KR20010013109A - Hairspray compositions containing silicone block copolymers - Google Patents

Abstract

.The present invention relates to hairspray compositions comprising from about 50 % to about 99.9 % by weight of an alcohol solvent, and from about 0.1 % to about 30 % by weight of a silicone-containing adhesive block copolymer having a weight average molecular weight from about 10, 000 grams/mole to about 10,000,000 grams/mole and which is formed from the free radical polymerization of an ethylenically unsaturated monomer with select silicone macroinitiators, preferably silicone macroazoinitiators. The hairspray compositions, when dried, preferably have a cohesive strength of greater than about 0.5 kgf/mm 2, a total energy absorption per unit volume of greater than about 0. 55 kgfmm/mm3, an impact strength of greater than about 7000 ergs, and an improved removeability from hair as defined by a hair stiffness value of from 0 to about 3.5 (0 to 4 scale) and a hair flaking value of from 0 to about 3.5 (0 to 4 scale). These hairspray compositions provide improved hair styling performance, and in particular provide improved maintenance or hold when applied to dry hair and causes minimal or no drooping of the hair during or immediately after application.

Description

Hairspray composition containing silicone block copolymer {HAIRSPRAY COMPOSITIONS CONTAINING SILICONE BLOCK COPOLYMERS}

The present invention is directed to a hairspray composition that provides improved hair style retention properties and hair feel. The compositions are typically applied to wet or dry hair, depending on the formulation, and to produce or adhere a thin hair styling film to the applied surface.

Hair styling compositions are typically formulated as a hairspray for applying to dry, fix or style the hair to hold or fix the position of the dried, styled hair in that position. The hairspray is typically applied to the hair as a pump spray or from a compressed air spray can. The composition provides a temporary fixative effect on dry and styled hair and can typically be removed by water or shampoo. Hair styling materials used in hairspray compositions are generally in the form of resins, gums and adhesive compositions.

However, many hairsprays tend to deposit hair styling material on the hair after the material is applied to the hair and dry, causing the hair to become excessively hard or excessively sticky. Excessively hard hairsprays are brittle, break under normal stress, such as wind, brushing, and combing, often with unnatural feeling or appearance. On the contrary, excessively sticky hairsprays become more flexible under stress and not easily brittle, but they are heavy, coated and have a slick appearance, such as slackness of the hair and wants hair. It is not easy to keep or fix it. This excessively sticky hairspray also causes hair to be rapidly contaminated from dust, dirt, lint, sebum and other common contaminants that more easily stick to the sticky hairspray.

Some hairsprays can be applied to clean, dry hair and are formulated to not be excessively hard or sticky after application. However, many of these hairsprays still cause excessive hair swelling immediately after application to dry, styled or immobilized hair. The applied hairspray is then solidified on the hair and then squeaks or otherwise makes the hair more ragged due to the initial application of the hairspray.

The hairspray compositions of the present invention are now particularly suitable for providing hair styling performance when applied to dry, stylized or immobilized hair, without being excessively hard or sticky and immediately without excessive hum after application to the hair. I found it effective. The hairspray composition comprises selecting a silicone-containing adhesive copolymer mixed with an alcohol solvent, wherein the composition contains at least 50% by weight of the alcohol solvent. The hairspray composition preferably has a cohesive strength of greater than about 0.5 kgf / mm ² , a total energy absorption per unit volume of greater than about 0.55 kgfmm / mm ^3, and an impact strength of greater than about 7000 ergs.

Also preferably the hairspray composition of the present invention has improved removal from the hair during shampooing and the removal ability is defined as the strength of the hair and the number of hair flakes in the range of 0 to about 3.5 (0 to 4 scale). The toughness and flake resin of the hair is an indirect measure of hair spray removal ability. Each of these values is measured according to the methodology defined herein.

It is therefore an object of the present invention to provide a hairspray composition that is not excessively sticky or stiff after application and further minimizes or eliminates the tingling of dry, styled or immobilized hair after application, and further herein It is to provide a hairspray composition with improved removal as defined. It is another object of the present invention to provide a composition comprising a select silicone-containing block polymer mixed with a high concentration of alcohol solvent and further to feel dry hair immediately after application without excessively damping and excessively hard or sticky hair. To provide a dry, styling or fixed hair styling method.

Summary of the Invention

The present invention is about 0.1 to about 30% by weight of a silicone-containing adhesive block polymer having an alcohol solvent of about 50 to about 99.9% by weight, a weight average molecular weight of about 10,000 g / mol to about 10,000,000 g / mol, which is a silicone macroinitiator And ethylenically unsaturated monomers are produced from free radical polymerization with the silicone macroinitiator comprising a chemical group selected from the group consisting of:

Wherein each R is independently selected from the group consisting of C ₁ -C ₁₀ alkyl, phenyl, C ₁ -C ₁₀ alkyl-substituted phenyl, and mixtures thereof; X is a divalent radical; Y is -N = N- , -OO-, and mixtures thereof, m, n, and p are each independently a positive integer having a value of 1 or more); Silicone macroinitiators have a number average molecular weight of about 500 g / mol to about 500,000 g / mol; When dried, the hairspray composition preferably has a cohesive strength of greater than about 0.5 kgf / mm ² , a total energy absorption per unit volume of greater than about 0.55 kgfmm / mm ^3, and an impact strength of greater than about 7000 ergs. The hairspray composition preferably has an improved removal ability, which is defined by the hair flake resin of 0 to 3.5 (0 to 4 scales) and the hardness level of the hair of 0 to about 3.5.

It has been found that the hairspray compositions are particularly effective at providing hair styling performance when applied to dry, styled or immobilized hair. In particular, after the spray composition is dried on the hair, it is not excessively hard or sticky, and immediately after the application of the hairspray composition and before the applied composition is solidified and solidified to the hair, the hair is immediately excessively dried, styled or immobilized. It can be applied to dry, styled or immobilized hair without slack.

1 shows a dumbbell-shaped flat dry hairspray membrane specimen useful for measuring physical properties such as cohesive strength and total energy absorption per unit volume, as described herein.

FIG. 2 shows the thickness of the dumbbell-shaped flat dry film described in FIG. 1.

Detailed description of the invention

The hairspray composition of the present invention comprises a selective silicone-containing adhesive block copolymer mixed with an alcohol solvent. Each of the above essential ingredients of preferred or meaning is described in detail below.

All percentages, parts and ratios are by weight unless otherwise specified. All of the above weights belonging to the listed ingredients are based on activity levels and, therefore, do not include solvents or by-products which may be included in commercial materials unless otherwise specified.

All molecular weights as used herein are weight average molecular weights expressed as g / mol, unless specifically specified.

As used herein, the term "suitable for application to human hair" means that its components or compositions described above are suitable for use in contact with human hair and scalp and skin without inappropriate toxicity, immiscibility, instability, allergic reactions, etc. it means.

The term "adhesive" as used herein, when applied as a solution or dispersion to a surface and when dried, such as hair fibers, block copolymers, is used in the hairspray composition of the present invention to form a film or adhesion on the applied surface. It relates to a containing block copolymer. The membrane or adhesive will have cohesive strength and cohesive strength, as is well known in the art.

As used herein, the term “kgf” is a unit of measurement characterized as a kilogram of force exerted on gravity acceleration, such as 9.82 m / s ² .

The hairspray composition of the present invention comprises or constitutes an essential element of the invention described herein, likewise any additional or optional ingredients, or other limitations described herein.

