JP5346518B2 - Aerosol spray hair styling composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an aerosol spray type hairdressing preventing clogging during jetting, having excellent hairdressing holding power, and smooth finger combing without a stiff feeling peculiar to a film-forming polymer, and capable of imparting a natural luster, and to provide the aerosol spray type hairdressing including the composition. <P>SOLUTION: The composition for the aerosol spray type hairdressing includes (A) the carboxy group-containing film-forming polymer; and (B) at least one selected from among the group consisting of an alkylamine compound and a fatty acid amidoamine compound; and optionally (C) a silicone compound may be contained. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an aerosol spray type hairdressing composition and an aerosol spray type hairdressing composition containing the composition.

  Conventionally, various film-forming polymers have been used in order to impart excellent hair styling properties in aerosol hair styling agents. Among these, anionic film-forming polymers containing a carboxyl group that is excellent in hair holding ability are widely used. However, when a carboxyl group-containing film-forming polymer in an amount effective for hair styling is blended, even if the hair can be sufficiently fixed and hair styling, a feeling of stiffness occurs and the smooth finger is inferior. There's a problem. Furthermore, there is a problem that the formed film gives the hair an unnatural glossiness.

  In order to solve such problems, attempts have been made to soften the film formed by the film-forming polymer and improve the feeling of use. Specifically, a hair cosmetic containing an anionic polymer and silicones (see, for example, Patent Document 1), an aerosol composition containing a film-forming polymer, a surfactant, and an oil (for example, Patent Document 2), foam hair cosmetics containing a film-forming resin and a sugar alcohol (for example, see Patent Document 3) have been proposed.

  However, although such a trial can improve the feeling of stickiness peculiar to the film-forming polymer to some extent, there is a problem that a sticky feeling is generated and the hair holding power is remarkably reduced. Also, these attempts are not satisfactory in the gloss of hair. In addition, in the case of a spray type among aerosol types, the content liquid is sprayed in the form of a mist, so it is difficult to thicken the hair, and it is necessary to add a large amount of the film-forming polymer. There is also a problem that appears more prominently. Furthermore, there is a problem that clogging occurs due to the film-forming polymer during ejection, resulting in ejection failure.

  On the other hand, attempts have been made to impart natural luster to hair. Specifically, it contains a hair cosmetic (for example, see Patent Document 4) containing a hair set polymer, a cationic surfactant and silicone oil, or a hair set polymer, silicone oil and polyhydric alcohol. Hair cosmetics (see, for example, Patent Document 5) have been proposed.

  However, although it is possible to give natural luster to such an attempt, there is a problem that the hair feels moist and is inferior in hair holding ability.

JP-A-6-100418 Japanese Patent Laid-Open No. 9-143039 Japanese Patent Laid-Open No. 2002-60321 JP-A-6-87725 JP 2005-255533 A

  The present invention has been made in view of the above prior art, and prevents clogging at the time of discharge, has excellent hair-styling retention force, has no wrinkle characteristic peculiar to a film-forming polymer, is excellent in smooth fingering, and natural. It is an object of the present invention to provide an aerosol spray type hairdressing composition capable of imparting a lustrous luster and an aerosol spray type hairdressing composition containing the composition.

That is, the invention according to claim 1 is a composition for an aerosol spray hairdressing agent that is a non-aqueous system substantially containing no water, and includes (A) a carboxyl group-containing film-forming polymer, and (B) the following general formula ( Contains at least one selected from the group consisting of alkylamine compounds represented by Formula 1) and (Formula 2) and fatty acid amide amine compounds represented by the following general formula (Formula 3), and (C) a silicone compound The (A) carboxyl group-containing film-forming polymer is an octylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer, or a vinyl acetate / crotonic acid / neodecanoate vinyl copolymer. Ri, wherein (C) a silicone compound, to the amino-modified silicone der Ru aerosol spray-type hair fixative composition.

(In the formula, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and R ₂ is a hydrogen atom, a 1-aminopropyl group, or a linear or branched group having 8 to 20 carbon atoms. A chain alkyl group or an alkenyl group.)

(In the formula, R ₃ is a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, and R ₄ is a methyl group or a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms. Group.)

(In the formula, R ₅ is a linear or branched alkyl group or alkenyl group having 11 to 24 carbon atoms, R ₆ is an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and n is 1 to 4) Is an integer.)

  The invention according to claim 2 relates to the aerosol spray hairdressing composition according to claim 1, wherein the component (B) is used for neutralization of the component (A).

The invention according to claim 3 relates to an aerosol spray-type hair styling composition comprising the aerosol spray-type hair styling composition according to claim 1 or 2 and a propellant.

