JPH06509807A - Hairspray composition containing ionic styling polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Hairspray composition containing ionic styling polymer Technical field The present invention relates to hairspray compositions containing high molecular weight asquilling polymers. do. More specifically, the present invention is modified to include a high molecular weight asquilling polymer. A hairspray composition having improved sprayability.

Background of the invention There is a widespread desire to keep hair in a specific shape. To implement this A common methodology for hair quilling or hair “setting” is to apply the composition to the hair. , typically applied to wet or dry hair.

These compositions exhibit a temporary setting effect and can be removed with water and/or hair washing. Should be. Substances used in compositions to exhibit a setting effect are usually Applied in the form of a mousse, gel, lotion or spray.

A high level of style retention or maintenance is typically achieved by applying hair sprays as a spray. This is expected from tiling compositions. Style retention is typically a national Amphomer (AMPH) supplied from the arch (Na oral 5 tarch) GANTREZ SP supplied by ONER) and GAF This is achieved by using a resin such as 225. Used in commercial hairspray products These resins have a weight average molecular weight of about 40,000 to about 150,000. usually has. Such resins are incorporated into pumps and aerosol hair sprays. When used, they exhibit a combination of adequate style retention and good sprayability. can do. “Spray suitability 2 relates to spray quality and pattern.

Good sprayability for hairspray formulations: wide, no dripping centers Characterized by a spray pattern and droplet size small enough to produce a fine mist It will be done.

However, hairspray compositions with improved maintenance and style retention performance Providing goods is still desired. Improvements regarding liquid hairspray compositions One technique that shows improved style retention utilizes high molecular weight hair styling resins. That would be the case. On the other hand, this is required in demonstrating a certain level of style preservation. The amount of resin can be reduced. High molecular weight hair styling polymers are commercially available When utilized, typically as a gel, lotion or other non-spray composition. has been prescribed.

Unfortunately, high molecular weight resins in liquid hairspray formulations have poor sprayability. It tends to make you feel tired. More specifically, such a formulation, as opposed to a fine mist, Decreased spray pattern diameter, increased incidence of wet dripping centers, and during spraying Spray products characterized by large droplet size or tendency to run off It tends to have a certain quality. This is caused by making the hairspray too concentrated in the hair area. This will make the hair stiff in these areas, while other areas will be affected by the applied hairspray. This results in poor style retention and maintainability.

This allows it to exhibit improved style retention and retain good sprayability characteristics. To provide a liquid hair spray composition that utilizes a high molecular weight styling resin. is the object of the present invention.

Recently, certain polymers with a silicone macromer portion have been developed that have good smear properties on hair. It has been discovered that it exhibits tile retention effects while also exhibiting improved hair feel. exchange In other words, such silicone macromer-containing polymers are superior to conventional non-silicone Providing soft texture and conditioning to hair compared to containing resins Can be done.

Asquilling polymers containing silicone macromers and formulations containing them For example, EPO Application No. 0 408 311 A2 dated January 11, 1991 EPO Application No. 90307528°1, 19 of Hayama et al., published as U.S. Pat. No. 5,061, issued October 29, 1991, No. 481, US Pat. No. 5, Bolich et al., issued April 21, 1992. , No. 106゜609, published on March 31, 1992 by Bolich et al. National Patent No. 5,100,658, issued on March 31, 1992^n5h er-Jackson et al., U.S. Patent No. 5°100.657, April 1, 1992 U.S. Pat. No. 5,104,646, Bollch et al. Bolich et al., filed on August 27, 2016, issued in the United States* Torg Application No. 07/758,319, filed August 27, 1991 As disclosed in U.S. Application Serial No. 07/758°3.2 million to Erson et al. All of which are incorporated herein by reference (as of February 13, 1991) (corresponding to published EP nos. 0412704 and 0412707).

These silicone macromer-containing hair styling polymers provide desirable hair styling. It can show good overall hair squilling performance along with conditioning effect. hairspray, but they have a relatively high molecular weight compared to most commercially available products. [However, they are more commonly used in hairspray resins.] molecular weight (e.g., from about 5'0.000 to about 150,000 weight average molecular i;k) can also be used]. Moreover, they are hairsprays with good sprayability characteristics. Difficult to formulate into compositions.

Therefore, high molecular weight silicone-containing hair stylists with improved spray characteristics It is an object of the present invention to provide a liquid hairspray composition containing a hair spray polymer. This is another purpose.

Hairspray with low levels of volatile organic solvents, e.g. ethanol, propatool, etc. It may also be desirable to formulate the composition. One way to do this is by sacrificing volatile organic solvents. The objective is to increase the amount of water present in the composition. Unfortunately, this Adversely affects aspray performance, especially drying time, spray quality and hair feel during application. Tends to give. This is especially true for hair setting resins containing silicone macromers. This is a problem related to the low-volatility organic solvent composition used. Good from high water content compositions Obtaining good spray quality and hair feel is particularly difficult.

Contains hair setting resin containing silicone macromer with low volatility organic solvent. It is yet another object of the present invention to obtain an improved hairspray composition having It is.

These and other objects, which will be apparent to those skilled in the art, can be achieved by the invention described below. can be done. Unless otherwise noted, all percentages and ratios are Here it depends on the weight.

Summary of the invention The present invention provides excellent hair styling/maintenance effects on hair when spray is applied. Improved sprayability with high molecular weight asquilling polymers A hairspray composition is provided.

According to the present invention, the sprayability of high molecular weight polymers is determined by non-surfactant anions and carbon. can be improved by the use of an ionic strength control system consisting essentially of a mixture of thiones. can. It is also an essential aspect of the invention that the hair styling polymer is ionic. Ru.

More particularly, the present invention provides a liquid hair styling product useful for spray application to hair. (a) a weight average molecular weight composition of at least about 300,000; (b) water, preferably C-C; -C-valent alcohol 1 6ゝ 24 liquid vehicle selected from the group consisting of:

(c) an effective amount of an ionic strength adjustment system to reduce the viscosity of the composition, the system being non-containing; consisting essentially of a mixture of surface-active cations and anions; the group is at least partially soluble in the liquid carrier); The composition has a pH of about 10 or less.

In one aspect of the invention, high molecular weight hair styling polymers are A styling or hair setting polymer, i.e. a polymer without silicone parts. It may be any of the conventional types of mer.

In another aspect of the invention, the high molecular weight polymer is suitable for hair styling and maintenance. Improved flexibility on hair compared to non-silicone containing polymers while showing a long lasting effect It is a hair setting polymer containing silicone macromer that also exhibits properties. of the present invention In yet another aspect, a silicone-containing hair setting polymer, as described above. an effective amount of an ionic strength adjustment system and water to reduce the viscosity of a composition such as The above C-C preferably C-C-16ゝ24 Contains a liquid vehicle consisting of a mixture of alcohols with improved hair feel A low volatility organic solvent hairspray composition is provided, the composition comprising at least about 1 Contains 0% water by weight.

Detailed description of the invention Essential and various optional ingredients are listed below.

hair styling polymer The compositions of the present invention contain a high amount of effective amount to provide a styling effect when applied to the hair. Contains molecular weight hair styling polymers. The “hair style” used here Hair styling polymers are any natural or synthetic polymers that have a hair setting effect. means polymer. This type of polymer is well known in the art. Usually used The level of hair styling polymer contained is at least about 0.1% by weight of the composition. be. Typically it will be about 0.1 to about 15%, preferably about 0.5 to about 8% Exist at the level.

This hair styling polymer is also ionic. The “ionic” used here Hair styling polymer.

or a hair styling polymer or a hair styling polymer such as The term “ionic” in relation to the constituent monomers refers to anionic and cationic properties. , in the liquid vehicle of the hair styling composition in amphoteric, bipolar or dissociated form. means a hair styling polymer that can be present in

Ionic hair style that is soluble or dispersible in a liquid carrier Polymers can also be used in the present invention. Various such types of hair styling polymers are known in the art.

This ionic hair styling polymer can be used as a homopolymer, copolymer, or terpolymer. Ma et al. The term “polymer” as used herein refers to all such types of polymeric materials.

Essentially, this polymer must contain ionic monomers. This port For convenience, the monomer units present in the polymer are These may also be referred to as monomers from which they can be derived. Ionic monomers are polymerizable Ionic starting monomers or polymerizable non-monomers that are modified to become ionic after polymerization. Can be derived from ionic monomers. Illustrated corresponding salts and acids and bases are also included.

