JP2003155377A - Aqueous gel composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both a uniform aqueous gel composition having shape stability, a high gel strength, a slight amount of syneresis and a beautiful appearance and affording a small amount of residues of a gelling agent at the completion of agent effects of the gel composition and an aqueous gel product capable of readily judging the end point of the use. SOLUTION: This aqueous gel composition is prepared by adding at least one kind of amine oxide amphoteric surfactant of a surfactant represented by formula (I) (wherein, R<1> is an 8-22C alkyl or an 8-22C alkenyl), a surfactant represented by formula (II) (wherein, R<2> is an 8-22C alkyl or an 8-22C alkenyl; and l+m is 1-10), a surfactant represented by formula (III) (wherein, R<3> is an 8-22C alkly or an 8-22C alkenyl; and n is 1-10) and a surfactant represented by formula (IV) (wherein, R<4> is an 8-22C alkyl or an 8-22C alkenyl) to at least one kind of a natural gum of a carboxymethly cellulose polyvalent metal salt, carrageenan, agar, a mixture of locust bean gum with xanthan gum and gelatin. The aqueous gel product is obtained by filling the aqueous gel composition in a container opened by pulling up an upper lid from a lower lid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous gel composition and an aqueous gel product comprising the same. More specifically, the aqueous gel composition has excellent shape stability, high gel strength, is uniform, has a small amount of water separation, and has a beautiful appearance, and has a small residue of the gelling agent when the drug effect of the gel composition ends. And an aqueous gel product in which a container is filled with the aqueous gel composition and the end point of use can be easily determined.

[0002]

2. Description of the Related Art To meet the demand for a more comfortable living space along with changes in lifestyle, various fragrances, deodorants, deodorants, mildew-proofing agents, germicides, repellents and other toiletry products have been developed. Has been done. Above all, solid type products using gelling agents have excellent release and sustainability of the contained drug,
It has the advantage of being easy to handle. As gelled toiletry products, an aqueous gel type product using water as a solvent and an oily gel type product using a terpene hydrocarbon as a solvent are known, but those on the market are aqueous. Gel type products are the mainstream.

The above-mentioned toiletry product exerts a drug effect by releasing a drug component together with water from the surface of the gel composition. For example, a gelling agent composed of carrageenan, locust bean gum and polyvinyl alcohol (JP-A-52). No. 136893), a gelling agent using locust bean gum and xanthan gum (JP-A-53-50346), and a gelling agent comprising a carboxymethylcellulose polyvalent metal salt (JP-A-7-90121).
Aqueous gel compositions such as Japanese Patent Publication No. 1989-242242).

[0004] In the conventional aqueous gel-type products, since the dry residue of the gelling agent is large even after the volatilization of the fragrance is completed, the end of use is unclear and the fragrance effect disappears. Even after that, there was a problem that it was left as it was, and improvement was long awaited.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has excellent shape stability, high gel strength, uniformity, a small amount of water separation, and a beautiful appearance, and a gel composition. To provide an aqueous gel composition having a small residue of a gelling agent at the time when the drug effect of the product is finished, and an aqueous gel product in which the container is filled with the aqueous gel composition and the end point of use can be easily determined. With the goal.

[0006]

The present invention comprises: General formula (I):

[0007]

[Chemical 5]

(Wherein R ¹ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms), an amine oxide type amphoteric surfactant (I) represented by the general formula (II):

[0009]

[Chemical 6]

An amine represented by the formula: wherein R ² is an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and 1 + m (the average number of moles of ethylene oxide added) is an integer of 1 to 10. Oxide type amphoteric surfactant (I
I), general formula (III):

[0011]

[Chemical 7]

(In the formula, R ³ is an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and n (average number of moles of ethylene oxide added) is an integer of 1 to 10)
The amine oxide type amphoteric surfactant represented by (II
I) and general formula (IV):

[0013]

[Chemical 8]

(In the formula, R ⁴ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms), at least one selected from amine oxide type amphoteric surfactants (IV). Is added to at least one natural gum selected from carboxymethyl cellulose polyvalent metal salt, carrageenan, agar, a mixture of locust bean gum and xanthan gum, and gelatin. The present invention relates to an aqueous gel composition, and an aqueous gel product obtained by filling the aqueous gel composition in a container having an upper lid and a lower lid, the upper lid being pulled up from the lower lid to open.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous gel composition of the present invention is characterized in that an amine oxide amphoteric surfactant and a natural gum are used in combination, and the amine oxide amphoteric surfactant is a gel of natural gum. It is added before conversion.

The amine oxide type amphoteric surfactant is
At the time when the drug effect of the aqueous gel composition is completed, the gel residue of the gelling agent which is a natural gum can be made small, and this can be automatically raised upward, and the action of preventing water separation. Also present.

The amine oxide amphoteric surfactant used in the present invention is an amine oxide amphoteric surfactant (I) represented by the general formula (I) or an amine oxide amphoteric surfactant represented by the general formula (II). At least one selected from the agent (II), the amine oxide-type amphoteric surfactant (III) represented by the general formula (III) and the amine oxide-type amphoteric surfactant (IV) represented by the general formula (IV). is there.