  The aerosol spray-type hairdressing composition of the present invention, and the aerosol spray-type hairdressing composition containing the composition, have an effect of preventing clogging at the time of discharge, and are excellent in hair-styling retention force and are unique to a film-forming polymer. There is no sticky feeling, it is excellent in smooth finger passage, and it has the effect of giving a natural gloss.

  The aerosol spray hairdressing composition of the present invention contains (A) a carboxyl group-containing film-forming polymer, and (B) at least one selected from the group consisting of an alkylamine compound and a fatty acid amidoamine compound.

Specific examples of the carboxyl group-containing film-forming polymer of the component (A) include, for example, an octylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer, an octylamide / acrylate copolymer, Vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, alkyl acrylate / methacrylic acid / silicone copolymer, acrylic acid / acrylic acid amide / ethyl acrylate copolymer, acrylates / Examples thereof include hydroxyalkyl acrylate copolymers, acrylates / acrylic acid hydroxy ester copolymers, vinyl methyl ether / ethyl maleate copolymers, vinyl methyl ether / butyl maleate copolymers, and the like. These components may be used alone or in combination of two or more. Suitable components (A) include octylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer, vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, acrylic, from the viewpoint of excellent hair retention. It is preferable to use an acid alkyl / methacrylic acid / silicone copolymer. In the present invention, the carboxyl group-containing film-forming polymer (A) is an octylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer, or a vinyl acetate / crotonic acid / vinyl neodecanoate copolymer. .

  In addition, the (A) component which can be used for this invention can use a commercial item as it is. Examples of commercially available products of acrylic acid octylamide / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer include AMPHOMER 28-4910, LV-41, LV-71, SH30, SH37, SH701, and SH701N (trade name, Any of them can be exemplified by Nippon NSC Co., Ltd.). As a commercial item of a vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, for example, RESYN-28-2930 (trade name, manufactured by NSC Japan) and the like can be exemplified. Examples of commercially available products of alkyl acrylate / methacrylic acid / silicone copolymer include Rubyflex Silk (trade name, manufactured by BASF).

  The content of the component (A) is not particularly limited as long as the desired effect is sufficiently imparted, but usually 0.1% by weight or more is preferable in the composition from the viewpoint of hair styling retention power, and more preferably Is 1% by weight or more. Further, from the viewpoint of usability and prevention of clogging, the content is preferably 20% by weight or less, more preferably 15% by weight or less. From these viewpoints, the content of the component (A) is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight.

  Usually, the carboxyl group-containing film-forming polymer of component (A) is an alkanolamine such as triethanolamine, monoethanolamine or aminomethylpropanol, an inorganic base such as ammonia, sodium hydroxide or potassium hydroxide; a base such as arginine Neutralized by basic substances such as functional amino acids. However, in the present invention, it will be described later from the viewpoint of reducing the feeling of stiffness peculiar to the component (A), providing smooth fingering, giving natural gloss, and preventing clogging during discharge. It is preferable to neutralize part or all of the component (A) using the alkylamine compound or the fatty acid amidoamine compound as the component (B). The unneutralized component (A) may be neutralized with a basic substance such as the alkanolamines, inorganic bases and basic amino acids.

  The alkylamine compound as the component (B) is a compound having the following general formulas (Formula 1) and (Formula 2).

(In the formula, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and R ₂ is a hydrogen atom, a 1-aminopropyl group, or a linear or branched group having 8 to 20 carbon atoms. A chain alkyl group or an alkenyl group.)

(In the formula, R ₃ is a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, and R ₄ is a methyl group or a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms. Group.)

  Specific examples of the compound of formula 1 include, for example, octylamine, laurylamine, myristylamine, stearylamine, cocoalkylamine, beef tallow alkylamine, cured beef tallow alkylamine, oleylamine, dicocoalkylamine, dicured tallow alkylamine N-coconut alkyl-1,3-diaminopropane, N-tallow alkyl-coconut alkyl-1,3-diaminopropane, and the like. Specific examples of the compound consisting of Formula 2 include, for example, N, N-dimethyllaurylamine, N, N-dimethylmyristylamine, N, N-dimethylpalmitylamine, N, N-dimethylstearylamine, N, N-dimethylbehenylamine, N, N-dimethylcocoalkylamine, N, N-dimethyl beef tallow alkylamine, N, N-dimethyl-cured tallow alkylamine, N, N-dimethyloleylamine, N-methyldidecylamine, N- Examples thereof include methyl cocoalkylamine, N-methyl hydrogenated beef tallow alkylamine, N-methyldioleylamine and the like. These components may be used alone or in combination of two or more.