Examples of anionic monomers include: (i) Acrylic acid, methacrylic acid, maleic acid, maleic acid half ester, itaco unsaturated carboxylic acid monomers such as phosphoric acid, fumaric acid and crotonic acid; (ii) Hydroxyethyl acrylate, hydroxyethyl methacrylate, Acrylates containing hydroxyl groups such as hydroxypropyl acrylate and and/or methacrylates such as succinic anhydride, phthalic anhydride, etc. Half esters of saturated polybasic acid anhydrides: (jii) styrene sulfonic acid, sulfoethylene Monomers with sulfonic acid groups such as acrylates and methacrylates; as well as (iv) acid phosphooxyethyl acrylate and methacrylate, 3-chloro- Phosphoric acids such as 2-acid phosphooxypropyl acrylate and methacrylate, etc. There are monomers that have groups.

Examples of cationic monomers are: (i) (meth)acryloxypropyltrimethylammonium chloride and ( meth) Acrylic Oxypropyl Triethylammonium Bromide Acrylic acid or methacrylic acid, collectively referred to as (meth)acrylic acid, and alkyl Quaternized epihalohydrin formation of trialkylamines having 1 to 5 carbon atoms in Monomers derived from substances; (if) dimethylaminoethyl (meth)acrylate, diethylaminoethyl ( meth)acrylate, dimethylaminopropyl(meth)acrylate or dimethyl (meth)acrylic acid or (meth)acrylic acid such as t) Dialkylalkanolamine having acrylamide and C-C alkyl group Amine derivatives of (meth)acrylic acid or (meth)acrylamide derived from amine derivative of; and (+ If) (1) Neutralization with acids such as hydrochloric acid or lactic acid, (2) Methyl chloride, salt modification with alkyl halides such as ethyl chloride, methyl bromide or ethyl iodide; (3) Halogens such as ethyl monochloroacetate or methyl monochloropropionate and (4) modification with dimethylated fatty acid esters such as dimethyl sulfate or diethyl sulfate. There are derivatives of the products of said group (11) by modification with dialkyl sulfates.

Furthermore, diallyldimethylammonium chloride is used as a cationic unsaturated monomer. There are amine derivatives of allyl compounds such as

These cationically unsaturated monomers can be polymerized in the cationic form or alternatively, They are polymerized in the form of their precursors and then treated with e.g. quaternizing agents (e.g. monomers). It may be modified to be cationic with ethyl chloroacetate, dimethyl sulfate, etc.).

Examples of ampholytic substances include potassium monochloroacetate and sodium monobromopropionate. Thorium, aminomethylpropanol salt of monochloroacetic acid, salt of monochloroacetic acid dimethylaminoethyl with halogenated fatty acid salts such as reethanolamine salts, etc. (meth)acrylate, dimethylaminopropyl (meth)acrylamide, etc. The above-mentioned amine derivatives of (meth)acrylic acid or amines of (meth)acrylamide dipolar derivatives of carbon derivatives; (meth) as above modified with propane sultone; There are amine derivatives of acrylic acid or (meth)acrylamide.

Like the cationic monomers mentioned above, these amphoteric monomers can be polymerized in their amphoteric form. or alternatively they can be polymerized in the form of their precursors and then converted to the amphoteric state. You may.

Preferred ionic monomers include acrylic acid, methacrylic acid, and dimethylamino Ethyl methacrylate, quaternized dimethylaminoethyl methacrylate, malein acid, maleic anhydride half ester, crotonic acid, itaconic acid, diallyl dimethyl acetate ammonium chloride, polar vinyl heterocycles such as vinyl imidazole, vinyl Lupyridine, styrene sulfonate and mixtures thereof. Particularly preferred Ionic monomers include acrylic acid, dimethylaminoethyl methacrylate, and graded dimethylaminoethyl methacrylate and mixtures thereof.

Salts of the acid and amine monomers, such as sodium, potassium or other alkali Alternatively, alkaline earth metal salts can also be used.

The polymer is at least about 1% by weight, preferably at least about 2%, more preferably at least about 2% by weight. It should contain at least about 5% ionic monomer.

This hair quilling polymer contains both high and low polar monomers. It may also contain nonionic monomers.

The ionic polymer usually contains about 1-100% ionic heptamers and non-ionic moieties. 0 to about 99% monomers, preferably about 2 to about 75% ionic monomers and nonionic monomers. about 25% to about 98% ionic monomers, more preferably about 5% to about 50% ionic monomers. and about 50 to about 95% nonionic monomers.

Typical examples of low polar nonionic monomers are methanol, ethanol, and 1-propyl alcohol. 2-propanol, 1-butanol, 2-methyl-1-propanol, 1- Pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butano alcohol, 1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl -1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-penta alcohol, t-butanol, cyclohexanol, 2-ethyl-1-butanol, 3-heptatool, benzyl alcohol, 2-octatool, 6-methyl-1- Heptatool, 2-ethyl-1-hexanol, 3゜5-dimethyl-1-hexane alcohol, 3,5.5-)trimethyl-1-hexanol, 1-decanol, 1-de C-C amines such as decanol, 1-hexadecanol, 1-octadecanol, etc. Acrylic or methacrylic acid esters of alcohols (alcohols have about 1 to 24 carbon atoms, and the average number of carbon atoms is preferably about 4 to 18, more preferably about 4 to 12); styrene; chlorostyrene; vinyl esters such as vinyl acetate; vinyl chloride; vinylidene chloride; acrylonitrile; α-methylstyrene: t-Butylstyrene; Butadiene; Cyclohexadiene, Ethylene; Propylene ; Vinyl toluene; Methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, t) Alkoxyalkyl (meth)acrylates such as acrylates and their It is a mixture of Other nonionic monomers include allyl acrylate and meth. acrylate, chlorohexyl acrylate and methacrylate, oleyl acrylate Acrylate and methacrylate, Benzyl acrylate and methacrylate, Tetra Hydrofurfuryl acrylate and methacrylate, ethylene glycol diac rylate and methacrylate, 1,3-butylene glycol diacrylate and Methacrylate, diacetone acrylamide, isobornyl (meth)acrylate There are acrylate and methacrylate derivatives such as et al.

Preferred nonionic monomers include n-butyl methacrylate and isobutyl methacrylate. tacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, t -butyl acrylate, t-butyl methacrylate and mixtures thereof.

Typical polar nonionic monomers include acrylamide and N,N-dimethyl. Acrylamide, methacrylamide, Nt-butylacrylamide, methacrylamide Laetrile, acrylate alcohols (e.g. hydroxyethyl acrylate) and C-C acrylate alcohols such as hydroxypropyl acrylate. ), methacrylate, hydroxypropyl methacrylate, vinylpyrrolidone , vinyl ethers such as methyl vinyl ether, acyl lactones, vinyl Pyridine, allyl alcohols, vinyl alcohols and vinyl caprolactam There is.

An example of an anionic hairspray polymer is a copolymer of vinyl acetate and crotonic acid. α-branched saturated fats such as vinyl acetate, vinyl crotonic acid and vinyl neodecanoate Terpolymers of vinyl esters of group monocarboxylic acids; methyl vinyl ether and Copolymers of maleic anhydride (1+1 molar ratio) (such copolymers are Saturated aliphatic alcohols containing 1 to 4 carbon atoms such as alcohol or butanol 50% esterified); methacrylic acid, butyl acrylate, methacrylic Acrylic acid or meth as an anionic group-containing moiety, such as a copolymer such as ethyl acid. Acrylic copolymers and terpolymers containing acrylic acid. The set of the present invention Another example of an acrylic polymer that can be used in the composition is tert-butyl acrylate. Polyamide, acrylic acid and ethyl acrylate.

An example of an amphoteric polymer that can be used in the present invention is N-1e with a molecular weight suitable for this purpose. rt-octylacrylamide, methyl methacrylate, hydroxypropyl methacrylate Polymers of tacrylate, acrylic acid and t-butylaminoethyl methacrylate octium, commonly described in U.S. Pat. No. 4,192,861 as being lylacrylamide/acrylates/butylaminoethyl methacrylate copolymer It's Ma.

An example of a cationic hairspray polymer is dimethylaminoethyl methacrylate. of lower alkylaminoalkyl acrylate or methacrylate monomers such as Compatibility with amino-functional acrylate monomers such as N-vinylpyrrolidone monomer or alkyl such as methyl methacrylate, ethyl methacrylate Alkyl such as methacrylate and methyl acrylate, butyl acrylate It is a copolymer with acrylate. Cation containing N-vinylpyrrolidone Polymers are commercially available from GAF.

Another organic ionic hair styling polymer is carboxymethyl cell. copolymer of loose, PVA and crotonic acid, copolymer of PVA and maleic anhydride Limer, sodium polystyrene sulfonate, PVP/ethyl methacrylate/ Methacrylic acid terpolymer, vinyl acetate/crotonic acid/vinyl neodecanoate copolymer Limer, octylacrylamide/acrylate copolymer, poly(methyl vinyl) monoethyl ester (maleic acid) and octylacrylamide/alcoholic acid There are acrylate/butylaminoethyl methacrylate copolymers. of polymer Mixtures may also be used.