Alcohol solvent

The hairspray composition of the present invention comprises an alcohol solvent which dissolves or disperses the silicone-containing block copolymer described in detail below. The concentration of the alcohol solvent ranges from about 50% to about 90%, preferably from about 50% to about 90%, more preferably from about 55% to about 80% by weight of the hairspray composition.

Suitable alcohol solvents for use in the hairspray compositions of the invention are preferably ethanol, n-propanol, isopropanol and mixtures, wherein the selected silicone-containing sticky block polymer is at least about 0.1 mg / mL, preferably about 0.5 mg / soluble in an alcohol solvent selected at about 22.7 ° C., at a concentration of at least mL, and more preferably at a concentration of about 1 mg / mL.

The hairspray composition may further comprise other additional solvents including water, provided that the silicone-containing block copolymer is dissolved or otherwise dispersed in the hairspray composition, and the additional solvent is chemically and physically present in the composition. Is miscible with the components of and does not bias product performance substantially and excessively. The hairspray composition further comprises up to about 45% by weight of water, preferably less than about 40% by weight of water.

Alcohol solvents at the concentrations described above are particularly effective when used in admixture with select silicone-containing adhesive block polymers, particularly when providing improved hair styling performance to the hairspray compositions of the present invention. Mixtures of the optional polymers and alcohol solvents are more effective in minimizing or eliminating unwanted looseness of hair that is immediately dried, styled or immobilized after application to the hair.

Adhesive block copolymer

The hairspray composition of the present invention comprises a select silicone-containing block copolymer as defined herein, which gives the composition improved hair styling performance and is dispersed or dissolved in the alcoholic solvent of the hairspray composition. The concentration of the block copolymer in the hairspray composition ranges from about 0.1% to about 30%, preferably from about 0.5% to about 20% and more preferably from about 0.5% to about 10% of the weight of the composition.

Silicone-containing adhesive block copolymers selected for use in the hairspray compositions of the present invention are prepared by free radical polymerization of select silicones and ethylenically unsaturated monomers containing macroinitiators (described in detail below). The resulting block copolymer comprises sequentially arranged portions or blocks composed of smaller repeat units. The silicone-containing sticky block copolymer contains a silicone-containing block derived from a silicone-containing macroinitiator (hereinafter block A) and another block derived from ethylenically unsaturated monomers (hereafter block B) as defined herein. The block copolymer comprises two block segments; ABA block structure containing three block segments,-(AB) _n -block structure containing multiple blocks, where n is an integer of 2 or more, or a mixture thereof.

The hairspray composition of the present invention comprises any of the block structures described above, comprises mixtures or combinations thereof, and also contains small amounts of derivatives thereof derived from the ethylenically unsaturated monomers described herein or combinations thereof with small amounts of unsaturated monomers. Homopolymers or silicone-containing macroinitiators described herein.

The silicone-containing adhesive block copolymers herein can be from about 10,000 g / mol to about 10,000,000 g / mol, preferably from about 20,000 g / mol to about 1,000,000 g / mol, more preferably from about 30,000 g / mol to about 1,000,000 g / Mol, even more preferably from about 60,000 g / mol to about 750,000 g / mol, and most preferably from about 70,000 g / mol to about 70,000 g / mol.

Silicone-containing adhesive block copolymers for use in the hairspray compositions herein have been prepared by free radical polymerization of ethylenically unsaturated monomers and the silicone-containing macroinitiators described herein. Polymerization reactions of this type are generally known in the polymer art and some are described in M. Mishra, Macromolecular Design: Concept and Practice, Polymer Frontiers International, Inc., p. 313-358 (1994); European Patent Application 766957A1, published April 9, 1997; and Odian, Principles of Polymerization, 3rd edition, John Wiley & Sons, p. 198-334 (1991), the entirety of which is incorporated herein by reference.

The free radical polymerization reactions cited herein can be achieved, for example, by incorporating an ethylenically unsaturated monomer and a polysiloxane macroinitiator in the reactor in an amount sufficient to ensure that the reaction is appropriate when the reaction viscosity is complete. Undesired terminators, especially oxygen, are removed as needed. This is done by venting or purifying as an inert base such as argon or nitrogen. Alternatively, redox or redox reactions or radiation initiators can be used. The polymerization proceeds for a period of time to achieve high levels of conversion, typically several hours to several days. The solvent is then removed by evaporation or precipitation of the copolymer by adding a nonsolvent. The resulting block copolymer is further clarified as desired and used in the formulation of the hairspray composition of the present invention by formulation techniques known in the art.

Silicone-containing adhesive block copolymers as used herein can also be prepared by semi-continuous or continuous methods. In a semi-continuous process, two or more monomers or macromonomers are prepared during the polymerization reaction. It is free when the copolymer is prepared from several monomers that react during polymerization at different rates. The proportion of monomers added to the reaction at separate addition points can be adjusted by one of the methods known in the art such that the polymer of the final product has a more uniform structure. In other words, the polymer of the final product may have a more uniform monomer content distribution for each monomer form charged to the reaction.

Examples of silicone-containing sticky block copolymers and methods for their preparation are described in Grag et al. 1996.6.4. US Patent No. 5,523,365 to US Pat. Crivelo on August 25, 1987. US Patent No. 4,689,289, licensed to US Pat. At Cribelo 1986.4.22. US Patent No. 4,584,356 to US Pat. Macromolecular Design, Concept & Practice, Ed: M.K.Mishra, Polymer Frontiers International, Inc., Hopewell Jct., NY (1994); and Block copolymers, A. Noshay and J.E. McGrath, Academic Press, NY (1977), the disclosure of which is incorporated herein.

Silicon-containing macroinitiators

The silicone-containing sticky block copolymers of the hairspray composition herein may be present in a weight of silicone-containing block from about 2% to about 50%, preferably from about 5% to about 40%, and more preferably from about 10% to about 30%, wherein the silicon-containing block is derived from the select silicon-containing macroinitiator described herein.

Silicone-containing macroinitiators for use in the hairspray compositions of the present invention are selected from the group consisting of the following formulas or combinations thereof:

Wherein R is independently selected from the group consisting of C ₁ -C ₁₀ alkyl, phenyl, C ₁ -C ₁₀ alkyl-substituted phenyl, and mixtures thereof, preferably a methyl group; each X is any given silicone- Divalent linking groups, which may be the same as or different from the containing macroa initiator, include: acyl, alkyl, aryl, amide, alkene, alkyne, ether, ester, sulfone, sulfoxide, thioether, halogen, nitrile and their Combinations, preferably amides or ester groups for each synthesis). Other divalent linking groups may also use the free radical polymerization reactions described herein, with substantially no bias.

In the macroinitiator formula described above, each Y is independently selected from the group consisting of chemical moieties represented by the formula -N = N-, -O = O-, or a combination thereof; The m, n, and p values are each independently a positive integer having a value of greater than 1, preferably m and p independently go from about 14 to about 700, while n is of the silicone-containing adhesive block copolymer There is no upper limit except that the applicability to practical reasons for the polymerization reaction (viscosity, processing, solvent miscibility, etc.) is not limited as much as possible, but is preferably about 1 to about 10.

The number average molecular weight of the silicon-containing macroinitiator is about 500 g / mol to about 500,000 g / mol, preferably about 2000 g / mol to about 250,000 g / mol, more preferably about 5,000 g / mol to about 100,000 g / Mole.

Preferably it is a silicon-containing macroinitiator (wherein Y is a silicon-containing macroinitiator corresponding to an azo group, even more preferably:

Wherein x has a value from about 50 to about 150, and n is an integer having a value from about 4 to about 12, more preferably from 6 to about 9. Most preferably it is a macroazo initiator represented by the above formula (where x is an integer having a value of about 135 or 67 and n is an integer having a value of about 6 to about 9).

