hydrophobic end group moiety. The semi-hydrophobic monomer is a poly for imparting ethylenically unsaturated terminal group moieties (i), selective hydrophilicity and / or hydrophobicity to the resulting polymer for addition polymerization with other monomers of the disclosed technology. It has an oxyalkylene intermediate section portion (ii) and a semi-hydrophobic terminal group portion (iii). The unsaturated end group moiety (i) that supplies vinyl or other ethylenically unsaturated end groups for addition polymerization is preferably derived from the α, β-ethylenically unsaturated monocarboxylic acid. Alternatively, the terminal group portion (i) may be derived from an allyl ether residue, a vinyl ether residue, or a residue of a nonionic urethane monomer.

The polyoxyalkylene intermediate section (ii) specifically includes a polyoxyalkylene segment that is substantially similar to the polyoxyalkylene portion of the associative monomer described above. In one aspect, the polyoxyalkylene moieties (ii) are arranged in a random or massive arrangement, about 2 to about 150 in one embodiment, about 5 to about 120 in another, and about 5 in a further aspect. Contains 10 to about 60 ethylene oxide, propylene oxide, and / or butylene oxide units.

The semi-hydrophobic end group moiety (iii) is a substantially non-hydrophobic end group selected from moieties containing hydroxyl or 1-4 carbon atoms. Exemplary carbon atom-containing semi-hydrophobic end groups include methyl, ethyl, propyl and butyl moieties.

In one aspect, the semi-hydrophobic monomer can be represented by the following formula:
In the formula, R ¹ is hydrogen or methyl, and A is -CH ₂ C (O) O-, -C (O) O-, -O-, -CH ₂ O-, -NHC (O) NH. -, -C (O) NH-, -Ar- (CE ₂ ) _z -NHC (O) O-, -Ar- (CE ₂ ) _z -NHC (O) NH-, or -CH ₂ CH ₂ NHC ( O)-, Ar is a divalent arylene (eg, phenylene), E is H or methyl, z is 0 or 1, and k is an integer in the range of about 0 to about 30. m is 0 or 1, where m is 0 when k is 0, m is 1 when k is in the range 1 to about 30, and (R ^15- O) _n is a poly. The oxyalkylene moiety, which is a homopolymer, random copolymer, or block copolymer of C _{2 to} C ₄ oxyalkylene units, where R ¹⁵ is C ₂ H ₄ , C ₃ H ₆ , or C ₄ H ₈ , And a divalent alkylene moiety selected from a combination thereof, n in the range of about 2 to about 150 in one embodiment, about 5 to about 120 in another aspect, and about 10 to about 60 in a further aspect. is an ^{integer, R 17} is hydrogen and linear or branched _C 1 -C ₄ alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert- butyl), D is vinyl Or represents an allyl moiety.

In one aspect, the semi-hydrophobic monomer can be represented by the following formula:
CH ₂ = C (R ¹ ) C (O) O- (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b- H
CH ₂ = C (R ¹ ) C (O) O- (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b- CH ₃
In the formula, R ¹ is hydrogen or methyl, where "a" ranges from 0 or 2 to about 120 in one embodiment, about 5 to about 45 in another, and about 10 to about 25 in a further aspect. It is an integer, where "b" is an integer in the range 0 or 2 to about 120 in one embodiment, about 5 to about 45 in another aspect, and about 10 to about 25 in a further aspect, provided that "a". "" And "b" are subject to the condition that they cannot be zero at the same time.

Examples of semi-hydrophobic monomers include trade names Blummer® PE-90 (R ¹ = methyl, a = 2, b = 0), PE-200 (R ¹ = methyl, a = 4.5, b). = 0), and polyethylene glycol methacrylate available at PE-350 (R ¹ = methyl, a = 8, b = 0); trade name Blummer® PP-1000 (R ¹ = methyl, b = 4 ~). 6, a = 0), PP-500 (R ¹ = methyl, a = 0, b = 9), PP-800 (R ¹ = methyl, a = 0, b = 13), polypropylene glycol methacrylate. Available under trade names Blummer® 50PEP-300 (R ¹ = methyl, a = 3.5, b = 2.5), 70PEP-350B (R ¹ = methyl, a = 5, b = 2) Polyethylene Glycol Polypropylene Glycol Methyl methacrylate; Trade Name Blummer® AE-90 (R ¹ = Hydrogen, a = 2, b = 0), AE-200 (R ¹ = Hydrogen, a = 2, b = 4.5) , AE-400 (R ¹ = hydrogen, a = 10, b = 0) available polyethylene glycol acrylate; trade name Bremmer® AP-150 (R ¹ = hydrogen, a = 0, b = 3). , AP-400 (R ¹ = hydrogen, a = 0, b = 6), AP-550 (R ¹ = hydrogen, a = 0, b = 9), polypropylene glycol acrylates available. Blummer® is a trademark of NOF Corporation, Tokyo, and Japan.

Further examples of semi-hydrophobic monomers include the trade names Visiomer® MPEG 750MA W (R ¹ = methyl, a = 17, b = 0), MPEG 1005MA W (R ¹ = methyl, a = 22, b =). Available from Evonik Rohm GmbH, Damstat, Germany at 0), MPEG 2005 MA W (R ¹ = methyl, a = 45, b = 0), and MPEG 5005 MA W (R ¹ = methyl, a = 113, b = 0). Methoxypolyethylene glycol methacrylate; GEO Specialty Chemicals, Bisomer® from Ambler PA MPEG 350MA (R ¹ = methyl, a = 8, b = 0), and MPEG 550MA (R ¹ = methyl, a = 12, b) = 0); Blummer® PME-100 (R ¹ = methyl, a = 2, b = 0), PME-200 (R ¹ = methyl, a = 4, b =), PME400 (R ¹ = methyl) , A = 9, b = 0), PME-1000 (R ¹ = methyl, a = 23, b = 0), PME-4000 (R ¹ = methyl, a = 90, b = 0).

In one aspect, the semi-hydrophobic monomer can be represented by the following formula:
CH ₂ = CH-O- (CH ₂ ) _d- O- (C ₃ H ₆ O) _e- (C ₂ H ₄ O) _f- H
CH ₂ = CH-CH _2- O- (C ₃ H ₆ O) _g- (C ₂ H ₄ O) _h- H
In the equation, d is an integer of 2, 3, or 4, e is an integer in the range of about 1 to about 10, in another aspect of about 2 to about 8, and in a further aspect of about 3 to about 7. F is an integer in the range of about 5 to about 50 in one aspect, about 8 to about 40 in another aspect, and about 10 to about 30 in another aspect, and g is 1 to about 10 in one aspect. In another aspect it is an integer in the range of about 2 to about 8, and in a further aspect it is an integer in the range of about 3 to about 7, h is an integer in the range of about 5 to about 50 in one aspect and about 8 to about 40 in another aspect. E, f, g, and h can be set to 0, except that e and f cannot be set to 0 at the same time, and g and h cannot be set to 0 at the same time. Follow the condition that you cannot.

Semi-hydrophobic monomers are sold by Clariant Corporation under the trade names Emulsogen® R109, R208, R307, RAL109, RAL208, and RAL307, Bimax, Inc. Commercially available in BX-AA-E5P5 sold by, and combinations thereof. EMULSOGEN® R109 is a randomly ethoxylated / propoxylated 1 having the experimental formula CH ₂ = CH-O (CH _{2) 4} O (C ₃ H ₆ O _{) 4} (C ₂ H ₄ O) ₁₀ H. , 4-Butandiol vinyl ether, Emulsogen® R208 has the experimental formula CH ₂ = CH-O (CH ₂ ) ₄ O (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) ₂₀ H. , A randomly ethoxylated / propoxylated 1,4-butanezyl vinyl ether, Emulsogen® R307 is an experimental formula CH ₂ = CH-O (CH ₂ ) ₄ O (C ₃ H _6). O) ₄ (CH ₂ H ₄ O) A randomly ethoxylated / propoxylated 1,4-butanediol vinyl ether having ₃₀ H, Emulsogen® RAL109 is the experimental formula CH ₂ = CHCH ₂ O. (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) A randomly ethoxylated / propoxylated allyl ether having ₁₀ H, Emulsogen® RAL208 is an experimental formula CH ₂ = CHCH ₂ O. (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) A randomly ethoxylated / propoxylated allyl ether having ₂₀ H, Emulsogen® RAL307 is an experimental formula CH ₂ = CHCH ₂ O. (C ₃ H ₆ O) ₄ (C ₂ H ₄ O) A randomly ethoxylated / propoxylated allyl ether having ₃₀ H, and BX-AA-E5P5 is the experimental formula CH ₂ = CHCH ₂ O. A randomly ethoxylated / propoxylated allyl ether having (C ₃ H ₆ O) ₅ (C ₂ H ₄ O) ₅ .

The associative and semi-hydrophobic monomers of the disclosed techniques can utilize the polyoxyalkylene intermediate section moieties contained in these monomers to adjust the hydrophilicity and / or hydrophobicity of the polymers they contain. it can. For example, the intermediate section portion rich in ethylene oxide moieties is more hydrophilic, while the intermediate section moiety rich in propylene oxide moieties is more hydrophobic. By adjusting the relative amount of ethylene oxide to the propylene oxide moiety present in these monomers, the hydrophilic and hydrophobic properties of the polymer containing these monomers can be adjusted as desired.

The amount of associative and / or semi-hydrophobic monomer utilized in the preparation of the polymer of the disclosed technique can vary widely and depends in particular on the final rheological and aesthetic properties desired for the polymer. When utilized, one or more monomers selected from the associative and / or semi-hydrophobic monomers disclosed above are about 0.1 to about 20% by weight, or about 0.5% to about 18% by weight. Weight%, or about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% to about 15% ( Available in amounts in the range (based on the total weight of monovalent unsaturated monomers in the polymerization medium) and utilized for preparing polymers.

Ionizable Monomers In one aspect of the disclosed technique, the cross-linked nonionic amphoteric polymer composition of the disclosed technique is the weight of the total monomer, as long as the rheological properties of the composition are not adversely affected. In one aspect about 0 to about 15.0% by weight, in another aspect about 0.1 to about 15% by weight, in yet another aspect about 0.5 to about 10% by weight, and in a further aspect about. It can be polymerized from a monomer composition comprising 1 to about 8% by weight, and in a further embodiment about 2 or 3 to about 5% by weight of ionizable and / or ionized monomers.

In another aspect, the amphoteric polymer composition of the disclosed technique is less than 3% by weight in one aspect, less than 1% by weight in a further aspect, and 0.5% by weight in a further aspect, based on the weight of the total monomer. It can be polymerized from a monomer composition containing less than%, in additional embodiments less than 0.1% by weight, and in additional embodiments less than 0.05% by weight of ionizable and / or ionized moieties.

Examples of the ionizable monomer include a monomer having a base neutralizing moiety and a monomer having an acid neutralizing moiety. Base-neutralizing monomers include olefinically unsaturated monocarboxylic acids and dicarboxylic acids, their salts containing 3-5 carbon atoms and their anhydrides. Examples include (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, and other acidic monomers such as combinations thereof include styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid (AMPS). (Registered Trademark) Monomer), vinyl sulfonic acid, vinyl phosphonic acid, allyl sulfonic acid, metallic sulfonic acid, and salts thereof.

Acid-neutralizing monomers include olefinically unsaturated monomers containing basic nitrogen atoms that can form salts or quaternized moieties upon addition of the acid. For example, these monomers include vinylpyridine, vinylpiperidin, vinylimidazole, vinylmethylimidazole, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminomethyl (meth) acrylate and methacrylate, dimethylaminoneopentyl. Examples include (meth) acrylates, dimethylaminopropyl (meth) acrylates, and diethylaminoethyl (meth) acrylates.