In the general formula (I) representing the amine oxide type amphoteric surfactant (I), R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, or Chain or branched chain carbon number 8 to 2
2, preferably 10 to 18 alkenyl groups.

Representative examples of the amine oxide type amphoteric surfactant (I) are, for example, N-octyl-N, N-dimethylamine, N-decyl-N, N-dimethylamine and N.
-Lauryl-N, N-dimethylamine, N-myristyl-N, N-dimethylamine, N-palmityl-N, N-
Dimethylamine, N-stearyl-N, N-dimethylamine, N-isostearyl-N, N-dimethylamine,
Alkyldimethylamines such as N-coconut oil alkyl-N, N-dimethylamine, N-hardened tallow alkyl-N, N-dimethylamine, N-behenyl-N, N-dimethylamine; N-octenyl-N, N- Dimethylamine, N-
Oleyl-N, N-dimethylamine, N-dococenyl-
Betaine compounds obtained by reacting an amine such as alkenyldimethylamine such as N, N-dimethylamine with hydrogen peroxide by a known method may be used alone or in combination with 2
It is possible to appropriately mix and use one or more species.

Amine oxide type amphoteric surfactant (II)
In the general formula (II), R ² is a linear or branched C 8-22, preferably 10-18 alkyl group, or a linear or branched C 8
-22, preferably 10-18 alkenyl groups.
Further, l and m represent the average number of moles of ethylene oxide added, and l + m is an integer of 1 to 10, preferably 2 to 8.

Amine oxide type amphoteric surfactant (II)
Representative examples of N-octyl-N, N-dipolyoxyethyleneamine, N-decyl-N, N-dipolyoxyethyleneamine, N-lauryl-N, N-dipolyoxyethyleneamine, N -Myristyl-N, N-dipolyoxyethyleneamine, N-palmityl-N, N-
Dipolyoxyethylene amine, N-stearyl-N, N
-Dipolyoxyethylene amine, N-isostearyl-
N, N-dipolyoxyethylene amine, N-coconut oil alkyl-N, N-dipolyoxyethylene amine, N-hardened tallow alkyl-N, N-dipolyoxyethylene amine,
Alkyldipolyoxyethyleneamines such as N-behenyl-N, N-dipolyoxyethyleneamine; N-octenyl-N, N-dipolyoxyethyleneamine, N-oleyl-N, N-dipolyoxyethyleneamine, Amines such as alkenyldipolyoxyethyleneamines such as N-dococenyl-N, N-dipolyoxyethyleneamine,
Examples thereof include betaine compounds reacted with hydrogen peroxide by a known method, and these can be used alone or in admixture of two or more kinds.

Amine oxide amphoteric surfactant (II
In the general formula (III) representing I), R ³ has a linear or branched carbon number of 8 to 22, preferably 10
It is an alkyl group having 18 or a linear or branched alkenyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. Further, n represents the average number of moles of ethylene oxide added, and n is an integer of 1 to 10, preferably 2 to 8.

Amine oxide amphoteric surfactant (II
Representative examples of I) include, for example, N-octylpolyoxyethylene-N, N-dimethylamine, N-decylpolyoxyethylene-N, N-dimethylamine, N-laurylpolyoxyethylene-N, N-dimethylamine. , N-
Myristyl polyoxyethylene-N, N-dimethylamine, N-palmityl polyoxyethylene-N, N-dimethylamine, N-stearyl polyoxyethylene-N,
N-dimethylamine, N-isostearyl polyoxyethylene-N, N-dimethylamine, N-coconut oil alkylpolyoxyethylene-N, N-dimethylamine, N-cured tallow alkylpolyoxyethylene-N, N-dimethyl Amine, alkyl polyoxyethylene dimethylamine such as N-behenyl polyoxyethylene-N, N-dimethylamine; N-octenyl polyoxyethylene-N, N
-Dimethylamine, N-oleyl polyoxyethylene-
Betaine compounds obtained by reacting an amine such as an alkenylpolyoxyethylenedimethylamine such as N, N-dimethylamine or N-dococenylpolyoxyethylene-N, N-dimethylamine with hydrogen peroxide by a known method can be given. These can be used alone or in admixture of two or more.

Amine oxide type amphoteric surfactant (IV)
In the general formula (IV), R ⁴ is a linear or branched C 8-22, preferably 10-18 alkyl group, or a linear or branched C 8
-22, preferably 10-18 alkenyl groups.

Amine oxide type amphoteric surfactant (IV)
Representative examples of N-octanoylamidopropyl-N, N-dimethylamine, N-decanoylamidopropyl-N, N-dimethylamine, N-lauroylamidopropyl-N, N-dimethylamine, N- Myristoylamidopropyl-N, N-dimethylamine, N-
Palmitoylamidopropyl-N, N-dimethylamine, N-stearoylamidopropyl-N, N-dimethylamine, N-isostearoylamidopropyl-N,
N-dimethylamine, N-behenoylamidopropyl-
Alkanoylamidopropyldimethylamine such as N, N-dimethylamine, N-cocoylamidopropyl-N, N-dimethylamine; N-octenoylamidopropyl-N, N-dimethylamine, N-oleoylamidopropyl-N, Betaine compounds obtained by reacting an amine such as an alkenoylamidopropyldimethylamine such as N-dimethylamine or N-docosenoylamidopropyl-N, N-dimethylamine with hydrogen peroxide by a known method may be mentioned. Can be used alone or in admixture of two or more.