Silicone-containing acrylic polymer Preferred ionic hair styling polymers are silicone-containing polymers.

Ionic silicone macromer-containing polymers are, for example, II a y a published as EPO Application No. 0 408 311 A2 in EPO Application No. 90307528.1 of Ip a et al., October 29, 1991 U.S. Pat. No. 5,061,481 to 5uzukj et al., issued in 1992. U.S. Pat. No. 5,106,609 to Bolich et al., issued April 21; U.S. Patent No. 5,100 to Bolich et al., issued March 31, 1992; Ansher-Jackson, No. 658, March 31, 1992 No. 5,100.657, issued April 14, 1992, U.S. Pat. No. 5,104,646 to orich et al., issued August 27, 1991. No. 07/758,319, filed by Bolich et al., 1991. Torgerson et al., U.S. Application No. 07/758,32, filed May 27, 2007. No. 0 No. 9 specification, all of which are incorporated herein by reference. (EP No. 0412704 and EP No. 04 published on February 13, 1991) 12707).

Examples of useful polymers and methods for making them also published September 15, 1987 No. 4,693,935 to Mazurek, March 1, 1988. In U.S. Pat. No. 4,728,571 to C1eIlens et al. are described in detail, both of which are incorporated herein by reference.

Preferred ionic silicone macromer-containing polymers have temperatures above about -20°C (and even An organic polymer backbone (preferably vinyl) having a Tg of preferably about 20°C or higher) backbone) and preferably at least about 500 grafted to the backbone. about 1000 to about 100,000, more preferably about 2000 to about 50,000, Most preferably a siloxane having a weight average molecular weight of about 5000 to about 20,000. It consists of a polymer. In addition to the above graft copolymers, silicone-containing polystyrene preferably within about 50% (more preferably from about 10 to about 40%) by weight of one or more siloxane blocks and one or more non-silicone blocks (e.g. acrylic) Also included are block copolymers containing esters or vinyls.

Preferred silicone macromer-containing polymers for use herein are The polymer phase contains silicone moieties when formulated into a composition and dried. It is a polymer that separates into a discontinuous phase containing organic moieties and a continuous phase containing organic moieties.

Ionic hair styling polymers containing silicone macromers are typically contains nonionic silicone-containing monomers along with ionic monomers, and The noted non-silicone-containing nonionic monomers may also be included. silicone The containing monomers can also be ionically charged and themselves contribute a portion to the overall charge density of the polymer. Or contribute entirely.

The silicone-containing hair styling polymer typically contains 0.01% to about 50%, preferably Preferably about 0.5 to about 40% silicone content, more preferably about 2 to about 25%. Contains monomer.

Silicone-containing monomers typically have the following formula: X(Y) 5t(R) Z n 3-m m In the above formula, X is a vinyl group copolymerizable with other monomers of the polymer; Y is a divalent is a linking group; R is hydrogen, lower alkyl (e.g. C-C), aryl, alkyl is alkylamino or alkoxy; Z is a number average of at least about 500 Part of the siloxane polymer has a molecular weight and is attached to the organic polymer backbone. n is 0 or 1; m is an integer from 1 to 3; Of course, Z is under polymerization conditions should be essentially non-reactive.

The silicone-containing monomer contains at least about 500. Preferably about 1000 to about 100 ,000. More preferably about 2,000 to about 50,000. Most preferably about 50 It is preferred to have a weight average molecular weight of from 0.00 to about 20,000. Preferably, It has the following formula: X-C-0-(CH2), -(0), -5i(R ) 3-mm In the above formula, m is 1.2 or 3 (preferably m-1); p is O or is 1; q is an integer from 2 to 6; X is: R is hydrogen or -〇〇〇OH (preferably R2 is hydrogen and R, R, R are each independently alkyl, alkoxy, alkylamino, aryl, alkaryl, water or hydroxyl (preferably alkyl, more preferably methyl); r is at least about 10. Preferably it is an integer from about 5 to about 1500 (more preferably r is about 75 to about 700, most preferably about 100 to about 250).

Particularly preferred are monomers that are p-0 and q-3.

The silicone-containing monomer of this ionic polymer is in the silicone-containing monomer form. Can be polymerized. On the other hand, they are polymerized in the form of their non-silicone-containing precursors, After binding, silicone groups may be added. For example, carboxylic acid such as acrylic acid The xylate-containing monomer is polymerized and then silicone-containing with terminal epoxy groups. It can be reacted with chemical compounds. The result is generally the formula X (Y) S i (R) 3, silicone in a polymer having a structure corresponding to Zm Containing monomers are included herein.

Preferred silicone-containing polymers useful in the present invention typically range from 0 to about 98% (preferably is about 5 to about 98%, more preferably about 50 to about 9096) of nonionic monomers. , consisting of 1 to about 98% (preferably about 15 to about 80%) of ionic monomers, about 0.1 to about 50% (preferably about 0.5 to about 40%, most preferably about 2 to about 25%) is a silicone-containing monomer. Non-silicone containing monomer The combination of about 99%, most preferably about 75 to about 95%).

Exemplary silicone-containing polymers useful in the present invention include = (1) acrylic acid/n- Butyl methacrylate/polydimethylsiloxane (PDMS) macromer-molecule Amount 20,000 (11) Dimethylaminoethyl methacrylate/isobutyl methacrylate/2 -Ethylhexyl methacrylate/PDMS macromer-molecule ff120,00 0(ill)t-butyl acrylate/acrylic acid/PDMS macromer-molecule Quantity 10,000 (iV) t-butyl acrylate/acrylic acid/PDMS macromer - fraction 1 There are 110,000.

Silicone-containing and non-silicones with carboxylate or other acidic functional groups Ionic hair styling polymers, including both polymers contained in the vehicle at least a portion in this composition to promote solubility or dispersibility of the polymer in It is preferable to use it in a neutralized form. In addition, the use of neutralized forms is Aids in the wash removability of the play composition. Generally, the preference for acidic monomers in polymers is preferably about 10 to 100%, more preferably about 20 to about 90%, even more preferably About 40 to about 85% neutralized.

Any conventional organic or metallic base may be used to neutralize the acidic polymer. a The hydroxides of alkaline metals and alkaline earth metals are commonly used in the present hairspray compositions. It is a neutralizing agent. Here various cations are supplied to neutralize the polymer. It will be recognized by those skilled in the art that it also contributes to ionic strength regulation systems such as those described in Ru.

Preferred neutralizing agents for use in the hairspray compositions of the present invention are potassium hydroxide and hydroxide. It is sodium chloride.

Examples of other suitable neutralizing agents that may be included in the hairspray compositions of the present invention include amines, especially amino alcohols, such as 2-amino-2-methyl-1,3-propylene Ropanediol (AMPD), 2-amino-2-ethyl-1゜3-propanedi All (AEPD), 2-amino-2-methyl-1-propatol (AMP) , 2-amino-1-butanol (AB), monoethanolamine (MEA), Jetanolamine (DEA), l-jetanolamine (TEA), monoiso Propaturamine (MIPA), Diisopropaturamine (DIPA), Lysopropaturamine (TIPA) and dimethylsteramine (DMS) There is. Mixtures of amines and metallic bases are particularly useful for neutralization.

Polymers with basic functional groups, such as amino groups, can be treated with acids, such as hydrogen chloride, at least a little. Preferably, it is also partially neutralized.

liquid vehicle The hairspray composition of the present invention also contains a liquid vehicle. This is resin hair spray - Can be anything commonly used in prescriptions. The liquid vehicle is about 80 to about 9 It is present in the hairspray composition at 9%, preferably from about 85% to about 99%. Even better Preferably, the liquid vehicle is present from about 90 to about 98% of the total composition.

Organic solvents suitable for use in the liquid vehicle of the present compositions include C-C alkanols, carbon Pitol, acetone and mixtures thereof. C- Preferred for use in this composition C alkanols such as ethanol, isopropanol and mixtures thereof. C-C-valent alcohols. Water may also be used in the liquid vehicle of the present hairspray compositions. It is a preferable solvent for practical use.

Preferably, the liquid vehicle for the composition is C-C alkanols, water, carpito. selected from the group consisting of alcohol, acetone and mixtures thereof. More preferably , the liquid vehicle for the composition is water and ethanol, C-C such as isopropanol. - selected from the group consisting of alcohols and mixtures thereof.

In general, water may be absent or all of the liquid vehicle. Good too. More preferably, the liquid vehicle is a mixture of water and an organic solvent.

water and organic solvent mixtures, e.g. water-ethanol or water-itubrobanol ether; When nol is used, the moisture content of the composition typically ranges from 0.5 to about 0.5% by weight of the total composition. 9906, preferably within the range of about 5 to about 50%. The smell of such a mixture The organic solvent usually accounts for 0.5% to about 99%, preferably about 50% to about 99%, by weight of the total composition. Exist within 95%.