Crosslinking Monomer In one aspect of the disclosed technique, the crosslinkable monomer is an amphipathic crosslinker. Amphiphile crosslinkers are utilized to polymerize covalent crosslinks to the amphipathic polymer backbone. In some cases, conventional cross-linking agents can affect the volume expansion or swelling of microgel particles in a fluid containing a surfactant. For example, high levels of conventional crosslinkers can provide high yield stresses, but the limited expansion of microgels results in undesired high polymer usage levels and low optical clarity. On the other hand, low levels of conventional cross-linking agents provide high optical clarity, but may provide low yield stresses. It is desirable that the polymeric microgel allow maximum swelling while maintaining the desired yield stress, and the use of amphipathic crosslinkers in place of or in combination with conventional crosslinkers provides these benefits. It turns out that it can be done. In addition, amphipathic crosslinkers have been found to be able to easily react with amphipathic polymers. In many cases, conventional crosslinkers may require specific processing techniques such as staging to achieve the proper balance between optical clarity and yield stress. In contrast, amphipathic crosslinkers have been found to be easily added in a single step with the monomer mixture during preparation.

In one aspect, exemplary amphipathic crosslinkers suitable for use in the present technology include compounds such as those disclosed in US 2013/0047892 (published to Palmer et al., February 28, 2013). This compound can be expressed by the following formula:
In the formula, R ²⁰ is CH ₃ , CH ₂ CH ₃ , C ₆ H ₅ , or C ₁₄ H ₂₉ , m is 1, 2, or 3, x is 2-10, y is 0. a to 200 DEG, Z is 4 to 200, in another embodiment about 5 to 60, in a further aspect from about 5 to 40, Z is SO ₃ ^- be either or _PO ^{3 2-of} can, and ^{M +} is _{^{Na +, K +, NH 4}} +, or, for example, an alkanolamine such as monoethanolamine, diethanolamine and triethanolamine,
In the equation, R ²⁰ is CH ₃ , CH ₂ CH ₃ , C ₆ H ₅ , or C ₁₄ H ₂₉ , n is 1, 2, 3, x is 2-10, y is 0-. 200, z is 4 to 200, another aspect is 5 to 60, and a further aspect is about 5 to 40.
In the formula, R ²¹ is C _{10 to 24} alkyl, alkaline, alkenyl, or cycloalkyl, R ²⁰ = CH ₃ , CH ₂ CH ₃ , C ₆ H ₅ , or C ₁₄ H ₂₉ , where x is 2 to. 10, y is 0-200, Z is 4-200, in another embodiment about 5-60, in a further embodiment about 5-40, R ²² is H or Z ^- M. a ^+, Z is, SO ₃ ^- or _PO ^{3 2-of} can be any, and ^{M + _{is, Na +, K +, NH}} 4 +, or, for example, monoethanolamine, diethanolamine, and triethanolamine It is an alkanolamine such as ethanolamine.

In one embodiment, the amphipathic crosslinker is based on the total weight of the monovalent unsaturated monomer utilized to prepare the nonionic amphipathic polymer of the disclosed technique, in one embodiment about 0. It can be used in an amount ranging from 01 to about 3% by weight, in another embodiment from about 0.05 to about 0.1% by weight, and in further embodiments from about 0.1 to about 0.9% by weight. In other words, the amount of amphipathic crosslinkers and / or conventional crosslinkable monomers discussed below is 100 parts by weight of the total monounsaturated monomers used to prepare the polymers of the disclosed techniques. It can be calculated based on parts by weight (100% active substance) per (100% active substance).

In another embodiment, the amphipathic cross-linking agent can contain on average about 1.5 or 2 unsaturated moieties to prepare a non-ionic amphipathic polymer of the disclosed technique. Based on 100 parts by weight of the monovalent unsaturated monomer utilized, about 0.01 to about 3 parts by weight in one aspect, about 0.02 to about 1 part by weight in another aspect, 0.05 to about 0.05 parts by weight in a further aspect. It can be used in an amount ranging from about 0.9 parts by weight, and in yet further embodiments from about 0.075 to about 0.5 parts by weight, and in another embodiment about 0.1 to about 0.15 parts by weight. ..

In one aspect, the amphipathic crosslinker is selected from compounds of formula (IV) or (V) below:
In the formula, n is 1 or 2, z is 4-40 in one embodiment, 5-38 in another embodiment, and 10-20 in a further embodiment, where R ²² is H, SO ₃ ^- M ⁺ or PO. ^_3-2 is M ^+, M is selected Na, K, and the NH _4.

The aforementioned amphipathic crosslinkers conforming to formulas (I), (II), (III), (IV) and (V) are disclosed in US Patent Application Publication No. US2014 / 0114006 (the disclosure of which is: (Incorporated herein by reference) and commercially available from Ethox Chemicals, LLC under the trade names of the E-Space ™ RS series (eg, product names RS-1617, RS-1618, RS-1684). ..

The amount of polyunsaturated amphipathic crosslinking monomers used to crosslink the polymers of the disclosed techniques is about 0.1 to about 5 parts by weight, or about 0.1, 0.2, 0.3. , 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 part to about 5 parts by weight (100 of monounsaturated monomers used to prepare the polymer) (Based on parts by weight).

In one embodiment, the cross-linking monomer can include a combination of an amphipathic cross-linking agent and a conventional cross-linking agent. These are polyunsaturated compounds with a relatively low molecular weight (less than 300 daltons). In one aspect, conventional crosslinkers are polyunsaturated compounds containing at least two unsaturated moieties. In another aspect, conventional crosslinkers contain at least three unsaturated moieties. Exemplary polyunsaturated compounds include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1, 6-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2,2'-bis ( Di (meth) acrylate compounds such as 4- (acrylicoxy-propyloxyphenyl) propane and 2,2'-bis (4- (acrylicoxydiethoxy-phenyl) propane; trimethylolpropane tri (meth) acrylate, tri Methylolethane tri (meth) acrylate and tetramethylolmethanetri (meth) acrylate tri (meth) acrylate compounds; dimethylolpropane tetra (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Tetra (meth) acrylate compounds such as; hexa (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate; allyls such as allyl (meth) acrylate, diallyl phthalate, diallyl itaconate, diallyl fumarate, and diallyl maleate. Compounds; sucrose polyallyl ethers having 2 to 8 allyl groups per molecule, pentaerythritol diallyl ethers, pentaerythritol trimethylolethers, and pentaerythritol tetraallyl ethers, and pentaerythritol polyallyl ethers such as combinations thereof; Trimethylolpropane diallyl ethers, trimethylolpropane triallyl ethers, and trimethylolpropane polyallyl ethers such as combinations thereof include polyallyl ethers. Other suitable polyunsaturated compounds include divinyl glycol, divinylbenzene, and methylene. Bisacrylamide can be mentioned

In another aspect, suitable polyunsaturated monomers are the esterification reaction of a polyol made from ethylene oxide or propylene oxide or a combination thereof with an unsaturated anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride. , Or can be synthesized via an addition reaction with 3-isopropenyl-α-α-dimethylbenzene isocyanate.

Mixtures of two or more of the polyunsaturated compounds mentioned above can also be used to crosslink nonionic amphipathic polymers. In one aspect, a mixture of conventional unsaturated crosslinked monomers contains an average of two unsaturated moieties. In another aspect, a mixture of conventional crosslinkers contains an average of 2.5 unsaturated moieties. In yet another aspect, the mixture of conventional crosslinkers contains an average of about 3 unsaturated moieties. In a further aspect, the mixture of conventional crosslinkers contains an average of about 3.5 unsaturated moieties.

In one embodiment, the conventional cross-linking agent component is based on 100 parts by weight of the monovalent unsaturated monomer utilized to prepare the nonionic amphoteric polymer of the disclosed technique, in one embodiment about 0. It can be used in an amount ranging from 0.01 to about 0.5 parts by weight, in another embodiment from about 0.05 to about 0.4 parts by weight, and in further embodiments from about 0.1 to about 0.3 parts by weight. ..

In another embodiment of the disclosed technique, conventional crosslinkers can contain on average about two unsaturated moieties and are utilized to prepare nonionic amphoteric polymers of the disclosed technique. Based on 100 parts by weight of the monovalent unsaturated monomer obtained, in one embodiment about 0.01 to about 0.3 parts by weight, in another aspect about 0.02 to about 0.25 parts by weight, and in a further aspect 0. Use in amounts ranging from .05 to about 0.2 parts by weight, and in yet more embodiments from about 0.075 to about 0.175 parts by weight, and in another aspect from about 0.1 to about 0.15 parts by weight. be able to.

In one aspect, conventional crosslinkers include trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, pentaerythritol triallyl ether, and three allyl groups per molecule. Is selected from sucrose polyallyl ethers having.

In another aspect, the nonionic amphipathic polymer can be crosslinked with a combination of conventional crosslinkers and amphipathic crosslinkers. Conventional cross-linking agents and amphipathic cross-linking agents are, in one aspect, about 0, based on 100 parts by weight of the monovalent unsaturated monomer utilized to prepare the nonionic amphipathic polymer of the disclosed technique. It can be used in a total amount ranging from 0.01 to about 1 part by weight, in another aspect from about 0.05 to about 0.75 parts by weight, and in a further aspect from about 0.1 to about 0.5 parts by weight.

In one aspect, the combination of conventional crosslinkers and amphoteric crosslinkers is trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, pentaerythritol triallyl ether. And a polyallyl ether of sucrose having three allyl groups per molecule, and conventional cross-linking agents selected from combinations thereof, and compounds of formulas (III), (V) and combinations thereof. It can include an amphipathic cross-linking agent.

Synthesis of Amphiphilic Polymers Cross-linked nonionic amphipathic polymers of the disclosed techniques can be made using conventional free radical emulsion polymerization techniques. The polymerization process is carried out in the absence of oxygen in an inert atmosphere such as nitrogen. The polymerization can be carried out in a suitable solvent system such as water. Small amounts of hydrocarbon solvents, organic solvents, and mixtures thereof can be used. To facilitate the emulsification of the monomer mixture, emulsion polymerization is carried out in the presence of at least one stabilizing surfactant. The polymerization reaction is initiated by any means that results in the production of suitable free radicals. Thermally induced radicals can be utilized in which radical species are generated from the thermal, homolytic dissociation of peroxides, hydroperoxides, persulfates, percarbonates, peroxyesters, hydrogen peroxides, and azo compounds. The initiator can be water-soluble or water-insoluble, depending on the solvent system used in the polymerization reaction.

The initiator compound is utilized in an amount of up to 30% by weight in one embodiment, 0.01-10% by weight in another aspect, and 0.2-3% by weight in a further aspect, based on the total weight of the dry polymer. be able to.

Exemplary free radical water-soluble initiators include inorganic persulfate compounds such as ammonium persulfate, potassium persulfate, and sodium persulfate; peroxides such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide. Substances; organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; organic peracids such as peracetic acid, and 2,2'-azobis (tert-alkyl) compounds having a water-soluble substituent on the alkyl group. Examples include, but are not limited to, water-soluble azo compounds. Exemplary free radical oil-soluble compounds include, but are not limited to, 2,2'-azobisisobutyronitrile. Peroxides and peracids can be activated as needed with reducing agents such as sodium bisulfite, sodium formaldehyde, or ascorbic acid, transition metals, hydrazine.

In one aspect, the azo polymerization catalyst includes a Vazo® free radical polymerization initiator available from DuPont, such as Vazo® 44 (2,2'-azobis (2- (4,5-dihydro)). Kimidazolyl Propane), Vazo® 56 (2,2'-azobis (2-methylpropionmidin) dihydrochloride), Vazo® 67 (2,2'-azobis (2-methylbuty)) (Ronitrile)), and Vazo® 68 (4,4'-azobis (4-cyanovaleric acid)).

