NL7809963A - Hair spray contg. drag reducing agent - giving better hair control, with lower resin content - Google Patents

Abstract

A hair spray, in a container from which the compsn. can be sprayed onto the hair, contains 0.4-7.k wt.% of a hair-spray resin, a solvent for the resin, opt. a propellant, and 0.3 wt.% of a drag reducing agent (I). The ratio by wt. of resin: I is 10000-2:1. The usual resins, solvents and propellants are used. I is pref. sol. in ethanol, CH2Cl2 or water, and esp. has a drag reducing capacity of >=2% (>=10%). PRef. I are non-ionic and are: (a) water-sol. polyoxyethylene with mol. wt. >4 x 105: amts of 50 ppm are effective: (b) hydroxypropylcellulose, esp. with mol. wt. >5 x 105, or (c) a polyacrylic elastomer, e.g. poly(ethyl acrylate). Cationic high-mol. cellulose polymers contg. quat. N atoms can also be used. The amt. of I is partic. =0.2 wt.% of the hair spray, and the ratio of resin: I is esp. 5000-5:1. The capacity of the spray for keeping the hair in place is increased and smaller amts. of resin can be used (esp. 0.4-5 wt.%). The amt. of spray which is inhaled by the user is lessened.

Description

'1 · t - 1 - J 498 (L)

Applicant: Unilever N.V. in Rotterdam Short designation: Hair spray product

* Applicant mentions as inventor: Roger William PENGILLY

35 Stoneleigh Avenue, Worcester Park, Surrey, England

The invention relates to hair spray products (hair sprays), also referred to as hair sprays.

Hair sprays are products containing film-forming resins that help keep the hair in place when applied to it. The film-forming resin can be sprayed onto the hair with different types of dispenser. For most hair sprays, aerosol containers are used from which the product is metered with a propellant, but currently pump atomizers are used, whereby a mechanical pump is used to dose the product, in which the film-forming resin is incorporated, as a dosing device more and more. usual. Hair sprays can also be applied to the hair from a so-called "squeeze package", the pressure being applied to the package by squeezing, for dosing the product through the spray opening. The product sprayed on the hair contains a solution of the hair spray resin (hair spray resin) in a suitable solvent, which usually consists of an alcoholic or aqueous alcoholic solvent.

The invention relates to an improvement in the ability of a hair spray to hold the hair in shape (shape holding capacity).

20 7809963 t - 2 - J 498 (L)

It has been found that an unexpected increase in the shape retention capacity of a hair spray can be easily achieved by adding a small amount of a drag reducing agent to the hair spray.

5

The invention relates to hair spray products which can contain a hair spray with 0.4 to 7.5 wt% hair spray resin, a hair spray resin solvent and, if desired, a propellant and are contained in a container suitable for spraying the hair spray on hair, characterized in that these products contain a frictional resistance reducing agent in a concentration of less than 0.3% by weight of the hairspray and in a hairspray resin to frictional resistance reducing agent weight ratio of 10,000 to 2: 1 and the shape retaining power of the hair spray is improved.

15

According to the present invention, the shape holding ability of the hair spray resin used can be greatly increased, and to an extent far exceeding the advantage that could be predicted. The amounts of friction-reducing agent added and effective to improve the shaping ability of the hairspray are so small, which will be explained hereinafter, that one would not expect any noticeable improvement in shaping ability at all.

It is known that adding even small amounts of certain high molecular weight polymers reduces the forces of the frictional resistances that occur between a turbulent flow on a solid surface over which the liquid flows (see "Drag Reduction Characteristics of Solutions of 30 Macromolecules in Turbulent Pipe Flow "from JGSavins, published in Society of Petroleum Engineers Journal, September 1964, pp. 203-214;" Turbulence Damping and Drag Reduction Produced by Certain Additives in Water ", published in Nature, 1 May 1965, pp. 463-467, and "Reduction of Friction in Oil 35 Pipelines by Polymer Additives," by A. Ram, E. Finkelstein, and C. Elata, published in I and EC Process Design and Development, Volume 6, No. 3, July 1967, pp. 309-313), A consequence of the addition of a frictional resistance-reducing polymer is an increase in the volume flow of a liquid by a pipe.

This phenomenon is used to describe the friction-reducing agent which is used in a hair spray according to the invention. The frictional resistance reducing agent must have a frictional resistance reducing ability of at least 2%, as determined.

A polymeric compound is tested for its friction-reducing ability by determining its effect on the flow rate of a solvent for the hairspray resin (in which it should be soluble), by dissolving the compound at room temperature (approximately 20 ° C) and an overpressure of 1 atm. (pressure of 15 PSIG) in a concentration 15 described below through a capillary tube with a length of 32 cm and a diameter of 1.5 mm. The frictional resistance-reducing ability of the compound, expressed in percent, can be calculated ____ according to the formula orj JS £ solution - 'solvent ------ x 100 f solvent f where "solvent" is the metering rate of the solvent and 25 " "solution" represent the dosing rate of the solution of the polymer in the solvent. The aforementioned frictional resistance-reducing ability is determined with 0.01 or 0.10 wt.% Solutions. It is noted that a raw material has a frictional resistance-reducing ability of at least 2%, when the resistance-reducing ability of a 0.01% by weight and / or 0.10% by weight solution is at least 2%. Tests have shown that the resistance-reducing ability is essentially independent of the nature of the hair spray solvent.

It is therefore usually practical to test the resistance-reducing ability of the compounds in water or, if they are not soluble therein, in methylene chloride. When a compound has a resistivity-reducing capacity of at least 2% 78 0 99 6 3 --- - ------ 4 ........ "- 4 - J 498 (L) in one of these solvents it is possible to formulate a hairspray resin solvent system and the friction-reducing agent based on one or more of the conventional hairspray solvents, especially without lower aliphatic alcohols, methylene chloride and mixtures thereof with or without water. In the practice of the present invention, it is preferable to use friction-reducing agents whose resistance-reducing ability is at least 10¾.

10

Certain polyoxyethylenes are a particularly effective group of compounds for increasing the shape retention capacity of hairspray resins. These nonionic polymeric compounds are soluble in water and mixtures of water and organic solvents for hair sprays and are effective at very low concentrations for increasing the shaping ability of a hair spray, especially when these polyoxyethylenes have an average molecular weight have a weight of more than one million, which work effectively even at concentrations of less than 50 parts per million of the hair spray 20. Water-soluble polymers of ethylene oxide are commercially available from the Union Carbide Corporation under the trade name POLYOX Water Soluble Resins (POLYOX is a trademark).