The amount of the amine oxide type amphoteric surfactant in the water-based gel composition of the present invention is sufficient to sufficiently exert the effect of reducing the gel residue and reduce the amount of water separation.
It is desirable to be 0.05% by weight or more, preferably 0.1% by weight or more, and 5% by weight or less, preferably 3% by weight from the viewpoint of not adversely affecting the gel properties such as shape stability and gel strength. % Or less is desirable.

In the present invention, at least one natural gum selected from carboxymethyl cellulose polyvalent metal salt, carrageenan, agar, a mixture of locust bean gum and xanthan gum, and gelatin is used as the gelling agent.

Carboxymethyl cellulose polyvalent metal salts include carboxymethyl cellulose (hereinafter referred to as CMC), sodium CMC or potassium CMC (hereinafter, referred to as CMC).
These are collectively referred to as CMCs) and are obtained by gelling with polyvalent metal ions.

As CMCs, from the viewpoint of obtaining the shape stability and gel strength required for an aqueous gel product,
It is desirable that the viscosity of a 1% aqueous solution (concentration of anhydride, measured at 25 ° C. with a B-type viscometer (rotation speed: 60 rpm)) is 5 mPa · s or more, preferably 50 mPa · s or more, and the aqueous gel From the viewpoint of the handling property of the aqueous solution of CMCs in the preparation step, the viscosity of the 1% aqueous solution is 10,000 mPa · s or less, preferably 5000 mP
It is preferably a or less.

The CMCs preferably have an average degree of substitution of carboxymethyl groups of 0.4 or more, and preferably 0.5 or more, from the viewpoint of good solubility in water. When gelled with a valent metal ion, intramolecular cross-linking proceeds preferentially due to the large amount of carboxymethyl groups present in the molecule, resulting in a gel with a high cross-linking density and a stable aqueous gel. In order to eliminate the possibility of not being obtained, it is desirable that the average substitution degree of the carboxymethyl group is 2 or less, preferably 1.8 or less.

The CMC can be used as a mixture of two or more kinds.

When the CMCs are gelled with polyvalent metal ions, a polyvalent metal salt aqueous solution can be used.
The polyvalent metal salt aqueous solution is, for example, an aqueous solution of at least one metal salt selected from aluminum salts, iron salts, calcium salts and barium salts.

Typical examples of the aluminum salt include potassium alum, burnt alum, aluminum acetate,
Examples thereof include aluminum sulfate, aluminum hydroxide, aluminum hydroxide gel, aluminum chloride, aluminum lactate, sodium aluminate and potassium aluminate.

Typical examples of iron salts include ferric chloride and ferrous sulfate.

Typical examples of the calcium salt include calcium hydroxide and the like.

Typical examples of barium salts include barium chloride.

Among the above metal salts, aluminum salts are preferable from the viewpoint of coloring and economy peculiar to metal salts. That is, among CMC polyvalent metal salts, CMC aluminum salt is preferable.

By adding the polyvalent metal salt aqueous solution to the aqueous solution of CMCs, a CMC polyvalent metal salt in which CMCs are gelled with polyvalent metal ions can be obtained. further,
If the polyvalent metal salt is a sparingly soluble salt, add it as an aqueous dispersion to an aqueous solution of CMCs, and further adjust the pH of the system with an acidic substance or basic substance to elute the polyvalent metal ion. CM in which CMCs are gelled by controlling
A C polyvalent metal salt can be obtained. The concentration of the polyvalent metal salt aqueous solution or the polyvalent metal salt aqueous dispersion is not particularly limited and may be appropriately adjusted.

When a CMC polyvalent metal salt is used as a gelling agent, the CMC content in the aqueous gel composition of the present invention varies depending on the viscosity of a 1% aqueous solution of CMC used, but sufficient gel strength is obtained. It is desirable that the amount of anhydride is 1.5% by weight or more, preferably 2% by weight or more, and the viscosity of the system before gelation becomes extremely high, so that it is not difficult to fill the container when commercializing. In order to do so, it is desirable that the amount is 5% by weight or less, preferably 4% by weight or less in terms of anhydride.

The amount of the polyvalent metal salt in the aqueous gel composition varies depending on the type of the polyvalent metal salt and the amount of the CMC compounded, but in order to obtain a suitable gel strength, 0% of the aqueous gel composition is used. It is desirable that 0.3% by weight or more, preferably 0.5% by weight or more, and 4% by weight or less, preferably 3% by weight or less, be composed of a polyvalent metal salt.