The silicon-containing block (Block A) of the block copolymer herein preferably contains at least about 10 repeating monomer units, more preferably at least about 40 monomer units, even more preferably at least about 60 monomer units; Each repeating monomer unit is derived from the optional silicon-containing macro initiators described herein, and the number average molecular weight of each silicon-containing block is preferably from about 500 g / mol to about 60,000 g / mol, more preferably about 1,000 g / Mol to about 25,000 g / mol, even more preferably from about 2,000 g / mol to about 15,000 g / mol.

Ethylenically unsaturated monomers

The silicone-containing sticky block copolymer of the hairspray composition is about 50% to about 98%, preferably about 60% to about 95%, and even more preferably about 70% by weight of the copolymerizable ethylenically unsaturated monomer. To about 90%.

The block (block B) of the silicone-containing sticky block copolymer is derived from ethylenically unsaturated monomers, and the block B is at least about −20 ° C., more preferably at least about −5 ° C., and also preferably below about 60 ° C. , More preferably less than about 50 ° C., and even more preferably less than about 40 ° C. (free transition temperature (Tg value)).

Ethylenically unsaturated monomers are copolymerizable with silicon-containing macroinitiators and contain one or more polymerizable carbon-carbon double bonds, which may be mono, di-, tri- or tetra-substituted. Preferred are vinyl monomers. A single form of an ethylenically unsaturated monomer or a combination of two or more ethylenically unsaturated monomers is selected to perform or meet the needs of the silicone-containing adhesive block copolymers described herein, and to perform hair styling or conditioning, selected silicone- Alcohol solvents selected from the above-described ranges, such as containing macromolecule initiators, and solubility in free transition temperature.

The ethylenically unsaturated monomers for use in preparing the silicone-containing sticky block copolymers may be hydrophilic or hydrophobic, water soluble or insoluble. The ethylenically unsaturated monomers are, however, preferably hydrophilic monomers, or combinations of hydrophilic and hydrophobic monomers, when the resulting block copolymer in the hairspray composition has essentially solubility and other properties as defined herein. The term "hydrophilic monomer" as used herein refers to a monomer that forms a water soluble homopolymer, while the term "hydrophobic monomer" as used herein refers to a monomer that forms a water-insoluble polymer. In this paragraph, the term "water-soluble" polymer is preferably used in water, ethanol, n-propanol, isopropanol, or at a concentration of at least about 0.5 mg / ml, even more preferably at least about 1 mg / mol, at 22.7 It is meant to be soluble in its formulation.

When copolymerized into repeat units or blocks (block B) in the silicone-containing sticky block copolymers herein, the ethylenically unsaturated monomer is preferably at least about 10 repeat monomers, more preferably at least about 20 repeat monomers, even more preferably. It contains at least about 50 repeat monomer units.

Non-limiting classifications of ethylenically unsaturated monomers useful herein include unsaturated alcohols, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated anhydrides, alcohol esters of unsaturated monocarboxylic acids, alcohol esters of unsaturated dicarboxylic acids, unsaturated anhydrides Alcohol esters, alkoxylated esters of unsaturated monocarboxylic acids, alkoxylated esters of unsaturated dicarboxylic acids, alkoxylated esters of unsaturated anhydrides, aminoalkyl esters of unsaturated monocarboxylic acids, aminoalkyl esters of unsaturated dicarboxylic acids , Aminoalkyl esters of unsaturated anhydrides, amides of unsaturated monocarboxylic acids, amides of unsaturated dicarboxylic acids, amides of unsaturated anhydrides, salts of monocarboxylic acids, salts of unsaturated dicarboxylic acids, salts of unsaturated anhydrides, unsaturated Hydrocarbons, unsaturated heterocycles, and combinations thereof.

Some examples of non-limiting, suitable ethylenically unsaturated monomers are acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, methacrylate, Nt-butyl Acrylamide, maleic acid, maleic anhydride and its half esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl pyrrolidone, (with methyl vinyl ether Vinyl ether, vinyl pyridine, vinyl imidazole, other polar vinyl heterocycles, styrene sulfonate, allyl alcohol, vinyl alcohol (such as produced by hydrolysis of vinyl acetate after polymerization), vinyl caprolactam, C ₁ -C ₁₈ alcohols, such as methanol, ethanol, methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentane Ol, 3-methyl-1-pentanol, t-butanol (2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2- Octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol Alcohols such as 1-dodecanol, 1-hexadecanol, 1-octadecanol, and preferably about 1 to about 12 carbon atoms; Dicyclopentenyl acrylate, 4-bisphenyl acrylate; Pentachlorophenyl acrylate; 3,5-dimethyladamantyl acrylate; 3, 5- dimethyl adamantyl methacrylate; 4-methoxycarbonylphenyl methacrylate; Trimethylsilyl methacrylate; Styrene; Alkyl substituted styrenes including alpha-methylstyrene and t-butylstyrene; Vinyl esters including vinyl acetate, vinyl neononanoate, vinyl pivalate and propionate; Vinyl chloride; Vinylidene chloride; Vinyl toluene; Alkyl vinyl ethers including isobutyl vinyl ether and s-butyl vinyl ether; Butadiene; Cyclohexadiene; Bicycloheptadiene; 2,3-dicarboxymethyl-1,6-hexadiene; Ethylene; Propylene; Indene; Norbornylene; β-pinene; α-pinene; Salts of the acids and amines listed above, and combinations thereof. The quaternized monomer was quaternized before or after the free radical copolymerization reaction with the macro initiator described below.

Preferred ethylenically unsaturated monomers are acrylic acid, methacrylic acid, N, N-dimethyl acrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, acrylic acid of C ₁ -C ₁₈ alcohol or Methacrylic acid esters, styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, n-butyl methacrylate, isobutyl Methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, any of the acids and amines listed above, and combinations thereof.

Neutralized block copolymer

Silicone-containing sticky block copolymers may include acidic functionality such as carboxyl groups and are typically used in at least partially neutralized form to promote solubility or dispersibility of the block copolymer in alcohol solvents as defined herein. In addition, the neutralized form is used to aid in hair styling spray compositions to be removed from the hair by shampoos. The content of neutralization is about 10% to 100%, more preferably about 20% to about 90%, even more preferably about 40% to about 85% as the neutralization of the acidic functionality of the silicone-containing adhesive block copolymer. Range.

Neutralization of the silicone-containing sticky block copolymers containing acidic functionality can be accomplished by conventional or known techniques for carrying out such neutralization using organic or inorganic base materials. Metallic bases are partially free for this purpose. Suitable base neutralizers include, but are not limited to, ammonium hydroxide, alkali metal hydroxides, or alkaline earth metal hydroxides, preferably potassium hydroxide and sodium hydroxide. Examples of other suitable neutralizing agents include, but are not limited to, amines or amino alcohols such as 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol ( AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB), monoisoprotanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA) , Monoisopropanolamine (MIPA), diisopropanolamine (DIPA), triisopropanolamine (TIPA) and dimethyl stearamine (DMS) and combinations thereof. Preferably amines and metallic bases.

Silicone-containing sticky block copolymers containing basic functionalities such as amino groups are preferably at least partially neutralized as organic or inorganic acids such as hydrogen chloride. Neutralization is achieved by conventional or otherwise known techniques to achieve this neutralization. The preferred content of neutralization is the same as described for neutralizing acidic functionality.

