JP2007119556A - Transparent gelling agent composition, transparent gel and method for preparing transparent gel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gelling agent composition which has stable quality and high stability against high temperatures and light, and furthermore can be used as a fragrant agent and a deodorant having high safety. <P>SOLUTION: The transparent gelling agent composition comprises (a) a copolymer of an ethylenically unsaturated compound and maleic anhydride and/or its basic salt and (b) at least one hydrazide compound represented by formula (I) (wherein n is an integer of 100-2,000) or formula (II) (wherein R<SB>1</SB>is a 1-10C alkylene group which may be branched or a phenylene group). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a transparent gelling agent composition, a transparent gel using the same, and a method for producing the transparent gel. More specifically, the gel is stable and transparent, without water separation, and has sufficient gel strength. The present invention relates to a transparent gelling agent composition that can be used for a fragrance or a deodorant, a transparent gel using the same, and a method for producing a transparent gel.

Conventionally, many gel-like fragrances and deodorants have been proposed. Of these, water-based gel-like fragrances use carrageenan, highly transparent gellan gum or gelatin as gelling agents. However, since these gelling agents are extracted from natural products, there are variations in components, and the physical properties of the finished gel may be unstable.
In addition, gels using these gelling agents are poor in releasability from the container, and stretch the film or volatilize in a mortar shape, which impairs the appearance. Furthermore, when manufacturing these, since it is necessary to heat at 60 to 90 degreeC, there existed a problem that components, such as a fragrance | flavor, would volatilize or deteriorate.

  On the other hand, many gels using a copolymer of an unsaturated monomer such as isobutylene and maleic anhydride as a gelling agent have been proposed. For example, an aqueous gelling agent and aqueous gel (Patent Document 1) comprising a reactive organism of gelatin or collagen and an olefin maleic anhydride copolymer, an ammonia reaction of a copolymer of an ethylenically unsaturated compound and maleic anhydride An aqueous liquid gelling agent comprising a reaction product of a product and gelatin as an essential component (Patent Document 2), at least one monomer selected from the group consisting of α-olefins and vinyl compounds, and maleic anhydride, There is known a hydrogel (Patent Document 3) obtained by mixing a reactive organism obtained by reacting ammonia with this copolymer, a polyvalent amine and water. In addition, a method for producing a transparent fragrance characterized by gelling a perfume-containing aqueous solution with a water-soluble isobutylene-maleic anhydride copolymer and polyethylene polyamine (Patent Document 4), isobutylene-maleic anhydride copolymer A transparent gel-like fragrance composition containing a combined ammonium salt, a polyamine, an oxalate, a fragrance and water (Patent Document 5), and a reactive organism of a methyl vinyl ether-maleic anhydride copolymer and ammonia. A transparent aqueous gel-like fragrance composition comprising a polyamine that cross-links with an aqueous solution and the reactive organism and a fragrance (Patent Document 6), a maleic anhydride copolymer comprising isobutylene and maleic anhydride A product made easily water-soluble by reaction with ammonia and a polyethyleneimine having a linear or branched chain, a highly water-absorbing resin, and And the like are known aqueous gel composition characterized by containing (Patent Document 7).

However, since the techniques described in Patent Documents 1 and 2 use gelatin, which is a natural product, the problems of the stability of the physical properties of the gel and the problems of volatilization and deterioration of the fragrance due to high-temperature heating are the above carrageenan and the like. In addition to the occurrence of the gelling agent, yellowing at a high temperature occurs. Also, the gel-like materials of Patent Documents 3 to 7 have problems that yellowing occurs with respect to temperature and light, the safety of polyamine drugs, and the drugs themselves have an amine odor.
Japanese Patent No. 2616960 JP 2000-192011 A Japanese Patent Application Laid-Open No. 55-144404 JP 59-25753 A Japanese Patent Laid-Open No. 7-126137 JP 2003-290330 A JP 2002-206038 A

  Accordingly, there is a need for a gelling agent composition that is stable in quality, highly stable against high temperatures and light, and that can be used for a highly safe fragrance or deodorant. Therefore, an object of the present invention is to provide such a gelling agent composition.

  In view of the above problems, the present inventor conducted intensive research on a gel using a copolymer of an unsaturated monomer and maleic anhydride as a gelling agent, and found that the unsaturated monomer and maleic anhydride. The present inventors have found that a gel that does not cause the above-mentioned problems can be obtained by using the above copolymer and a specific hydrazide compound as a gelling agent.