Carrageenan is a seaweed ( Chondrus Crisspus , Gig) belonging to the red seaweed Suginotoriaceae .
artina Stellata , Chondrus
It is a type of galactan extracted from Ocellus etc.). Carrageenan contains two types of galactose (1-
3-linked β-D-galactose and 1-4-linked 3,6-
Anhydro-α-D-galactose) has a continuous structure and is an acidic polysaccharide having a sulfate group. Depending on the binding position of the sulfate group and the presence or absence of 3,6-anhydro-α-D-galactose, the formula:

[0042]

[Chemical 9]

Κ-carrageenan having a repeating unit represented by the formula:

[0044]

[Chemical 10]

Ι-carrageenan having a repeating unit represented by and a formula:

[0046]

[Chemical 11]

It is classified into three kinds of λ-carrageenan having a repeating unit represented by:

Since 3,6-anhydrogalactose is involved in the gel formation of carrageenan, ι-carrageenan and κ-carrageenan having anhydrogalactose can be used as a gelling agent in the present invention. Among ι-carrageenan and κ-carrageenan, κ-carrageenan having a lower sulfuric acid content is
The gel-forming ability is higher than that of ι-carrageenan, and λ-carrageenan is sometimes used as an agent for improving the physical properties of gel.

Carrageenan can be easily hydrated by mixing with water and heating, and when it is left to cool, it becomes a gel, but by adding cations such as calcium ion and potassium ion, A strong gel can be formed.

When carrageenan is used as a gelling agent, the amount of carrageenan in the aqueous gel composition is preferably 0.5% by weight or more, preferably 1% by weight or more in order to obtain sufficient gel strength. Further, in order to prevent gelation from becoming difficult, it is desirable that the content be 5% by weight or less, preferably 3% by weight or less.

Agar is a red alga, the agaraceae ( Gelid).
iaceae ), Gracilariaceae ( Gracilariac )
eae ), squid ( Ceramiaceae ), Noriaceae ( Gracilaria ), Otteraceae ( Ptero )
cladia), those contained in the rerun family (Ahnfeltia) cell membrane of various seaweed such. It has an amorphous form, a semi-transparent powder form, a flake form, a fragment form, a rod form, a string form, and the like, and is water-insoluble but water-swellable. Such agar is easily dissolved in hot water, for example, 0.
Even at a low concentration of about 5% by weight, gelation can be sufficiently achieved.

When agar is used as the gelling agent, the amount of agar in the aqueous gel composition is such that sufficient gel strength is obtained.
The content is preferably 0.2% by weight or more, preferably 0.5% by weight or more, and is 5% by weight or less, preferably 3% by weight or less in order to prevent gelation from becoming difficult. .

Locust bean gum is a polysaccharide whose main component is galactomannan, and the ratio of galactose and mannose is about 1: 4. Its structure is similar to guar gum, but differs from it in the proportion of galactose and mannose. The locust bean gum is dispersed in cold water to form a dispersion, but when heated, it is completely dissolved to form a high-viscosity solution.

Xanthan gum is a gram-negative bacterium ( Xanthomonas cam) whose substrate is corn syrup.
is a polysaccharide composed of sodium, potassium and calcium salts of D-glucose, D-mannose and D-glucuronic acid, which is obtained by separation from a culture solution of P. It is composed of D-glucose, and D-mannose attached to its main chain is acetylated. The side chains are in a form in which the D-mannose 2 component and D-glucuronic acid are bonded to every other main chain, and the terminal D-mannose is in the form of pyruvate. The xanthan gum is dissolved in water and boiling water to form a neutral solution, which forms a thermoreversible gel with the locust bean gum.

When a mixture of locust bean gum and xanthan gum is used as a gelling agent, the mixing ratio of these locust bean gum and xanthan gum is not particularly limited and can be appropriately changed.

When a mixture of locust bean gum and xanthan gum is used as the gelling agent, the amount of the mixture in the aqueous gel composition is 0.
It is desirable that the amount is 2% by weight or more, preferably 0.5% by weight or more, and 5% by weight or less, preferably 3% by weight or less in order not to make gelation difficult.

Gelatin is obtained by partially hydrolyzing collagen, which is a protein constituting animal connective tissue, and is industrially used as cow bone, cow hide,
Pig skin is used as a raw material. Gelatin does not dissolve in cold water but swells, and dissolves in warm or hot water to form a strong gel, but when the aqueous solution is boiled for too long, hydrolysis causes gelatin to become a low molecular weight product, resulting in gel strength. Will decrease. Gelatin is extracted by immersing a raw material pretreated with an acid or an alkali in warm water.

The chemical structure of gelatin is a long-chain polypeptide in which 18 kinds of amino acids are peptide-bonded.

The sol-gel change of gelatin gel is thermoreversible, and the melting point of a 10% gelatin solution is generally 2
It is about 0 to 30 ° C. Such gelatin solutions are not suitable for gel compositions used in aqueous gel products. Therefore, a method of insolubilizing the gelatin molecules by a crosslinking reaction to maintain the high temperature stability of the gel can be adopted. Examples of the crosslinking agent (curing agent) in this case include salts of chrome, aluminum, ferric iron and the like, aldehydes, ketones, quinones and the like.

When gelatin is used as a gelling agent, the amount of gelatin in the aqueous gel composition is preferably 0.5% by weight or more, preferably 1% by weight or more in order to obtain sufficient gel strength. Further, in order to prevent gelation from becoming difficult, it is desirable that the content is 10% by weight or less, preferably 8% by weight or less.