The solubility of the selected silicone-containing sticky block copolymer must be measured after the desired acid or base neutralization, if the selected copolymer contains acidic or basic functionality.

Preferred Silicone-containing Adhesive Block Copolymers

Non-limiting examples of preferred silicone-containing sticky block copolymers include, but are not limited to, the following block copolymers derived from the macro azo initiators identified by the following formulas.

[Poly (dimethyl siloxane) -block-poly (t-butyl acrylate-co-n-butyl acrylate-co-acrylic acid-co-methacrylic acid)] _n

t-butyl acrylate: 40%; n-butyl acrylate: 28%; Acrylic acid: 12%; Methacrylic acid: 10%;

Silicone macro azo initiators (formulations described above, x = 135, n is about 6 to about 9) 10%;

Molecular weight of silicon block: 10,000 g / mol

Polymer molecular weight: 114,000 g / mol.

[Poly (dimethyl siloxane) -block-poly (t-butyl acrylate-co-acrylic acid)] _n

t-butyl acrylate: 40%; n-butyl acrylate: 24%; Acrylic acid: 21%;

Silicone macro azo initiators (formulations described above, x = 135, n is about 6 to about 9) 15%;

Molecular weight of silicon block: 10,000 g / mol

Polymer molecular weight: 86,000 g / mol.

[Poly (dimethylsiloxane) -block-poly (t-butyl acrylate-co-ethyl acrylate-co-acrylic acid)] _n

t-butyl acrylate: 32%; Ethyl acrylate: 33%; Acrylic acid: 20%;

Silicone macro azo initiators (formulations described above, x = 67, n is about 6 to about 9) 15%;

Molecular weight of silicone block: 110,600 g / mol

Polymer molecular weight: 5,000 g / mol.

Preferred silicone-containing macrozo initiators described above are commercially available as VP1001 and VPS 0501 (poly (dimethylsiloxane) initiators) from Wako Chemical USA, Richmond, VA, USA.

Properties of Dried Hairspray Composition

Upon drying, the hairspray composition of the present invention preferably has certain physical properties such as defined by cohesive strength (defined in terms of hair hardness and flake number), total energy absorption per unit of area, impact strength and improved removal ability. Have Each of these preferred physical properties is described in detail below.

Cohesive Strength (kgf / mm ² )

Aggregation is the strength of bonds formed in a specimen, such as dried hairspray compositions. (kg of force per mm ² ) The cohesive strength, expressed as kgf / mm ² , is the maximum unit stress that resists when the material deforms upon stretching. Stress is the ratio of the measured load (kg X f) to the original cross-sectional area (mm ² ) of the specimen.

The cohesive strength of the dried hairspray composition of the present invention is measured according to the following method. The method is based on ASTM guidelines: D 638-91, Stnadard Test Method for Tensile Properties of Plastics, Published January 1992, the entirety of which is incorporated herein. The following method for measuring the cohesive strength is similar to the ASTM standard, but is better for indicating the tensile properties of some modified and dried hairspray membranes. The measurement was made at about 22.7 ° C. and about 50% relative humidity. The test method described herein uses a modified dumbbell form, specifically about 0.4 mm thick, and istron model Mini-55 (Instron, Canton, MA) as a test machine for applying force to polymer membrane specimens. Use

The dried membrane specimens were prepared in flat aluminum molds coated with PFA (perfluoroalkyloxy) Teflon® with hairspray compositions (e.g., water, ethanol, n-propanol, isopropanol, and mixtures thereof and optional additional ingredients). Solvents and silicone-containing adhesive block copolymers) selected from the group consisting of: quantitatively drying. The copolymer membrane is dried at about 22.7 ° C. and dried at about 50% relative humidity until the membrane reaches a “constant weight”. By "constant weight" is meant a weight variation of less than 1% in the sample for 24 hours. The dry film must be kept in an area protected from the air flow, resulting in the production of air bubbles and non-uniform drying. The copolymer membrane is cut into dumbbells for testing. The specimens should be virtually flawless, ie free from cracks, crevices, tears, etc. 1 and 2 illustrate planar dumbbell-like membranes to be used in the tensile tests described herein for cohesive strength and total energy absorption per unit volume. 1 shows a top view of a dumbbell sample. 2 shows a cross section through a dumbbell sample. The narrow cross section 1 of the dumbbell shape is about 3 mm (1 = 3 mm) wide. The narrow length of part 3 mm of dumbbell 3 is about 13 mm (3 = 13 mm). The gauge length of the narrow part 2 is the initial membrane length used when deforming the strand of the specimen. The gauge length is equal to or less than the narrow part length, preferably equal to the length of the narrow part (ie 2 = 3). The width of the dumbbell 4 is about 10 mm (4 = 10). The distance between the ends of membrane 5 is about 28 mm (5 = 28). The overall length of act 6 is about 64 mm (6 = 64 mm). The wide end of the membrane is about 18 mm ((6-5) / 2 = 18 mm). The length of the wide end and the narrow part of the membrane is about 6.5 mm (eg (5-3) /2=6.5 mm). In addition, the narrow central end should be smoothly curved to avoid any stress viscosity in the specimen. The curve of the tension has a radius 7 of about 0.5 inches to about 5 inches and is tangent to the narrow portion. The film produces a thickness 8 (8 = 0.4 mm) that is 0.4 mm. Dumbbell-shaped specimens are equilibrated at "constant weight". "Constant weight" means less than 0.2% by weight average weight gain or loss compared to the weight of the dumbbell measured during the selected 4 days, compared to the previous 4 days, and less than ± 0.2% by weight between two consecutive measurements over a 4 hour drying time. The move should be observed.

Test on calibrated Instron model Mini-55 tensile tester. Before shaping the specimen into an instron of length 3, width 1, and thickness 8, measure the nearest micron of the narrow sample of the dumbbell-shaped specimen with the graduated micrometer. Dimensional measurements are required by Instron for force per theoretical unit area. The wide end of the dumbbell specimen is bent on the Instron and pushed at a crosshead speed of 5 mm / min. Instron testers measure the overall force (eg, kgf) applied to the membrane. The force spreads over the cross-sectional area of the narrow part of the membrane. The cohesive strength of the copolymer is the maximum unit force measured by Instron divided by the cross section of the narrow portion of the membrane.

The dried hairspray composition of the present invention has a cohesive strength of greater than about 0.5 kgf / mm ² , preferably greater than about 0.6 kgf / mm ² , and more preferably greater than about 0.7 kgf / mm ² .

Total energy absorption per unit volume (eg kgfmm / mm ³ )

The total energy absorption per unit volume, expressed in kgfmm / mm ^3, is the ratio of the total energy (kgf X mm) required to reach the autodisconnect point to the original sample volume (mm ³ ). The total energy required to reach the automatic break point is calculated using the gravimetric method by measuring the area under the load versus strain curve for the specimen. Total energy absorption per unit volume is also known as "roughness" in the polymer science and material testing arts.

The measurement is carried out at about 22.7 ° C. and about 50% relative humidity.

The dried hairspray composition of the invention is preferably greater than about 0.55 kgfmm / mm ³ , more preferably greater than about 0.75 kgfmm / mm ³ , even more preferably greater than about 1.10 kgfmm / mm ³ , and most preferably Have a total energy absorption per unit volume of greater than about 2.15 kgfmm / mm ³ .

Impact strength

Impact strength is, for example, the average breaking energy (mass X gravity X height) required to obtain specimen breakage in a dried hairspray composition. Sample breakage is characterized by cracks or crevices caused by the impact of breakage masses that may be exhibited by exposure under normal laboratory light conditions.