In one aspect of the invention, the hair setting resin has a particularly high weight average molecular weight, i.e. having a weight average molecular weight of about 300,000 or more, especially about 5C10,000 or more . Incredibly effective hairspray performance is achieved by combining these highly effective hair sprays with an ionic strength control system. It was found that this can be obtained using a molecular weight resin. The present invention is particularly useful at relatively high molecular weights. Regarding the silicone macromer-containing hair setting resin that is preferably used and in hairspray compositions they are sprayed with good spray quality. It is particularly effective in imparting moisturizing properties to resins.

In another aspect of the invention, provided are silicone macromer-containing Ionic hair setting resins, ionic strength adjustment systems as described herein and A low volatility organic solvent hairspray composition comprising a liquid vehicle. The low volatility of the present invention Volatile organic solvent hairspray compositions contain no more than 80% volatile organic solvent (for our purposes) (contains volatile silicone fluids, but excludes water). In other aspects herein, The hairspray composition is about 65%, 55%, as selected by the product formulator. Volatile organic solvents can be included up to 50% or other levels. This low volatility In organic solvent hairspray products, the hairspray composition contains at least 10% by weight Contains water. They are at least about 11%, 1296.13%, 14%, 15% or It is particularly contemplated that the water may contain more water. Contains silicone macromer The weight average molecular weight of ionic hair setting resins allows for effective hair styling. may be at any level suitable for It typically is at least about 5 0,000, more typically at least about 70,000, preferably at least about 1 It is 00.000. As used herein, volatile organic solvents are those containing at least one carbon means a solvent that has atoms and exhibits a vapor pressure of 0, 1 s+sHg or more at 20°C do.

In a more preferred embodiment of this aspect of the invention, the weight average molecular weight of the resin is about 70.0 00 to about 1,000,000, most preferably about 100,000 to about 750,000 It is 00.

Generally, the low volatility organic solvent composition will be within about 90%, preferably within about 70% , more preferably within about 60%, even more preferably within about 50% water and about 10% ~ about 80%, preferably about 20 to about 80%, more preferably about 40 to about 80% Contains volatile organic solvents. Its composition is below other maximum limits with respect to volatile organic solvents. It is particularly contemplated that the scale may be limited to less than, for example, about 75%, 65% or 55%. Ru.

Generally, for this composition, the weight average molecular weight of the styling polymer is Limited only by interest.

It is usually less than 10,000,000, preferably less than about 3,000,000 , more preferably about 1,000°000 or less.

Ionic strength adjustment system The compositions of the invention have no ionic strength modifier as an essential element compared to the same compositions lacking ionic strength modifiers. an effective amount of an ionic strength control system to reduce the viscosity of a hair styling composition. Contains. Generally, the composition contains at least about 0.01% by weight of an ionic strength modifier. including. As will be understood by those skilled in the art, as the ionic strength of the composition increases, The astyling polymer will eventually settle out of solution or even in a liquid carrier. No longer dissolves or disperses. The upper limit of the ionic strength adjustment system level is determined by Specific ionic strength modifiers, liquid vehicles, hair styling polymers present and other ingredients. For this reason, ionic strength modifiers that can be used, e.g. The maximum amount of liquid vehicle contained less water compared to a more aqueous composition. composition, it tends to be less. The composition generally contains about 4% or less by weight; It also generally contains less than about 2%, typically less than about 1%, of an ionic strength modifier.

The composition preferably contains about 0.01% to about 0.5%, more preferably about 0.01% to about 0.5% Contains approximately 0.1% ionic strength adjustment system.

The ionic strength control system includes a mixture of monomer cations and anions. This ion The ions of the strength-modulating system are non-surface active, i.e. they do not significantly reduce surface tension. I won't let you. For this purpose, non-surface active means that the surface tension is 5 at a concentration of 0.5% aqueous solution. , Odyn/cJ or less. Typically, this ionic strength Ions of the regulatory system can be found in either aliphatic chains or linear or branched organic heterochains. having at most 4 or less carbon atoms per charge, preferably 2 or less carbon atoms; It is characterized by

Ionic strength control systems contain monomer ions of the type that are the products of acid-base reactions. . Therefore, basic and acidic ions OH- and H+ are part of this ionic strength adjustment system. however, they may be present in the composition.

The ions are such that they can be present in the composition as free ions, i.e. in dissociated form. It is incorporated into the composition in the form of

It is not necessary that all of the added ions be present in the composition as free ions. Yes, unless they are at least partially dissolved or dissociated in the composition. No. Ionic strength modifiers include, for example, the addition of soluble salts, mixtures of acids and bases. They can be incorporated into hair styling compositions by addition or combinations thereof. ion It is a feature of the present invention that both strength-adjusting anions and cations are contained in the composition. It is an essential aspect of

Suitable cations for use include, for example, lithium, sodium and potassium. Alkali metals such as magnesium, calcium and strontium There are potash earth metals. Among the divalent cations, magnesium is preferred. preferable Some metal ions include lithium, sodium and potassium, especially sodium and potassium. It is um.

Suitable means of addition to this composition include, for example, bases such as hydroxides, hydroxides, etc. Salts that are soluble as sodium and potassium hydroxide as well as in liquid carriers, e.g. For example, the following monomer anions may be added as salts.

Other suitable cations include quaternary ammonium ions and cationic amines, e.g. For example, ammonium di- and triethanolamine, triethylamine, mole Holin, aminomethylpropanediol (AMP), aminoethylpropanediol There are organic ions such as Le et al. Ammonium and amines are salts such as hydrochloride Preferably, it is provided in the form of

Monomeric anions that can be used in hair styling compositions include: Halogen ions such as chloride, fluoride, promide and iosito can be present. especially chloride, sulfuric acid, ethyl sulfate, methyl sulfate, cyclohexyl sulfamide acid, thiosulfuric acid, toluenesulfonic acid, xylenesulfonic acid, citric acid, nitric acid, Hydrogen carbonate, adipic acid, succinic acid, saccharic acid, benzoic acid, lactic acid, boric acid, There are setionic acid, tartaric acid and other monomer anions. Anions are e.g. Acids or salts that are at least partially soluble in the vehicle, such as acetic acid, citric acid, nitric acid. It may be added to this composition in the form of sodium or potassium salts of acids, chlorides, sulfuric acids, etc. I can do it. Preferably, such salts are completely soluble in the vehicle.

The composition may contain up to about 10, preferably about 3 to about 10, more preferably about 5 to about 1 It has an aqueous phase optical pH of 0. For this purpose, the aqueous phase photopH is determined by any nonaqueous pH of the carrier. All of the compositions were different, except that the sexual ingredients were also substituted with an equal weight of double reverse osmosis (DRO) water. It corresponds to the pH of the composition containing all the components.

Preferred low volatility organic solvent hairspray compositions of the invention contain about fluorosurfactants. 0.01 to about 2%; weight average molecular weight of 300,000 or more and less than 300,000 including those having a certain amount of silicone macromer and having and not having a silicone macroma part. from about 0.1% to about 15% ionic resins, including from about 10 to about 45% water and preferably ethanol, by weight of the strength-adjusting system acid. By weight of a composition selected from the group consisting of isopropanol and mixtures thereof. Contains a liquid vehicle consisting of about 50 to about 80% organic solvent.

The levels of commonly used ionic strength control systems are described above. however, or to improve hairspray performance with respect to a particular hairspray composition. The specific level of ionic strength control system that must be used for best performance depends on the specific type of resin selected, its molecular weight and level in the composition, the specific Ionic strength control system, water level, type and level of volatile organic solvents and It is recognized that this can vary depending on a variety of factors, including the presence of optional components in Should. Generally, the lower the resin molecular weight and/or water level, the higher the ionic strength control system is required for performance effects. Generally, this composition The product improves hair feel with a given level of hair retention performance or improved spray quality. It should contain at least an effective amount of ionic strength control system to

Optional ingredients In addition to the ionic strength adjustment system, this composition improves the sprayability of the composition. Other substances may optionally be included. In particular, this ionic strength adjustment system Ionic surfactants can be used in combination with surfactant anions and cations. Conceivable.

Various surfactants are advantageously incorporated into this composition.

These include anionic, cationic, amphoteric and zwitterionic surfactants, including: It includes both fluorinated surfactants and non-fluorinated surfactants such as.

Anionic surfactants include, for example, alkyl and alkenyl sulfates; and alkenyl ethoxylated sulfates (preferably 1 to 10 average ethoxylated sulfates) xylation degree); alkyl sulfosuccinamate and sulfosuccinic acid Succinamate surfactants such as alkyl esters; neutralized fats of isethionic acids acid esters; e.g. olefin sulfonates and β-alkoxyalkane sulfonates; alkyl and alkenyl sulfonates, including esters. C-C sulfate and an ethoxylated sulfate having a degree of ethoxylation of 1 to about 6, preferably 1 to about 4. Alkyl and alkenyl sulfates such as sodium and ammonium salts of and alkyl and alkenyl ethoxylated sulfates, such as lauryl sulfate. ate and laureth (3,0) sulfate are preferred.