The members of the commercially available group of polyoxyethylene resins, which are friction-reducing agents, are mentioned below; the viscosity data and approximate values of the average molecular weight cited therein are taken from the commercial literature provided by the Union Carbide Corporation.

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Characteristic values of the resistivity of the polyoxyethylene resins are listed below. Water is a suitable solvent for determining the resistance-reducing capacity.

5

Polyoxyethylene Resistance-reducing ability (%) concentration concentration 0.01 wt% 0.10 qew%

Polyox Coagulant 15 - 10 Polyox 301 25 - *)

Polyox 305 22 - *)

Polyox 3000 23 13

Polyox 750 10 20

Polyox 80 less than 2 5 ^ *) more negative values 5

The polyoxyethylene designated as Polyox 10 (average molecular weight about 1x10) is not a frictional reducing agent. Both at concentrations of 0.01% and 0.10% in Water, it was found not to exhibit resistance-reducing properties. With regard to the above-mentioned negative values of the resistivity-reducing ability obtained in some cases, it should be noted that these polymers tend to increase the viscosity of solvents, which will lead to a decrease in the flow rate of the solvent through the capillary tube. As a result, above a certain addition percentage - depending on the molecular weight of the polyoxyethylene - reducing the flow rate is the net effect of the additive. However, this effect appears to be insignificant as far as the present invention is concerned. It is only important that the polymer has a resistivity reducing ability of at least 2% as determined above.

Certain hydroxypropyl cellulose polymers that are soluble in the polar organic solvents, such as lower aliphatic 7809963 »1 - 7 - J 498 alcohols, commonly used as solvents for hairspray resins, are a particularly suitable group of improvers for modeling the hair. These nonionic polymers, which are also water-soluble, are therefore particularly suitable as additives for a wide variety of hair spray products for improving shape retention. Hydroxypropyl celluloses are marketed by Hercules Incorporated under the trademark KLUCEL. These hydroxypropyl celluloses have a degree of substitution (MS) within the range of 2.5 to 10, MS meaning the average number of hydroxypropyl groups per anhydroglucose unit.

The members of the commercially available group of hydroxypropyl cellulose resins of the Klucel brand which can be used as friction reducing agents are listed below; The reported viscosity and average molecular weight data are taken from the commercial literature of Hercules Incorporated.

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Characteristic values of these hydroxypropyl celluloses for the resistance-reducing ability are given below. Water is a suitable solvent for determining the resistance-reducing capacity.

5

Hydroxypropyl cell 1 µSe Resistance-reducing ability (%) concentration concentration 0.01 wt% 0.10 wt%

Klucel H (HF) 9 20 10 Klucel M (MF) 6 12

Klucel G (GF) 3 8

Klucel J (JF) 2 5

The L (LF) type with a lower molecular weight and a viscosity of 75-150 cP (Brookfield spindle 1, 30 rpm) in 5% 1s solution and an average molecular weight of about 1x10, and type E (EF), with a viscosity of 300-700 cP (Brookfield spindle no. 2.60 rpm) in a 10% Vs aqueous solution and an average molecular weight of about 0.6x10 are not frictional resistance reducing agents. None of these hydroxypropyl celluloses were found to exhibit frictional resistance-reducing properties at concentrations of both 0.01¾ and 0.10% in water.

Furthermore, polyacrylic elastomers, for example, the poly (ethyl acrylate) elastomer available under the tradename "Hycar 4021-45" can be used as suitable frictional reducing agents for increasing the shape retention capacity of a hair, spray resin. at BF Goodrich Chemical Company. This nonionic raw material mainly consists of polymerized ethyl acrylate, although it contains from 1 to 5% of a compound with reactive cores (cure sites), which is believed to be 2-chloroethyl vinyl ether, as this polymer is suitable for use as a vulcanizable rubber. Poly (ethyl acrylate) is not soluble in water or alcoholic solvents, but is soluble in methylene chloride and can therefore be used in hair sprays containing methylene chloride as a solvent. It has a 7809963-10 - J 498 (L) resistance-reducing power of 12% at a 0.0U's concentration and of 30¾ at a 0.10% concentration.

Another type of polymer which has been found to have an effective action as a friction-reducing agent are the cationic cellulose polymers with a very high molecular weight and the following structural formula: R R R * 10 °.

Rcell

Jy where Rce- | - | a residue of an anhydroglucose unit, wherein each R individually represents a substitution group of the following general formula:

(C2H40) m -CH2 ^ H0) n- (C2H4 °) pH

CH, I 1 20 C, Ho-N + -CH, Cl v | Ó CH3 where m is an integer between 0 and 10, n is an integer between Q and 3, and p is an integer between 0 and 10, and Y is a number such that the polymer in a U's aqueous solution 25 ° C has a viscosity of 1000 to 2500 cPoise (Brookfield viscometer LVF, 30 rpm, spindle No. 3). The mean values peranhydroglucose unit are: n between 0.35 and 0.45 and the sum of m + p from 1 to 2. The cationic cellulose resin commercially available from the Union Carbide Corporation under 30 under the trade name "Polymer JR 30M" is a suitable resin. This polymer is less suitable than the other aforementioned friction-reducing agents since it requires relatively large amounts of water as a solvent in the hair spray because it is not soluble in ethanol or methylene chloride. Types of this 7809963 - 11 - J 498 *. . lower viscosity cationic cellulose polymers such as those available under the brand name Polymer JR 125 (viscosity of 75-175 cPoise, Brookfield spindle No. 1 at 30 rpm and 25 ° C in 2% solution) and Polymer JR 400 (viscosity of 300-500 cPoise, Brookfield spindle No. 2, at 30 rpm and 25 ° C in 2% solution are not friction reducing agents.

None of these lower molecular weight cationic cellulose polymers were found to exhibit frictional resistance-reducing properties at concentrations of 0.01% and 0.10%.

10

Friction-reducing agents that are soluble in either ethanol or methylene chloride are preferred. It is also preferable to use friction reducing agents which are solid at normal temperature (25 ° C).

15.