（ｎは１００〜２０００の整数を表す）

（Ｒ_１は、分岐しても良い炭素数１〜１０のアルキレン基又はフェニレン基を表す）
で表されるヒドラジド化合物の１種又は２種以上
を含有する透明ゲル化剤組成物を提供するものである。 That is, the present invention
The following components (a) and (b)
(A) Copolymer of ethylenically unsaturated compound and maleic anhydride and / or basic salt thereof (b) The following general formula (I) or general formula (II)

(N represents an integer of 100 to 2000)

(R ₁ represents a C 1-10 alkylene group or phenylene group which may be branched)
The transparent gelling agent composition containing 1 type, or 2 or more types of the hydrazide compound represented by these is provided.

The present invention also includes the following components (a) and (b)
(A) a copolymer of an ethylenically unsaturated compound and maleic anhydride and / or a basic salt thereof (b) one of the hydrazide compounds represented by the general formula (I) or the general formula (II) A transparent gel obtained by reacting two or more kinds in the presence of water is provided.

Furthermore, the present invention provides
The following components (a) and (b)
(A) a copolymer of an ethylenically unsaturated compound and maleic anhydride and / or a basic salt thereof (b) one of the hydrazide compounds represented by the general formula (I) or the general formula (II) The present invention provides a method for producing a transparent gel in which an aqueous solution containing two or more kinds is gelled.

  The transparent gelling agent composition of the present invention has high gel stability because the components that form the gel are composed only of synthetic products with stable quality. In addition, since gels can be easily formed by heating at room temperature or at a relatively low temperature, the volatilization and deterioration of the blended components are less than in the case of heating at 60 ° C. to 90 ° C. as in the past. A gel can be produced. Furthermore, there is an advantage that a highly transparent gel can be formed. In addition, since the gel is rich in elasticity, the shrinkage of the gel accompanying the volatilization of the compounding components shrinks in a similar shape to the storage container, so that the end point of the volatilization becomes clear and the appearance is good. In the present specification, transparent means that the transmittance is 50% or more when a 1 cm thick gel is irradiated with light having a wavelength of 600 nm in a spectrophotometer.

One component of the transparent gelling agent composition of the present invention is a copolymer of an ethylenically unsaturated compound and maleic anhydride and / or a basic salt thereof (component (a)).
As said ethylenically unsaturated compound, what is necessary is just to have a double bond which can superpose | polymerize in a molecule | numerator, and specifically, a linear or branched unsaturated hydrocarbon and a vinyl compound are mentioned.

  Examples of the linear or branched unsaturated hydrocarbon include ethylene, propylene, butene-1, butene-2, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2 -Methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, diisobutylene, 1,3-butadiene, 1,3-pentadiene, 1,3- Examples include hexadiene, 1,3-octadiene, 2-methyl-4-dimethyl-1-pentene, and 2-methyl-4-dimethyl-2-pentene. Examples of the vinyl compound include styrene, vinyl chloride, vinyl propionate, acrylonitrile, methyl vinyl ether, acrylic esters, vinyl alcohol, and the like. Of these, α-olefins such as ethylene and isobutylene are preferable, and isobutylene is particularly preferable.

  A copolymer of the ethylenically unsaturated compound of component (a) and maleic anhydride (hereinafter sometimes referred to as “copolymer”) is obtained by using the ethylenically unsaturated compound and maleic anhydride. And can be produced by a known method described in JP-A No. 55-144044.

  Further, as the component (a), a basic salt of a copolymer of the ethylenically unsaturated compound and maleic anhydride can be used together with the copolymer or in place of the copolymer. The use of such a basic salt of the copolymer is preferable because the solubility in water is improved. Examples of the basic salt of the copolymer include sodium salt, potassium salt, ammonium salt and the like. These basic salts may not be completely neutralized in the copolymer, and partially neutralized ones can also be used.

  Copolymers of ethylenically unsaturated compounds and maleic anhydride and their basic salts are trade names such as Isoban-110, Isoban-104, Isoban-10, and Isoban-06, all of which are commercially available from Kuraray. Therefore, these can also be used as component (a).

  In the transparent gelling agent composition of the present invention, the amount of the component (a) is not particularly limited, but is 1.0 to 40% by mass (hereinafter simply referred to as “%”) in the transparent gel composition, preferably Is 1.0 to 20%. If it is less than this, a gel may not be formed, and if it is more than this, it may not be dissolved and transparency may be inferior.

  Moreover, the transparent gelatinizer composition of this invention contains a specific hydrazide compound (component (b)) as the structural component.