If necessary, the use of a known redox initiator system as the polymerization initiator can be adopted. Such redox initiator systems include oxidizing agents (initiators) and reducing agents. Suitable oxidants include, for example, hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, sodium perborate, sodium perborate and salts thereof, excess. Potassium permanganate, as well as ammonium or alkali metal salts of peroxydisulfate, are mentioned and are usually used in levels of 0.01% to 3.0% by weight based on the weight of the dry polymer. Suitable reducing agents include alkali metals and ammonium salts of sulfur-containing acids such as, for example, sodium sulfite, hydrogen sulfite, thiosulfate, hydrosulfite, sulfides, hydrosulfides or dithionates, formazine sulfic acid, hydroxymethanesulfone. Acids, amines such as acetone sulfite, ethanolamine, glycolic acid, glyoxylic acid hydrate, ascorbic acid, isoascorbic acid, lactic acid, glyceric acid, malic acid, 2-hydroxy-2-sulfinatoacetic acid, tartaric acid, and the aforementioned Acid salts are mentioned and are usually used at a level of 0.01% to 3.0% by weight based on the impression polymer weight. In one aspect, a combination of peroxodisulfate and alkali metal or ammonium bisulfate, such as ammonium peroxodisulfate and ammonium bisulfate, can be used. In another aspect, a combination of a hydrogen peroxide-containing compound (t-butyl hydroperoxide) as an oxidizing agent and ascorbic acid or erythorbic acid as a reducing agent can be utilized. The ratio of peroxide-containing compound to reducing agent is in the range of 30: 1 to 0.05: 1.

In one aspect, the polymerization can be carried out in the presence of a chain transfer agent. Suitable chain transfer _agents, thio, such as C 1 _{-C 18} alkyl mercaptans - and disulfide containing compounds, for example, tert- butyl mercaptan, n- octyl mercaptan, n- dodecyl mercaptan, tert- dodecyl mercaptan, hexadecyl mercaptan, Dodecyl mercaptan, octadecyl mercaptan; mercapto alcohols such as 2-mercaptoethanol, 2-mercaptopropanol; mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; butyl thioglycolate, isooctyl thioglycolate, dodecyl thioglycolate, 3 - mercaptopropionic acid isooctyl, and 3-mercapto mercaptocarboxylic acid esters such as propionic acid butyl; thioesters; C ₁ -C ₁₈ alkyl disulfides, aryl disulfides, trimethylolpropane - tris - (3-mercaptopropionate), pentaerythritol Polyfunctional thiols such as -tetra- (3-mercaptopropionate), pentaerythritol-tetra- (thioglycolate), pentaerythritol-tetra- (thiolactate), dipentaerythritol-hexa- (thioglycolate); phosphites and hypophosphites; formaldehyde, acetaldehyde, C ₁ -C ₄ aldehydes, such as propionaldehyde; carbon tetrachloride, haloalkyl compounds such as bromotrichloromethane; hydroxylammonium salts such as hydroxylammonium sulfate; formic acid; sulfite Sodium hydrogen; isopropanol; and catalytic chain transfer agents, such as, but not limited to, cobalt complexes (eg, cobalt (II) chelate).

Chain transfer agents are generally used in amounts in the range 0.1-10% by weight, based on the total weight of the monomers present in the polymerization medium.

The polymerization reaction can be carried out at a temperature in the range of 20 to 200 ° C. in one embodiment, 50 to 150 ° C. in another embodiment, and 60 to 100 ° C. in a further aspect.

In the emulsion polymerization process, it may be advantageous to stabilize the monomer / polymer droplets or particles with a detergent. Usually these are emulsifiers or protective colloids. The emulsifier used can be anionic, nonionic cationic or amphoteric. Examples of anionic emulsifiers are alkylbenzene sulfonic acids, sulfonated fatty acids, sulfosuccinates, aliphatic alcohol sulfates, alkylphenol sulfates and aliphatic alcohol ether sulfates. Examples of nonionic emulsifiers that can be used are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkylpolyglucosides. Examples of cationic and amphoteric emulsifiers used are quaternized amine alkoxylates, alkyl betaines, alkyl amide betaines and sulfo betaines.

Examples of typical protective colloids are cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, poly (vinyl alcohol), partially hydrolyzed poly (vinyl alcohol), polyvinyl ether, starch. And starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-methylsuccinimide, polyvinyl-1,3-oxazolido-2-one, polyvinyl-2-methylimidazolin and maleic acid or It is an anhydride copolymer. The emulsifier or protective colloid is typically used in a concentration of 0.05-20% by weight based on the weight of the total monomer.

In one aspect, the emulsion process can be carried out in the absence of protective colloids. In this aspect, the emulsion process uses amphipathic additives. According to one aspect of the art, the amphipathic additive is mixed with the polymerizable monomer mixture containing the amphipathic crosslinker before introducing the monomer mixture into the polymerization medium. Monomer mixtures (dispersed phase) and polymerization media (continuous phase) lack protective colloids and / or polymer stereostabilizers such as poly (vinyl alcohol) and poly (vinyl acetate). Surprisingly, the clarity and turbidity of the surfactant composition containing the resulting polymer product by mixing the amphipathic additive with the polymerizable monomer mixture and removing the protective colloid from the emulsion polymerization medium. The properties have been found to improve.

The amphipathic additive of the present invention is nonionic and contains at least one hydrophilic segment and at least two hydrophobic segments.

In one embodiment, the amphipathic additive of the present technology is represented by the following formula:
In the formula, Q represents a polyol residue, A represents a poly (ethylene glycol) residue, and R is selected from saturated and unsaturated C _10- C ₂₂ acyl groups and poly (propylene glycol) residues. , R ²³ are independently selected from H, saturated and unsaturated C _10- C ₂₂ acyl groups and poly (propylene glycol) residues, where a is 0 or 1, b is 0 or 1, and c. Is a number from 1 to 4, where a and c are 1 when b is 0, a is 0 when b is 1, and R ²³ is a poly (propylene glycol) residue. Follow the condition that there is none.

In one aspect of the disclosed technique, the amphipathic additive is a polyethoxylated alkyl glucoside ester represented by the following formula:
In the formula, R ²³ is selected independently of the H and saturated and unsaturated C _10- C ₂₂ acyl groups, R ²⁴ is selected from the C _1- C ₁₀ alkyl groups, and the sum of w + x + y + z is one aspect. It ranges from about 60 to about 150, about 80 to about 135 in another aspect, and about 90 to about 125 in a further aspect, and about 100 to about 120 in a further aspect, provided that 2 of R ^23. According to the condition that one or less can be H at the same time.

In one embodiment, R ²³ is lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, ricinoleic acid vaccenic acid, linoleic acid (alpha and gamma), arachidic acid, behenic acid, and an acyl residue of a mixture of, R ²⁵ is methyl.

Suitable polyethoxylated alkyl glucoside esters are trade name Glucamete ™ LT (INCI name: PEG-120 methyl glucose (and) propylene glycol (and) water), Glucamete ™ VLT (INCI name: triolein). PEG-120 methyl glucose (and) propanediol acid), and Glucamate ™ DOE-120 (INCI name: PEG-120 methyl glucose dioleate) are commercially available.

In one aspect of the disclosed technique, the amphipathic additive is selected from poly (ethylene glycol) diesters in which poly (ethylene glycol) (PEG) is saturated with saturated and unsaturated C _10- C ₂₂ fatty acids. Expressed by the following formula:
In the formula, B is independently selected from saturated and unsaturated C _10- C ₂₂ acyl radicals, n is about 10 to about 120 in one embodiment, about 12 to about 110 in another, and about 15 in a further embodiment. It is in the range of ~ about 100.

In one aspect, B is an acyl residue of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, ricinolic acid vaccenic acid, linoleic acid (alpha and gamma), arachidic acid, behenic acid, And the acyl residue of these mixtures.

Exemplary PEG diesters include lauric acid, palmitic acid, palmitic acid, stearic acid, isostearic acid, and oleic acid diesters of PEG-400, PEG-600, PEG-1000, PEG-2000, and PEG-4000. However, it is not limited to these.

In one aspect of the disclosed technique, the amphipathic additive is a poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) -block copolymer represented by the following formula:
In the formula, r = t, in the range of about 5 to about 20, in one aspect about 6 to about 15, and in a further aspect about 8 to about 14, and s is about 20 to about 20 in one aspect. It ranges from about 30, in another aspect about 21 to about 27, and in a further aspect about 23 to about 25.

In one aspect, the poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) -block copolymer has a number average molecular weight in the range of about 1500 to about 3500 Da.

Poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) -block copolymers are about 35 to about 60 in one embodiment, about 40 to about 55% by weight in another, and yet another. In the embodiment, it contains about 45 to about 50% by weight of poly (ethylene glycol). Suitable poly (propylene glycol) -block-poly (ethylene glycol) -block-poly (propylene glycol) -block copolymers are products of Pluronic ™ 10R5 and Pluronic ™ 17R4 by BASF Corporation, Poloxamer Park, NJ. It is commercially available under the name.

The amount of amphipathic additive mixed with the polysynthetic monomer mixture is based on 100 parts by weight of the monovalent unsaturated monomer used to prepare the nonionic amphipathic polymer of the disclosed technique. In one aspect, it ranges from about 1 to about 15 parts by weight, in another aspect it ranges from about 2 to about 10 parts by weight, and in yet another aspect it ranges from about 3 to about 6 parts by weight.

The emulsion process can be carried out in a single reactor or in multiple reactors, as is well known in the art. The monomers can be added as a batch mixture, or each monomer can be metered to the reactor in a stepwise process. Typical mixtures in emulsion polymerization include water, monomers (s), initiators (usually water soluble), and emulsifiers. The monomer may be emulsion polymerized in a one-step, two-step or multi-step polymerization process according to methods well known in the art of emulsion polymerization. In the two-step polymerization process, the first-step monomer is first added and polymerized in an aqueous medium, and then the second-step monomer is added and polymerized. The aqueous medium can contain an organic solvent, if desired. When used, the organic solvent is less than about 5% by weight of the aqueous medium. Preferable examples of the water-miscible organic solvent include, but are not limited to, esters, alkylene glycol ethers, alkylene glycol ether esters, low molecular weight aliphatic alcohols and the like.

To facilitate the emulsification of the monomer mixture, emulsion polymerization is carried out in the presence of at least one stabilizing surfactant. The term "stabilizing surfactant" is used with respect to surfactants used to promote emulsification. In one embodiment, the emulsion polymerization is from about 0.2% to about 5% by weight in one embodiment, from about 0.5% to about 3% by weight in another aspect, and from about 1% to about 1% by weight in a further aspect. It is carried out in the presence of a stabilizing surfactant (based on active weight) in the range of 2% by weight. The emulsion polymerization reaction mixture also comprises one or more free radical initiators present in an amount ranging from about 0.01% to about 3% by weight based on the total monomer weight. The polymerization can be carried out in an aqueous or aqueous alcoholic medium. Stabilizing surfactants for promoting emulsion polymerization include anionic, nonionic, amphoteric, and cationic surfactants, as well as reactive derivatives thereof, and mixtures thereof. "Their reactive derivatives" means a surfactant or a mixture of surfactants having an average of less than one reactive moiety. Most commonly, anionic and nonionic surfactants are available as stabilized surfactants and mixtures thereof.