A wide variety of hair spray resins are used in commercial hair sprays. These include polyvinyl pyrrolidones; the copolymers with from 92.5 to 87.5% vinyl acetate and from 7.5 to 12.5% crotonic acid as described in U.S. Patent 2,996,471, eg.

Resyn 28-1310 from National Starch; the terpolymers with from 7 to 89% vinyl acetate, from 6 to 13% crotonic acid and from 5 to 80% of a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid with at least five carbon atoms in the carboxylic acid group and the formula RgC ( R ^) (R2) C00H, wherein R ^ and R2 are alkyl radicals and R8 is selected from the group consisting of hydrogen, alkyl, alkaryl, aralkyl and aryl radicals, which terpolymers are described in British Patent No. 1,169,862 and the U.S. Patent 3,810,977, wherein a terpolymer of this type is commercially sold under the trade name 30 National Starch Resyn 28-2930; the terpolymers of vinyl acetate, crotonic acid and either a vinyl ester of the formufe R * C00CH = CH2, wherein R represents a straight or branched chain hydrocarbon group having 10 to 22 carbon atoms, or an alkyl or methallyl ester of the formula R'-C00CH2-C (R ") = CH 2, wherein 36 R 'represents a straight or branched chain hydrocarbon group having 10 to 22 carbon atoms and R" represents a hydrogen atom or a methyl group, which terpolymers are described in British Patent No. 1,153 and U.S. Patent No. 7809963 12 J 498 (L) 3,579,629; the copolymers with from 20 to 60 N-vinyl pyrrolidone and from 40 to 80% vinyl acetate as described in U.S. Patent 3,171,784 and commercially available under the designation Luviskol 37E and Luviskol 281; the copolymers of 5 maleic anhydride {1 mol) and an olefin (1 mol) with 2 to 4 carbon atoms, in particular ethylene, which copolymer has a molecular weight of about 25,000 to 70,000, and is preferably 50 to 70% esterified with a saturated aliphatic alcohol containing from 1 to 4 carbon atoms, as described in U.S. Patent 2,957,838; the amphoteric acrylic resins as described in U.S. Patent 3,726,288, including the acrylamide / acrylate / butylaminoethyl methacrylate terpolymer containing carboxyl groups and commercially available under the trade name Artphomer; the copolymers of methyl vinyl ether 15 and maleic anhydride (molar ratio about 1: 1), and those copolymers esterified with a saturated aliphatic alcohol of 1 to 4 carbon atoms, such as, for example, the resin sold under the trade name Gantrez ES425. However, it will be apparent to those skilled in the art that other resins are also suitable for use in hair sprays; see, for example, the article entitled "Hair Lacquers or Hair Sprays", beginning on biz. 352 of Part 2 of "Cosmetics Science and Technology", 2nd edition, published by M.S.Balsam and Edward Sagarin (1972), and the article entitled "Hair Spray Resins", beginning on biz. 411 of 25 "Harry's Cosmeticology", 1973.

Those copolymers which contain acidic groups and are water soluble are usually used in neutralized water soluble form. As suitable neutralizing agents which can be included in the hair sprays 30 can be mentioned: amines, in particular amino alcohols, preferably 2-amino-2-methyl-1,3-propane-diol and 2-amino-2-methyl- 1-propanol. Other suitable neutralizing agents are also disclosed in U.S. Patent 2,996,471.

As carrier fluids or solvents for hair spray resin commonly used in formulating hair sprays, there may be mentioned ethanol, isopropanol, methylene chloride, 2-methoxyethanol and 2-ethoxyethanol and mixtures thereof with water. The carrier liquid can contain more than one of these organic solvents. It is a requirement that the resin carrier fluid 5 also be a solvent for the friction reducing agent. Usually the solvent is from about 5 to about 99.5% by weight of the product. In aerosol products, the solvent is used in amounts from about 5 to about 95% by weight, usually from about 10 to about 90% by weight.

10

In the case of hair sprays packed in an aerosol can, the product in the container also contains a propellant, for example a liquefied or compressed gaseous propellant. Known liquefied gaseous propellants are the halogenated hydrocarbons and the hydrocarbons densifiable to liquids. As the liquefied gaseous propellants, trichlorofluoromethane (propellant 11), dichlorodifluoromethane (propellant 12), butane and propane, and mixtures thereof, are usually used. Other suitable propellants are described in U.S. Pat. Nos. 3,026,250, 3,145,147 and 2,957,838, and a more general description is found in the article entitled "Propellants", beginning on page 443 of Part 2 of the previously mentioned work "Cosmetics Science and Technology". Liquefied gaseous propellants are generally used in an amount within the range of 10 to 90% by weight of the hair spray. Examples of compressed gaseous propellants are carbon dioxide, nitrogen and nitrous oxide. These propellants are usually used in an amount from about 1 to about 10% by weight of the total hair spray. Liquefied gaseous propellants may or may not be miscible with the solvent for the hair spray resin and the friction reducing agent.

The use of a pump sprayer for dosing a wide variety of products is known. Its use for dispensing hair sprays is described in "Soap, Perfumery and Cosmetics" (SPC), March 1977, pages 89-93. A number of mechanical pumps 7809963-14 - J 498 (L) Pumps are described in "Modern Packaging" of October 1975, biz. 15-20.

The amount of friction-reducing agent that is included in the hair sprays to increase the holding power of the hair spray resin is relatively small. The amount required is dependent on both the molecular weight and the chemical type of the friction reducing agent, as far as it is concerned. frictional resistance-reducing ability 10 is affected. In certain instances, shape retention improvements were obtained with amounts of frictional resistance reducing agent as low as 0.001% by weight of the product, or even with less. In general, slightly larger amounts will be desired for aerosol products as the amount of propellant in the product is increased. In general, the more effective the frictional reducing agent, the smaller the amount needed to improve the shaping ability of the hairspray. For this reason, a choice from the range of, for example, the polyoxyethylene resins or the hydroxypropyl cellulose resins, the use of the higher molecular weight members is preferred. Therefore, the use of the polyoxyethylene and hydroxypropyl cellulose polymers having a molecular weight of at least resp. 400,000 and 500,000 are particularly preferred. However, any arbitrary frictional resistance-reducing agent is cf amount that can be included in a hair spray. Excess amounts adversely affect the spray properties, so that the product is no longer considered acceptable in that case. The use of excessive amounts of friction-reducing polymer 30 can lead to a spray cloud with a very small cone angle (or even a jet or stream instead of a spray cloud) or an unacceptably coarse spray in which the droplets are too large. For these reasons, the amount of frictional reducing agent should be less than 0.3% by weight of the hair spray.