Amphoteric surfactants are broadly defined as derivatives of aliphatic secondary and tertiary amines. There are compounds in which the aliphatic group can be straight-chain or branched; , one of the aliphatic substituents has about 8 to about 18 carbon atoms and one is anionic. Contains water-soluble groups such as carboxy, sulfonic acid, sulfuric acid, phosphoric acid or phosphonic acid ing. An example of a compound falling within this definition is sodium 3-dodecylaminopropionate. dodecylamine according to the disclosure of U.S. Pat. No. 2,658,072. N-alkyl tau as produced by reaction with sodium isethionate Phosphorus, such as produced according to the disclosure of U.S. Pat. No. 2,438,091. N-higher alkyl aspartic acid and trade name “Miranol” The product described in U.S. Pat. No. 2,528,378, sold as Ru. Others are alkyl, preferably C6-C most preferably C-C amphoglycine 22' 8 12 Alkyl, preferably C-C, most preferably C810 amphopropionate and mixtures thereof.

1 Suitable zwitterionic surfactants for use in the present compositions include aliphatic quaternary ammonium, phosphonic Compounds that can be broadly described as derivatives of umium and sulfonium compounds In that case, the aliphatic group is straight chain or branched, and the aliphatic substituent group is exemplified by One has a carbon radical reservation of 8 to 18 and one has an anionic water-soluble group, e.g. It has boxy, sulfonic acid, sulfuric acid, phosphoric acid or phosphonic acid. These compounds The general formula for the product is: where R2 is an alkyl group of about 8 to about 18 carbon atoms. alkenyl or hydroxyalkyl group, from 0 to about 10 ethylene oxide moieties and 0 to about 1 glyceryl moieties; Y consists of nitrogen, phosphorus, and sulfur atoms; selected from the group consisting of; R3 is alkyl having 1 to about 3 carbon atoms; is a xyalkyl group; X is 1 when Y is sulfur or phosphorous, and when Y is nitrogen R4 is alkylene or hydroxyalkyl of 1 to about 4 carbon atoms; is: Z is from carboxylic acid, sulfonic acid, sulfuric acid, phosphonic acid and phosphoric acid groups A group selected from the group consisting of:

Bipolar types include alkylaminosulfonates, alkylbetaines, and alkylaminosulfonates. Contains rukylamidobetaines.

The cationic surfactants useful in the compositions of the invention are dissolved in the aqueous compositions of the invention. contains an amino or quaternary ammonium hydrophilic moiety that is positively charged when useful here All cationic surfactants contained in the material are incorporated herein for reference. Disclosed in the literature: M.C.Publishing Co., McCut cheon’s, DeLergents & Eils+rlers (Nor th American editlon, 1979); Schwartz et al. , 5surface Active Agents, Their CherAis Tryand Technology, New York: Interscj ence Publishers.

1949; It　i　I　f　e　R rice issued on November 3, 1964 National Patent No. 3,155,591; Lau issued on December 30, 1975 No. 3,929°678 to Ghlin et al.; issued May 25, 1976; U.S. Pat. No. 3,959.461 to Balley et al., June 7, 1983. No. 4,387°090 to BOllehir, issued on .

Useful quaternary ammonium-containing cationic surfactants include the following general formula: There is: In the above formula, R is an aliphatic group having 1 to 22 carbon atoms or an aromatic group having 12 to 22 carbon atoms. is an aromatic aryl or alkylaryl group: R2 has 1 to 22 carbon atoms; R and R4 are each an alkyl group having 1 to 3 carbon atoms; Ru;X is! - an alkyl selected from halogen, acetic acid, phosphoric acid, nitric acid and alkyl sulphate groups; It is Nion.

Aliphatic groups include, in addition to carbon and hydrogen atoms, others such as ether linkages and amide groups. It may also contain a group of Other quaternary ammonium salts useful here are diquaternary ammonium salts. It is mu salt.

Preferred quaternary ammonium salts include hydrogen atoms with 12 to 22 carbon atoms in the alkyl group. Dialkyldimethylammonium derived from long chain fatty acids such as added tallow fatty acids There are chlorides (tallow fatty acids are tetrachlorinated fatty acids in which R and R2 mainly have 16 to 18 carbon atoms). ).

Salts of -class, secondary and tertiary fatty amines are also used here.1 Suitable cationic surfactants It is a drug. The alkyl group of such amines preferably has 12 to 22 carbon atoms. may be substituted or unsubstituted. Secondary and tertiary amines are preferred, with tertiary amines being preferred. Mines are particularly preferred. Such amines useful here include stearamide. Propyl dimethylamine, diethylaminoethyl stearamide, dimethyl stear Lamin, dimethyl soyamine, soyamine, myristylamine, tridecylamine N, ethylstearylamine, N-tallowbrobandiamine, ethoxylation (5 Mol E, O,) stearylamine, dihydroxyethylstearylamine and a Laxylbehenylamine is present.

Among those useful in the present invention are cationic amine surfactants (for reference only). (Incorporated herein) Nachtigal, dated June 23, 1981 It is disclosed in U.S. Pat. No. 4,275,055 to et al.

Suitable cationic surfactant salts include halogen, acetic, phosphoric, nitric, citric, Lactic acid and alkyl sulfate salts are also included in the composition as nonionic surfactants. be able to. Preferably, the nonionic surfactant has an average HLB of about 7 or less ( It has a hydrophilic-lipophilic balance).

Methods for determining HLB are well known in the art, and any such method is commonly used. For an explanation of the HLB system and HLB determination method, see 'Thet+LB　S system: a timesaving guide to eIlluls irler 5 selection” (HL B system: time saving for emulsifier selection) Guide), IcI Hericas Inc,.

VIImington, Delavare, 197 [i.

Polyethylene oxide condensation of alkylphenol is used as a nonionic surfactant. (preferably C-C alkoxy, degree of ethoxylation from about 1 to about 6), ethyleneoxy The condensation product of hydrogen and the reaction product of propylene oxide and ethylene diamine, Aliphatic alcohols and ethylene oxide, long chain (i.e. typically C-C) tertiary amide long chain tertiary phosphine oxide, one long chain alkyl or hydroxy A dialkyl sulfo group containing an alkyl group and one short chain (preferably a C-C> group) acid, silicone copolymer, C-C alkanoate of acid with C-C acyl moiety There are condensation products with Ruamide.

The fluorosurfactants (i.e., fluorinated surfactants) useful in the present compositions are preferably is a fully or partially fluorinated straight chain with a chain length of 3 to 18 carbon atoms or a branched alkyl, alkenyl or alkylarylfluorohydrocarbon. . Hydrophilic moieties are e.g. sulfuric acid, phosphoric acid, phosphonic acid, sulfonic acid, amine, amine salts, quaternary ammoniums, carboxylic acids, and combinations of any of these. Furthermore, There are also bridging moieties between hydrophilic and hydrophobic moieties, such as amide alkaline groups. good.

Ionic fluorosurfactants useful in the present compositions include perfluorinated surfactants of the formula: There is a compound: CF3- (CF2) x-(CH2), -Z In the above Z is either an organic or inorganic water-soluble group; X is usually 2 to 17, especially 7 to 11 is an integer of: y is an integer of 0 to 4: The above compound depends on the nature of the group contained in Z. They are cationic, anionic, amphoteric or dipolar, depending on the case. Z group is sulfuric acid, sulfone Acids, carboxylic acids, amine salts, quaternary ammonium, phosphoric acids, phosphonic acids and the like or a combination thereof.

Perfluorinated compounds are known in the art. These compounds were introduced on November 2, 1979. U.S. Pat. No. 4,176,176 to Ce1la et al., issued on 7th, 1976. No. 3,993°745 issued to Ce1la et al. ; U.S. Pat. No. 3,993 to Cela et al., issued November 23, 1976; , 744, each of which is incorporated herein by reference.

Preferred cationic fluorosurfactants for use in the present compositions include ioside, chloride, Various anionic counterions, preferably is a fluorinated alkyl quaternary ammonium salt having iosite; E, 1. dupont DuPont deNemours and Co. mpany) (Wilmington, Plowea.

Formulas such as ZONYL FSC supplied by DuPont, USA %formula%) There are fluorosurfactants that comply with. Preferred fluorinated alkyl quaternary ammonium Yoshit is a member of Minnesota Mining & Manufacturing (Mlnnneso). ta Mining & Manuf'acturlng) (St. Paul, MI) FLUORAD FC supplied by Nesota, USA; 3M) -135.