  The fatty acid amidoamine compound is a compound having the following general formula (Formula 3).

(In the formula, R ₅ is a linear or branched alkyl group or alkenyl group having 11 to 24 carbon atoms, R ₆ is an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and n is 1 to 4) Is an integer.)

  Specific examples of the compound of formula 3 include, for example, myristic acid dimethylaminoethylamide, myristic acid dimethylaminopropylamide, myristic acid diethylaminoethylamide, myristic acid diethylaminopropylamide, palmitic acid dimethylaminoethylamide, palmitic acid dimethylamino Propylamide, palmitic acid diethylaminoethylamide, palmitic acid diethylaminopropylamide, stearic acid dimethylaminoethylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminoethylamide, stearic acid diethylaminopropylamide, stearic acid dipropylaminoethylamide, stearin Acid dipropylaminopropylamide, behenic acid dimethylaminoethylamide, beheny Acid dimethyl aminopropyl amide, behenic acid diethylaminoethylamide, can be exemplified behenic acid diethylaminopropylamide. These components may be used alone or in combination of two or more.

  In addition, the (B) component which can be used for this invention can use a commercial item as it is. As a commercial item of an alkylamine compound, for example, Armin series (manufactured by Lion Akzo) can be exemplified. Moreover, as a commercial item of a fatty-acid amide amine compound, NIKKOL amide amine series (made by Nikko Chemicals) etc. can be illustrated, for example.

  The content of the component (B) is not particularly limited as long as part or all of the component (A) can be neutralized, but usually 0.001% by weight or more is preferable in the composition, More preferably, it is 0.01 weight% or more. Moreover, 10 weight% or less is preferable from a viewpoint of the deterioration of a usability | use_condition, More preferably, it is 5 weight% or less. From these viewpoints, the content of the component (B) is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight.

The aerosol spray-type hair fixative composition of the present invention, from the viewpoint of further reducing the feeling stiff, Ru is contained (C) a silicone compound. Examples of the component ( C) include chain silicone, cyclic silicone; amino-modified silicone, carboxy-modified silicone, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, epoxy-modified silicone, fluorine-modified silicone, alkyl-modified silicone, and the like. And modified silicones. These components may be used alone or in combination of two or more. As a suitable component (C), it is preferable to use a chain silicone or an amino-modified silicone. In the present invention, amino-modified silicone is used as the component (C).

  Specific examples of the chain silicone include methylpolysiloxane, highly polymerized methylpolysiloxane having an average polymerization degree of 650 to 7000, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and dimethiconol.

  In addition, these chain silicone can use a commercial item as it is. Examples of commercially available products of methylpolysiloxane include SH200C (trade name, manufactured by Toray Dow Corning Silicone). Examples of commercially available highly polymerized methylpolysiloxane having an average degree of polymerization of 650 to 7000 include SH200, BY11-034, BY11-026 (trade names, all manufactured by Toray Dow Corning Silicone). be able to. Examples of commercially available methylphenylpolysiloxane include KF54, KF56 (trade names, both manufactured by Shin-Etsu Chemical Co., Ltd.), SF557, SF558 (trade names, both manufactured by Toray Dow Corning Silicone Co., Ltd.), etc. Can do. Examples of commercially available dimethiconol include 1501 FLuid (manufactured by Toray Dow Corning Silicone).

  Examples of amino-modified silicones include aminopropylmethylsiloxane / dimethylsiloxane copolymer, aminoethylaminopropylsiloxane / dimethylsiloxane copolymer, aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer, etc. Can do.

  These amino-modified silicones can be used as they are on the market. Examples of commercially available aminopropylmethylsiloxane / dimethylsiloxane copolymers include SF3551, SF3552 (trade names, both manufactured by Toray Dow Corning Silicone), SS-3551, SS-3552 (trade names, both Nippon Unicar Co., Ltd.) can be exemplified. Examples of commercially available aminoethylaminopropylsiloxane / dimethylsiloxane copolymers include SM8702C and SM8704C (trade names, both manufactured by Toray Dow Corning Silicone). Examples of commercially available aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer include SF8452C (trade name, manufactured by Toray Dow Corning Silicone).

  The content of the component (C) is not particularly limited as long as the desired effect is sufficiently imparted, but usually 0.01% by weight or more is preferable in the composition from the viewpoint of further reducing the feeling of stiffness. More preferably, it is 0.1% by weight or more. Moreover, from a viewpoint of hair-styling retention power, 10 weight% or less is preferable, More preferably, it is 5 weight% or less. From these viewpoints, the content of the component (C) is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.