Preferably, the friction-reducing agent should not exceed 0.2% by weight of the hair spray. In general, the more effective the frictional resistance of the polymer, the smaller the amount that can be incorporated into a hair spray. However, suitable amounts of the friction-reducing agent can be determined by those skilled in the art without effort.

5

The shaping ability of a hair spray is, of course, also dependent on the amount of hair spray resin contained therein. Usually, in the conventional products, at least about 1 weight percent hair spray resin is used to obtain a product that satisfactorily keeps the hair in shape. In commercially available products, amounts ranging from about 1 to 3% by weight are therefore quite normal; however, if a form holding property of a product is required which is higher than normal, the resin content can be increased accordingly. Being able to significantly reduce the hairspray resin content without loss of product performance is an important practical consequence of the observation that the addition of a frictional deterrent to a hairspray retains the shape retention capacity. can improve that. Therefore, in hair sprays of the invention, the hair spray resin can be used at levels less than about 0.4 weight percent of the hair spray, while retaining the good shape retaining properties. The upper limit of the resin is not critical. The hair spray resin can generally be used in concentrations ranging from 0.4 to 7.5 wt%, more generally from 0.4 to 5 wt%, based on the hair spray.

From the foregoing discussion of the detrimental effect of high percentages of frictional resistance reducing agents on the spraying properties of hair sprays, it will be apparent that the hairspray resins used in commercial products are not themselves frictional resistance reducing agents. The hair spray polymers commonly used have a relatively low molecular weight compared to the aforementioned frictional reducing agents.

The fact that the frictional resistance reducing agent provides a significant improvement in the shape retention capacity of the hairspray is a surprising feature of the present invention, even when added in a small amount compared to 7809963 35 - 16 - J 498 (L). the hair spray resin contained therein. In the hair sprays according to the invention, the hair spray resin is preferably used in a weight ratio to the added friction-reducing agent of at least 5: 1. When a frictional reducing agent having a particularly high effective action is used, the amount to be added can be very small, even less than one ten thousandth of the resin, especially when higher percentages of hairspray resin are used. The hair spray resin to frictional resistance reducing agent weight ratio will normally range from 5000 to 5: 1.

In addition to the hair spray resin, the solvent, the frictional resistance reducing agent and optionally the propellant, the hair spray product may also contain various other ingredients known in the relevant industry. Examples of such other ingredients are perfume, denaturing agents, for example, benzyl diethyl, 2,6-xylylcarbamoyl methylamuonium benzoate and sucrose octaacetate; conditioners such as lanolin derivatives; and plasticizers such as silicone oils with a viscosity of 10 centi-stokes at 25 ° C.

The addition of the friction-reducing agent can also lead to a significant reduction in the respirable portion of the spray. Some particles of the spray cloud, which is created by spraying a hair spray, can be inhaled by the user or others in the immediate vicinity. By adding the friction-reducing agent, the amount of hair spray inhaled into the lungs can be reduced. The portion of the metered product that reaches and is deposited in the lungs is hereinafter referred to as the "respirable portion" of the product.

The invention will now be further elucidated on the basis of the experiments nos. 1 to 23. The percentages are percentages by weight unless otherwise indicated.

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The two methods referenced in Runs 1 to 15, comparing the holding power of hair sprays, will be described first.

5 Her! Ok test method

In this test method, a number of experienced evaluators compared, according to a subjective evaluation method, the holding power of different hair sprays applied to hair strands. The evaluators selected for both test methods gave a rating of the shape retention and other properties of hair spray products that was reasonably consistent with large-scale user test results.

In this test, hair strands of good quality hair were used with a length of 20-25 cm, a width of 2 cm and a weight of about 8 to 10 grams. To prepare the hair strands for the test, they were washed with shampoo, dried, hung and then brushed. The strands were brushed between successive hair spray treatments until it was judged that the hairs 20 did not bond together.

The strands were divided into groups, the number of strands in each group corresponding to the number of hair sprays to be compared.

The number of groups of locks varied from 3 to 5.

25

Throughout the test, from one group, each product was applied to the same strand, and applied at least three times. After each application, the conformability of the spray of each strand to which it was applied was assessed by one of the evaluators. After each application, for example the first one, each strand of a group was judged by the same evaluator, but each group was judged by a different evaluator. However, different uses of the products for a given group were usually evaluated by another evaluator. The number of applications varied from 3 to 5.

For a given test, the spraying distance and the spraying time were the same for each product. However, these differed for the different tests, and the individual products tested.

After each spray cloud application, the strands were allowed to dry, which is reflected in the effect of the spray applied by the evaluator on a ten-piece scale, 1 indicating the best shape retention and 10 g and shape retention. The numerical observations for each product were then averaged to obtain a shape retention value for a given product. Thus, when there were three groups of hair strands and three applications with the spray to be tested, the shape retention value was an average of 9 observations; if there were 5 groups and 5 applications, the shape retention value was an average of 25 observations. Repeating the tests found that the shape retention values varied by about 0.5 unit.

15

• V

The shape retention values obtained from different tests of the products cannot be compared, since the spraying distance and the spraying time for the different tests were not necessarily the same and - more importantly - for spraying the test products a number of different spray valves and different pressure cap combinations were used, although of course they were kept the same for a given test.

25 Salon test method

The method of testing hair sprays is performed in a hair salon and is known as the "half-head" test. After shampooing and styling the hair, a subject's head was sprayed on one side with a control product and on the other side with a test product, with a shield placed in the center of the crown of the head to limit a spray to one side of the head. After the spray was allowed to dry (10 to 30 minutes), the shape retention of the hair was comparatively assessed by blowing air separately on each side of the head with a hand-operated hairdryer (without heat) and noting which side during and after blowing the least confused, respectively, the least out of style.

7809963 - 19 - J 498 (L)

The following day, the subject's hair is brushed and modeled, after which the control and test products were used as before and the result assessed. The procedure followed on the second day is then repeated on the third, fourth and fifth days.

The results of the test are then statistically analyzed.

The number of subjects in a test ranged from 18 to 24.