Water is used as a medium for the aqueous gel composition of the present invention. For example, ethylene glycol, propylene glycol, 1,3-butanediol, if necessary, may be used to prevent the gel from freezing in severe cold. Hexylene glycol, polyhydric alcohols such as glycerin; glycol ethers such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and other glycol monomethyl ethers and monoethyl ethers are appropriately added to the aqueous gel composition. be able to.

The aqueous gel composition of the present invention comprises an amine oxide type amphoteric surfactant added before gelation of a natural gum which is a gelling agent. Use of the resulting aqueous gel composition Depending on the purpose, fragrance, deodorant, deodorant, mildew,
It is preferable to contain at least one drug selected from bactericides and repellents.

The drug is not particularly limited, and any conventionally used drug can be used.

Typical examples of the fragrance include various fragrances and essential oils. As a concrete example,
For example grapefruit oil, costus oil, citronella oil, jasmine oil, sweet orange oil, spearmint oil, pine oil, patchouli oil, peppermint oil, bitter orange oil, hiba oil, peppermint oil, bergamot oil, mandarin oil, eucalyptus oil, lavender oil. , Natural oils such as lemon oil, lemongrass oil, rose oil, rosemary oil, peppermint oil, plant extractant as deodorant; terpene hydrocarbons such as α-pinene, β-pinene and limonene, linalool, geraniol , Terpene alcohols such as nerol, benzyl alcohol, phenethyl alcohol, other alcohols such as γ-phenylpropyl alcohol, diphenyl ether, isosafroeugenol, phenol derivatives such as p-methylanisole, heptanal, octane , Aldehydes such as nonal, terpene aldehydes such as citral, citronellal, hydroxycitronellal, benzaldehyde, phenylacetaldehyde, aromatic aldehydes such as 3-phenylpropionaldehyde, citral dimethyl acetal, acetals such as citral diethyl acetal. , 2-heptanone, 3-octanone, aliphatic ketones such as 2-octanone, carvone,
Terpene ketones such as menthone and pulegone, aromatic ketones such as p-methylacetophenone, benzophenone and benzylideneacetone, α, β, γ-ionone, alicyclic ketones such as theaspirane and jasmine lactone, ethers, lactones, muscone, annes Macrocyclic ketones such as bulletlet, lactones, synthetic musks such as musk xylene, musk ketone, musk ambrette, cyclic ethers such as rose oxide, 1,8-cineole, bicyclodihydrohomofarnesyl oxide, indole, 6-methylquinoline, 2 -Heterocyclic compounds such as furylmethanethiol, esters of aliphatic acids such as benzyl formate, ethyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, ethyl phenylacetate, ethyl cinnamate, iso salicylate Esters of aromatic acids, such as chill, .gamma.-heptyl butyrolactone, synthetic fragrances, such as so-called aldehydes such as allyl hexanoate and the like,
These may be used alone or in admixture of two or more.

Typical examples of deodorizers and deodorants are Sancha flowers, leaf extracts of persimmons, abies oil, origanum oil, geranium oil, sweet orange oil, bitter almond oil, peppermint oil, lavender oil, eucalyptus oil. ,
Extracts of plant extracts such as cypress oil, rosemary oil and lemon oil, and mixed essential oils of these plant extracts; alkyl dimethylaminoacetic acid betaine having an alkyl group having 8 to 20 carbon atoms, alkylimidazolinium betaine, and fatty acid residues Examples thereof include amphoteric surfactants such as fatty acid amide propyl betaine having 8 to 20 carbon atoms, which may be used alone or in admixture of two or more.

Typical examples of the fungicide and bactericide include volatile compounds such as thymol, stabilized chlorine dioxide, and allyl isothiocyanate, which may be used alone or in admixture of two or more kinds. You can

Typical examples of repellents include N, N
-Diethyl-m-toluamide (diet), dimethyl phthalate, dibutyl phthalate, 2-ethyl-1,3-
Hexanediol, di-n-propylisocinchomeronate, p-dichlorobenzene, di-n-butylsuccinate, carane-3,4-diol, 1-methylpropyl-2- (2-hydroxyethyl) -1- Examples thereof include piperidine carboxylate and allyl isothiocyanate. Furthermore, when natural allyl isothiocyanate is used, mustard ( Brassica juncea Czer) is used.
n. et Coss ), Black Mustard ( Brassican )
igra Koch. ), Wasabi (Wasabi ja
ponica Matsum. ) And other plants may be used. Further, wood vinegar and the like are exemplified as the repellent, and these can be used alone or in admixture of two or more kinds.

The content of the drug should be 0.1% of the total amount of the aqueous gel composition so that the effect of each drug is sufficiently expressed.
It is desirable that the content is at least 1% by weight, preferably at least 1% by weight, and in order not to reduce the gel strength of the aqueous gel composition, 15% by weight or less, preferably 10% by weight or less of the entire aqueous gel composition. Is desirable.

Further, as an emulsifying / solubilizing agent for the above-mentioned drug, the aqueous gel composition includes an anionic surfactant, an amphoteric surfactant other than the amine oxide type amphoteric surfactant, and a nonionic surfactant. An activator can be included.

Examples of the anionic surfactant include alkane sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, α-olefin sulfonate, etc. Can be given.