The impact strength of the dried hairspray composition of the present invention is measured using the following method. The method is based on ASTM guidelines: D 5420-93, Standard Test Method for Impact Resistance of Flat, Rigid Plastics by Stricker Method Impacted by Breaking Mass (Gardner Impact), (published 1995), Its entirety is cited herein. However, some modifications are better for indicating the impact properties of the dried film. The measurement was made at about 22.7 ° C. and about 50% relative humidity.

The test method described herein specifically uses a rectangular shaped specimen with a thickness of about 0.4 mm and is a Precision Scientific solenoid controller for GCA Penetrometer, a blunt cylindrical probe with a surface area of 8 mm ² (OK M & T Corp. -part # WSU30) and a GCA / Precision Scientific Penetrometer modified to drop blunt probes at a distance of 70 mm, equipped with a self-measurement measured in 1 mm increments.

Samples are prepared using the membrane drying method described above in determining the cohesive strength. The copolymer film is cut into rectangles, for example 10 mm X 20 mm. The thickness of the specimen is 0.4 mm. The film thickness of the various test specimens should be kept within ± 15% of 0.4 mm.

The following measurement method is used. Turn on the solar-powered probe release regulator. The regulator starts drawing a circle as indicated by red light. The probe surface hits the impact surface so that the sharp edges of the probe do not block. Membrane specimens are placed on an impact tester over a target area. Face the meter gently on the membrane specimen. Point the light source along the surface of the specimen so that the light source is in the same plane as the surface of the film. Small fractions in the film are optically refracted and easily measured. Move the probe to the desired drop distance. The proposed distance course is: 1 mm, 3 mm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm and in additional 5 mm increments up to 70 mm (70 mm is the upper limit of the instrument).

To drop the probe on the specimen, switch on the instrument. The first step in the impact energy measurement is to measure the probe height needed to break the membrane. Start at 1 mm in 1 step. Continue to move according to the proposed elapsed distance until breakage is observed. When breakage is observed, record it and move to a new specimen. The second stage of impact energy measurement sets up a new specimen and moves the probe to the next lowest set point. If the film breaks, record the results and repeat the previous step. If the film does not break, set a new specimen and move to the next distance. Continue to set up new specimens and increase the drop distance until the membrane breaks. Continue the procedure until there are 5 breakages. Calculate the work energy, ie breakage strength using the formula:

W = m X g X h, where

W = amount of energy, ergs

m = mass of the probe (59.53 g) (the probe can be removed and replaced with one of a different mass or impact surface area).

g = gravity constant (980.665 cm / sec ² )

h = average distance traveled by the probe in impact (cm).

The dried hairspray compositions of the present invention preferably have an impact strength of greater than about 7000 ergs, more preferably greater than about 20,000 ergs, even more preferably greater than about 50,000 ergs.

Hair spray removal

The adhesive copolymer herein has an improved removal ability when used in the preferred hairspray embodiments of the present invention. In this paragraph, improved removal means that the tacky copolymer is more easily removed from hair or other applied surfaces during shampooing.

To define a preferred hairspray composition of the present invention, the removal capacity is measured indirectly by assessing the hardness of the hair and the appearance of white flakes that can be observed after treating the hair according to the method of removal ability described below. The ability to remove hair spray formulations after shampooing was found to aggregate as a result of the stiffness / softness of the hair and white flakes on the hair after a series of shampooing operations. Hairspray compositions of the present invention have a high removal capacity, ie reduced hardness and reduced white flakes. Thus, as used herein, the term "removability" refers to the hard number (0-4 scale) and the white flake value (0-4 scale) of hair, as measured according to the methodology described below.

To define a preferred hairspray composition of the present invention, the ability to remove the hairspray composition is defined as a mixture of the hardness of the hair and the number of hair flakes, the hairspray composition being from 0 to about 3.5, preferably from 0 to about 2.5, more preferably. Preferably having a hair flake value in the range from 0 to about 2.0, with a range from 0 to about 3.5, preferably from 0 to about 2.5, more preferably from 0 to about 2.0.

Methodology: Hairspray Removal

The removal ability of the hairspray composition of the present invention, evaluated indirectly by the hardness of the hair and the appearance of white flakes, is measured according to the following methodology. The methodology simulates multiple applications and multiple circulation applications of the hairspray composition to indirectly determine how easily and effectively the hairspray composition can be removed from the hair.

The methodology described herein provides a means of evaluating hair switches randomly treated with the hairspray embodiments of the present invention. Described below are the methods by which each hair switch was treated with a hairspray embodiment and each treated hair switch was then evaluated for removal.

Two trained participants assessed the setting of the same treated hair switch or hair switch of the hair switch for the appearance of stiffness and white flakes. Participants are then assigned a treated hair switch to independently write a numerical value (0-4 scale) for the hair hardness and a numerical value (0-4 scale) for the flakes. The order in which hair switches are processed with other hairspray embodiments is randomized and performed in a round robin fashion. Two identically set switches are prepared as described below for each participant to evaluate each with a new set of switches. Before evaluating randomly treated hair switches, each participant also evaluates untreated hair switches (not randomly) that are not considered at all for the hardness and flakes of the hair. Each participant also evaluates the hair switch control treated as flakes (score 4.0) and the hair switch control treated as hair stiffness (score 4.0). The hardness level of hair as defined herein is measured by averaging the hardness score of hair provided by two participants. Similarly, hair flake values as defined herein are measured by averaging hair flake scores provided by two participants.

The hair switch is treated with an aerosol or non-aerosol hairspray embodiment of the present invention according to the following steps. Hardness and flakes of hair are prepared according to the following steps, except that they are treated with the corresponding hairspray formulations as described below in Tables 2 and 3.

1) Vertically clean the hair switch (10 inch European virgin brown hair, 20 g) from the end comb (black rubber comb, 5 inch x 1 inch, 1/2 micro tooth) with the hair tied through the switch to remove any tangles. Suspend with.

2) If necessary, use an electrostatic gun to eliminate any electrostatic buildup on any switch.

3) For the non-aerosol product, apply 10 pumps of product to the switch and spray the switch from a distance of 4 inches while moving the sprayed spray pattern during the up and down movement of the fluid to make the entire switch effective, and the aerosol product For, apply an aerosol stream to the switch for a period of 3 seconds and spray each switch from a distance of 6 inches while moving the aerosol stream during fluid up and down motion to effect the entire switch.

4) Repeat step 3 on the opposite side of the switch.

5) After spraying the opposite side of the switch, hang the treated switch from the tied end to dry for 1 hour under ambient temperature, pressure and humidity.

6) Compress the black rubber comb by making the stroke smaller and combing away from the tied end of the switch by initially starting in the untied end direction and then making the stroke larger until it passes through the untied full length of the normally processed switch. (5 inches x 1 inch, 1/2 fine teeth) is used to comb the dried switch.

7) Repeat steps 1-6.

8) Wet the treated switch with water (+ 15-20 gain hardness, 38 ° C., 1 gal / min, water pressure).

9) Apply 1 ml of shampoo along the length of the front of the wet hair switch (Table 1: Methodology Shampoo) and 1 ml of the other shampoo along the entire length of the opposite side of the wet hair switch.

10) Gently milk the switch from the top to the bottom (hand over hand between thumb and finger) for 15 seconds at 1 stroke per second.