The respirable data of Runs 16 to 23 were determined with a Hexhlet eluator (elutriator) - see Brit. J. Industr. Med., 1954, U. " 284 - which separates particles into air at their falling speed. The aerosol is passed horizontally at a controlled speed through a parallel plate elution device; the vertical distance of the plates is such that particles deposited thereon when passing the aerosol through the eluator correspond to the particles that would aerodynamically secrete into the upper respiratory tract of man. Thus, the particles that pass through the eluator and are collected on a filter are a measure of the particles that will penetrate the lungs of humans. The upper aerodynamic size limit of respirable particles collected in the Hexhlet device is about 7 microns.

5

The method was as follows. A dried and weighed glass fiber filter was placed in the Hexhlet apparatus and the package containing the product to be tested was weighed. The vacuum was adjusted so that the manometer of the Hexhlet device indicated about 300 mm Hg. After shaking the package thoroughly for 3 hours, the product was sprayed into a cabinet attached to the front of the Hexhlet device. With aerosols, the dosing lasted 2 seconds each; the shaking was repeated every 20 seconds and the dose repeated a total of 20 times. In pump injectors, dosing was performed 10 times in rapid succession to a total of 200 doses at the beginning of each 20 second period. Sampling was continued up to 5 minutes after the last dose. The package was reweighed to determine the weight of the metered product 78 0 99 63-20 J 498 (L). The weight collected on the filter was expressed in milligrams per 100 g of dosed product. This weight (hereinafter referred to as the RFO value) is a measure of the amount of respirable components in an aerosol cloud. In some cases, the filter was heated at 50 ° C for 24 hours and then weighed again. In this way, the weight of the collected non-volatile components was determined; this weight was also expressed in milligrams per 100 g of dosed product. This weight (hereinafter referred to as the 10 RF1 value) is a measure of the respirable, non-volatile components in an aerosol cloud. The use of the Hexhlet apparatus for determining respirable particles is also described in "Aerosol Age", Vol. 21, No. 11, November 1976, pp. 20-25.

15

Respiratory particles were determined at a relative humidity of 50 vochtigheid and a temperature of 20 ° C. Each of the two RFO values (ie, the RFO values for the test product and for the control product) and also the RF1 values as far as 20 determined, from which the percentage reduction of the RF0 or RF1 value was calculated, consisted of the average of 6 measurements (two determinations for each of the three packages). The actual numerical values of RF0 and RF1 depend on the special combination of valve and pressure cap used and therefore the same combination was used for a comparative test.

The table below shows the composition of the various hair spray products used as controls in the experiments.

7809963 - 21 - J 498 (L)

Composition of Control Products Components

No. Description _I Π_ III · IV

1 Resyn 28-2930 1.20 - 1.35 5 2 Resyn 28-1310 - 1.80 3 Luviskol 37E - 2.00 4 PVP K30 - - 5 Gantrez ES 425 - - 6 Amphomer - - - 10 7 2- Amino-2-methyl-1-propanol 0.12 0.16 - 0.13 8 Silicone glycol 0.04 - - 0.04 9 Sucrose octaacetate - 0.06 10 Bitrex - 0.04 11 Lanolin derivative (Lanexol) - 0, 04 15 12 Perfume 0.06 0.13 0.08 0.12 13 Absolute alcohol 8.58 - 7.92 14.36 * 14 methylated spirits ..- 37.77 * - 15 Methylene chloride 27.00 * - 24.00 * 16 Water - - - - 20 17 Propellant 11 37.80 39.00 39.60 55.50 18 Propellant 12 25.20 21.00 26.40 18.50 19 CAP 40 - - - 10.00 7809 963 - 22 - J 498 (L)

Composition of Control Products (continued)

Component No. V VI VH VIII

1 1.40 - - 1.22 2 5 3 ---.

4 - 1.00 5 - - 3.00 6. .

7 0.12 - 0.64 0.12 10 8 - - -9 ---.

10 ---.

11 ---.

12 0.14 - 0.15 0.08 15 13 48.34 * 29.00 * - 4.95 14 - - 36.21 * 15 ... 20.63 * 16 -.-- 17 25.00 21 .00 39.00 43.80 20 18 25.00 49.00 21.00 29.20 19 -.-- 7809 963 - 23 - J 498 (L)

Composition of Control Products (continued)

Component No. IX X. 211 XII XIII

1 1.20 - 1.35 3.00 2.00 2 - 5 3 - ---- 4 --- 5 --- 6 - 1.50 - 7 0.12 0.31 0.13 0.30 0.19 10 8 0.04 - 0.05 9 - 10 - - 0.10 - 11 --- - - 12 - 0.15 0.06 - 15 13 5.00 - '13.31 * 4 , 95 44.81 * 14 - 38.04 * - 15 35.00 * - - 18.75 * 16 - 28.00 17 25.23 39.00 51 ", 00—— 43.80 ----- - = ----— ______ 20 18 8.41 21.00 34.00 29.20 19 25.00 - - - 25.00 7809 963 - 24 - J 498 (L)

The compounds used in the above control products, indicated by their brand names, are described below.

Resyn 28-2930 is a terpolymer of vinyl acetate (75¾), croton-5 acid (10%) and vinyl versatate (15%), available from the National Starch and Chemical Corporation. It has a number average molecular weight of about 22,500.

Resyn 28-1310 is a copolymer of vinyl acetate (90%) and croton-10 acid (10%), also available from the National Starch and

Chemical Corporation. It has a number average molecular weight of about 25,000.

Luviskol 37E is a 50 wt% solution of a copolymer of vinyl pyrrolidone (30%) and vinyl acetate (70%) in ethanol, available from the GAF Corporation.

PVP K-30 is a vinyl pyrrolidone polymer with a molecular weight of 40,000, also available from the GAF Corporation.

20

Gantrez ES 425 is a 50 wt% solution of a copolymer of methyl vinyl ether and maleic anhydride butyl monoester in ethanol, also available from the GAF Corporation.

Amphomer is an amphoteric acrylic amide / acrylate / butylaminoethyl metacrylate terpolymer containing unneutralized carboxy groups available from the National Starch and Chemical Corporation.

Bitrex is a 0.256 wt% solution of benzyl diethyl-2,6-xylyl-30 carbomoylmethyl ammonium benzoate in water.

CAP 40 is a hydrocarbon consisting essentially of a mixture of propane and butanes with a vapor pressure of about 3.2 bar at 25 ° C, available from Cal or Gas Ltd.