Suitable anionic surfactants for promoting emulsion polymerization are well known in the art and include (C _6- C ₁₈ ) alkyl sulphates and (C _6- C ₁₈ ) alkyl ether sulphates. Amino and alkali metal salts of dodecylbenzenesulfonic acid, such as (eg, sodium lauryl sulfate and sodium laureth sulfate), sodium dodecylbenzenesulfonate and dimethylethanolamine dodecylbenzenesulfonate, sodium (C _6- C ₁₆ ) alkylphenoxybenzene sulfonate. , Disodium (C _6- C ₁₆ ) alkylphenoxybenzene sulfonate, disodium (C _6- C ₁₆ ) dialkylphenoxybenzene sulfonate, laures-3 disodium sulfosuccinate, sodium dioctyl sulfosuccinate, di-sec-butylnaphthalene sulfonic acid Examples include, but are not limited to, sodium, disodium dodecyldiphenyl ether sulfonate, disodium n-octadecyl sulfosuccinate, phosphate esters of branched alcohol ethoxylates, and their reactive derivatives.

Nonionic surfactants suitable for promoting emulsion polymerization are well known in the field of polymer technology, and include capryl alcohol ethoxylates, lauryl alcohol ethoxylates, myristyl alcohol ethoxylates, cetyl alcohol ethoxylates, and stearyls. Linear or branched C _8- C ₃₀ fatty alcohol ethoxylates such as alcohol ethoxylates, cetearyl alcohol ethoxylates, sterol ethoxylates, oleyl alcohol ethoxylates, and behenyl alcohol ethoxylates; and polyoxyethylene polyoxypropylene block copolymers, etc. And their reactive derivatives, but are not limited to these. Additional fatty alcohol ethoxylates suitable as nonionic surfactants are described below. Other useful nonionic surfactants include C _{8 to} C ₂₂ fatty acid esters of polyoxyethylene glycol, ethoxylated mono and diglycerides, sorbitan esters and ethoxylated sorbitan esters, C _{8 to} C ₂₂ fatty acid glycol esters, ethylene oxide. Block copolymers of and propylene oxide, their combinations, and their reactive derivatives. The number of ethylene oxide units in each of the aforementioned ethoxylates can range from 2 or more in one embodiment and from 2 to about 150 in another.

If desired, other emulsion polymerization additives and processing aids known in the field of emulsion polymerization, such as solvents, protective colloids, buffers, chelating agents, inorganic electrolytes, biogenic agents, and pH regulators. , Can be included in the polymerization system.

In one aspect, a two-step emulsion polymerization reaction is utilized to prepare a polymer of the present technology. A mixture of monovalent unsaturated monomer, amphipathic cross-linking agent and protective colloid or amphipathic additive is first added to a solution of emulsified surfactant (eg, anionic surfactant) in water under an inert atmosphere. Add to the reactor. When amphipathic additives are used, the monomer mixture does not contain protective colloids and / or polymer stereostabilizers such as poly (vinyl alcohol or poly (vinyl acetate)). Contents of the first reactor To prepare a monomeric emulsion (dispersed phase). In a second reactor equipped with a stirrer, an inert gas inlet, and a feed pump, a desired amount of water and additional anions under an inert atmosphere. A sex surfactant (dispersion medium or continuous phase) is added. The contents of the second reactor are heated with stirring. The contents of the second reactor have a temperature in the range of about 55-98 ° C. After reaching, the free radical initiator is injected into the aqueous surfactant solution and the monomer emulsion from the first reactor is applied to the second reactor, typically for a time ranging from about 30 minutes to about 4 hours. The reaction temperature is controlled in the range of about 45 to about 95 ° C. After completion of the monomer addition, an additional amount of free radical initiator is added to the second reactor as needed. The resulting reaction mixture is usually held at a temperature of about 45-95 ° C. for a sufficient time to complete the polymerization reaction and obtain a polymer emulsion.

In one embodiment, the crosslinking nonionic amphiphilic polymers of the disclosed technology, and from about 20 to about 60 wt% of at least one _C 1 -C ₅ hydroxyalkyl (meth) acrylate, from about 10 to about 50 wt% At least one C _{1 to} C ₅ alkyl (meth) acrylate and at least one associative and / or semi-hydrophobic monomer of about 0.1, _{1, 5} , or 7 to about 15% by weight (here all). The monomer weight percent of is based on the total weight of the monovalent unsaturated monomer), and in one embodiment about 0.01 to about 5 parts by weight, in another aspect about 0.1 to about 3 parts by weight, and in a further aspect. An emulsion polymerized from a monomer mixture containing from about 0.5 to about 1 part by weight of at least one amphoteric crosslinker (based on 100 parts by weight of the monovalent unsaturated monomer used to prepare the polymer). Selected from polymers.

In one aspect, the crosslinked nonionic diamogenic polymers of the disclosed technique are about 20 to about 50% by weight of hydroxyethyl methacrylate, about 10 to about 30% by weight of ethyl acrylate, and about 10 to about 35% by weight. With% by weight of butyl acrylate and about 1 to about 10 or 15% by weight of at least one associative and / or semi-hydrophobic monomer (here, all monomer weight percent is based on the total weight of the total monomer). About 0.01 to about 5 parts by weight in one aspect, about 0.1 to about 3 parts by weight in another aspect, and about 0.5 to about 1 part by weight in a further aspect, and about 1 to about 15 parts by weight in one aspect. From a monomer mixture containing parts by weight, in another aspect about 2-10 parts by weight of at least one amphoteric crosslinker (based on 100 parts by weight of the monovalent unsaturated monomer used to prepare the polymer). Selected from polymerized emulsion polymers.

In one aspect, the crosslinked nonionic amphoteric polymers of the disclosed techniques are about 40 to about 50% by weight of hydroxyethyl methacrylate, about 10 to about 25% by weight of ethyl acrylate, and about 20 to about 30%. By weight% butyl acrylate and about 5 or 6 to about 15% by weight lauryl polyethoxylated (meth) acrylate, cetyl polyethoxylated (meth) acrylate, cetearyl polyethoxylated (meth) acrylate, stearyl polyethoxylated (Meta) acrylate, arachidyl polyethoxylated (meth) acrylate, behenyl polyethoxylated (meth) acrylate, cellotyl polyethoxylated (meth) acrylate, montanyl polyethoxylated (meth) acrylate, melisyl polyethoxylated (meth) At least one associative monomer selected from (meth) acrylates (where the polyethoxylated moiety of the monomer contains about 2 to about 50 ethylene oxide units) (where all monomer weight percent is total monomer In one embodiment, about 0.01 to about 5 parts by weight, in another aspect, about 0.1 to about 3 parts by weight, and in a further aspect, at least about 0.5 to about 1 part by weight. It is selected from emulsion polymers polymerized from a monomer mixture containing one polyvalent unsaturated amphoteric cross-linking agent (based on 100 parts by weight of the monovalent unsaturated monomer utilized to prepare the polymer).

Detergency Surfactants The fatty acid soap compositions of the present technology are anionic, amphoteric, zwitterionic, nonionic, and any synthetic detergency surfactant (synthetic detergent) selected from a combination thereof. ) Can be included.

The anionic surfactant can be either known in the art of aqueous surfactant compositions or previously used anionic surfactants. Suitable anionic surfactants include alkyl sulphates, alkyl ether sulphates, alanine sulfonates, alkyl succinates, alkyl sulfosuccinates, taurine salts (eg, potassium cocoyl taurate, potassium methyl cocoyl taurate). , Caproyl methyl taurate sodium, cocoyl taurate sodium, lauroyl taurate sodium, methyl cocoyl taurate sodium, methyl lauroyl taurate sodium, methyl lauryl taurate sodium, methyl oleoyl taurate sodium, methyl palmitoyl taurate sodium, methyl N-acylamino acid surfactants such as stearyl taurate sodium), glutamates (eg, dipotassium capryloyl glutamate, dipotassium undecilenoyl glutamate, disodium capryloyl glutamate, disodium cocoyl glutamate, disoyl lauroyl glutamate, stearoyl). Disodium glutamate, disoyl undecylenoyl glutamate, potassium capilloyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate, potassium myristyl glutamate, potassium stearoyl glutamate, potassium undecylenoyl glutamate, sodium capilloyl glutamate , Sodium myristyl glutamate, Sodium olivoylglutamate, Sodium palmitoyl glutamate, Sodium stearoyl glutamate, Sodium undecilenoylglutamate), Glycinate (eg, Sodium palmitoylglycine, Sodium lauroylglycine, Sodium cocoylglycine, Sodium myristylglycine , Potassium lauroyl glycine, potassium cocoyl glycine, sodium stearoyl glycine), alanine and alanine (eg, cocoyl methyl β-alanine, lauroyl β-alanine, lauroyl methyl β-alanine, myristol β-alanine, lauroyl methyl β − Potassium alanine, sodium cocoyl alanine, sodium cocoyl methyl β-alanine, sodium myristylmethyl β-alanine) sarcosates (eg, potassium lauroyl sarcosinate, potassium cocoyl sarcosinate, cocoyl sa) Sodium lucosate, sodium lauroyl sarcocinate, sodium myristyl sarcosate, sodium palmitoyl sarcosate), aspartate (eg, sodium lauroyl aspartate, sodium myristol aspartate, sodium cocoyl aspartate, sodium caproyl aspartate, lauroyl aspartate) Disodium, disodium myristoyl aspartate, disodium cocoyl aspartate, disodium caproyl aspartate, potassium lauroyl aspartate, potassium myritoyl aspartate, potassium cocoyl aspartate, potassium caproyl aspartate, dipotassium lauroyl aspartate, myritoyl Dipotassium aspartate, dipotassium cocoyl aspartate, dipotassium caproyl aspartate), alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates alkyl ISEthionates, and alpha-olefin sulfonates, especially These include, but are not limited to, sodium, potassium, magnesium, ammonium and mono, di- and triethanolamine salts. Alkyl groups generally contain 8-18 carbon atoms and may be unsaturated. Alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates contain 1 to 10 ethylene oxide and / or propylene oxide units per molecule in one embodiment and about 1 to 1 per molecule in another embodiment. It may contain about 4 ethylene oxide units.

Examples of suitable anionic surfactants are sodium lauryl ether sulfate and ammonium (ethoxylated with 1, 2, and 3 mol of ethylene oxide), sodium trideces sulfate (1, 2, 3, and 4 mol of ethylene oxide). Ethoxylated with), sodium, ammonium, and triethanolamine lauryl sulfate, disodium lauryl sulfosuccinate, sodium cocoyl isetionate, C _12-14 sodium olefin sulfonate, sodium laureth-6 carboxylate, C _12-15 Examples include sodium palace sulfate, sodium methylcocoyl taurate, sodium dodecylbenzene sulfonate, sodium cocoyl sarcosinate, and triethanolamine monolauryl phosphate.

Amphoteric and zwitterionic surfactants are compounds that have the ability to act as either acids or bases. These surfactants can be either known in the art of aqueous surfactant compositions or previously used surfactants. Suitable materials include alkylbetaine, alkylamide propylbetaine, alkylsulfobetaine, alkylglycinate, alkylcarboxyglycinate, alkylamphopropionate, wherein the alkyl and acyl groups have 8-18 carbon atoms. Alkylamide propyl hydroxysultaine, acyl taurates, and aacyl glutamates include, but are not limited to. Examples include cocamidopropyl betaine, sodium cocoamphoacetate, cocamidopropyl hydroxysultaine, and sodium cocanfopropionate.