Examples of the amphoteric surfactant other than the amine oxide type amphoteric surfactant include alkyl betaine and fatty acid amidopropyl betaine.

Examples of nonionic surfactants include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and fatty acids. Alkanol amide ethylene oxide adduct, ethylene oxide adduct of oil and fat, ethylene oxide-propylene oxide block copolymer, fatty acid ester of glycerol, fatty acid ester of pentaerythritol, fatty acid ester of sorbitol and sorbitan, fatty acid ester of sucrose, polyvalent Examples thereof include alkyl ethers of alcohols and fatty acid amides of alkanolamines.

The various surfactants can be used alone or in admixture of two or more.

The content of the surfactant is 0.2% by weight or more, preferably 0. 0% by weight, based on the total amount of the aqueous gel composition, so that the emulsifying / solubilizing effect for each drug is sufficiently exhibited.
It is preferably 5% by weight or more, and 10% by weight or less, preferably 8% by weight or less of the total amount of the aqueous gel composition in order not to reduce the gel strength of the aqueous gel composition.

Further, the aqueous gel composition may appropriately contain a colorant, an antioxidant, an ultraviolet absorber, a preservative, a chelating agent and the like, if necessary.

The method for producing the aqueous gel composition of the present invention is not particularly limited. For example, an amine oxide type amphoteric surfactant and, if necessary, a drug are added to a natural gum which is a gelling agent. , Mixing and stirring may be performed. The timing for adding the amine oxide type amphoteric surfactant is not particularly limited as long as it is before the natural gum gels. This aqueous gel composition can be filled in a desired molding container, and the molding container can be cooled to obtain an aqueous gel product.

The temperature in the process of producing the aqueous gel composition varies depending on the gelling mechanism of the gelling agent used,
For example, when the gelling agent is a CMC polyvalent metal salt, the temperature in the process of producing the gel layer may be room temperature, or the system may be adjusted to 5 to 60 ° C. as necessary to control the progress of gelation.
It is preferable to adjust to the range. The temperature of this system is 6
If the temperature is higher than 0 ° C., for example, chemical loss occurs due to volatilization of low-volatile organic substances, which is not preferable. When carrageenan, agar, a mixture of locust bean gum and xanthan gum and / or gelatin is used as a gelling agent, these gelling agents are mixed with water and then dissolved at 60 ° C or higher. Then, it is preferable to cool and gel.

The aqueous gel composition of the present invention is shown in FIG.
The aqueous gel product of the present invention can be obtained by filling the container shown in. That is, the aqueous gel product of the present invention comprises an upper lid and a lower lid, and a container in which the upper lid is pulled up from the lower lid and opened to be filled with the aqueous gel composition.

FIG. 1 is a schematic explanatory view showing one embodiment of the aqueous gel product of the present invention. In FIG. 1, 1 is an aqueous gel composition of the present invention which is a gel layer. The container shown in FIG. 1 includes a lower lid 2, an upper lid 3 including a main body portion 5 and a top lid portion 6, a tubular portion 4, and a columnar portion 7, and is filled with an aqueous gel composition 1.

Since the aqueous gel product of the present invention is a container such as the container shown in FIG. 1 in which the lower lid 2 to the upper lid 3 are pulled up to the upper portion and the aqueous gel composition 1 is filled, At the time when the drug effect of the aqueous gel composition 1 is finished, for example, as shown in the schematic explanatory view of FIG. 2 showing the use of the aqueous gel product of the present invention shown in FIG. It can be pulled up and hidden in the upper lid 3, and the end point of use can be easily determined.

The aqueous gel composition of the present invention is excellent in shape stability, has high gel strength, is uniform, has a small amount of water separation, and has a beautiful appearance, and further, gels at the time when the drug effect of the gel composition is completed. Since the residue of the agent is small, in the aqueous gel product of the present invention in which the aqueous gel composition is filled in the container, the gel is pulled up, and the end point of use is extremely easy to judge.

[0082]

EXAMPLES Next, the aqueous gel composition of the present invention and the aqueous gel product comprising the same will be described in more detail based on examples, but the present invention is not limited to such examples unless the gist thereof is exceeded. Not something.

Examples 1 to 8 and Comparative Examples 1 to 8 (Preparation of Aqueous Gel Composition) According to the compounding amounts shown in Table 1, aqueous gel compositions were prepared by the following method.

First, CMCs and aluminum hydroxide gel were added to water and mixed and stirred at room temperature to obtain a uniform CMC mixed dispersion solution.

Next, an amine oxide amphoteric surfactant is melt-mixed with a mixed solution of a fragrance and an emulsifier or a deodorant, and this is added to the CMC mixed dispersion solution while stirring at 4000 rpm with a homomixer, Stir for 2 minutes. Furthermore, after adding an organic acid and a preservative,
The mixture was stirred for 3 minutes to obtain a mixed solution.

140 g of the mixed solution was filled from the top cover 6 of the container shown in FIG. 1, gelled, and then allowed to stand in a thermostat at 25 ° C. to prepare an aqueous gel filled with the aqueous gel composition of the present invention. Got the product.