35

The silicone glycol consisted of a polydimethylsiloxane polyoxyethylene block copolymer, as described in U.S. Patent 7809963-2549,93928,558.

In the following description, the results of the above control products and test products obtained by altering the control products are reported. In such test products, a corresponding amount of the constituent marked with an asterisk in the preceding table is taken up (i.e., so that the sum of all components is still 100 parts by weight in total). The compound added when formulating the test products was first dissolved either in alcohol or in methylene chloride (alcohol in the case of hydroxypropyl cellulose or methylene chloride in the case of polyoxyethylene or acrylic elastomer) under mixing conditions with high shear rate and high turbulence.

15 Trial 1

The products used in this test were: 1) Control Product I; 2) Test product IA - as Control product I, but with only 0.4¾20 resin; 3) Test product IB - as Test product IA, but with only 0.05¾ hydroxypropyl cellulose with a molecular weight of about 10 (Klucel H); 4) Test product IC - as Test product IA, but with 0.04 0,0 hydroxypropyl cellulose of Test product IB.

Products I, IA and IB were compared using the lock of hair test method to give the following shape retention values.

30

Product Retaining value

Control product 8.3

Test product IA 8.8

Test product IB 6.5 35

Test products IA and IC were compared separately with Control product I by the Salon test method. With Control Product I

7809963 - 27 - J 498 (L) shape retention then gave product IID at a significance level of 0.1% and that products II and IIE showed no significant difference in shape retention.

5 Trial 3

The products used in this test were: 1) Control Product III; 2) Test Product IIIA - as Control Product III, but with 0.05% hydroxypropyl cellulose having a molecular weight of about 10® (Klucel H); 3) Test product IIIB - as Test product IIIA, but with 0.15% hydroxypropyl cellulose; 4) Test product IIIC - as Test product IIIA, but with 0.10% hydroxypropyl cellulose.

Products III, IIIA and IIIB were compared using the lock of hair test method, yielding the following shape retention values:

Product Retaining value:

Control product III 7.6

Test product UIA 5.1

Test product IIIB 4.0 25

Products III and IIIC were compared to each other by the Salon test method, and product IIIC was found to have better shape retention than product III, and the result was significant at a level of less than 1%.

30

Trial 4

The products used in this test were: 1) Control product IV; 2) Test Product IVA - as Control Product IV, but with only 0.75% hair spray resin and 0.04% hydroxypropyl cellulose with a molecular weight of about 10 (Klucel H).

7809963 - 26 - J 498 (L) a better shape retention was obtained than with product IA, at a level of significance of less than 1%, while there was no difference in shape retention between products I and IC.

5 Trial 2

The products used in this test were: 1) Control Product II; 2) Test Product IIA - as Control Product II, but with 0.02% hydroxy-10-propyl cellulose with a molecular weight of about 10 ^ (Klucel H); 3) Test Product IIB - as Control Product II, but with 3.00% resin; 4) Test product IIC - as Test product IIA, but with 0.03% hydroxypropyl cellulose; 5) Test product IID - as Control product II, but with only 0.90% hair spray resin; 6) Test Product IIE - as Test Product IID, but with 0.02% hydroxypropyl cellulose of Product IIA.

Products II, IIA and IIB were compared with each other by the lock of hair test method, yielding the following shape retention values:

Product Retaining value 25 Control product II 4.2

Test product IIA 2.9

Test product IIB 3.5

Products II and IIC were compared using the Salon test method. Product IIC provided better shape retention than product II; the result was significant at a level of less than 1%.

Products II, IID and IIE were used in a group test, each product being given to a separate group of about 130 women who used the respective products for two weeks. A statistical analysis of the subjects' assessment of the products showed that product IIE is a better 78 0 9 9 6 3 - 29 - J 498 (L) with a molecular weight of approximately 5 1 x 10 (Klucel L), which does not frictional resistance reducing agent; 3) Test Product VIB - as Control Product VI, but with only 0.55% hair spray resin and 0.07¾ hydroxypropyl cellulose with a molecular weight of about 1 x 106 (Klucel H); 4) Test product VIC - as Control product VI, but with 0.07¾ hydroxy propyl cellulose of test product VIB.

10

These products were compared with each other according to the lock of hair test method, yielding the following shape retention values: 15 Product shape retention value

Control product VI * 5.7

Test product VIA 5.5

Test product SDS 3.9

Test product VIC 2.5 20 _______ ____________

Trial 7

The products used in this test were: 1) Control e-product VII; 2) Test product VIIA - as Control product VII, but with 0.02¾ hydroxypropyl cellulose having a molecular weight of about 1 x 10 (Klucel H); 3) Test product VUB - as Test product VIIA, but without hair spray resin; 30 4) Test product VIIC - as Control product VII, but without hairspray resin.

These products were compared to each other according to the lock of hair test method, yielding the following shape retention values: 780 99 6 3 - 28 - J 498 (L)

These products were compared using the Haar! Ok test method to yield the following shape retention values: 5 Product Shape Retention Value

Control product IV 6.2

Test product IVA 5.3

The products were also compared with each other according to the Salon test method, where it was found that they did not differ in shape holding capacity.

Trial 5

The products used in this test were: 15 V 1) Control Product V; 2) Test product VA - as Control product V, but with only 0.70% hair spray resin; 3) Test product VB - as Test product VA, but with 0.06% hydroxypropyl cellulose with a molecular weight of about 10® (Klucel H).

These products were compared to each other by the lock of hair method, thereby obtaining the following shape retention values:

Product Retaining value

Control product V 2.1

Test product VA 5.3 30 Test product V 2.3

Trial 6

The products used in this test were: 1) Control product VI; 2) Test product VIA - as Control product VI, but with only 0.55% hairspray resin and 0.45% hydroxypropyl cellulose 7809963 - 30 - J 498 (L)

Product Retaining value

Control product VII 4.7

Test product VIIA 2.2

Test product VIIB 9.3 5 Test product VIIC 9.7

Trial 8

The products used in this test were: 1) Control product VIII; 2) Test Product VIIIA - as Control Product VIII, but with 0.005% polyoxyethylene with a molecular weight of about 6 x 10 ^ (Polyox 205); 3) Test product VIIIB - as Test product VIIIA, but with 0.010% polyoxyethylene; 4) Test Product VIIIC - as Control Product VIII, but with 0.001% of a polyoxyethylene with a molecular weight β of about 4 x 10 (Polyox 301); 5) Test Product VII ID - as Test Product VII IC, but with 0.004% polyoxyethylene; 6) Test Product VIIIE - as Control Product VIII, but with 0.15% polyoxyethylene with a molecular weight of about 2 x 10 (Polyox 80).