The nonionic surfactant can be either known in the art of aqueous surfactant compositions or previously used nonionic surfactants. Suitable nonionic surfactants include aliphatic (C _6- C ₁₈ ) primary or secondary linear or branched chain acids, alcohols or phenols, alkylethoxylates, alkylphenol alkoxylates (particularly ethoxylates and mixtures). Ethoxy / propoxy), blocked alkylene oxide condensates of alkylphenols, alkylene oxide condensates of alkanols, ethylene oxide / propylene oxide block copolymers, semipolar nonionic substances (eg amine oxides and phosphine oxides), and alkylamine oxides. However, it is not limited to these. Other suitable nonionic substances include mono or dialkyl alkanolamides and alkyl polysaccharides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol esters, polyoxyethylene acids, and polyoxyethylene alcohols. Be done. Examples of suitable nonionic surfactants include cocomono or diethanolamide, cocodiglucoside, alkylpolyglucoside, cocamidopropyl and lauramine oxide, polysorbate 20, ethoxylated straight chain alcohol, cetearyl alcohol, lanolin alcohol, Included are stearic acid, glyceryl stearate, PEG-100 stearate, and oleth 20.

Other surfactants that can be utilized in the present invention are WO99 / 21530, US Pat. No. 3,929,678, US Pat. No. 4,565,647, US Pat. No. 5,720,964, and It is described in detail in US Pat. No. 5,858,948. Other suitable surfactants are described in McCutcheon's Emulsifiers and Detergents (North American and International Editions by Schwartz, Perry and Berch), which are fully incorporated herein by reference.

In one embodiment of the disclosed technique, the amount of surfactant, if present, can vary widely. Frequently used amounts (activity criteria) are generally about 0 or 1 to about 15% by weight in one embodiment, about 2 to about 12% by weight in another, and in additional aspects, based on the total weight of the composition. It ranges from about 2.5 to about 10% by weight, and in more embodiments from about 5 to about 8% by weight, provided that the total amount of surfactant used in the composition is the fatty acid salt utilized in the composition. Follow the condition that it is less than the amount of soap.

In other embodiments, the amount of any surfactant utilized in the composition can be based on the amount of fatty acid soap present in the liquid cleansing composition and is expressed as the weight ratio of the fatty acid soap to the surfactant. Can be done. In one aspect of the disclosed technique, the fatty acid soap to surfactant ratio ranges from about 1: 1 to about 5: 1, and in another aspect the soap to surfactant ratio is about 1.5. : 1 to about 3: 1 and in a further aspect the soap to surfactant ratios range from about 2: 1 to about 2.5: 1 (all ratios are weight / weight basis). based on).

In one aspect of the disclosed technique, the surfactant is selected from a mixture of an anionic surfactant (s) and an amphoteric surfactant (s). In one aspect, the anionic surfactant is selected from at least one alkyl ether sulfonate that fits the formula below:
In the formula, R is C _{10 to} C ₁₆ alkyl, m is an integer of 1, 2, 3 or 4, and CA is a cation selected from alkali metals (eg sodium, potassium) or ammonium. In one aspect, the anionic surfactant is sodium laureth sulphate or sodium trideces sulphate containing 1 to 4 moles of ethoxylation.

In one aspect, the amphoteric surfactant is selected from alkyl betaines and / or amide alkyl betaines that fit their respective formulas:
In the formula, R ¹ is a C _{8 to} C ₂₂ alkyl group, R ₂ and R ³ independently represent a C _{1 to} C ₄ alkyl group or a hydroxy C _{1 to} C ₄ alkyl group, where n is 1. Or 2.
In the formula, R ⁴ is a C _{9 to} C ₂₁ alkyl group, R ₅ and R ⁶ independently represent a C _{1 to} C ₄ alkyl group or a hydroxy C _{1 to} C ₄ alkyl group, where p is about. It is an integer in the range of 1 to about 6, and q is 1 or 2.

In one aspect, the mixture of anionic and amphoteric surfactants comprises cocamidopropyl betaine along with sodium laureth sulfate (containing 1-3 mol ethoxylated portions). In one aspect, the surfactant comprises cocamidopropyl betaine along with sodium trideces sulfate.

Water Water is also a component in the composition according to the disclosed embodiment of the technique. In one aspect, the liquid cleansing composition described herein is in the form of a non-emulsion liquid in which water is the primary carrier / diluent / carrier. Considering the desired amount (% by weight) of other active ingredients utilized to formulate the soap composition of the disclosed technique, the amount of water used in the composition will always be the total weight of the composition. It corresponds to the weight percent required to bring to 100 (ie, an amount sufficient to make (the balance) 100). In another aspect, the amount of water is from about 25 to about 89.5% by weight, in a further aspect from about 35 to about 85% by weight, and in yet further aspects from about 40 to about 80% by weight, based on the total weight of the composition. %, About 40 to about 75% by weight in additional embodiments, about 50 to about 70% by weight in additional embodiments, and about 55 to about 65% by weight in further additional embodiments.

pH regulator The pH of the cleansing composition of the disclosed technique is 7 or more in one embodiment, about 7.5 to about 10.5 in another, and about 7.8 to about 9.8 in yet another aspect. In a further aspect it is about 8 to about 9.5, and in a further aspect it is about 8.2 to about 9.2. For base saponification of precursor animal and plant-derived fatty acids and / or base neutralization of free fatty acids to obtain fatty acid salt soap components of the disclosed technique, soap compositions are typically in the basic pH range. That is, it will be over pH 7. However, it may be desirable or necessary to adjust the pH of the final composition to the desired pH value. A sufficient amount of a pH regulator (base and / or acid) can be added to the soap composition of the disclosed technique to achieve the desired pH.

Many types of alkaline (basic) pH regulators can be used, including inorganic and organic bases, and combinations thereof. Examples of inorganic bases are hydroxides of ammonium and alkali metals (especially sodium and potassium), and alkali metal salts of inorganic acids such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and theirs. Examples include, but are not limited to, mixtures. Examples of organic bases include triethanolamine (TEA), diisopropanolamine, triisopropanolamine, aminomethylpropanol, dodecylamine, cocamine, oleamine, morpholine, triamilamine, triethylamine, tetrakis (hydroxypropyl) ethylenediamine, L- Examples include, but are not limited to, arginine, aminomethylpropanol, tromethamine (2-amino2-hydroxymethyl-1,3-propanediol), and PEG-15 cocamine.

In one aspect, the acidic pH regulator is an organic such as citric acid, acetic acid, alpha-hydroxy acid, beta-hydroxy acid, salicylic acid, lactic acid, fumaric acid, glutamate, glycolic acid, tartaric acid, natural fruit acid, or a combination thereof. Selected from acids. In addition, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, sodium bisulfate, sulfamic acid, phosphoric acid, and combinations thereof can be utilized. Mixtures of organic and inorganic acids are also contemplated.

Moisturizer The fatty acid liquid soap composition of the disclosed technology optionally comprises at least one moisturizer. Moisturizers are defined as materials that absorb or release water vapor depending on the relative humidity of the environment (Harry's Cosmeticology, Chemical Publishing Company Inc., 1982 p. 266). Suitable moisturizers that can be included in the soap composition include allantin; pyrrolidone carboxylic acid and salts thereof; hyaluronic acid and salts thereof; sorbic acid and salts thereof; urea, lysine, arginine, cystine, guanidine, and other amino acids. Polyhydric alcohols such as glycerin, propylene glycol, hexylene glycol, hexanetriol, ethoxydiglycol, dimethiconecopolyol, and sorbitol, and their esters; polyethylene glycol; glycolic acid and glycolate (eg ammonium and quaternary). Alkylammonium); chitosan; aloe vera extract; algae extract; honey and its derivatives; inositol; lactic acid and lactates (eg ammonium and quaternary alkylammonium); sugar and starch derivatives (eg alkoxylated glucose); DL- Pantenol; magnesium ascorbate phosphate, albutin, kodiic acid, lactamido monoethanolamine; acetamide monoethanolamine and the like, and mixtures thereof, but not limited to these. Wetting agents, C ₃ -C ₆ diols and triols, such as glycerin, propylene glycol, hexylene glycol, hexanetriol, and mixtures thereof can also be mentioned. Ethoxylated methylglucose ethers containing an average of 5 to 30 moles of ethoxylated moiety, such as those available under the INCI names Methylglucose-10 and Methylglucose-20, are preferred. When used, moisturizers typically make up about 1% to about 10% by weight of the total weight of the soap composition of the disclosed technology. In another aspect, this amount can range from about 2% to about 8% by weight of the total weight of the soap composition, and in a further aspect from about 3% to about 5% by weight.

Moisturizer The fatty acid liquid soap composition of the disclosed technology optionally comprises at least one emollient. Moisturizers are defined as substances that regulate the rate and amount of water absorption by the skin (Handbook of Cosmetic Science and Technology, Elsevier Science Publishing, 1993, p. 175). Suitable emollients include mineral oil; vegetable oil; hydrogenated vegetable oils, stearic acid; cetyl alcohol, cetearyl alcohol, myristyl alcohol, behenyl alcohol, and fatty alcohols, cetyl acetate acetylated lanolin alcohol, such as lauryl alcohol, C ₁₂ -C ₁₅ alkyl benzoate, benzoic acid esters such as isostearyl benzoate, dicaprylyl maleate, petrolatum, lanolin, Kokobata, shea butter, beeswax and esters thereof, ethoxy, such as ceteareth-20, oleth -5, and ceteth -5 Alkalined fatty alcohol esters such as chemical fatty alcohol esters, polyethylene glycol 400 propoxydated monolaurates, avocado oil or glyceride, sesame oil or glyceride, Benibana oil or glyceride, sunflower oil or glyceride, and other monos of natural vegetable oils and vegetable oils , And triglycerides such as capric acid triglyceride, capric acid triglyceride, capric acid / capric acid triglyceride, and capric acid / capric acid / laurate triglyceride, Lubrizol Advanced Materials, Inc. Guerbet esters such as G-20, G-36, G-38, and G-66 sold by, vegetable seed oils, volatile silicone oils, non-volatile emollients, and mixtures thereof.

Suitable non-volatile emollients include fatty acids and fatty alcohol esters, highly branched hydrocarbons and the like, and mixtures thereof. Such fatty acid and fatty alcohol esters include decyl oleate, butyl stearate, octyl stearate, myristyl myristate, actyldodecyl stearoyl stearate, octyl hydroxystearate, diisopropyl adipate, isopropyl myristate, isopropyl palmitate. , Echiruekishiru palmitic acid, isodecyl neopentanoate, benzoate _C 12 _{-C 15} alcohol, maleic acid diethyl hexyl, propionic acid PPG-14 butyl ether and PPG-2 myristyl ether, etc. cetearyl octanoate, and mixtures thereof. Suitable highly branched hydrocarbons include isohexadecane and the like, and mixtures thereof.

Suitable volatile emollients include volatile silicones such as cyclic or linear polydimethylsiloxane. The number of silicon atoms in the cyclic silicone can range from about 3 to about 7 in one aspect of the invention and 4 to 5 in another. Both cyclic and linear exemplary volatile silicones are available from Dow Corning Corporation as Dow Corning 344,345, and 200. Linear volatile silicones typically have a viscosity of less than about 5 cP at 25 ° C, while cyclic volatile silicones typically have a viscosity of less than about 10 cP at 25 ° C. By "volatile" is meant that the silicone has a measurable vapor pressure. A description of volatile silicones can be found in Todd and Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, Vol. 91, January 1976, pp. It can be found at 27-32.

Other skin softener silicones include polydimethylsiloxane rubber, aminosilicone, phenylsilicone, polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane rubber, polyphenylmethylsiloxane rubber, amodimethicone, and trimethylsilylamodimethicone. , Diphenyldimethylpolysiloxane rubber and the like.

In the presence of emollients (alone or in combination), based on the total weight of the soap composition, in one aspect from about 1% to about 15% by weight, in another aspect from about 2% to about 10% by weight. %, And in a further aspect, in the range of about 3% to about 5% by weight.