11) Rinse the hair switch with water (38 ° C, + 15, -20 gain hardness, 1 gal / min, water pressure) for 15 seconds. Gently press the hair between the first and second fingers and pull the finger under the switch after 5 seconds, 10 seconds and after the final rinse.

12) Hang the treated switch and dry at 60 ° C for 2 hours in a heating box.

13) Remove the dried switch from the heating box.

14) Black rubber comb by making the stroke smaller and combing away from the tied end of the switch by initially starting in the untied end direction and then making the stroke larger until it passes through the untied length of the normally processed switch. (5 inches x 1 inch, 1/2 fine teeth) is used to comb the dried switch.

15) Step 1-14

16) Step 1-13

17) The participant assesses the treated switch by feeling it between the first and second fingers of the frequently used hand and between its thumb and other fingers for hardness and bend resistance (next to 4 to 4). Scale). The assigned score value is related to the hardness of the hair reference score (4) and the untreated reference score (0).

18) The participant then combs the switches evaluated according to the procedure set out in step 14 above, then visually evaluates the combed switches for white flakes, coatings and white turbidity and calculates hair flake scores (0-4 scale). Assign. The assigned score value is related to the hardness of the hair reference score (4) and the untreated reference score (0).

: Methodological Shampoo Ingredient list Percent Composition Added Composition Chemical Content Percentage Sodium laureth sulfate 40.0000 10.0000 Water-USP Purification 30.3000 30.3000 Sodium lauryl sulfate 29.1000 8.0025 Cocamide DEA 0.5000 0.4000 Carton CG 0.1000 0.0015 Citric acid solution (50% active) 0-1% adjacency (Note: 100 to 100% water)

High flake control Raw material Percent Composition Added Composition Chemical Content Percent Octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymer (international starch lot AF-6713) 4.50 4.50 Water-USP Purification 15.50 15.50 Ethanol (SDA 40) 80.00 80.00

: High rigidity control Raw material Percent Composition Added Composition Chemical Content Percent Octyl acrylamide / acrylate / butylaminoethyl methacrylate copolymer (international starch lot AF-6713) 4.50 4.50 Aminomethylpropanol, 95% 1.04 0.99 Water-USP Purification 15.50 15.50 Diisobutyl adipate 0.20 0.20 Ethanol (SDA 40) 80.00 80.00

Each formulation described in Tables 1-3 is prepared by conventional blending and mixing techniques.

Optional ingredients

The hairspray of the present invention may further contain one or more optional ingredients known or effective in the use of hairsprays and other hair styling compositions. Any of the above components can be used to enhance or modify the aesthetics, performance or stability of the hairspray composition. The concentration of the optional constituents varies depending on the type of material added and its desired performance, but are typically and collectively about 0.005% to about 50%, more typically about 0.05% to about 30% by weight of the composition. It will be a range.

Plasticizers for silicone-containing adhesive block copolymers are particularly useful in the hairspray of the present disclosure. Suitable plasticizers include known or effective plasticizers suitable for use in hair care or other personal care compositions, including, but not limited to, glycerin, diisobutyl adipate, butyl stearate, propylene glycol, tri-C ₂ -C ₈ Alkyl citrate (including triethyl citrate and homologues of triethyl citrate such as tripropyl, tributyl, tripentyl, etc.), and combinations thereof. Triethyl citrate is preferred.

Plasticizers are typically used at a concentration of about 0.01 to about 10 weight percent, preferably about 0.05 to about 3 weight percent, more preferably about 0.05 to about 1 weight percent of the hairspray composition. Preferably the weight ratio of silicone-containing block copolymer to plasticizer is about 1: 1 to about 40: 1, preferably about 2: 1 to about 30: 1, more preferably about 3: 1 to about 25: 1 to be.

Other optional ingredients include an effective amount of a non-surface active ionic strength modifier system to reduce the viscosity of the hairspray composition. A minimum concentration of at least about 0.01% by weight of the hairspray composition is preferred, and the maximum concentration is low enough for the selective system in which the silicone containing adhesive block copolymer is dissolved or dispersed in the hairspray composition. As will be appreciated by those skilled in the art, as the ionic strength of the composition increases, the solubility of the silicone-containing sticky block copolymer in the hairspray composition remains until it is no longer dissolved or dispersed in the composition and until the non-composition is precipitated. It will increase. The upper limit of the ionic strength modifier level will vary depending upon the particular ionic strength modifier, alcohol solvent, other liquid carrier, block copolymer, and other components present in the composition. The concentration of the optional ionic strength modifier will typically range from about 0.01 to about 4 weight percent of the composition, preferably from about 0.01 to about 2 weight percent, more preferably from about 0.01 to about 0.1 weight percent.

The optional ionic strength modifier system contains a mixture of monomeric cations and anions. Ions of its ionic strength modifier systems do not significantly reduce their specific surface activity, ie surface tension. For this purpose, non-surface active shells refer to ions that reduce the surface tension by 5.0 dyne / cm ² or less at a concentration of 0.5% aqueous solution. Typically, the ions of their ionic strength modifier systems are characterized by having up to 4 carbon atoms per charge, preferably up to 2 carbon atoms, in any aliphatic chain or linear or branched chain organic heterochain.

The optional ionic strength modifier system includes monomeric ions in the form that are the product of an acid group reaction. Thus, although present in the composition, the basic and acidic ions OH ⁻ and H ⁺ do not form part of their ionic strength modifier system. Its ions are incorporated into the composition in a form that may be present in the composition, ie in dissociated form. Although all the added ions are present as free ions in the composition, it is necessary to be at least partially dissolved or dissociated in the hairspray composition. Ionic strength modifiers can be incorporated into the hairspray composition, for example, by the addition of soluble salts, or the addition of a mixture of acids and bases, or the addition thereof. When using the arbitrary ionic strength modifier system, it is necessary to include both the anion and the cation of the arbitrary ionic strength modifier system in the hairspray composition.

Non-limiting examples of suitable optional cations used in the composition are alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium, calcium and strontium. Preferred divalent cations are magnesium. Preferred monovalent metal ions are lithium, sodium and potassium, more preferably sodium and potassium. Suitable means for addition to the composition thereof are, for example, bases, such as addition of hydroxides, sodium hydroxide and potassium hydroxide, and salts soluble in liquid carriers, for example salts of monomeric anions such as those described below. Include. Other non-limiting examples of suitable cations include organic ions such as quaternary ammonium ions and cationic amines such as ammonium mono-, di- and triethanolamine, triethylamine, morpholine, aminomethylpropanol (AMP), aminoethylpropanediol And the like. Ammonium and amines are preferably provided in the form of salts such as hydrochloride salts.

Monomeric anions that can be used are halogen ions such as chloride, fluoride, bromide, and iodide, in particular chloride, sulfate, ethyl sulfate, methyl sulfate, cyclohexyl sulfamate, thiosulfate, toluene sulfonate, Present in dissociated form in xylene sulfonate, citrate, nitrate, bicarbonate, adipate, succinate, saccharate, benzoate, lactate, borate, isethionate, tartrate, and hair styling compositions Other monomeric cations that may be present. Anions can be added to the compositions thereof, for example in the form of salts which are at least partially dissolved in a liquid carrier, for example sodium or potassium salts such as acetates, citrate, nitrates, chlorides, sulfates, or acids. . Preferably, the salt is completely soluble in the carrier.