The products were compared in three different tests according to the lock of hair test method, yielding the following shape retention values:

Product Retaining value 30 Control product VIII 8.6 9.1 8.8

Test product VIIIA 6.1

Test product VIIIB 5.2

Test product VIIIC - 6.8

Test product VIIID - - 3.9 35 Test product VIIIE - - 4.5 7809963 - 31 - J 498 (L)

Trial 9

The products used in this test were: 1) Control Product IX; 2) Test Product IXA - as Control Product IX, but with 0.002% polyoxyethylene having a molecular weight of about 4 x 10 ^ (Polyox 301); 3) Te product IXB - as Test product IXA, but with 0.004% polyoxyethylene.

10

The products were compared using the lock of hair test method to give the following shape retention values: 15 Product shape retention value

Control product IX 6.8

Test product IXA 3.6

Test product IXB 3.2 20 Test 10

The products used in this test were: 1) Control Product IX; 2) Test product IXC - as Control product IX, but with 0.01% poly (ethyl acrylate) rubber with a Mooney viscosity of 45 on average (Hycar 4021-45); 3) Test Product IXD - as Test Product IXC, but with 0.03% of the acrylic elastomer.

These products were compared with each other according to the lock of hair test method, thereby obtaining the following shape retention values:

Product Form Preservative Value 35 Control Product IX 7.3

Test product IXC 5.2

Test product IXD 3.8 7809963 - 32 - J 498 (L)

Trial 11

The products used in this test were: 1) Control product X; 2) Test Product XA - as Control Product X, but with 0.02 hydroxypropyl cellulose having a molecular weight of about 1 x 10 (Klucel H); 3) Test product XB - as Control product X, but with only 1.00% hair spray resin; 4) Test product XC - as Test product XB, but with 0.02% hydroxypropyl cellulose of Test product XA.

The products were compared to each other according to the lock of hair test method, yielding the following shape retention values:

Product Retaining value

Control product X 5.5

Test product XA 2.1 20 Test product XB 6.3

Test product XC 4.3

Trial 12

The products used in this test were: 1) Control product XI; 2) Test Product XIA - as Product XI, but with 0.05% hydroxypropyl cellulose having a molecular weight of about 1 x 106 (Klucel H); 3) Test product XIB - as product XIA, but with 0.15% hydroxypropyl cellulose.

The products XIA and XIB were compared separately with the control product XI according to the Salon test method. Both products XIA and XIB gave better shape retention than Control product XI. The result with Product XIA was significant at a level of 1% and the result with Product XIB was significant at a level 7809963 - 33 - J 498 (L) of less than 1%.

Trial 13

The products used in this test were: 1) Control product XII; 2) Test Product XIIA - as Product XII, but with 0.00075¾ polyoxyethylene with a molecular weight of approximately 4 x 10® (Polyox 301).

10

The products were compared to each other according to the lock of hair test method, yielding the following shape retention values: 15 Product> shape retention value

Control product XII 4.4

Test product XIIA 3.1

Test 14 The products used in this test were: 1) Control product XIII; 2) Test Product XIIIA - as Product XIII, but with 0.10% hydroxypropyl cellulose with a molecular weight of about 1 x 10® (Klucel H).

The products were compared with each other according to the lock of hair test method, thereby obtaining the following shape retention values: 30

Product Retaining value

Control product XIII 5.3

Test product XIIIA 4.0 35 Test 15

The following hair sprays were prepared and packaged in containers fitted with a pump dispenser known as the CALMAR MISTETTE pump, 7809963 - 34 - J 498 (L) as described in Modern Packaging, October 1975, biz. 15-20.

Control product XIV Test product XIVA Hair spray resin ^ 4.00 4.00 5 2-Amino-2-methyl-1-propanol 0.40 0.40

Methylated spirits 95.60 95.57

Hydroxypropyl cellulose ^ - 0.03 ^ As in Control Product II 10 ^ Molecular weight about 1 x 10® (Klucel H)

These products were compared to each other according to the lock of hair test method, yielding the following shape retention values: 15

Product Retaining value

Control product XIV 4.4

Test product XIVA 3.3 The above tests show that a very favorable effect on the shaping ability of a hair spray is obtained when a small amount of a friction-reducing polymer is incorporated therein. Many of the tests clearly demonstrate the favorable result obtained by simply adding the friction-reducing polymer; in particular reference is made to the comparative test according to the Salon test method (between products IIC and II; products IIIC and III; and between the two products XIA and XIB and product XI), with the product containing the small amount of frictional resistance -30 reducing agent, in each case gave an improvement in shape retention, which exceeded that of the control product at a significance level of 1% or less.

The tests also show that the addition of a frictional resistance reducing agent allows the amount of hairspray resin to be reduced very significantly, without loss of shape retention. This most surprising result is demonstrated by the comparative test performed with the products I (1.2% hair spray 7809963-35 - J 498 (L) resin) and IC (0.4% hair spray resin); products II (1.8% hairspray resin) and IIE (0.90% hairspray resin); products IV (1.35% hair spray resin) and IVA (0.75% hair spray resin); the products V (1.40% hair spray resin) and VB (0.70% hair spray resin); the products VI (1.00% hair spray resin) and VIB (0.55% hair spray resin); and the products X (1.50% hair spray resin) and XC (1.00% hair spray resin).

The advantage for the shape retention, caused by the addition of the friction-reducing agent, is - as is evident - much greater than one could have predicted, 10 and the added amounts of friction-reduced polymer are so small that there is no measurable benefit reasonably. the shape holding ability could be expected.

Adding a friction-reducing agent to a hairspray to improve shape retention also has the advantage of thereby reducing the respirable portion of the spray cloud. Reduction of the respirable portion is demonstrated by tests conducted with various hair spray compositions indicated below.

20

Trial 16

In this test, the Test products XIA and XIB (see Test 12) were compared with the Control product XI, the RFO values of the Test products XIA and XIB, expressed as a percentage of the RFO value of the Control product were 28% and 16% respectively.