（ｎは１００〜２０００の整数を表す）

（Ｒ_１は、分岐しても良い炭素数１〜１０のアルキレン基又はフェニレン基を表す） The component (b) hydrazide compound has at least a side chain of a hydrazide group that undergoes a crosslinking reaction with a copolymer of the ethylenically unsaturated compound and maleic anhydride and / or a basic salt thereof as the component (a). The hydrazide compound represented by the following general formula (I) or general formula (II) is specifically mentioned as long as it contains two or more.

(N represents an integer of 100 to 2000)

(R ₁ represents a C 1-10 alkylene group or phenylene group which may be branched)

  Among these, the hydrazide compound represented by the general formula (I) is polyacrylic acid hydrazide, and the weight average molecular weight is preferably 10,000 to 150,000. The hydrazide compound represented by the general formula (II) is a dihydrazide compound, and specific examples thereof include adipic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, and isophthalic acid dihydrazide. These dihydrazide compounds are commercially available from Otsuka Chemical Co., Ltd. under the trade names ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH-S (dodecanediohydrazide), and IDH (isophthalic acid dihydrazide). This can be used.

  Of these hydrazide compounds (I) or (II), it is preferable to use adipic acid dihydrazide in terms of solubility in water and transparency.

  In the transparent gelling agent composition of the present invention, the blending amount of the component (b) is not particularly limited, but is 0.1 to 10%, preferably 1.0 to 10% in the transparent gel composition. If it is less than this, a gel may not be formed, and if it is more than this, it may not be dissolved and transparency may be inferior.

  The blending ratio of the component (a) and the component (b) in the transparent gelling agent composition of the present invention is such that the ratio of the component (a) to the component (b) is 10: 1 to 1:10, preferably 8: 1 to 1: 1, more preferably 5: 1 to 2: 1.

  Furthermore, in order to produce | generate a transparent gel using the transparent gelling agent composition of this invention, it is preferable to adjust pH to 4.0-6.5, and adjusting to 4.5-5.5. Further preferred. If the pH is lower than 4 or higher than 6, no gel is formed or it may take a long time to gel. Moreover, by making pH into 4.5-5.5, gelling is accelerated | stimulated and a highly transparent gel can be formed while gelling is possible in a short time.

  Adjustment of pH can be adjusted by using a conventionally well-known pH adjuster, for example, it can adjust by mix | blending an acid in a transparent gelatinizer composition. The acid may be either an organic acid or an inorganic acid, but a water-soluble organic acid such as citric acid, malic acid, acetic acid, tartaric acid, benzoic acid, and succinic acid is preferable. Among these organic acids, citric acid and malic acid are particularly preferable in terms of safety, ease of pH adjustment, ease of handling, and odorlessness.

  The blending amount of the acid is not particularly limited and can be appropriately selected depending on the type and amount of the gelling agent to be blended and the pH to be adjusted, but is 0.1 to 20%, preferably 0.1 to 0.1% in the composition. 10%, more preferably 0.1 to 5.0%. When less than this, a gel may not be formed, and when more than this, transparency may be inferior.

  In addition to the above components, a medicinal component can be blended in the transparent gelling agent composition of the present invention. Examples of the medicinal component include insect repellents, fragrances, and deodorants.

  Among the above-mentioned medicinal ingredients, examples of insect repellents include pyrethroid insect repellents such as enpentrin, transfluthrin, allethrin, phenothrin, and Eminence, paradichlorobenzene, naphthalene, camphor, 2-phenoxyethanol, and the like. A mixture of seeds or more can be used.

  Examples of the fragrances include animal fragrances such as musk, ghost cat fragrance, and Ryu nobu fragrance, Abies oil, Akjon oil, Almond oil, Angelica root oil, paging oil, bergamot oil, perch oil, bore bellows oil, kayabuchi oil, Gananga oil, capsicum oil, caraway oil, cardamom oil, cassia oil, celery oil, cinnamon oil, citronella oil, cognac oil, coriander oil, cumin oil, camphor oil, jill oil, estgolan oil, eucalyptus oil, fennel oil, garlic Examples include vegetable flavors such as oil, ginger oil, grapefruit oil, hop oil, lemon oil, lemongrass oil, nutmeg oil, mandarin oil, mint oil, orange oil, sage oil, star anise oil, and turpentine oil. As this fragrance, artificial fragrance such as synthetic fragrance or extracted fragrance can be used, for example, hydrocarbon fragrance such as pinene and limonene, linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anis alcohol, β-phenethyl alcohol. Alcohol flavors such as anetol, eugenol, etc., aldehyde flavors such as n-butyraldehyde, isobutyraldehyde, hexyl aldehyde, citral, citronellal, benzaldehyde, cinnamic aldehyde, carvone, menthone, camphor, acetophenone, ionone Ketone flavors such as γ-butyl lactone, coumarin, cineol and other lactone flavors, octyl acetate, benzyl acetate, cinnamyl acetate, butyrate propionate And ester-based fragrances such as methyl benzoate. Furthermore, the mixing | blending fragrance | flavor which mixed 2 or more types of the said fragrance | flavor can also be used.