Preferred anionic fluorosurfactants for use in the present compositions are supplied by DuPont. general formula %formula%) mono- and bisperfluoroalkyl phosphates such as Zonyl FSP according to; ammonium, sodium, carbonate, such as Zonyl FSJ supplied by DuPont. various cations such as triethanolamine and jetanolamine salts. non-fluorinated quaternary, preferably is a mono- and bisfluoroalkyl phosphate complexed with aliphatic quaternary methosulfate. Sphate; Formula % Formula % supplied by DuPont ammonium, sodium, potassium, such as Zonyl TBS according to NH4') , various cationic pairs such as triethanolamine and jetanolamine salts perfluoroalkylphosphonic acids with ions, preferably ammonium salts; Ammonium, sodium, potassium, such as Zonyl RP supplied by DuPont Various cations such as um, triethanolamine and jetanolamine salts a telomer phosphate with a sexual counterion, preferably a jetanolamine salt; Amine perfluoroalkyl such as Fluorad FC-99 supplied by 3M Sulfonate; Fluorad FC-93, Fluorad FC-1 supplied by 3M Ammonium perfluoroalkyl sulfonates such as 20 and L-12402 ; such as Fluorad FC-95 and Fluorad FC-98 supplied by 3M; Potassium perfluoroalkyl sulfonate; Fluorad FC supplied by 3M -129 and fluorinated alkyl carboxylic acids such as Fluorad F C-109. Perfluorinated metals such as Fluorad FC-1430 supplied by 3M Ammonium alkylcarboxylate; such as Zonyl FSA supplied by DuPont general formula %formula%)) It is a fluorosurfactant according to the following.

Preferred anionic fluorosurfactants are mixed mono- and bisperfluoroalkyl surfactants. complexed with aliphatic quaternary methosulfates Mixed mono- and bisfluoroalkyl phosphates, ammonium salts; perfluorinated Roalkyl sulfonic acid, ammonium salt: mixed telomer phosphate jetano amine salt; amine perfluoroalkyl sulfonate; perfluoroalkyl Ammonium sulfonate; Potassium perfluoroalkyl sulfonate; Fluorinated Potassium alkyl carboxylate; ammonium perfluoroalkylsulfonate, Ammonium perfluoroalkylcarboxylate.

Preferred amphoteric fluorosurfactants for use in the present compositions are 3M to Fluorad FC. -100, a fluorinated alkyl amphoteric surfactant.

Preferred zwitterionic fluorosurfactants for use in the present compositions are supplied by DuPont. Formula % formula % like Zonyl FSK ( 1' (CI'' CI')).

Preferably, an amphoteric or dipolar fluorosurfactant and an anionic fluorosurfactant are used. A mixture with an active agent or a mixture of anionic and cationic fluorosurfactants is used.

The use of fluorosurfactants is particularly useful in low volatility organic solvent compositions, most specifically silicon Preferred in compositions containing corn macromer-containing polymers.

The surfactant is preferably from about 0.01% to about 2%, more preferably from about 0.01% to about 1%. ．． It is included in the composition at a level of 5%, most preferably from about 0.01 to about 1%.

plasticizer The performance of hair styling polymers is determined by the optional inclusion of non-volatile plasticizers in the composition. can be improved. The plasticizer is typically 1:20 to about 1:1, preferably about 1:1. present in the composition in a weight ratio of plasticizer to styling polymer of from 15 to about 1.2; . “Non-volatile” as used herein with respect to plasticizers means that it has a vapor pressure at atmospheric pressure and 25°C. This means that it essentially does not show. The polymer-liquid vehicle solution contains volatile capacitors. This is the reason why there is no substantial plasticizer weight loss when the rear is evaporated. This may be because it excessively reduces plasticization of the polymer during use. Plasticity useful here The agent should normally have a boiling point of about 250°C or higher.

Plasticizers are well known in the art and include the Lurk-Othmer Encyclopedia. a or Chemical Technology, 5econd edlti on.

Volume 15. pp, 720-789 (John Wiley & 5 ons, lnc, NevYork, 1968)) Tube heading “Plasticizer” and and J, Kern 5ears and Joseph I? , Darby, The T. technology or plasticizers (John Vlley & 5ons, Inc., New York, 1982). , both of which are incorporated herein by reference. In particular, various plasticizers have been disclosed. Appendlx of 5ears/Darby, Table^, 9,9 See 83-1063.

Plasticizers include both cyclic and non-cyclic non-volatile substances. Suitability of non-volatile plasticizers Important categories include adipates, phthalates, isophthalates, azelates, and sulphates. Tearate, citrate, trimellitate, silicone copolyol, isoC- C alcohol, methylalkyl silicone, carbonate, sebacate, isobutylene Tograte, Oleate, Phosphate, Myristate, Lysylate, Veral Gonate, valerate, oleate, camphor, castor oil and silicone copo Including Riolu.

Examples of adipate plasticizers include diisobutyl adipate, bis(2- ethylhexyl), diisodecyl adipate, bis(2-butoxyethyl adipate) di-n-hexyl adipate) and adipic acid derivatives such as di-n-hexyl adipate.

Examples of phthalate plasticizers include dibutyl phthalate, butyloctyl phthalate, and phthalate. Di-n-octyl talate, diisooctyl phthalate, bis(2-ethyl phthalate) hexyl), n-octyl n-decyl phthalate, di-n-hexyl phthalate, Isooctyl isodecyl tarate, diisodecyl phthalate, ditridecyl phthalate , butylcyclohexyl phthalate, butylbenzyl phthalate, dicyclophthalate Hexyl, diphenyl phthalate, isodecylbenzyl phthalate and bis phthalate There are phthalic acid derivatives such as (2-butoxyethyl).

Isophthalate plasticizers include bis(2-ethylhexyl) isophthalate. .

Examples of azelate plasticizers include di(2-ethylhexyl azelate) and azelate plasticizers. There are azelaic acid derivatives such as bis(2-ethylhexyl)lineate.

Examples of stearate plasticizers include n-butyl stearate and acetoxy stearate. stearic acid derivatives such as butyl stearate and butoxyethyl stearate. .

Examples of citrate plasticizers include acetyl tri-n-butyl citrate, tri-n-butyl citrate, Ene such as tri-2-butyl and acetyl tri-2-ethylhexyl citrate There are acid derivatives.

An example of a trimellitate plasticizer is tri(2-ethylhexyl trimellitate) and triisooctyl trimellitate.

Other examples of plasticizers include dibutyl carbonate, butyl oleate, n-butyl butyrate, and Isobutyl acid, isopropyl butyrate, ethyl palmitate, isooctate valmitate Chil, methyl ricinoleate, butyl ricinoleate, diisooctyl sebacate, Triisobutyl phosphate, isodecyl pelargonate, ethyl valerate, isocetyl acetate alcohol, octadodecanol, isopropyl myristate, isostearyl alcohol, C-C alkyl and siloxane monomer units having from 1 to about 500 Tylalkyl silicone, silicone copolyol, e.g. dimethicone covolio There is a rule.

hair spray composition The hair spray composition of the present invention can be used in an aerosol dispenser or pump spray dispenser. It can be dispensed from a container that is a dispenser. dispenser like this , containers are well known to those skilled in the art and are manufactured by American National Can Company. ican National Can Corp.) and Continental Can Corp. Various manufacturers including Continental Can Corp. It is commercially available.

When the hairspray composition is dispensed from a pressurized aerosol container, one or more conventional A propellant consisting of an aerosol propellant known as It will be done.

A suitable propellant for use is any liquefied gas commonly used in aerosol containers. It's okay.

Propellants suitable for use are volatile hydrocarbon propellants, including propane, butane, There are liquefied lower hydrocarbons of 3 to 4 carbon atoms such as carbon and isobutane. other suitable The propellant is supplied by DuPont as Dymel 152A. Hydrocarbons such as 1,2-difluoroethane (hydrofluorocarbon 152A) It is a fluorocarbon.

Other examples of propellants are dimethyl ether, nitrogen, carbon dioxide, nitrous oxide and atmospheric gas. It is

Hydrocarbons, especially isobutane, used alone or mixed with other hydrocarbons are preferred. Delicious.

Aerosol propellants may be mixed with the composition, and the amount of propellant mixed is governed by standard factors well known in the aerosol industry. Liquefied propellant field the propellant level usually ranges from about 10% to about 60% by weight of the total composition, preferably from about 15 to about 50% by weight of the product. On the other hand, from American National Can Co. A spout like a two-compartment can sold under the product name SEPRO. Pressurized aerosol dispenser in which the propellant is separated from contact with the hairspray composition - can also be used.