Other Optional Ingredients The fatty acid soap compositions of the present invention can contain a variety of other conventional optional ingredients suitable for making cleansing compositions more desirable. Such optional ingredients are well known to those skilled in the art of formulating soap compositions, which include one or more preservatives, one or more thickeners, and one or more viscosity regulators. Examples include, but are not limited to, one or more skin conditioners, one or more antibacterial agents, one or more fragrances, one or more colorants, and one or more insoluble materials.

Suitable preservatives and antibacterial agents, if present, include polymethoxybicyclic oxazolidine, methylparaben, propylparaben, ethylparaben, butylparaben, salts of benzoic acid and benzoic acid, such as sodium benzoate, benzyltriazole, DMDM hydantin ( (Also known as 1,3-dimethyl-5,5-dimethylhydantoin), imidazolidinyl urea, phenoxyethanol, phenoxyethylparaben, methylisothiazolinone, methylchloroisothiazolinone, benzoisothiazolinone, triclosan, sorbic acid, salicylate Etc., and mixtures thereof. Preservatives typically make up about 0.01% to about 1.5% by weight of the total weight of the personal care compositions of the invention.

Suitable thickeners can be any natural and / or synthetic agent (or combination thereof) for obtaining enhanced thickening properties. One of ordinary skill in the art will readily select suitable thickeners (s) and amounts thereof (s) to obtain the desired rheology. Non-limiting examples of natural thickeners are tree and pectin exudates (Kalaya gum, tragacant gum, Arabic gum, gati gum), seed extracts (guar gum, cassia gum, locust bean gum, tamarind seed), seaweed extracts (carrageenan, alginic acid). Salt, agar), fruit extracts (pectin, wax), grains and roots (corn starch, potato starch, etc.), microbial polysaccharides (xanthan gum, dextran), modified natural products (hydropropyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, cellulose) A cellulose derivative such as gum) and hydrophobically modified ethoxylated methyl glucosides, such as PEG 120 methyl glucose dioleate, PEG-120 methyl glucose trioleate, and PEG-20 methyl glucose sesquistearate (each commercial. The names Glucamate ™ DOE-120, Glucamate ™ LT and VLT, and Glucamate ™ SSE-20 (available from Lubrizol Advanced Materials, Inc.) are also suitable as thickeners. Non-limiting examples of synthetic thickeners include, for example, INCI names PEG-6, PEG-8, PEG-12, PEG-20, PEG-30, PEG-23, PEG-75, PEG-90, PEG. Polyethylene glycol (PEG) having 5 to 200 glycol units, such as those available in -100 and PEG-200; eg, trade names Carbopol® 934, Carbopol 940, Carbopol 941, Carbopol 980, Carbopol. 981, Carbopol 2984, Carbopol 5984, Carbopol ETD 2050, Carbopol Ultrez 10, Carbopol Ultraz 30 (INCI name: Carbomer), etc. Acrylic acid / methacrylic acid homopolymers and copolymers; Carbo Carbopol ETD 2020, Carbopol Ultrez 20, Carbopol Ultrez 21, Pemulen ™ TR-1 and Pemulen TR-2 (INCI name: Acrylate / Alkyl acrylate C _10- C ₃₀ crosspolymer); (LubricaclideA. , Cleverand, OH); acrylamide homopolymers and copolymers; (prepared from 2-acrylamide-2-methylpropanesulfonic acid (AMPS® monomer)).

Another class of synthetic thickeners suitable for use includes hydrophobically modified alkaline swelling emulsion polymers, commonly referred to as (HASE) polymers. Typical HASE polymers are pH sensitive or hydrophilic monomers (eg acrylic acid and / or methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid), hydrophobic monomers (eg acrylic acid and / or methacrylic acid). , C ₁ -C ₃₀ alkyl esters, acrylonitrile styrene), "associative monomer", and a free radical addition polymers polymerized from any crosslinking monomer. The associative monomer comprises an ethylenically unsaturated polymerizable end group, a nonionic hydrophilic intermediate section terminated with a hydrophobic end group. The nonionic hydrophilic intermediate section contains a polyoxyalkylene group, such as polyethylene oxide, polypropylene oxide, or a mixture of polyethylene oxide / polypropylene oxide segments. Terminal hydrophobic end groups are typically C _{8 to} C ₄₀ aliphatic moieties. Exemplary aliphatic moieties are linear and branched alkyl substituents, linear and branched alkenyl substituents, carbocyclic substituents, aryl substituents, aralkyl substituents, arylalkyl substituents, and alkylaryl substituents. Is selected from. In one aspect, the associative monomer contains a polyethoxylated and / or polypropoxylated aliphatic alcohol (typically containing a branched or unbranched C _8- C ₄₀ aliphatic moiety) and a carboxylic acid group (eg, for example. Acrylic acid, methacrylic acid), unsaturated cyclic anhydride monomers (eg maleic anhydride, itaconic anhydride, citraconic anhydride), monoethylenically unsaturated monoisocyanates (eg α, α-dimethyl-m-isopropenylbenzyl) It can be prepared by condensation with an ethylenically unsaturated monomer (eg, vinyl alcohol, allyl alcohol) containing an isocyanate) or a hydroxyl group. Polyethoxylated and / or polypropoxylated fatty alcohols are ethylene oxide and / or propylene oxide adducts of monoalcohols containing C ₈ -C ₄₀ aliphatic moiety. Non-limiting examples of alcohols containing C _{8 to} C ₄₀ aliphatic moieties include capryl alcohol, isooctyl alcohol (2-ethylhexanol), pelargone alcohol (1-nonanol), decyl alcohol, lauryl alcohol, myristyl alcohol. , Cetyl alcohol, cetyl alcohol, cetearyl alcohol (mixture of C _{16 to} C ₁₈ monoalcohol), stearyl alcohol, isostearyl alcohol, ellaidyl alcohol, oleyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, Monta alkenyl alcohol, melissyl, easy ceryl alcohol, gate benzyl alcohol, and _C 2 _{-C 20} alkyl-substituted phenols (e.g., nonylphenol), and the like.

Exemplary HASE polymers are U.S. Pat. Nos. 3,657,175, 4,384,096, 4,464,524, 4,801,671, and 5,292. , 843, which are incorporated herein by reference. In addition, an extensive review of HASE polymers is available from Gregory D. et al. Shay, Chapter 25, "Alkali-Swellable and Alkali-Soluble Thickener Technology A Review", Polymers in Aqueous Media Chemistry, Technology, Technology, Technology, Technology, Technology, Technology, Technology, Technology, Technology. Edward Glass (ed.), ACS, pp. Seen in 457-494, Division Polymeric Materials, Washington, DC (1989), this related disclosure is incorporated herein by reference. Commercially available HASE polymers are available from Rohm & Haas under the trade names Aculyn® 22 (INCI name: Acrylate / Stearless Methacrylate-20 Copolymer), PEG-150 / Decyl Alcohol / SMDI Copolymer), Aculyn® 44 (INCI). Name: PEG-150 / Decyl Alcohol / SMDI Copolymer), Acculin 46® (INCI Name: PEG-150 / Stearyl Alcohol / SMDI Copolymer), and Acculin® 88 (INCI Name: Acrylate / Steareth Methacrylate) -20 cross-polymer), as well as Lubrizol Advanced Materials, Inc. Sold by Novethix ™ L-10 (INCI name: Acrylate / Behenes-25 Copolymer Methacrylate). Other thickeners are commercially available under the INCI label, acryloyl dimethyl taurine ammonium / VP copolymer, acryloyl dimethyl taurine ammonium / carboxyethyl crosspolymer acrylate, and acryloyl dimethyl taurine ammonium / behenes-25 cross polymer methacrylate. There is.

When utilized, the thickener can constitute from about 0.01% to about 5% by weight of the total weight of the personal care composition, and in another aspect, this amount is the amount of the personal care composition. It ranges from about 0.1% to about 3% by weight, and in a further aspect from about 0.1% to about 2.0% by weight.

Viscosity modifiers are used in cosmetics to improve the fluidity of products without significantly reducing the concentration of active ingredients. Suitable viscosity modifiers, if present, include organic and inorganic compounds, and combinations thereof. Examples of organic compounds include ethanol, isopropyl alcohol, sorbitol, propylene glycol, diethylene glycol, triethylene glycol, dimethyl ether, butylene glycol and the like, and mixtures thereof. Examples of inorganic compounds include sodium chloride, sodium sulfate, potassium chloride, potassium nitrate, and mixtures thereof. When utilized, the viscosity modifier is typically, in one aspect, from about 0.1% to about 20% by weight, and from about 1% by weight to the total weight of the fatty acid soap composition of the disclosed technology. Consists of about 5% by weight.

For skin and / or hair conditioning polymers, quaternized guar gum (INCI name guar hydroxypropyltrimonium chloride), quaternized cassia gum (INCI name cassia hydroxypropyltrimonium chloride), eg, Lubrizol Advanced Materials, Inc. Products available under the trade name of Sensor ™ from, quaternium cellulose, polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-22, polyquaternium-39, polyquaternium-52, silicone quaternium-8 (Dimethicone copolyol quaternized with alkylamide dimethylamine), polyquaternium 10, polyquaternium 11, polyquaternium 39, polyquaternium 44 and the like, and mixtures thereof. Such suitable conditioning agents, if present, usually make up about 0.01% to about 3% by weight of the total weight of the compositions of the invention.

Examples of suitable antimicrobial agents that can be used herein are 2-hydroxy-4,2', 4'-trichlorodiphenyl ether (TCS), 2,6-dimethyl-4-hydroxychlorobenzene (PCMX), 3,4. , 4'-Trichlorocarbanilide (TCC), 3-trifluoromethyl-4,4'-dichlorocarbanilide (TFC), 2,2'-dihydroxy-3,3', 5,5', 6, 6'-Hexachlorodiphenylmethane, 2,2'-dihydroxy-3,3', 5,5'-tetrachlorodiphenylmethane, 2,2'-dihydroxy-3,3', dibromo-5,5'-dichlorodiphenylmethane, 2 -Hydroxy 4,4'-dichlorodiphenyl ether, 2-hydroxy-3,5', 4-tribromodiphenyl ether, 1-hydroxy-4-methyl-6- (2,4,5-trimethylpentyl) -2 (1H) −Pyridinone (Octopyrox), salts of 2-pyridinethiol-1-oxides, salicylic acid, and other organic acids include, but are not limited to. Other suitable antibacterial agents are described in US Pat. Nos. 3,835,057, 4,714,653, and 6,488,943. The disclosed soap compositions are from about 0.001% to about 2% by weight in one aspect and from about 0.01% to about 1.5% by weight in another aspect, based on the total weight of the composition. And in a further aspect, about 0.1% to about 1% by weight of antibacterial agent (s) can be included.

Perfume substances that can be used in soap compositions of the disclosed techniques include natural and synthetic fragrances, perfumes, scents, and essences, as well as other substances and mixtures that release fragrances. Natural flavors include those of plant origin, such as flowers (eg lilies, lavenders, roses, jasmine, neroli, ylang ylang), stems and leaves (geranium, pachicholi, petitgrain, peppermint), fruits (aniseed, coriander, fennel). , Nezu), peel (bergamot, lemon, orange, mace), roots angelica, celery, cardamon, costas, iris, shobu), wood (pine, biakdan, fennel, cedar, rosewood, cinnamon), herbs and grass (tarragon) , Lemongrass, sage, thyme), conifers and twigs (tohi, pine, scots pine, stone pine), and oil extracts from resins and balsams (galvanum, elemi, benzoin, millula, flankinsense, opoponax), and animal origin. There are, for example, fennel, civet, castorium, balsam, etc., and mixtures thereof.