  Further, as a deodorant, metal salts of inorganic acids such as aluminum sulfate, ammonium chloride, alum, copper sulfate, zinc sulfide, metal salts of organic acids such as zinc stearate and aluminum stearate, titanium oxide and zinc oxide And metal oxides such as flavonoid compounds, plant extracts such as catechins and polyphenols or derivatives thereof, cyclodextrins or derivatives thereof, zeolites, activated carbon and the like.

  Although the compounding quantity of the said medicinal component in the transparent gelatinizer composition of this invention is not specifically limited, It is 0.01 to 30% in a composition, Preferably it is 0.1 to 10%, More preferably, it is 1 to 10%. is there. If it is less than this, a sufficient effect may not be obtained, and if it is more than this, it may be colored, transparency may be inferior, or a gel may not be formed.

  The medicinal component may be either aqueous or oily, but when an oily medicinal component is used, it is preferable to use a surfactant. As this surfactant, any one of conventionally known anionic surfactants, cationic surfactants, nonionic surfactants or amphoteric surfactants can be used, and one or more of these can be used. Can also be used in combination.

  Among the surfactants, anionic surfactants include, for example, higher fatty acid soaps, soap bases, metal soaps, triethanolamine N-acyl-L-glutamate, sodium N-acyl-L-glutamate, sodium alkyl sulfate. Sodium alkyl sulfonate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, coconut oil fatty acid methyl taurine sodium (N-cocoyl-N-methyl taurine sodium), lauryl Mix one or more of triethanolamine sulfate, sodium lauryl sulfate, sodium lauroyl sarcosine, sodium lauroylmethyl β-alanine solution, sodium lauroylmethyl taurine, etc. It can be used Te.

  Examples of cationic surfactants include ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearyltrimethylammonium chloride, benzalkco chloride. One kind or a mixture of two or more kinds such as nium and benzethonium chloride can be used.

  Furthermore, examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid alkanolamide, and tertiary amine oxide. In this polyoxyethylene alkyl ether, the polyoxyethylene chain has 3 to 18, preferably 7 to 12, the alkyl chain may be either linear or branched, and the alkyl chain length is 8 to 22, preferably 12 to 14. Examples of the fatty acid alkanolamide include coconut oil fatty acid, stearic acid, lauric acid monoethanolamide, diethanolamide, and the like. Examples of the tertiary amine oxide include lauryl dimethylamine oxide, coconut oil fatty acid dimethylamine oxide, and the like. Is mentioned.

  Furthermore, as the amphoteric surfactant, one or more kinds of 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, lauryldimethylaminoacetic acid betaine, etc. are mixed. Can be used.

  Of the above-mentioned surfactants, it is preferable to use an anionic surfactant in terms of gel stability and transparency.

  The blending amount of the surfactant in the transparent gelling agent composition of the present invention can be appropriately selected depending on the type and amount of the oil component to be blended, but is 0.01 to 30% in the composition, preferably 0. 0.1 to 20%, more preferably 1 to 15%. If it is less than this, the oily component cannot be dispersed or solubilized, which may affect the stability of the gel. Moreover, when more than this, a gel may not be formed.

  Furthermore, in the transparent gelling agent composition of the present invention, as long as the effects of the present invention are not impaired, a solvent such as alcohol or glycol, another gelling agent, a thickener, an antifungal agent, Antibacterial agents, ultraviolet absorbers, antioxidants, pigments, efficacy enhancers, deodorizers and the like can also be blended.