Other optional ingredients may be surfactants (anionic, cationic, amphoteric, or zwitterionic, including fluorinated surfactants and silicone copolyols), accelerators, hair conditioners (eg, silicone fluids, fats) Esters, fatty alcohols, long chain hydrocarbons, cationic surfactants, etc.); Emollients; Lubricants and penetrants such as various lanolin compounds; Protein hydrolysates and other protein derivatives; Ethylene adducts and polyoxyethylene cholesterol; Dyes, hair dyes, bleaches, reducing agents and other dyeing agents; pH regulators; Sunscreens; Preservatives; Thickeners (eg, polymeric thickeners such as xanthan gum); And fragrances.

Hairspray products

The hairspray composition of the invention is dispersed as a spray or spray from a container or package known or effective for providing delivery. The container or package will typically be in the form of a pump spray disperser or aerosol absorber, all of which are known to those skilled in the art.

The hairspray composition of the present invention further contains an accelerator when dispersed from a pressurized aerosol container. Combinations or any promoters of such promoters are known or effective and suitable for application to human skin or hair can be used here. Suitable promoters include volatile hydrocarbon promoters which may include liquefied gases conventionally used for aerosol containers, most typically liquefied lower hydrocarbons having 3 to 4 carbon atoms such as propane, butane, isobutane, and combinations thereof.

Other suitable promoters include 1,2-difluoroethane (hydrofluorocarbon 152A) which is supplied as Dymel 152A by hydrofluorocarbons such as DuPont. Other suitable promoters include dimethyl ether, nitrogen, carbon dioxide, nitrogen monoxide, atmospheric gases, and combinations thereof. Preferably a combination of a hydrocarbon promoter and a hydrocarbon promoter, in particular a combination containing isobutane and isobutane.

The aerosol promoter can be mixed with the present hairspray composition and the amount of promoter mixed is controlled by the general factors known in the aerosol technology. Typically, as a liquefiable accelerator, the concentration of the accelerator is about 10 to about 60 weight percent, preferably about 15 to about 50 weight percent of the total hairspray composition comprising the promoter.

Other suitable containers or packages include pressurized aerosol dispersants wherein the accelerator is separated from contact with the hairspray composition. An example of such a package or container is a two compartment can in the form sold under the SEPRO tradename from American National Can Corp.

Other suitable aerosol dispersants are those characterized by a promoter, which is a compressed gas that can be filled into the dispersant by a pump or equivalent device prior to use. Examples of such dispersants include U.S. Patent 4,077,441 (Olofsson, March 7, 1978); US Patent 4,850,577 (TerStege, July 25, 1989); American series No. 07 / 839,648 (Gosselin et al., Filed Feb. 21, 1992), which is incorporated herein by reference. The hairspray composition of the present invention may also be dispersed by any known or effective means for delivery to the hair, including any known or effective atomization means such as a non-aerosol pump spraying device.

Manufacturing method

The hairspray composition of the present invention can be prepared using conventional blending and mixing techniques. For example, the silicone containing tacky block copolymer and the alcohol solvent are combined and mixed together to form a homogeneous solution or dispersion. The other ingredients are then added to a homogeneous solution or dispersion and mixed to obtain the hairspray composition of the present invention. If the silicone-containing sticky block copolymer is neutralized, a neutralizing agent is preferably added prior to the addition of the other components. The hairspray composition is then packaged in a conventional or suitable mechanical pump spray device, or instead, in the case of an aerosol spray composition, the hairspray composition is packaged in a conventional or suitable aerosol absorber with a suitable accelerator system.

How to use

The hairspray compositions of the invention can be used in a conventional manner to provide the desired hair styling benefits. The method usually consists of applying an effective amount of the composition to dry the hair arranged or positioned in the desired style. In this context, the term “effective amount” means an amount sufficient to provide the desired hair retention and styling benefits, typically from about 0.5 g to about the composition, depending on the selected hairspray composition and formulation, dispersant form, hair length, hair style, and the like. Means in the range of 30 g. The composition is applied to the hair by spraying or spraying the composition using a mechanical pump spray device, pressurized aerosol container or other suitable delivery means. The composition is then dried or dried on the applied surface.

The following experimental examples and examples further demonstrate embodiments within the scope of the present invention. This is provided for the purpose of demonstration only and many variations of the invention are not to be interpreted as a limitation of the invention wherever possible without departing from its spirit and scope.

Example

The following non-limiting examples demonstrate certain embodiments of the hairspray compositions of the invention, and methods of providing hair styling benefits for drying hair using the compositions. However, it is understood that various additives or modifications of the illustrated embodiments can be made without departing from the spirit and scope of the invention. In the following claims, it is intended to cover all such modifications that fall within the scope of the main invention.

Polymers 1.1 and 1.2, which are given below, are silicone-containing tacky block copolymers suitable for use in the hairspray compositions of the present invention. Each of the block copolymers exemplified above is then inserted as examples 2.1, 2.1, 2.3 into certain hairspray embodiments of the present invention.

Polymer 1.1

[Poly (dimethyl siloxane) -block-poly (t-butylacrylate-co-acrylic acid) _n

62.4 parts of t-butyl acrylate, 20.8 parts of acrylic acid, 200 parts of acetone (solvent), and 15 parts of isopropanol (chain transfer agent) are placed in a round bottom flask. Separately, dissolve 16.8 parts of VPS-1001 (poly (dimethyl siloxane) initiator) macroazo initiator (available from Wako Chemical USA, INC., Richmond, VA) in 200 parts of ethyl acetate and add Add solution to the funnel. The reaction vessel is purged with argon for 1 hour as appropriate. After purge, a constant positive pressure is maintained with argon on a closed reaction system. The reaction mixture is heated to 58 ° C. The VPS-1001 solution is added dropwise to the reaction flask for 1 hour. Maintain heating and stir for 20 hours. The reaction is terminated by opening the reactor and cooling to room temperature.

One part of the polymer solution is added to 15 parts of water to precipitate the block copolymer from the solution. The resulting polymer is redissolved in acetone and again precipitated from 15 parts of water. The resulting block copolymer is then placed in a vacuum oven for heat drying. After drying, the polymer is milled and extracted with hexane for 20 hours using a soxhlet extractor. The polymer is then dried by heating in an oven. The glass transition temperature of block B of the resulting polymer is about -20 ° C to 60 ° C.

Polymer 1.2 [Poly (dimethyl siloxane) -block-poly (t-butyl acrylate-co-n-butyl acrylate-co-acrylic acid-co-methacrylic acid)] _n

80 parts t-butyl acrylate, 56 parts n-butyl acrylate, 12 parts acrylic acid, 10 parts methacrylic acid, 400 parts acetone (solvent) and 50 parts isopropanol (chain transfer agent) are placed in a round bottom flask. Individually, 20 parts of the VPS-1001 (poly (dimethyl siloxane) initiator) macroazo initiator (available from Wako Chemical, Richmond, VA) was dissolved in 400 parts of ethyl acetate and 12 parts of acrylic acid and 10 parts of meta in the solution Krylic acid is added and the solution is added to the addition funnel. The reaction vessel is purged with argon for 1 hour as appropriate. After purge, a constant positive pressure is maintained with argon on a closed reaction system. The reaction mixture is heated to 58 ° C. The VPS-1001 solution is added dropwise to the reaction flask for 1 hour. Maintain heating and stir for 20 hours. The reaction is terminated by opening the reactor and cooling to room temperature.

One part of the polymer solution is added to 15 parts of water to precipitate the block copolymer from the solution. The resulting polymer is redissolved in acetone and again precipitated from 15 parts of water. The resulting block copolymer is then placed in a vacuum oven for heat drying. After drying, the polymer is milled and extracted with hexane for 20 hours using a soxhlet extractor. The polymer is then dried by heating in an oven. The glass transition temperature of block B of the resulting polymer is about -20 ° C to 60 ° C.