Examples of synthetic fragrances and perfumes are aromatic esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons, which include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linaryl acetate, Dimethylbenzylcarvinyl acetate, phenylethylacetate, linarylbenzoate, benzylformate, ethylmethylphenylglycineto, allylcyclohexylpropionate, styralylpropionate, and benzylsalicylate; benzylethyl ether; 8-18 pieces Linear alkanols with carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitroneral, lyrial, and benzene (ionone compounds, α-isomethylionone, and methylsedrill ketones; anetol) , Citronellal, eugenol, isoeugenol, geraniol, labandurol, neoridol, linalol, phenylethyl alcohol, and terpineol, alpha-pinene, terpen (eg, limonene), and balsam, and mixtures thereof.

The amount of perfume material (s) available will depend on the taste of the skilled compounder. In one aspect, the amount of perfume material is from about 0.05% to about 3% by weight, in another aspect from about 0.1% to about 1.5% by weight, based on the weight of the total soap composition. In yet another embodiment it can range from about 0.3% to about 1% by weight, and in yet another aspect it can range from about 0.5% to 0.75% by weight.

Colorants include water-soluble dyes such as copper sulphate, iron sulphate, water-soluble sulfopolyester, rhodamine, natural dyes such as carotene and beetroot juice, methylene blue, caramel, disodium salts of tartrazine, and disodium salts of fucin. , As well as mixtures thereof. The amount of colorant (s) used in the soap composition will depend on the aesthetic taste of the skilled formulator.

Insoluble materials include materials that impart pearly luster and other aesthetic visual, sensory and / or beneficial effects to the soap composition. By deliberately incorporating a pearl luster material to achieve a cosmetically attractive pearly appearance known as pearl luster, some formulations are opaque. A detailed discussion of the effects is incorporated herein by reference in the Hunting literature "Opacifers and peeling agents in shampoos", Cosmetic and Toiletries, Vol. 96, found in pages 65-78 (July 1981).

For pearl luster materials, titanium dioxide-coated mica, iron oxide-coated mica, ethylene glycol monostearate, ethylene glycol distearate, polyethylene glycol distearate, bismuth oxychloride-coated mica, myristyl myristate, guanine, glitter (polyester or glitter). Metallic), and mixtures thereof. Other pearl luster materials can be found in US Pat. No. 4,654,207 and US Pat. No. 5,019,376, which are incorporated herein by reference.

The amount of pearl luster material can generally be used in an amount of about 0.05% to about 10%, preferably about 0.15% to about 3% by weight, based on the total weight of the composition.

In addition to the generally insoluble compounds described above, a number of other substantially insoluble compounds in need of stabilization can be utilized in the composition. Examples of such other insoluble compounds include titanium dioxide; pebble; calcium carbonate, talc, potato starch, tapioca starch, jojoba beads, polyethylene beads, walnut shells, hechima, apricot seeds; almond meal, corn meal, Paraffin, starch bran / starch hull, gelatin beads, alginate beads, stainless steel fibers, iron oxide pigments, bubbles, mica-coated iron oxide, kaolin clay, salicylic acid, zinc oxide, zeolite, foamed styrol beads, phosphates, silica, etc. Be done. Other commonly insoluble compounds include tea tree powder, microsponge, Confetti (trademark of united guardian company), talc, beeswax and the like. The amount of various insoluble compounds that require stabilization will vary depending on their purpose, desired end result, and their effectiveness. Therefore, the amount can vary widely, but will often be in the general range of about 0.1% to about 20% by weight, based on the total weight of the soap composition.

The fatty acid salt soap-based composition according to the disclosed technique is used as a means of transferring the composition to a specific region (s) of the human body, eg, in the hands of the user, on the region of the body to be treated. Can be distributed directly to or on a cloth such as wash cloth, sponge, rufa or taolette. In another aspect of the disclosed technique, the composition may be impregnated with carrier means such as taolets or wipes. If the carrier means is impregnated with the carrier means, the carrier means may not react harmfully with the composition prior to use and may be sealed in a container that helps prevent the composition from being exposed to the environment prior to use. Good.

Fatty acid salt soap compositions formulated according to the techniques of the present disclosure can be applied to different parts of the body for rinse and / or leave-on applications. For example, such compositions can be applied to a part of the body and then dried in place as they may be harmless to the user (eg, leave-on applications such as lotions or creams). In other embodiments, the area to which the composition is applied is wiped or sucked with a towel, which allows the composition to evaporate or otherwise soak into the applied area. To. In a further embodiment, the composition can be applied to an area and then rinsed off after a predetermined time. The application area can be hydrated (pre-wetted) prior to application of the composition. The composition can be applied by cloth, bath sponge (eg, loofah or loofah sponge), hands and the like. In some examples, the composition is subjected to, for example, mechanical action by hand, sponge, etc. over a period ranging from 1 second to 2 minutes, eg, a period ranging from about 15 seconds to about 1 minute. It can be applied by rubbing the composition over the area (using). The mechanical rubbing action helps to create bubbles, loosen and remove debris from the hair and skin, and help the composition penetrate the affected area. The composition can be applied to selected areas suffering from prurigo, including prurigo in winter, as disclosed above, or as a personal care body cleanser during showering or bathing. it can. The personal care cleansing composition can be formulated as a shampoo, body soap, shower gel, facial wash or scrub, hand cleanser, or make-up remover.

The soap wash composition is applied to the affected area of the body and / or scalp (by mechanical rubbing) for more than about 5 seconds (residence time) before being washed away, eg, more than about 20 seconds in one aspect. It is possible to stay on the region for more than about 25 seconds in another aspect, more than 30 seconds in yet another aspect, more than 1 minute in another aspect, and more than about 5 minutes in yet more aspects. .. The recommended dwell time range is about 10 seconds to about 5 minutes in one aspect, about 20 seconds to about 1 minute in another aspect, about 1 minute to about 2 minutes in yet another aspect, or clinical need. Depending on the other time length range. The residence time and residence time range described above may include the amount of time the composition is actively rubbed on the user's skin and the amount of time the composition remains on the patient's skin without being actively rubbed.

In some application examples, the user can apply the composition to a skin area that is particularly larger than the area to be treated (eg, the affected area). For example, the user applies the composition to the skin of the entire limb, specifically including the area to be treated, the skin of substantially the entire body (eg, irrigation of the entire body), or other suitable parts of the body. May be good. Such a broader application of the composition is by prophylactically treating the development of adjacent areas of the skin, in particular the areas of interest (eg, areas or parts of the body that are already suffering from pruritus). The effectiveness of the composition can be enhanced.

The compositions according to the present disclosure can be applied to any part of the body at any suitable frequency. In some examples, the composition may be used relatively rarely, for example once a month, once a week, twice a week. Alternatively, the composition may be applied more frequently, for example, at least twice a week, at least once a day, at least twice a day. In some examples, the user's skin can be hydrated (eg, wetted with water) before applying the soap-based composition.

Example 1
Monomer composition = EA / n-BA / HEMA / BEM (35/15/45/5) weight Emulsion polymer was prepared as follows. Monomer premix with 140 grams of DI water, 5 grams of E-Space® RS-1618 amphoteric crosslinker, 175 grams of (EA), 75 grams of (n-BA), 225 grams of ( HEMA), made by mixing 33.3 grams (BEM). Initiator A was made by mixing 2.86 grams of TBHP in 40 grams of DI water. Initiator A was prepared by dissolving 0.13 grams of erythorbic acid in 5 grams of DI water. Initiator B was prepared by dissolving 2.0 grams of erythorbic acid in 100 grams of DI water. A 3 liter reactor was loaded with 800 grams of DI water, 10 grams of 40% AOS, and 25 grams of Selfol® 502PVA. The contents of the reactor were heated to 70 ° C. under a nitrogen blanket with stirring. After holding the contents of the reactor at 70 ° C. for 1 hour, the initiator A was added to the reactor, followed by the reducing agent A. After about 1 minute, the monomer premix was metered into the reaction vessel over 180 minutes. Approximately 3 minutes after the start of introduction of the monomer premix, the reducing agent B was measured and supplied to the reactor over 210 minutes. The reaction temperature was maintained at 65 ° C. After the supply of the reducing agent B was completed, the temperature of the contents of the reaction vessel was maintained at 65 ° C. for 60 minutes. The contents of the reactor were then cooled to 60 ° C. A solution of 1.79 grams of TBHP and 0.13 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The contents of the reactor were maintained at 60 ° C. After 30 minutes, a solution of 1.79 grams of TBHP and 0.13 grams of 40% AOS in 15 grams of DI water was added to the reactor. After 5 minutes, a solution of 1.05 grams of erythorbic acid in 15 grams of DI water was added to the reactor. The contents of the reactor were maintained at 60 ° C. for about 30 minutes. The reactor was then cooled to room temperature and filtered through a 100 micron filter cloth. The pH of the resulting emulsion was adjusted to 4.5 with ammonium hydroxide. The polymer product had a solid content of 30.4%, a viscosity of 21 cps, and a particle size of 119 nm.

Example 2
Monomer composition = HEMA / n-BA / EA / BEM / AM * (45/25/15/15 / 0.8 *) (% by weight of total monomer) (* AM = based on total weight of monounsaturated monomers 0.8% by weight).
The emulsion polymer was prepared as follows. 200 grams of monomer premix, D.I. I water, 4 grams of E-Space RS-1618 amphipathic crosslinker, 28.41 grams of Glucaate ™ VLT ethoxylated MEG amphipathic additive, 125 grams of n-BA, 225 grams of HEMA , 100 grams of BEM was prepared by mixing. Initiator A was prepared by dissolving 4 grams of azoVA-086 in 40 grams of DI water. Initiator B was prepared by dissolving 0.75 grams of azoVA-086 in 100 grams of DI water. In a 3 liter reactor, 770 grams of D. I. It was filled with water, 6.67 grams of SLS, and then the contents were heated to 90 ° C. under a nitrogen blanket with stirring. Initiator A was then added to the reactor. After 3 minutes, the monomer premix was metered into the reaction vessel over 120 minutes. Approximately 1 minute after the start of supply of the monomer premix, the initiator B was metered into the reactor over 150 minutes. The reaction temperature was then maintained at 87 ° C. After the feed of the initiator B was completed, the temperature of the contents of the reaction vessel was maintained at 85 ° C. for 60 minutes. The reactor was then cooled to 49 ° C. 16.8 grams of D. I. A solution of 0.61 grams of TBHP and 0.38 grams of SLS in water was added to the reactor. After 5 minutes, 16.8 grams of D. I. A solution of 0.59 grams of erythorbic acid in water was added to the reactor. The contents of the reactor were maintained at 49 ° C. After 30 minutes, 16.8 grams of D. I. A solution of 0.64 grams of TBHP and 0.38 grams of SLS in water was added to the reactor. After 5 minutes, 16.8 grams of D. I. A solution of 0.59 grams of erythorbic acid in water was added to the reactor. The contents of the reactor were maintained at 49 ° C. for 30 minutes. The contents of the reactor were then cooled to room temperature (about 22 ° C.) and filtered through a 100 micron mesh cloth. The resulting emulsion had a pH of 3.1, a solid content of 29.1% by weight, a viscosity of 125 mPa · s, and a particle size of 82 nm.

Example 3
A liquid soap composition is prepared using the ingredients in Table 1.

Part A is prepared by dissolving potassium hydroxide in deionized water and heating the composition to 80 ° C. Part B is prepared individually by adding glycerin and a rheology modifier to deionized (DI) water with mixing. Fatty acids (component numbers 3, 4, 5) are added to the glycerin / rheology modifier / water mixture with stirring to raise the temperature to 80 ° C. Once the fatty acids have melted and mixed homogeneously, the other Part B components are added to the composition. Part A is added to Part B while maintaining the temperature at 80 ° C. The part AB composition is mixed for 30-60 minutes. Once a homogeneous mixture is obtained, the Part AB composition is cooled to ambient room temperature. After cooling to 40 ° C., component 9 is added to part AB. Cool the formulation to ambient room temperature with stirring.