  The transparent gel of the present invention is performed by dissolving a transparent gelling composition containing the above components (a), (b) and the like in water to form an aqueous solution, and these components react to form a gel. . As a method for preparing this aqueous solution, for example, a method in which component (a) and component (b) are dissolved together in water, another component is further dissolved in this aqueous solution, if necessary, or other components A method of mixing an aqueous solution in which is dissolved is exemplified. Moreover, the method of dissolving the component (a) and then dissolving the other component in the aqueous solution in which the component (b) is dissolved, or mixing the aqueous solution in which the other component is dissolved is also exemplified. Furthermore, a method of dissolving other components in either one or both of an aqueous solution in which the component (a) is dissolved and an aqueous solution in which the component (b) is dissolved is also exemplified. Among these, the method of dissolving other components in either one or both of the aqueous solution in which component (a) is dissolved and the aqueous solution in which component (b) is dissolved, and mixing the components (a) and ( Since it is not necessary to stir b) more than necessary after mixing b), it is easy to form a gel, and transparency is also excellent, which is preferable.

  The aqueous solution thus prepared is then filled into a suitable mold and gelled. The temperature at this time is not particularly limited and can be gelled at a normal gelation temperature, but it is preferable to gel at a temperature of room temperature to about 50 ° C. because there is little deterioration and volatilization of the blended components. . The transparent gel of the present invention can form a gel in several minutes to several days even at a relatively low temperature of about room temperature to 50 ° C.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

Example 1
An aqueous solution in which component (a) is dissolved in 20 g of water is mixed with an aqueous solution in which component (b) and component (c) are dissolved in 74 g of water. After stirring, the mixture is placed in a cylindrical sample bottle with a capacity of 100 ml at room temperature. After standing for a time, transparent gels (Products 1 and 2 of the present invention) having the following composition were obtained. About the obtained transparent gel, the following evaluation method evaluated the state and elasticity of the gel. The results are shown in Table 2.

(Evaluation methods)
<Gel state>
The state of the gel after standing for 12 hours was evaluated according to the following criteria.
(Evaluation criteria)
Solidified ○
Almost solid △
Not solidified ×
<Elasticity of gel>
The measured value with a rheometer (manufactured by Sun Science Co., Ltd.) was used. The gel breaking strength (kg) when a circular plate with a diameter of 15 mm is applied to the gel and pressed at a speed of 20 mm / min, and the gel strength (kg) when the plate is made to enter 4 mm from the gel surface are measured. The elasticity of the gel was determined by the following formula and evaluated according to the following criteria.
Gel elasticity = gel breaking strength (kg) / gel strength (kg)
(Evaluation criteria)
3 or more ○
2 to less than 3
Less than 2 ×

  The products of the present invention were all transparent gels rich in elasticity.

Example 2
A solution in which component (a) is dissolved in 20 g of water is mixed with a solution in which component (b) is dissolved in 50 g of water, and citric acid and water are added to a total of 100 g while stirring to adjust the pH to 4 Adjusted to 0.0-6.1. This aqueous solution was put into a cylindrical sample bottle having a capacity of 100 ml and allowed to stand at room temperature for 12 hours to obtain Invention Products 3 to 6 having the compositions shown in Table 3 below. The gel state and elasticity were evaluated by the same evaluation method as in Example 1. The results are shown in Table 4.

  The products of the present invention were all transparent gels rich in elasticity.

Example 3
A solution in which component (a) was dissolved in 20 g of water and a solution in which components (b) to (e) were dissolved in 50 g of water were mixed, and water was added to a total of 100 g while stirring. . This was then placed in a cylindrical sample bottle with a capacity of 100 ml and allowed to stand at room temperature for 12 hours to obtain a transparent gel having the composition shown in Table 5 below. The gel state and elasticity were evaluated by the same evaluation method as in Example 1. The results are shown in Table 6.

  Invention products 7 to 11 were all transparent gels rich in elasticity.

Example 4
A solution in which component (a) was dissolved in 20 g of water and a solution in which components (b) to (e) were dissolved in 50 g of water were mixed, and water was added to a total of 100 g while stirring. Next, this was put into a cylindrical sample bottle having a capacity of 100 ml and allowed to stand at room temperature for 12 hours to obtain Invention Products 12 to 15 having the compositions shown in Table 7 below.

Comparative product 1 (Carrageenan gel)
2.5 g of carrageenan (manufactured by Takaragen Co., Ltd., κ-type carrageenan), 3 g of propylene glycol and 3 g of ethanol were mixed, and 60 g of water was added thereto, heated to 80 ° C. and dissolved. 4 g of polyoxyethylene hydrogenated castor oil (Matsumoto Yushi Seiyaku Co., Ltd.), 2 g of polyoxyethylene (11-13) alkyl ether (Matsumoto Yushi Seiyaku Co., Ltd.), 2 g of fragrance (lavender-like fragrance) and 3 g of ethanol Was dissolved in 20.5 g of water to make 100 g. This aqueous solution was left at 25 ° C. for 3 hours to obtain a gel.