Example 2

The following examples illustrate certain aerosol hairspray embodiments of the present invention.

Example number Ingredient (% by weight) 2.1 2.2 2.3 2.4 2.5 2.6 Copolymer 1.1 5.00 4.00 3.50 - - - Copolymer 1.2 - - - 5.00 4.00 3.50 Isodo decan ¹ 0.50 - - 0.50 - - Triethyl citrate ² - - 0.21 - - 0.21 Diisobutyl adipate 0.70 0.45 - 0.70 0.45 - Propylene glycol - - 0.30 - - 0.30 Sodium hydroxide ³ 1.00 - - 1.00 - - Potassium Hydroxide ⁴ - 0.94 1.20 - 0.94 1.20 air freshener 0.10 0.10 0.10 0.10 0.10 0.10 water QS100 QS100 QS100 QS100 QS100 QS100 Sodium benzoate 0.10 0.10 - 0.10 0.10 - Ethanol ⁵ 56.69 57.42 72.0 56.69 57.42 72.0 Accelerator-Isobutane - - 7.02 - - 7.02 Accelerator-n-butane 10.00 - - 10.00 - - Accelerators-Dimethyl Ether ⁶ 10.00 - - 10.00 - - Accelerators-Hydrofluorocarbon 152a ⁷ - 25.0 15.98 - 25.0 15.98 1 PERMETHYL 99A (Presperse, Inc., South Plainfield, NJ, USA.) 2 CITROFLEX-2, from Morflex, Inc., Greensbore, NC, USA. 3 Sodium hydroxide is 30% active. 4 Potassium hydroxide is 45% active. 5 SDA 4 O (100% ethanol) 6 DYMEL-A, (Dupont) 7 DYMEL- 152a (Dupont)

Hairspray compositions 2.1-2.6 are prepared by first mixing a silicone-containing sticky block copolymer (polymer 1.1 or 1.2) with ethanol, neutralizing the polymer with sodium or potassium hydroxide, and then continuously (possibly) Deccans, plasticizers, perfumes, and water are mixed and added. If sodium benzoate is used, it is added after the addition of water. Most preferably a preliminary mixture of water and sodium benzoate is prepared and added after most water additions. After the residue of the prepared composition is added, the propellant for the aerosol embodiment is filled in the aerosol container.

Example 3

The following examples show the aerosol hair spray compositions of the present invention.

Example number ingredient (%) 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 Copolymer 1.1 4.00 5.00 6.00 4.00 --- --- --- --- Copolymer 1.2 --- --- --- --- 3.00 3.50 2.50 4.00 Isodo decan ¹ 1.00 --- --- --- --- 1.0 2.0 --- Diisobutyl adipate 0.40 --- 0.90 0.55 --- --- --- 0.40 Sodium hydroxide ² 0.96 1.20 1.44 --- --- 1.20 --- 1.35 Potassium Hydroxide ³ - - - 1.21 1.00 - 0.70 - perfume 0.10 0.10 0.10 0.10 0.10 0.15 0.10 0.15 water QS100 QS100 QS100 QS100 QS100 QS100 QS100 QS100 Sodium benzoate - - - - 0.10 0.10 - 0.10 Ethanol ⁴ 76.54 71.95 81.56 71.25 79.40 69.26 78.00 55.00 1 PERMETHYL 99A, (Presperse, Inc., South Plainfield, NJ, USA.) 2 Sodium hydroxide is 30% active. 3 Potassium hydroxide is 45% active. 5 SDA 4O (100% ethanol)

Hairspray compositions 3.1-3.8 are prepared by first mixing a silicone-containing sticky block copolymer (polymer 1.1 or 1.2) with ethanol, neutralizing the polymer with sodium or potassium hydroxide, and then continuously (possibly) Deccans, plasticizers, perfumes, and water are mixed and added. If sodium benzoate is used, it is added after the addition of water. Most preferably a preliminary mixture of water and sodium benzoate is prepared and added after most water additions.

Each of the experimental hairspray compositions tested in Examples 2 and 3 is a specific embodiment of the hairspray compositions of the present invention and provides improved hair styling performance when applied to dried, styled or immobilized hair, in particular dry hair. Provides improved retention or fixation when applied to and minimizes or eliminates hair slack immediately after or during application.

Each of the experimental hairspray compositions tested in Examples 2 and 3 also provides improved removal from hair and is evaluated by the removal methodology described herein and provides hardness values of hair less than 2.0 and hair flake values less than 2.0.

Claims (10)

(a) about 50 to about 99.9 weight percent alcohol solvent; (b) a hair spray composition comprising from about 0.1 to about 30 weight percent of a silicone-containing adhesive block polymer having a weight average molecular weight of about 10,000 g / mol to about 10,000,000 g / mol, Wherein each R is independently selected from the group consisting of C ₁ -C ₁₀ alkyl, phenyl, C ₁ -C ₁₀ alkyl-substituted phenyl, and mixtures thereof; X is a divalent radical; Y is -N = N- , -OO-, and mixtures thereof, m, n, and p are each independently a positive integer having a value of 1 or more); And The silicone macroinitiator has a number average molecular weight of about 500 g / mol to about 500,000 g / mol, and the ethylene-based monomer is copolymerizable and has at least one polymer in the tacky block copolymer having a Tg value of about -20 ° C to about 60 ° C. A hair spray composition comprising producing a block. The composition of claim 1, wherein the alcohol solvent is selected from the group consisting of ethanol, n-propanol, isopropanol, and mixtures thereof, wherein the tacky block copolymer is soluble in the hairspray composition. The composition according to claim 1 or 2, wherein the silicone macro initiator is a silicone macro azo initiator, wherein Y is an azo group. The block copolymer of claim 1, wherein the block copolymer comprises from about 60% to about 95% by weight of the copolymerizable ethylenically unsaturated monomer, and from about 5% to about 40% by weight of the copolymerized silicone macroinitiator. A composition, characterized in that. The method according to any one of claims 1 to 4, wherein m has a value of about 14 to about 700, n has a value of about 1 to about 10, and the silicon macro azo initiator is between 5,000 grams / mol and about 100,000 grams /. A composition having a number average molecular weight of moles. The composition of claim 1, wherein upon drying the composition exhibits a cohesive strength of greater than about 0.5 kgf / mm ² , a total energy absorption per unit volume of greater than about 0.55 kgfmm / mm ^3, and an impact strength of greater than about 7000 ergs. Having a composition. The composition of claim 1, wherein upon drying the composition exhibits a cohesive strength of greater than about 0.7 kgf / mm ² , a total energy absorption per unit volume of greater than about 1.10 kgfmm / mm ^3, and an impact strength of greater than about 50,000 ergs. Having a composition. The vinyl monomer unit according to any one of claims 1 to 7, wherein the vinyl monomer unit is acrylic acid, methacrylic acid, N, N-dimethyl acrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone Acrylic or methacrylic acid esters of C ₁ -C ₁₈ alcohols, styrene, alpha-methylstyrene, t-butylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl toluene, butadiene, cyclohexadiene , Ethylene, propylene, n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, any of the acids listed above and A composition characterized in that it is selected from the group consisting of salts of amines and combinations thereof. The composition of claim 1, wherein the composition provides a level of hardness of the hair from 0 to about 2.5 and a number of hair flakes of from 0 to about 2.5. 10. A method of styling hair comprising applying an effective amount of the composition of claims 1 to 9 to dry or immobilized hair.