Trial 17

The products used in this test were: 1) Control product VIII; 2) Test Product VIIIF - as Control Product VIII, but with 0.05% hydroxypropyl cellulore with a molecular weight of approximately 10 x 10 (Klucel H); 3) Test product VUIG - as product VIIIF, but with 0.10% hydroxy propyl cellulose; 7809963 -4 - 36 - J 498 (L) 4) Test product VIIIH - as product VIIIF, but with 0.15¾ hydroxypropyl cellulose; 5) Test product VIIIJ - as product VIIIF, but with 0.20% hydroxypropyl cellulose.

5

The RF0 and RF1 values for products VIII F, 6, H and J, expressed as a percentage of the corresponding RF0 and Rfl values for Control Product VIII, are given below: 10 RFO value in% of RFl value in% of

Product Control product Control product

Test product VIIIF 46 47

Test product DIRTY 36 35

Test product VIIIH 30 30 15 Test product VIIIJ 25. 26

Trial 18

The products used in this test were Control Product II and Test Product IIC (see Test 12).

20

With the Test product IIC, RF0 and RF1 values were obtained which were only 24% and 21%, respectively, of the corresponding values for Control Product II.

25 Trial 19

The products used in this test were Control product XIII and Test product XIIIA (see Test 14).

With the Test product XIIIA, an RFO value was obtained which was only 36% of the corresponding value for the Control product XIII.

Trial 20

The products used in this test were Control product XIV 35 and Test product XIVA (see Test 15).

With the Test product XIVA, an RFO value was obtained which was only 7809963 - 37 - J 498 (L) 34% of the corresponding value for the Control product XIV.

Experiment 21 5 The following aerosol hair spray product (Control Product XV) containing carbon dioxide as a propellant was formulated:%

Hair spray resin ^ 2.85 10 2-Amino-2-methyl-1-propanol 0.28

Methylene chloride 25.00

Methylated spirits 65.11

Lanolin derivative (Lanexol) 0.10

Bitrex solution ^ 0.07 15 Sucrose octa-acetate '0.10

Perfume 0.20

Carbon dioxide * ^ up to 100.00

^ As in Control Product II 20 ^ As in Control Product II

^ Provides an overpressure of 6.3 kg / cm at 25 ° C.

The Test Product XVA was formulated with the above ingredients, except that it contained 0.01% hydroxypropyl cellulose 25 with a molecular weight of about 1 x 10® (Klucel H) and the amount of methylated spirits was reduced accordingly.

The RF0 and RF1 values of the Test Product XVA were 78% and 77% of the corresponding values for the Control Product XV, respectively.

Trial 22

The following aerosol hair spray product (Control Product XVI), which contained a hydrocarbon as the propellant, was formulated.

7809963 '«1 * - 38 - J 498 (L)%

Hair spray resin ^ 2.00 2-Amino-2-methyl-propanediol 0.18

Ethanol 64.82 5 Water 16.00 CAP 40 2) 17.00

^ As in Control Product II

2) A commercially available hydrocarbon mixture consisting essentially of a mixture of propane and butanes with a vapor pressure of about 3.2 bar at 25 ° C.

The Test product XVIA was also composed of the above ingredients, except that it contained 0.01 0,0 hydroxypropyl cellulose 15 with a molecular weight of about 1 x 10 4 (Klucel H) and the amount of ethanol was reduced accordingly.

The RF0 and RF1 values for the Test product XVIA were 61¾ and 63¾ of the corresponding values for the Control product XVI, respectively.

Trial 23

A hair spray product (Control Product XVII) was prepared with the ingredients listed below and packed in an aerosol container.

%

Hair spray resin ^ 2.50 2-Amino-1-methyl-1-propanol 0.25 Ethanol 47.25

Water 20.00

Propellant 12 30.00.

^ As in Control Product II.

Test products were prepared containing polyoxyethylene resins in an amount of 0.0W, while the amount of water was correspondingly reduced.

The RFO and RF1 values obtained with the Test products, expressed as a percentage of the corresponding values obtained with the Control product XV, are shown below.

Mol.weight of RFO value in% of RFl value in%

Test product polyoxyethylene Control e-product of Control e-product XVI IA 4x10 ° 12 13 10 XVIIB 6 x 105 25 34 7809963

Claims (14)

40. J 498 (L) 1. Hair spray products which may contain a hair spray containing 0.4 to 7.5% by weight hair spray resin, a solvent for the hair spray resin and, if desired, a propellant and contained in a container suitable for applying the hair spray to hair spray, characterized in that these products contain a frictional resistance reducing agent in a concentration of less than 0.3% by weight of the hairspray and in a weight ratio of hairspray resin to frictional resistance reducing agent of 10,000 to 2: 1 and the shaping ability of the hair spray is improved. Hair spray product according to claim 1, characterized in that the friction-reducing agent is a non-ionic compound. Hair spray product according to any one of the preceding claims, characterized in that the friction-reducing agent has a friction-reducing ability of at least 10¾. Hair spray product according to one or more of the preceding claims, characterized in that the friction-reducing agent is soluble in ethanol. Hair spray product according to one or more of claims 1 to 3, characterized in that the friction-reducing agent is soluble in methylene chloride. Hair spray product according to one or more of claims 1 to 25 and 3, characterized in that the friction-reducing agent is soluble in water. Hair spray product according to claim 4, characterized in that the friction-reducing agent is a hydroxypropyl cellulose. Hair spray product according to claim 7, characterized in that the hydroxypropyl cellulose has an average molecular weight of at least 5 x 10. Hair spray product according to claim 5, characterized in that the friction-reducing agent is a polyoxyethylene. Hair spray product according to claim 9, characterized in that the polyoxyethylene has an average molecular weight of at least 4 x 105. 78 0 99 63 41. J 498 (L) Hair spray product according to claim 5, characterized in that the frictional resistance reducing agent is a polyacrylic elastomer. Hair spray product according to one or more of the preceding 5 claims, characterized in that the weight ratio of the hair spray resin to the friction-reducing agent is at least 5: 1. Hair spray product according to claim 12, characterized in that the weight ratio of the hair spray resin to the frictional reducing agent is from 5000 to 5: 1. Hair spray product according to any one of the preceding claims, characterized in that the amount of friction-reducing agent constitutes less than 0.2% by weight of the hair spray product. * 7809963