Comparative product 2 (gelatin gel)
60 g of water was added to 5 g of gelatin (Nitta Gelatin Co., Ltd.) and heated to 50 ° C. to dissolve. A solution prepared by dissolving 4 g of polyoxyethylene hydrogenated castor oil, 2 g of polyoxyethylene (11-13) alkyl ether, 2 g of fragrance (lavender-like fragrance) and 3 g of ethanol in 24 g of water was added to make 100 g. This aqueous solution was left at 25 ° C. for 3 hours to obtain a gel.

Comparative product 3 (gellan gum gel)
1 g of gellan gum (manufactured by San-Ei Gen FFI Co., Ltd.), 3 g of propylene glycol and 3 g of ethanol were mixed, 60 g of water was added and heated to 90 ° C. to dissolve. A solution prepared by dissolving 4 g of polyoxyethylene hydrogenated castor oil, 2 g of polyoxyethylene (11-13) alkyl ether, 2 g of fragrance (lavender-like fragrance) and 3 g of ethanol in water 21.98 was further added. 0.02 g was added to make 100 g. This aqueous solution was left at 25 ° C. for 3 hours to obtain a gel.

Comparative product 4 (gelatin-isobutylene maleic anhydride copolymer ammonia adduct)
30.5 g of water was added to 1.5 g of gelatin and heated to 50 ° C. to dissolve. A solution prepared by dissolving 4 g of polyoxyethylene hydrogenated castor oil, 2 g of polyoxyethylene (11-13) alkyl ether, 2 g of a fragrance (lavender-like fragrance) and 3 g of ethanol in 20 g of water was further added. 1 g of polymer ammonia adduct (manufactured by Kuraray Co., Ltd.) was dissolved in 36 g of water, and a solution heated to 50 ° C. was added to make 100 g. This aqueous solution was left at 25 ° C. for 12 hours to obtain a gel.

Test example 1
The inventive products 12 to 15 and comparative products 1 to 4 obtained in Example 4 were evaluated by the following evaluation methods. The results are shown in Table 8.
<Gel state>
Evaluation was performed by the same evaluation method and standard as in Example 1.
<Elasticity of gel>
Evaluation was performed by the same evaluation method and standard as in Example 1.
<Transparency of gel>
The measured value with a spectrophotometer was used. The gel was filled in a 1 cm-thick container and irradiated with light having a wavelength of 600 nm with a U-3210 self-recording spectrophotometer (manufactured by Hitachi, Ltd.), and the transmittance (% T) was measured. Transparency was evaluated according to the following criteria.
(Evaluation criteria; 600 nm transmittance)
90% or more ○
50% or more and less than 90%
Less than 50% ×
<Coloring of gel (measurement of yellowness)>
Measured with a spectrophotometer. The gel was filled in a 1 cm-thick container, irradiated with light having a wavelength of 400 nm using a U-3210 self-recording spectrophotometer (manufactured by Hitachi, Ltd.), and the transmittance (% T) was measured. The degree of coloring was evaluated according to the following criteria.
(Evaluation criteria; 400 nm transmittance)
80% or more ○
50% to less than 80%
Less than 50% ×
<State of volatilization of gel>
The gel was placed in a bowl-shaped container and evaporated at room temperature. The initial, middle, and late states of volatilization were visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
Volatilized in a similar manner to the shape of the container ○
Volatilized almost similar △
Volatilized regardless of the shape of the container ×
<Aroma preference>
The scent of each gel was evaluated by 12 panelists according to the following evaluation criteria (A), and the average score was evaluated based on the following criteria (B).
(Evaluation criteria)
(B) (b)
Like 5 points Average 3.5 or more ○
Slightly like 4 points 2.5 to less than 3.5 △
Neither 3 points Less than 2.5 ×
Slightly dislike 2 points Dislike 1 point

  As is apparent from the results in Table 8, the inventive products 12 to 15 all had good gel elasticity, gel transparency, gel yellowness, volatility, and high scent preference. On the other hand, the comparative product 1 was a hard gel having no elasticity compared to the product of the present invention, having a low transparency and a yellowish gel. Moreover, the state of volatilization was also bad. Comparative product 2 had elasticity, but was opaque and the state of volatilization was poor. Comparative product 3 was a hard gel with no elasticity, low transparency and a yellowish gel. Comparative product 4 was good in elasticity, transparency, and distress, but the gel was slightly yellowish.