Other suitable aerosol dispensers require that the propellant be pumped or characterized by being compressed air that can be filled into a dispenser It is. Both such dispensers are incorporated herein for reference. No. 01 ofsson U.S. Pat. No. 4,077.4, issued March 7, 978. No. 41 and TerStege U.S. Pat. No. 41, issued July 25, 1989. No. 4.850,577, incorporated herein by reference. U.S. Application No. 07/839, 64 of Gosseln et al., filed February 21. It is described in Specification No. 8. Compressed air aerosol containers suitable for use also block - From Procter & Gamble Company Their product name Baidal Sassoon Airsuf 1/-(VIDAL 5ASSO ON　AIR3PRAYo)　He7 spray plate is currently available on the market.

Also uses conventional non-aerosol pump spray dispensers, i.e. atomizers can.

other ingredients The hairspray formulations of the present invention may be combined with a variety of other hairspray supplements as known in the art. Auxiliary agents may optionally be included. The composition typically contains 0.05-5% by weight, Preferably it contains about 0.1 to 3% adjuvant. As a hairspray adjunct, it is emollients; lubricants and penetrants such as various lanolin compounds; Protein hydrolysates and other protein derivatives; ethylene adducts and polyoxygenates cyethylene cholesterol; dyes, hair dyes and other coloring agents; sunscreens; fragrances; There is a fee.

how to use The hair spray composition of the present invention exhibits the hair quilling/holding effect of the present invention. It is commonly used to

Such methods usually involve applying an effective amount of product before or after the hair is styled, or both. Spray on dry or wet hair. “Effective amount ° refers to the length and texture of the hair. It means an amount sufficient to provide the desired hair volume and style effect in consideration.

The following examples illustrate the invention. The examples are given merely for illustrative purposes and are not intended to limit the invention. Many variations of the invention may be construed as limiting its spirit and scope. possible without deviating from

example Example I-XV1 The hairspray composition of the present invention is manufactured according to the following recipe.

■60% t-butyl acrylate/20% acrylic acid/20% silicone (PD MS) Macromer - Example 11 Weight average molecular weight approximately 150,000° Example + 1-Vl, weight Weight average molecular weight approximately 1.7 million; Example Vll-XIV, weight average molecular weight approximately 800°0 00; Example xv-xv+, weight average molecular weight approximately 1.2 million potassium dihydroxide 45%, Potassium hydroxide solution containing 55% water and trace components, except for examples xv and x■1. A 10% aqueous solution of potassium hydroxide is used.

3 double reverse osmosis water 'E, 1. DuPont de Nemours (Wilmington, Plowea, US) Fluorosurfactant 4 according to formula F(CF20F2)3-8) supplied from A) 7%, acetic acid 53% and trace components. Lu-1-brono-pai-nol hairspray formulation is a polymeric formulation in isopropanol. Produced by forming a remix and then adding ethanol. Example 1. For XV and XVI, add the polymer directly to the ethanol. magnetic or pneumatic Using a stirrer, stir the ingredients until the polymer is dissolved, typically about 1 to 2 hours. mix. If used, then add a neutralizing agent (KOH, AMP or ) and mix to make a premix. The fluoro field may then be applied The surfactant, any salt and water are combined into a composition.

Adjuvants may also be added to the compositions, including, for example, perfumes and fragrances. manufactured hairs The play composition is particularly suitable for pump spray applications. Its composition has a good spray It is characterized by its hair suitability characteristics and hair styling performance.

Example XV11 Hairspray compositions of the present invention suitable for pump spray dispensers include: Sea urchin production: Ingredients weight% Ethanol 200 proof 78.5 Isoproper tool l014 hair styling polymer 12.6 K OH (45%) 0.7 DRO water 7,0 Fluorad PC-12020,4 Zonil F S K O, 5 ! 60% t-butyl acrylate/20% acrylic acid/20% PDMS macroma - has a weight average molecular weight of about 1,700,000.

2 Ammonium perfluoroalkyl sulfonate 25%, ethanol 37.5% , Minnesota Mining and Manufacturers containing 37.5% water and trace ingredients. Supplied by Factoring Corporation (3M) (St. Ball, Minnesota, USA) Fluorad FC-120 is prepared as in Example 1-XVI.

Example XVII+ Hairspray compositions of the present invention suitable for pump spray dispensers include: Sea urchin production: Ingredients weight% Ethanol 200 proof 89.1 hair styling polymer 12.6 K OH (45%) 0.7 DRO water 7.0 Fluorad PC-12020,1 Zonil F S K O, 5 ■60% t-butyl acrylate/20% acrylic acid/20% PDMS macroma - has a weight average molecular weight of about 1,700,000.

Prepared as in Example 1-XVI.

Example XIX Hairspray compositions of the present invention suitable for pump spray dispensers include: Sea urchin production: Ingredients weight% Ethanol 200 proof 78.8 Isoproper tool 10.4 hair styling polymer 12.6 K OH (45%) 0.8 DRO water 7.0 Fluorad FC-12020, 4 Zonyl F S K 0.04 ■60% t-butyl acrylate/20% acrylic acid/20% PDMS macroma - has a weight average molecular weight of about 580,000.

Prepared as in Example 1-XVI.

Example XX-XX I + Hairspray compositions of the present invention suitable for pump spray dispensers include: Sea urchin production: Ethanol 200 proof 71.1 71.2 71.2 iso Property Tools 9.5 9.5 9.5 ■ Hair quilling polymer-2, 42, 42, 4K OH (45%) 0.6 0 ．． 6 0.8 DRO water 16.2 16.2 1B, 2 Zonyl T B S 20 ．． 15 0.05 Zonyl F S K O,050,10,07160% t-butylene Acrylate 720% acrylic acid/20% PDMS macromer, approx. soo,o It has a weight average molecular weight of oo.

2 Perfluoroalkyl sulfonic acid ammonium salt 30-35%, acetic acid 2.4% and an anionic surfactant solution supplied by DuPont containing 65-70% water. Nil TS Prepared as in Example 1-XVI.

Examples XXIII-XXV Ethanol 200 proof 78.9 79.4 78.2 Isopropanol 10.4 10.4 11.2 Aquiring Polymer' 2.8 2.6 2.8AMP　O,2-- K OH (45%) 0.6 0.4 0.5 DRO water 7.0 7.0 7. 0 Fluorad PC-1200, 10, L O, 2zonyl F S K O, 050, 050,09 Zonyl TBS O,07- Air freshener 0.07 0.03 - 'About 860. 000 (Example XXII+), 1. 5 million (Example XXIV) and 1 ．． 60% t-butyl acrylate with a weight average molecular weight of 7 million (Example XXV) /20% acrylic acid/20% silicone macromer Prepared as in Examples IX-XVI.

Example XXV + Hairspray concentrate compositions of the present invention suitable for aerosol dispensers include: Sea urchin production: Ingredients weight% Ethanol 200 proof 95.8 Hair styling polymer 13. O K OHO, 8 A　M　P　0.4 Zonil F S K O, 25 '60% t-butyl acrylate/20% acrylic acid/20% silicone macro has an average molecular weight of about 690,000.

Mono- and bisfluoroalkyl phosphates complexed with two aliphatic methosulfates. Contains 40% sphate, 15% isopropyl alcohol and 40-45% water. Zonyl FSK supplied by DuPont Prepared as in Example 1-XVI. Pour the concentrate into a conventional aerosol spray can. packaged with a conventional liquefied propellant at a propellant:concentrate weight ratio of 30 nia Fill.

Example, XXVII-XXX Ingredients (vt%) XXVII XXVIII XXIX XXX Ethanol 20 0 proof 79.3 80.1 79.3 79.5 isopropanol 10 ．． 4 10.4 10.4 10.4 Hair Styling Polymer '2.6- Hair Styling Polymer 2-1.8 Hair Styling Polymer 3- −2.0− Hair styling polymer' --1,8KOH (10% aqueous solution) --1,2 1,2MCI (10% aqueous solution) 0.60. [i--DRO water 7.0 7. 0 7.0 7.0 Potassium chloride o, to o, to o, io o, t.

115% t-butylaminoethyl methacrylate/15% t-butylacryl Mido/70% ethyl methacrylate, having a weight average molecular weight of approximately 1.2 million.

215% t-butylaminoethyl methacrylate/15% t-butylacryl Mido/60% ethyl methacrylate/10% PDMS7 chromer (approximately 10.OO o) has a weight average molecular weight of approximately 1.2 million.

315% N,N-dimethylacrylamide/70% isobutyl methacrylate/ 15% acrylic acid, with a weight average molecular weight of approximately 1.2 million.

415% N,N-dimethylacrylamide/60% isobutyl methacrylate/ 15% acrylic acid/10% PDMS macromer (weight average molecular weight of approximately 10,000 weight average molecular weight of about 1.2 million.

Prepared as in Examples I-XVl, except that in Examples XXVII and XXV I Add MCI as a neutralizing agent.