Example 4
Liquid soap / surfactant blend compositions are prepared using those listed in Table 2.

Part A is prepared by dissolving potassium hydroxide in deionized water and heating to 80 ° C. The components of Part B are heated with slow mixing until melted and further heated until the temperature reaches 80 ° C. Combine parts A and B while mixing. Part C is added to the combined Part AB composition, maintained at 80 ° C. and mixed until dissolved. The components of parts D and E are added in numerical order with complete mixing while cooling the combined part ABC compositions at ambient room temperature. The viscosity of the liquid soap composition is adjusted by adding 10 g of sodium chloride. The initial pH, viscosity, and yield value of the composition are measured. Following the measurement of viscosity and yield at the initial pH, the pH was continuously raised to a pH of 9.5 with potassium hydroxide (85% solution) followed by the addition of citric acid (25% solution). , The pH is continuously lowered to 8.6. The initial viscosity and yield values, as well as the viscosity and yield values after a continuous increase and decrease in pH of the liquid soap composition are reported in the table below.

Claims (36)

A method for treating or alleviating pruritic skin conditions, said method comprising applying the composition to the scalp and / or the skin, wherein the composition is:
a) Liquid soap containing at least one fatty acid salt,
b) Cross-linked amphipathic non-ionic polymer
i. At least one (meth) acrylic of 35% to about 55% by weight, or about 40% to about 50% by weight, or about 42% to about 48% by weight, or about 44% to about 46% by weight. C _{1 to} C ₅ hydroxyalkyl esters of acids (based on the total weight of monovalent unsaturated monomers) and
ii. At least one (meth) acrylic acid of about 10% to about 50% by weight, or about 10% to about 40% by weight, or about 12% to about 35% by weight, or about 15 to about 25% by weight. C _{1 to} C ₅ alkyl esters and
iii. About 0.1% to about 20% by weight, or about 0.5% to about 18% by weight, or about 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight , 7% by weight, 8% by weight, 9% by weight or 10% by weight to about 15% by weight of associative monomers (i, ii, and weight percent of all monomers under iii are the monovalent unsaturated monomers. Based on the total weight of)
iv. At least one polyunsaturated of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 to about 5 parts by weight A cross-linked amphipathic nonionic polymer prepared from a monomer mixture containing a saturated cross-linking agent monomer (based on 100 parts by weight of the monounsaturated monomer).
c) With water
d) A method comprising, if necessary, at least one surfactant other than a). The at least one fatty acid salt is from about 10 to about 35% by weight in one embodiment, from about 12 to about 30% by weight in another embodiment, from about 15 to about 25% by weight in a further aspect, and from about 18 to about 18% in yet further embodiments. The method of claim 1, which is present in an amount in the range of about 20% by weight (based on the total weight of the composition). The polymer (by activity criteria) is about 0.5 to about 5% by weight, or about 0.6 to about 4% by weight, or about 1 to 3% by weight, or about 1.5 to about 2% by weight. The method of any one of the preceding claims, which is present in a range of amounts (based on the total weight of the composition). The at least one surfactant (by activity criteria) is about 0 to about 15% by weight, or about 1 to about 12% by weight, or about 2.5 to about 10% by weight, or even about 5 in a further embodiment. The method according to any one of the preceding claims, which is present in an amount in the range of ~ about 8% by weight (based on the total weight of the composition). The pH of the at least one composition is from about 7.5 to about 10.5 in one embodiment, from about 7.8 to about 9.8 in another embodiment, from about 8 to about 9.5 in a further aspect, and even more so. The method according to any one of the preceding claims, which is in the range of about 8.2 to about 9.2. The method according to any one of the preceding claims, wherein the salt of at least one fatty acid is selected from alkali metal salts and / or ethanolamine salts of C _{8 to} C ₂₂ fatty acids. The method according to any one of the preceding claims, wherein the fatty acid is derived from a vegetable oil, a seed oil, and a mixture thereof. A fatty acid in which the fatty acid salt is selected from octanoic acid, decanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid, nonadecanic acid, arachidic acid, behenic acid, and mixtures thereof. The method according to any one of the preceding claims, which is derived from. The method according to any one of the preceding claims, wherein the fatty acid salt is an alkali metal salt or an alkanolammonium salt of the fatty acid. The method according to any one of the preceding claims, wherein at least the surfactant is selected from an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a mixture thereof. The anionic surfactant is alkyl sulfate, alkyl ether sulfate, alkyl monoglyceryl ether sulfate, alkyl sulfonate, alkyl aryl sulfonate, alkyl sulfosuccinate, alkyl ether sulfosuccinate, alkyl sulfosuccinate. , Alkylamide sulfosuccinate, alkylcarboxylate, alkylamide ether carboxylate, alkylsuccinate, N-acylamino acid, alkylphosphate, or any of the preceding claims selected from a combination thereof. The method described in paragraph 1. The method of any one of the preceding claims, wherein the amphoteric surfactant is selected from alkyl betaine, alkyl amino betaine, and alkyl amide betaine, as well as the corresponding sulfo betaine. The method according to any one of the preceding claims, wherein the at least one surfactant is selected from a combination of an anionic surfactant and an amphoteric surfactant. The at least one surfactant is selected from a combination of an anionic surfactant and an amphoteric surfactant, and the weight ratio of the anionic surfactant to the amphoteric surfactant is about 1: 1 to about 10: 1. The method according to any one of the preceding claims, which is within the scope of. The composition is from moisturizers, emollients, hair conditioners, skin conditioners, air fresheners, antibacterial agents, preservatives, colorants, plant extracts, chelating agents, pH regulators, thickeners, and combinations thereof. The method of any one of the preceding claims, further comprising a component of choice. The composition
a) With at least one salt of about 10 to about 20% by weight of C _{12 to} C ₂₂ fatty acids,
b) A crosslinked nonionic amphipathic emulsion polymer of about 0.5 to about 5% by weight.
i. With about 45% by weight 2-hydroxyethyl methacrylate,
ii. With about 20.5% by weight ethyl acrylate,
iii. With about 27.5% by weight butyl acrylate,
iv. With about 7% by weight behenyl ethoxylated methacrylate (based on 100 parts by weight of the monounsaturated monomer used in the preparation of the polymer),
v. Includes about 0.1 to about 1 part by weight of at least one polyvalent unsaturated amphipathic crosslinker monomer (based on 100 parts by weight of the monovalent unsaturated monomer used to prepare the polymer). A crosslinked nonionic amphipathic emulsion polymer prepared from a monomer mixture and
c) With water
d) The method according to any one of the preceding claims, which optionally comprises at least one surfactant other than a). The composition
a) With at least one salt of about 10 to about 20% by weight of C _{12 to} C ₂₂ fatty acids,
b) A crosslinked nonionic amphipathic emulsion polymer of about 0.5 to about 5% by weight.
i. With about 45% by weight 2-hydroxyethyl methacrylate,
ii. With about 15% by weight ethyl acrylate,
iii. With about 25% by weight butyl acrylate,
iv. With about 15% by weight behenyl ethoxylated methacrylate (based on 100 parts by weight of the monounsaturated monomer used in the preparation of the polymer),
v. Contains from about 0.5 to about 2 parts by weight of at least one polyvalent unsaturated amphipathic crosslinker monomer (based on 100 parts by weight of the monovalent unsaturated monomer utilized to prepare the polymer). A crosslinked nonionic amphipathic emulsion polymer prepared from a monomer mixture and
c) With water
d) The method according to any one of claims 1 to 15, comprising at least one surfactant other than a), if necessary. The at least one polyunsaturated amphipathic crosslinker monomer has a structure:
In the formula, R ²¹ is C _{10 to 24} alkyl, alkanol, alkenyl, or cycloalkyl, R ²⁰ = CH ₃ , CH ₂ CH ₃ , C ₆ H ₅ , or C ₁₄ H ₂₉ . x is 2-10, y is 0-200, Z is 4-200, in another embodiment it is about 5-60, in a further embodiment it is about 5-40, and R ²² is H. Or Z ⁻ M ⁺ , where Z can be either SO ₃ ⁻ or PO ₃ ^2- , and M ⁺ can be Na ⁺ , K ⁺ , NH ₄ ⁺ , or, for example, monoethanolamine, The method according to any one of the preceding claims, which is an alkanolamine such as diethanolamine and triethanolamine. The at least one polyunsaturated amphipathic crosslinker monomer has a structure:
In the formula, n is 1 or 2, z is 4 to 40, or 5 to 38, or 10 to 20, and R ²² is H, SO ₃ ⁻ M ⁺ or PO ₃ ^{−. 2} M ⁺ , wherein M is selected from Na, K, and NH _{4, according} to any one of the preceding claims. The at least one polyunsaturated amphipathic crosslinker monomer has a structure:
The method according to any one of the preceding claims, represented by. The preceding claim, wherein the monomer mixture further comprises polyvinyl acetate, poly (vinyl alcohol), partially hydrolyzed poly (vinyl alcohol), and a protective colloid selected from a mixture thereof. Method. The monomer mixture has the formula:
Further comprising an amphipathic additive selected from the polyethoxylated alkyl glucoside esters represented by, in the formula, R ²³ is selected independently of H and saturated and unsaturated C _10- C ₂₂ acyl groups. R ²⁴ is selected from the C _{1 to} C ₁₀ alkyl groups and the sum of w + x + y + z ranges from about 60 to about 150, or about 80 to about 135, or about 90 to about 125, or about 100 to about 120. However, the method according to any one of the preceding claims, subject to the condition that two or less of R ²³ can be H at the same time. The method according to any one of the preceding claims, wherein the fatty acid salt is derived from a fatty acid selected from lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, or a combination thereof. The method according to any one of the preceding claims, wherein the fatty acid salt is derived from a mixture of fatty acids selected from lauric acid, myristic acid, and palmitic acid. The method according to any one of the preceding claims, wherein the fatty acid salt is derived from a mixture of fatty acids selected from lauric acid, myristic acid, and stearic acid. The method according to any one of the preceding claims, wherein the fatty acid salt is derived from a mixture of fatty acids selected from lauric acid, myristic acid, and isostearic acid. The method according to any one of the preceding claims, wherein the fatty acid salt is an alkali metal salt or an alkanolammonium salt of the fatty acid. The composition is about 7.5 to about 10.5 in one embodiment, about 7.8 to about 9.8 in another aspect, about 8 to about 9.5 in a further aspect, and about 8 in a further aspect. .. The method of any one of the preceding claims, having a pH in the range of 2 to about 9.2. The method according to any one of the preceding claims, wherein the ratio of anionic surfactant to amphoteric surfactant is in the range of about 1: 1 to about 10: 1. The preceding claim, wherein the anionic surfactant is from an alkyl ether sulphate containing approximately 1-3 mol of an ethoxylated moiety and the amphoteric surfactant is selected from alkylamide betaines. The method according to any one item. The method of any one of the preceding claims, comprising hydrating the scalp and / or skin prior to the application. The method of any one of the preceding claims, comprising rubbing the at least one composition to create foam after application to the scalp and / or skin. It is possible to allow the at least one composition to remain on the scalp and / or skin for a time of more than about 20 seconds in one embodiment, more than about 25 seconds in another aspect, and more than about 30 seconds in a further aspect. The method of any one of the preceding claims, including. The method of any one of the preceding claims, comprising rinsing the scalp and / or skin after the application. The method of any one of the preceding claims, wherein the pruritic skin sensation is caused by long-term exposure to a low relative humidity environment. The method according to any one of the preceding claims, wherein the prurigo cutaneous sensation is caused by winter prurigo irritation.