Example 5
40 g of water was added to 4 g of isobutylene maleic anhydride copolymer ammonia adduct and dissolved. 1 g of adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.), 6 g of sodium polyoxyethylene alkyl ether sulfate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), 3 g of sodium alkyl sulfonate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and 2 g of phenoxyethanol Was dissolved in 44 g of water to make 100 g.

  This aqueous solution was left in a 100 ml beaker container at room temperature for 12 hours to obtain the transparent gel insect repellent of the present invention. When this was installed in a wardrobe, it exhibited an insect repellent effect for about one month. Moreover, about this gel, the state and elasticity of the gel were evaluated by the same evaluation method as in Example 1, and the transparency, coloring, and volatilization state of the gel were evaluated by the same evaluation method as in Test Example 1. The results are shown in Table 9.

Example 6
40 g of water was added to 4 g of isobutylene maleic anhydride copolymer ammonia adduct and dissolved by heating to 50 ° C. 1 g of adipic acid dihydrazide (Otsuka Chemical Co., Ltd.), 6 g of polyoxyethylene alkyl ether sodium sulfate (Matsumoto Yushi Seiyaku Co., Ltd.), 3 g of sodium alkyl sulfonate (Matsumoto Yushi Seiyaku Co., Ltd.) and lavender flavor 2 g was dissolved in 44 g of water, and a solution heated to 50 ° C. was added to make 100 g.

  This aqueous solution was placed in a 100 ml beaker and allowed to stand at about 25 ° C. for about 1 hour to obtain the fragrance of the present invention. This fragrance was an elastic transparent gel, and the gel was not colored. When this fragrance of the present invention was installed in a toilet, it scented for about 3 months, and the gel contracted in a similar shape to the container along with the volatilization and looked good.

Example 7
40 g of water was added to 4 g of isobutylene maleic anhydride copolymer ammonia adduct (Isoban-110: manufactured by Kuraray Co., Ltd.) and dissolved therein. 1 g of adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.), 6 g of sodium polyoxyethylene alkyl ether sulfate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), 3 g of sodium alkyl sulfonate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), acetic acid 0 A solution prepared by dissolving 0.5 g and 2 g of lavender fragrance in 43.5 g of water was added to make 100 g.

  This aqueous solution was placed in a 100 ml beaker and allowed to stand at room temperature for about 12 hours to obtain the fragrance of the present invention. This fragrance was an elastic transparent gel, and the gel was not colored. When this fragrance of the present invention was installed in a toilet, it scented for about 3 months, and the gel contracted in a similar shape to the container along with the volatilization and looked good.

Example 8
40 g of water was added to 4 g of gelatin-isobutylene maleic anhydride copolymer ammonia adduct (Isoban-110: manufactured by Kuraray Co., Ltd.) and dissolved. 1 g of polyacrylic hydrazide (mixture of n = 100 to 2000) (Otsuka Chemical Co., Ltd.), 0.2 g of polyoxyethylene alkyl ether (Matsumoto Yushi Seiyaku Co., Ltd.), alkylamine oxide (Matsumoto Yushi Seiyaku) A solution prepared by dissolving 0.6 g, 0.75 g of citric acid and 0.3 g of lavender fragrance in 53.15 g of water was added to make 100 g.

  This aqueous solution was placed in a 100 ml beaker and allowed to stand at room temperature for about 12 hours to obtain the fragrance of the present invention. This fragrance was an elastic transparent gel, and the gel was not colored. When this fragrance of the present invention was installed in a toilet, it scented for about 3 months, and the gel contracted in a similar shape to the container along with the volatilization and looked good.

Example 9
40 g of water was added to 4 g of isobutylene maleic anhydride copolymer ammonia adduct and dissolved. 1 g of sebacic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.), 6 g of sodium polyoxyethylene alkyl ether sulfate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), 3 g of sodium alkyl sulfonate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and lavender flavor A solution of 2 g in 44 g of water was added to make 100 g.

  This aqueous solution was placed in a 100 ml beaker and allowed to stand at room temperature for 12 hours to obtain the fragrance of the present invention. The fragrance was a transparent gel that was elastic. When this fragrance of the present invention was installed in a toilet, it scented for about 3 months, and the gel contracted in a similar shape to the container along with the volatilization and looked good.

Example 10
40 g of water was added to 4 g of isobutylene maleic anhydride copolymer ammonia adduct and dissolved. 1 g of isophthalic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.), 6 g of sodium polyoxyethylene alkyl ether sulfate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), 3 g of sodium alkyl sulfonate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and lavender flavor A solution of 2 g in 44 g of water was added to make 100 g.