(Gel Residue Evaluation Test) The upper lid (the portion indicated by reference numeral 3 in FIG. 1) of the aqueous gel products obtained in Examples 1 to 8 and Comparative Examples 1 to 8 was slid up by 20 mm to give an aqueous gel composition. Open by exposing part of the object, 25
It was left at room temperature in a room without wind.

While checking the state of the aqueous gel composition every other week, the weight loss was completed when the weight loss rate was 90 to 95% by weight, and the following method was used to (a) gel residue volume and (b) gel residue position. , Were evaluated. The results are shown in Table 2.

(A) Gel residue volume [Measurement of bulk volume] The gel residue was immersed in water and the increased bulk volume (cm ³ ) was measured. Note that the smaller the value of such bulk volume, the smaller the residue.

(B) Gel residue position Visual confirmation ⊚: The residue is hidden by the upper lid and almost invisible. ○: Most of the residue is hidden by the top cover and is difficult to see. Δ: Part of the residue is hidden by the top lid. X: The entire residue is visible. Measurement of Height The height (mm) from the upper end of the lower lid (the portion indicated by reference numeral 2 in FIG. 1) of the aqueous gel product to the bottom of the gel residue was measured. The height from the upper end of the lower lid to the lower end of the upper lid is 30m
m. The larger the height, the higher the residue is.

Examples 9 to 14 and Comparative Examples 9 to 14 According to the blending amounts shown in Table 3, aqueous gel compositions were prepared by the following method.

First, the gelling agent is dispersed in water, and then the mixture is stirred at 8000 rpm with a homomixer to give 70-
Heated to 90 ° C. After maintaining at this temperature for about 20 minutes and confirming that the gelling agent was completely dissolved, it was slowly cooled to 60 ° C. to obtain a uniform gel dispersion solution.

Next, while maintaining the gel dispersion solution at 60 ° C., a mixed solution of a fragrance and an emulsifier or a solution of an amine oxide amphoteric surfactant melt-mixed with a deodorant is added and stirred for 2 minutes. I did. Furthermore, after adding a preservative, the mixture was stirred for 3 minutes to obtain a mixed solution.

The mixed solution 140 g was filled from the top cover 6 of the container shown in FIG. 1, further cooled to 10 ° C. if necessary, gelled, and then allowed to stand in a thermostat at 25 ° C. An aqueous gel product filled with the above aqueous gel composition was obtained.

By the same method as in Examples 1 to 8 and Comparative Examples 1 to 8, (a) gel residue volume and (b) gel residue position were evaluated. The results are shown in Table 4.

The components shown in Tables 1 and 3 are as shown below. CMC-1: CMC sodium carboxymethyl group average degree of substitution 0.6 1% aqueous solution viscosity (25 ° C.) 100 mPa · s CMC-2: CMC sodium carboxymethyl group average degree of substitution 0.7 1% aqueous solution viscosity (25 ° C. ) 3500 mPa · s CMC-3: average substitution degree of CMC sodium carboxymethyl group 0.8 1% aqueous solution viscosity (25 ° C.) 500 mPa · s CMC-4: average substitution degree of CMC sodium carboxymethyl group 1.1 1% aqueous solution Viscosity (25 ° C.) 1000 mPa · s CMC-5: CMC sodium carboxymethyl group average degree of substitution 1.75 1% aqueous solution viscosity (25 ° C.) 3000 mPa · s AOSA-1: amine oxide amphoteric surfactant (I) N -Decyl-N, N-dimethylamine oxide AOSA-2: amine oxide type amphoteric interface Agent (I) N-lauryl-N, N-dimethylamine oxide AOSA-3: amine oxide amphoteric surfactant (I) N-isostearyl-N, N-dimethylamine oxide AOSA-4: amine oxide amphoteric Surfactant (I
I) N-Cured beef tallow alkyl-N, N-dipolyoxyethylene amine oxide AOSA-5: amine oxide type amphoteric surfactant (II
I) N-behenyl polyoxyethylene (4) -N, N-dimethylamine oxide AOSA-6: amine oxide type amphoteric surfactant (I
V) N-cocoylamidopropyl-N, N-dimethylamine oxide aluminum hydroxide gel: dried aluminum hydroxide gel (Al ₂ O ₃ content 54.0% by weight) Deodorant: green tea extract preservative: caison CG / ICP (trade name, Rohm &
Haas Ltd. Surfactant: Polyoxyethylene (20) lauryl ether LX: Mixture of locust bean gum and xanthan gum Locust bean gum / xanthan gum (weight ratio) 50
/ 50

Further, the amount (residual amount) of ion-exchanged water in Tables 1 and 3 is such that the total amount becomes 100% by weight.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

From the results shown in Tables 2 and 4, the following can be seen.

As shown in Table 2, the aqueous gel products of Examples 1 to 8 obtained by adding the amine oxide type amphoteric surfactant to the CMC polyvalent metal salt had a weight loss rate of 90 to 95% by weight. The gel residue was small and the bulk volume was 4 at the end of
Whereas a ～6Cm ³ mm, an aqueous gel product using no amine oxide type amphoteric surfactants of Comparative Examples 1-8, the gel residue is large, bulk volume has exceeded 7 cm ^3, the weight loss It may be judged that the product can be used even though the weight loss is 90 to 95% by weight.
In addition, in the aqueous gel products of Examples 1 to 8, the gel residue was almost as high as 30 mm from the lower lid to the upper lid at the end of weight loss, and was almost invisible because it was hidden by the upper lid. In the aqueous gel products of Examples 1 to 8, the gel residue is several millimeters above the lower lid, and the whole is visible.