  The aerosol spray-type hairdressing composition of the present invention includes components that are usually used in cosmetics, such as hydrocarbon oils, higher alcohols, ester oils, in addition to the above-described components, as long as the effects of the present invention are not impaired. Oils such as ethanol, lower alcohols such as isopropanol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol Polyhydric alcohols such as: sugar alcohols such as sorbitol, maltitol, trehalose; surfactants, sequestering agents, preservatives, antioxidants, plant extracts, dyes, pigments, pH adjusters, etc., depending on the purpose It can mix | blend suitably.

Further, aerosol spray-type hair fixative composition of the present invention, from the viewpoint of solubility of the component (B), Ru is prepared in a non-aqueous system that does not blending substantially water. In the present invention, “non-aqueous system containing substantially no water” means “not containing water separately”, and excludes a small amount of water contained in each compounding component. is not.

  The aerosol spray type hairdressing agent of the present invention may be produced by a known method. For example, a solution in which each component to be blended in the aerosol spray type hairdressing composition is uniformly dispersed in an aerosol container. After filling and clinching the container with an aerosol valve, a method of filling a specified amount of propellant from the stem and mounting an injection button suitable for the stem can be exemplified.

  The propellant used is not particularly limited as long as it is used in cosmetics. Examples thereof include liquefied petroleum gas, isobutane, and dimethyl ether. These propellants may be used alone or in combination of two or more. In the present invention, it is preferable to use dimethyl ether alone or a mixed gas of liquefied petroleum gas and dimethyl ether from the viewpoint of the storage stability of the preparation.

  When a mixed gas of liquefied petroleum gas and dimethyl ether is used, the mixing ratio (weight ratio) is not particularly limited, but from the viewpoint of storage stability of the preparation, it is preferable to contain 30% by weight or more of dimethyl ether in the mixed gas. More preferably, it is 50% by weight or more. Further, the mixing ratio (weight ratio, composition / propellant) of the aerosol spray type hairdressing composition and the above propellant is not particularly limited, but is usually 70/30 to from the viewpoint of spraying into a fine mist. It is preferable to prepare in the range of 40/60, more preferably 60/40 to 50/50.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples. The blending amount represents “% by weight” unless otherwise specified. Moreover, the compounding quantity was converted into the pure part as each film forming agent.

(Sample preparation 1)
According to the composition described in Table 1 and Table 2, each aerosol spray hairdressing composition was prepared according to a conventional method and then filled into an aerosol container. Next, after the aerosol valve was clinched in the container, the propellant was filled from the stem so that the weight ratio of the stock solution / propellant was 60/40, and Reference Examples 1, 2, Example 3, Reference Examples 4, 5 And the aerosol spray type hairdressing agent of Comparative Examples 1-5 was prepared, and it used for the following evaluation. The results are shown in Table 1 and Table 2, respectively. In addition, all evaluation was implemented on the constant conditions of constant temperature and humidity of 23 degreeC and 60% of humidity.

(Test Example 1: Evaluation of clogging)
Real 施例, stored reference examples and the aerosol spray-type hair fixative obtained in Comparative Examples in a thermostat at 45 ° C., a daily repeated following operation was performed discharge stability test.

(operation)
Each aerosol spray type hair styling agent was taken out from the thermostatic bath, immediately shaken well for 15 seconds, and then discharged for 5 seconds. After discharge, each sample was returned to the incubator and the same test was performed the next day. This operation was repeated until the content liquid disappeared completely or until the content was not discharged due to clogging, and the state was evaluated according to the following criteria.

<Evaluation criteria for clogging>
○: No abnormality is observed in the discharge state within the observation period. Δ: The discharge state is slightly weaker within the observation period, but is discharged. ×: No discharge occurs during the observation period.

(Test Example 2: Evaluation of hair holding ability)
Each of the samples obtained in the Examples , Reference Examples and Comparative Examples was used by 20 professional panels using wigs (Lesson Mannequin: manufactured by Eucalyptus Japan), and the hair styling retention was sensory evaluated according to the following evaluation criteria .

  The hair styling retention strength is evaluated by performing the operation of squeezing the hair from the tip of the hair 10 times, and if the squeezed shape is clearly held in the formed style, the hair styling retention strength is good. It was.

<Evaluation criteria for hair styling retention power>
○: Answer that 16 or more of 20 people are excellent in hair holding ability. Δ: Answer that 10 to 15 of 20 people are excellent in hair holding ability. ×: Answer that 9 or less of 20 people are excellent in hair holding ability.