  This aqueous solution was placed in a 100 ml beaker and allowed to stand at room temperature for 12 hours to obtain the fragrance of the present invention. The fragrance was a transparent gel that was elastic. When this fragrance of the present invention was installed in a toilet, it scented for about 3 months, and the gel contracted in a similar shape to the container along with the volatilization and looked good.

Example 11
40 g of water was added to 4 g of isobutylene maleic anhydride copolymer ammonia adduct and dissolved. 1 g of dodecanediohydrazide (manufactured by Otsuka Chemical Co., Ltd.), 6 g of sodium polyoxyethylene alkyl ether sulfate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), 3 g of sodium alkyl sulfonate (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and lavender flavor A solution of 2 g in 44 g of water was added to make 100 g.

  This aqueous solution was placed in a 100 ml beaker and allowed to stand at room temperature for 12 hours to obtain the fragrance of the present invention. The fragrance was a transparent gel that was elastic. When this fragrance of the present invention was installed in a toilet, it scented for about 3 months, and the gel contracted in a similar shape to the container along with the volatilization and looked good.

  As described above, the transparent gelling agent composition of the present invention has high gel stability and can be easily gelled at a low temperature, and a transparent gel using the same has excellent transparency and elasticity. It is.

  Therefore, the transparent gelling agent composition of the present invention is very advantageously used as a gel-like fragrance or deodorant.

Claims (14)

The following components (a) and (b)
(A) Copolymer of ethylenically unsaturated compound and maleic anhydride and / or basic salt thereof (b) The following general formula (I) or general formula (II)

(N represents an integer of 100 to 2000)

(R ₁ represents a C 1-10 alkylene group or phenylene group which may be branched)
The transparent gelatinizer composition containing 1 type, or 2 or more types of the hydrazide compound represented by these.   The transparent gelling agent composition according to claim 1, wherein the hydrazide compound represented by formula (I) has a weight average molecular weight of 10,000 to 150,000.   The transparent gelling agent composition according to claim 1 or 2, wherein the hydrazide compound represented by the formula (II) is adipic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide or isophthalic acid dihydrazide. The following components (a) and (b)
(A) Copolymer of ethylenically unsaturated compound and maleic anhydride and / or basic salt thereof (b) The following general formula (I) or general formula (II)

(N represents an integer of 100 to 2000)

(R ₁ represents a C 1-10 alkylene group or phenylene group which may be branched)
A transparent gel obtained by reacting one or more of the hydrazide compounds represented by   The transparent gel according to claim 4, wherein the pH is 4.5 to 6.5.   The content of the component (a) is 1 to 40% by mass, the content of the component (b) is 0.1 to 10% by mass, and the content of water is 30 to 98% by mass. The transparent gel as described.   The transparent gel according to any one of claims 4 to 6, further comprising an oily medicinal ingredient and a surfactant.   The transparent gel according to claim 7, wherein the oily medicinal component is a fragrance or an insect repellent.   The transparent gel according to claim 7 or 8, wherein the surfactant is an anionic surfactant.   The acid according to any one of claims 4 to 9, comprising 0.1 to 10% by weight of an acid, 0.1 to 10% by weight of a medicinal component, and 0.1 to 30% by weight of a surfactant. The transparent gel according to item. The following components (a) and (b)
(A) Copolymer of ethylenically unsaturated compound and maleic anhydride and / or basic salt thereof (b) The following general formula (I) or general formula (II)

(N represents an integer of 100 to 2000)

(R ₁ represents a C 1-10 alkylene group or phenylene group which may be branched)
A method for producing a transparent gel, comprising gelling an aqueous solution in which one or more of the hydrazide compounds represented by formula (1) is dissolved. Component (a) An aqueous solution in which a copolymer of ethylenically unsaturated compound and maleic anhydride and / or a basic salt thereof is dissolved, and component (b), the following general formula (I) or general formula (II)

(N represents an integer of 100 to 2000)

(R ₁ represents a C 1-10 alkylene group or phenylene group which may be branched)
A method for producing a transparent gel, comprising mixing an aqueous solution in which one or more of the hydrazide compounds represented by formula (1) is dissolved to cause gelation.   The transparent gel according to claim 11 or 12, wherein the aqueous solution in which the component (a) and / or the component (b) is dissolved further contains an acid, a medicinal component and / or a surfactant. Production method. The method for producing a transparent gel according to any one of claims 11 to 13, wherein the gelation is performed at a temperature of room temperature to 50 ° C.