As shown in Table 4, gelling agents other than CMC polyvalent metal salts, carrageenan, agar, a mixture of locust bean gum and xanthan gum, obtained by adding an amine oxide amphoteric surfactant to gelatin. The resulting aqueous gel products of Examples 9 to 14 had a small gel residue at the end of the weight loss of 90 to 95% by weight and a bulk volume of 4c.
While it is m ³ approximately, an aqueous gel product using no amine oxide type amphoteric surface active agents of Comparative Examples 9-14,
The gel residue is large and the bulk volume exceeds 6 cm ³ ,
There is a possibility that it can be judged that the product can be used even though the weight reduction rate is 90 to 95% by weight at the end of the weight reduction. In addition, in the aqueous gel products of Examples 9 to 14, the gel residue was almost as high as 30 mm in height from the lower lid to the upper lid at the end of the weight reduction, and was almost invisible because it was hidden by the upper lid. In the aqueous gel products of Examples 9 to 14, the gel residue is at a height of 10 mm or less from the lower lid, and almost the entire gel residue is visible.

Therefore, in the aqueous gel composition using the specific amine oxide type amphoteric surfactant of the present invention, the residue of the gelling agent is small at the end of the drug effect, and the aqueous gel composition is in a container. It can be seen that in the aqueous gel product of the present invention filled in, the gel is pulled up, and the end point of use can be judged very easily.

[0106]

The aqueous gel composition of the present invention is excellent in shape stability, has high gel strength, is uniform, has a small amount of water separation, and has a beautiful appearance, and at the time when the drug effect of the gel composition ends, Excellent gelling agent residue is small.

Further, in the aqueous gel product of the present invention in which a container is filled with the above-mentioned aqueous gel composition, the gel is pulled up and the end point of use can be judged very easily. For example, in the entrance, the living room, the bathroom, the bathroom, etc. It can be installed in a car and used effectively.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view showing one embodiment of an aqueous gel product of the present invention.

FIG. 2 is a schematic explanatory view showing one embodiment after using the aqueous gel product of the present invention.

[Explanation of symbols]

1 Aqueous gel composition 2 Lower lid 3 Upper lid

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A61L 9/04 A61L 9/04 9/12 9/12 B65D 83/00 C08K 5/32 C08K 5/32 C08L 5/00 C08L 5/00 B65D 83/00 F (72) Inventor Masayuki Fukue 1-30-3 Toyokawa, Ibaraki City, Osaka Prefecture Kobayashi Pharmaceutical Co., Ltd. Machi 55, Daiichi Kogyo Seiyaku Co., Ltd. (72) Inventor Miho Shibata 55, Nishi Shichijo, Higashikubo-cho, Shimogyo-ku, Kyoto F-Term (Dai) Kogyo Seiyaku Co., Ltd. 4C002 AA06 BB02 DD03 EE01 FF04 4C080 AA04 BB02 BB03 BB05 CC01 HH06 JJ03 LL06 MM11 NN22 NN23 NN24 QQ18 4C083 AB222 AC302 AC561 AC562 AD211 AD212 AD271 AD272 AD351 AD352 AD411 AD412 BB41 BB48 CC01 CC20 DD27 DD41 DD47 FF06 4J002 AB031 AB041 AB051 AF031 ES006 FD187 FD207 FD316 HA04

Claims (5)

[Claims] 1. A compound represented by the general formula (I): (Wherein R ¹ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms), an amine oxide amphoteric surfactant (I) represented by the general formula (II): ] (In the formula, R ² is an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and 1 + m (the average number of moles of ethylene oxide added) is an integer of 1 to 10). Surfactant (II), general formula (III): (In the formula, R ³ is an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and n (the average number of moles of ethylene oxide added) is an integer of 1 to 10). Surfactant (III) and general formula (IV): (In the formula, R ⁴ represents an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms), at least one amine oxide selected from amine oxide amphoteric surfactants (IV). An aqueous gel characterized by adding a type amphoteric surfactant to at least one natural gum selected from carboxymethyl cellulose polyvalent metal salt, carrageenan, agar, a mixture of locust bean gum and xanthan gum, and gelatin. Composition. 2. The aqueous gel composition according to claim 1, which contains at least one drug selected from fragrances, deodorants, deodorants, fungi, bactericides and repellents. 3. The aqueous gel composition according to claim 1, wherein the carboxymethyl cellulose polyvalent metal salt is a carboxymethyl cellulose aluminum salt. 4. The aqueous gel composition according to claim 1, which has an upper lid and a lower lid, and is filled in a container which is opened by pulling up the upper lid from the lower lid. 5. An aqueous gel product obtained by filling the aqueous gel composition according to claim 1, 2 or 3 in a container having an upper lid and a lower lid, the upper lid being pulled up from the lower lid to open.