(Test Example 3: Stiffness and finger evaluation)
A hair bundle (length 10 cm, width 0.8 cm, weight 1 g) left overnight under constant temperature and humidity at 23 ° C. and 60% humidity was 0.8 g from each sample obtained in Examples , Reference Examples and Comparative Examples. After spray coating, the sample was allowed to stand for 2 hours under constant temperature and humidity of 23 ° C. and 60% humidity, and the sensory evaluation panel was subjected to sensory evaluation according to the following evaluation criteria.

<Evaluation criteria for the feeling of stiffness>
○: 16 or more out of 20 responded that they did not feel △: 15 out of 20 responded that they did not feel sticky ×: 9 or less of 20 responded that they did not feel sticky

<Evaluation criteria as per finger>
○: 16 or more people out of 20 are smooth and excellent if they are easy to finger. △: 10 to 15 people are smooth and good if they are easy to finger. ×: 9 or less of 20 people are smooth. Yes, it ’s good to follow your finger

(Test Example 4: Evaluation of glossiness)
After the evaluation of Test Example 2, the glossiness was visually evaluated according to the following evaluation criteria by 20 evaluation panels.

<Evaluation criteria for glossiness>
○: At least 16 out of 20 responded that they had natural gloss. △: 10-15 out of 20 responded that they had natural gloss. ×: 9 or less of 20 responded that had natural gloss.

Table 1 and the results shown in Table 2, the real 施例, the aerosol spray-type hair fixative reference example, in contrast to that of the comparative examples, it can be seen that clogging does not occur at the time of discharge. Moreover, it is understood that the hair holding ability is excellent, and the film-forming polymer has no wrinkle feeling, and it is smooth and excellent as a finger. Furthermore, it turns out that natural gloss is given rather than the unnatural glossiness which gave glare.

Hereafter, the reference prescription example which concerns on this invention is shown. The content is% by weight.

(Prescription Example 1)
(Raw solution part)
Octylamide acrylate / hydroxypropyl acrylate / butylaminoethyl methacrylate copolymer 6.0
Laurylamine 2.3
Methyl polysiloxane / highly polymerized methyl polysiloxane 1.5
Glycerin 0.5
Ethanol remaining part Total 100.0
(Propellant)
Liquefied petroleum gas 30.0
Dimethyl ether 70.0
Total 100.0
Stock solution part 50.0
Propellant 50.0
Total 100.0

(Prescription example 2)
(Raw solution part)
Vinyl acetate / crotonic acid / vinyl neodecanoate copolymer 4.0
Amidoamine 2.0
Methylphenylpolysiloxane 1.5
Isoparaffin 0.5
Ethanol remaining part Total 100.0
(Propellant)
Liquefied petroleum gas 30.0
Dimethyl ether 70.0
Total 100.0
Stock solution part 50.0
Propellant 50.0
Total 100.0

(Prescription Example 3)
(Raw solution part)
Alkyl acrylate / methacrylic acid / silicone copolymer 2.0
N-methyldicocoalkylamine 0.3
Aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer 1.5
Ethanol remaining part Total 100.0
(Propellant)
Liquefied petroleum gas 30.0
Dimethyl ether 70.0
Total 100.0
Stock solution part 55.0
Propellant 45.0
Total 100.0

Claims (3)

It is a composition for aerosol spray hairdressing agent that is a non-aqueous system substantially containing no water,
(A) a carboxyl group-containing film-forming polymer;
(B) at least one selected from the group consisting of alkylamine compounds represented by the following general formulas (formula 1) and (formula 2), and fatty acid amide amine compounds represented by the following general formula (formula 3) ;
(C) comprising a silicone compound ,
Wherein (A) a carboxyl group-containing film-forming polymer, octyl amide acrylate hydroxypropyl methacrylate butylaminoethyl acrylate copolymer, or vinyl acetate / crotonic acid / vinyl neodecanoate copolymer der is,
The (C) silicone compounds, amino-modified silicone der Ru aerosol spray-type hair fixative composition.

(In the formula, R ₁ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and R ₂ is a hydrogen atom, a 1-aminopropyl group, or a linear or branched group having 8 to 20 carbon atoms. A chain alkyl group or an alkenyl group.)

(In the formula, R ₃ is a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, and R ₄ is a methyl group or a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms. Group.)

(In the formula, R ₅ is a linear or branched alkyl group or alkenyl group having 11 to 24 carbon atoms, R ₆ is an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and n is 1 to 4) Is an integer.)   (A) Component (B) is used for neutralization of component, The composition for aerosol spray type hairdressing agents of Claim 1 characterized by the above-mentioned. An aerosol spray type hair styling composition comprising the aerosol spray type hair styling composition according to claim 1 or 2 and a propellant.