The above composition exhibits good sprayability and has good sprayability on hair (when applied to hair). Demonstrates styling effects.

The above examples and their combinations using silicone macromer grafted styling resins The composition has a viscosity of less than about 10,000,000 centistokes at 25°C. unreacted silicone-containing upper layer and silicone macromer-grafted polyester with It is desirable to purify the styling resin by removing the mer. It's your turn? JE+? This can be done by hexane extraction. Dry the resin from the reaction solvent After that, the reaction product is extracted with hexane. This can be done by heating the polymer to near the Tg of the non-silicone portion of the polymer.

The mixture is kept at this temperature with stirring for about 30 minutes and allowed to cool to room temperature. Hexa Remove the tube by vacuum suction. (Same as above for these two hexane extraction cycles) 1 cycle (preferred; remove residual hexane remaining with product after third cycle) Remove by distillation and vacuum drying.

A low molecular weight polysiloxane-containing monomer and a polymer are heated to a supercritical temperature for about 1 hour. A transfer line fused with carbon oxide and maintained at the same temperature and pressure as the extraction vessel. and remove it from the residual polymer. Collect the extracted material in an extraction vessel. After extraction, The system is dried under vacuum and the extracted polymer is collected from the extraction vessel.

The above examples and their combinations using silicone macromer grafted styling resins In the composition, the resin has a temperature of greater than about 10,000,000 centistokes at 25°C. Unreacted silicone-containing monomers and silicone macromers with viscosity below It can be purified by removing the fluorinated polymer. For example, this is hexane This can be done by extraction. After drying the resin from its reaction solvent, the reaction product is Extraction involves adding excess hexane to the reaction product to remove the T of the non-silicone portion of the polymer. This can be done by heating to close to g. Stir the mixture for about 30 minutes. temperature and allow to cool to room temperature. The hexane is removed by vacuum suction. Furthermore Preferably, two hexane extraction cycles are performed as described above. third cycle Afterwards, the residual hexane remaining with the product is removed by distillation and vacuum drying.

, --N@PCT/US 92106975 Front page continuation (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, SE), 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD , TG), AtJ, BB, BG, BR, CA, C3, FI, HU.

JP, KP, KR, LK, MG, MN, MW, No, PL, R O,RU,5D (72) Inventor Torgerson, Beater Mart, Ohio, USA Shinton,

Claims (19)

[Claims] 1. (a) an ionic hair stylist having a weight average molecular weight of at least 300,000; (b) water, C1-C6-hydric alcohols and mixtures thereof; (c) a liquid vehicle selected from the group consisting of; (c) for reducing the viscosity of the composition; an effective amount of an ionic strength control system, in which the monomer cation and monomer anion consisting essentially of a mixture, said cations and anions being non-surface-active; at least partially soluble in the liquid vehicle); , and has a pH of 10 or less, which is useful for spray application to hair. illing composition. 2. Ionic hair styling polymer 0.1-15% by weight, liquid vehicle 80% ~99.5% by weight and 0.01-4% by weight of an ionic strength adjustment system. Liquid hair styling composition as described. 3. Ionic hair styling polymers contain 2-75% ionic monomers and non-ionic monomers. Liquid hair style according to claim 1 or 2, comprising 25 to 98% of onic monomer. composition. 4. (a) an ionic hair stylist having a weight average molecular weight of at least 300,000; hair styling polymer (its ionic hair styling polymers are silicone-containing polymers) When the composition is dried, the hair styling polymer A discrete phase containing the silicone portion of the remer and a continuous phase containing the non-silicone portion separate into phases); (b) selected from the group consisting of water, C2-C4-hydric alcohols and mixtures thereof; (c) an effective amount of ionic strength to reduce the viscosity of the composition; Regulatory system (which system consists essentially of a mixture of monomer cations and monomer anions) The cations and anions are non-surface active and present in small amounts in the liquid vehicle. spiders are at least partially soluble); and having a pH of 10 or less, which is useful for spray application to hair. illing composition. 5. the polymer comprises at least 0.5% silicone macromer-containing monomer; 5. A liquid hair styling composition according to claim 4. 6. The claimant contains 5-95% ionic monomers and 5-95% non-ionic monomers. Liquid hair styling composition according to claim 4 or 5. 7. the cation is sodium, potassium, magnesium or a mixture thereof , the anion is sulfuric acid, acetic acid, chloride or a mixture thereof, Liquid hair styling composition according to 3, 4, 5 or 6. 8. A weight average of at least 500,000 ionic hair styling polymers The liquid hair style according to claim 1, 2, 3, 4, 5, 6 or 7, having a molecular weight. composition. 9. Ionic monomers include acrylic acid, methacrylic acid, dimethylaminoethyl meth Acrylate, quaternized dimethylaminoethyl methacrylate, maleic acid, anhydrous Half ester of leic acid, crotonic acid, itaconic acid, diallyldimethylammonium muchloride, vinylpyridine, vinylimidazole, styrene sulfonate or It is a mixture of these, in which the nonionic monomer is an acrylate of C1-C24 alcohols. Lyric acid ester, methacrylic acid ester of C1-C24 alcohols, styrene , polystyrene macromer, vinyl acetate, vinyl chloride, vinyl propionate, salt vinylidene, α-methylstyrene, t-butylstyrene, butadiene, cyclo From hexadiene, ethylene, propylene, vinyltoluene and mixtures thereof The liquid hair spray composition according to claim 3 or 6, selected from the group consisting of: 10. Hairspray composition and spray containing the composition for spraying A liquid hairspray product comprising a dispenser means, said composition is contained in said spray dispenser means, said hair spray The composition is; (a) hair styling polymer containing ionic silicone macromer; (b) selected from the group consisting of water, C1-C6-hydric alcohols and mixtures thereof; (c) an effective amount of ionic strength to reduce the viscosity of the composition; Regulatory system (which system consists essentially of a mixture of monomer cations and monomer anions) The cations and anions are non-surface active and present in small amounts in the liquid vehicle. spiders are at least partially soluble); , the composition has a pH of 10 or less, 10 to 90% by weight of water and the monovalent Products containing 10 to 80% alcohol by weight. 11. Hair styling polymer 0.1-15% by weight, C2-C4-valent alcohol 80-99.5% by weight of a liquid vehicle selected from the group consisting of water and water; Liquid hairspray product according to claim 10, comprising from 0.01 to 4% by weight of strength-adjusting system. Goods. 12. The cation is sodium, potassium, magnesium or a mixture thereof. and the anion is sulfuric acid, acetic acid, chloride or a mixture thereof. is a liquid hair spray product according to item 11. 13. The silicone macromer-containing monomer has the following formula; mZm 1 In the above formula, X is a vinyl group; Y is a divalent linking group; R is hydrogen, lower alkyl Z has a number average molecular weight of at least 500 is a monovalent siloxane polymer moiety; n is 0 or 1; m is an integer from 1 to 3 The liquid hairstylist according to claim 4, 5, 6, 10, 11 or 12, having Tiling composition or product. 14. Silicone macromer-containing monomer; ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formula, m is 1, 2 or 3, p is 0 or 1, q is an integer from 2 to 6; X is: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (R1 is -H or -COOH; R2 is -H, -CH3 or CH2COOH ); R4 is alkyl, alkoxy, alkylamino, aryl or is hydroxyl; Z is; ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (in the above formula, r is an integer from 5 to 700)] according to claim 13. Liquid hair spray composition or product. 15. the polymer contains at least 0.5% silicone macromer-containing monomer , a liquid hairspray product according to any one of claims 10 to 14. 16. Containing 5-95% ionic monomers and 5-95% non-ionic monomers, A liquid hairspray product according to any one of claims 10 to 15. 17. Ionic monomers include acrylic acid, methacrylic acid, and dimethylaminoethylmethane. Tacrylate, quaternized dimethylaminoethyl methacrylate, maleic acid, anhydride Half ester of maleic acid, crotonic acid, itaconic acid, diallyldimethylammonium Umchloride, vinylpyridine, vinylimidazole, styrene sulfonate or 17. A liquid hairspray composition or product according to claim 16, wherein is a mixture thereof. . 18. The polymer contains 15-80% ionic monomers and C1-C24 alcohols. Acrylic acid ester, methacrylic acid ester of C1-C24 alcohols, steel Ren, polystyrene macromer, vinyl acetate, vinyl chloride, vinyl propionate , vinylidene chloride, α-methylstyrene, t-butylstyrene, butadiene, silica Chlorexadiene, ethylene, propylene, vinyltoluene and mixtures thereof 50-90% of a nonionic monomer selected from the group consisting of 18. A liquid hairspray composition or product according to claim 17, comprising 2-25% Nomer. . 19. Spraying an effective amount of the composition according to any one of claims 1 to 18 onto the hair. A method for giving hair a setting effect, which consists of curling the hair.