JP2006169505A - Hydrogel composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a hydrogel composition which needs no heating, can incorporate an additive weak to heat, and is transparent, free of water separation and high in gel strength. <P>SOLUTION: The hydrogel composition comprises a water-soluble polymer (component (A)) consisting of one or more glucan derivatives and a water-soluble titanium compound (component (B)), wherein the molar ratio of the component (B) and the component (A) is ≥0.005 and ≤0.8 in terms of the former/the latter. Preferably, the water-soluble polymer (component (A)) is a carboxymethyl cellulose and/or its alkali metal salt, and the water-soluble titanium compound (component (B)) is titanium lactate (chemical formula: [TiC<SB>6</SB>H<SB>10</SB>O<SB>7</SB>]). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous gel composition and a method for producing the same. More specifically, the gel strength, water separation, transparency and uniformity are excellent, there is no odor, the gel stability is excellent, the gelation time is adjustable, and a transparent gel is formed by reaction at room temperature. The present invention relates to an aqueous gel composition that further contains a fragrance, a heat-sensitive additive, and the like, and a method for producing the same.

  And the water-based gel composition of the present invention makes use of such properties, and fresh foods such as seafood, ham, vegetables and the like, and a cold-reserving agent used for the purpose of keeping freshness and cold-retaining juice, wine, blood, etc. , Air fresheners used in cars, indoors, toilets, etc., poultices that give a refreshing sensation or cooling sensation by applying to the skin, cooling sheets, and especially those with low gel strength, Suitable for use as hair gels such as hair shampoos and hair conditioners, skin creams, skin care lotions, facial treatments, skin care gels such as body and facial cleansers, ointments, toothpastes and gel soaps.

  Aqueous gel compositions have been widely used as base materials for hydrous explosives, civil mudguards, cryogens, deodorants, fragrances and the like. The functions required for these aqueous gel compositions vary depending on the intended use, but gelation speed, gel strength (shape retention), gel transparency, gel stability (retention rate), gel odor, non-water separation properties Such as sustained release.

  Conventionally, in the case of a hydrous explosive base material, a low polymerization degree guar gum in which propylene oxide is added to a gel composition has been used. There was a problem.

  In the case of a fragrance base material, carrageenan or agarose was used for the gel composition, but it was also a natural material, so there was a problem in terms of price and quality. Furthermore, these carrageenans and agarose have essentially utilized the property of being dissolved at a high temperature and then gelled by lowering the temperature in the same manner as gelatins.

  For this reason, when additives, such as a fragrance | flavor and a medicinal component which are desired to add to these gel compositions, are weak at high temperature, since they cannot be used, the aqueous gel composition which gelatinizes at room temperature was calculated | required.

  On the other hand, polyacrylic acid and polyacrylic acid salt, which are synthetic materials, have been studied as gel materials that are cheaper and easier to control quality.

  Examples of aqueous gel compositions using polyacrylic acid and polyacrylate are Japanese Patent Application Laid-Open No. 59-110616 (Patent Document 1), Japanese Patent Application Laid-Open No. 59-110617 (Patent Document 2), No. 61-043678 (Patent Document 3), JP-A-2-311549 (Patent Document 4), JP-A-3-070707 (Patent Document 5) and the like. However, in recent years, in the field of life chemical supplies such as cold-retaining agents, deodorants, and fragrances, from the viewpoint of environmental problems, materials that are easy to dispose of and that are close to natural materials with excellent natural degradability have been required. It has become.

  Carboxymethylcellulose and / or alkali metal salt of carboxymethylcellulose (hereinafter abbreviated as CMC) is a semi-synthetic water-soluble polymer using cellulose, which is a natural material, and has various substitution degrees and molecular weights depending on the application. Products with (aqueous solution viscosity) are manufactured and sold. As described above, CMC is a semi-synthetic polymer and a substance that is also recognized as a food additive. Therefore, CMC is applied to life chemical supplies such as cold-retaining agents, deodorants, and fragrances. That was in line with social demands.

  Therefore, many attempts have been made so far to prepare an aqueous gel composition using CMC. By using a polyvalent metal compound such as aluminum as a gelling agent, the gelation reaction is promoted, and a network structure based on ionic bonds. Methods are already known for preparing three-dimensional aqueous gel compositions having However, although certain gelling agents that are polyvalent metal compounds give a transparent gel, the gelation rate becomes very fast due to the high solubility of the polyvalent metal compound in water. There was a problem that the workability in the manufacture of was poor.

  On the other hand, some other gelling agents, which are polyvalent metal compounds, can be added to the gel in an amount that is not dissolved in the gel when the gelling agent is added in an amount necessary to maintain the gel strength (shape retention). The metal compound remains, and the transparency of the gel composition is remarkably lowered.

  Furthermore, if the gelation rate can be adjusted, a gel composition can be formed without heating, and additives that are weak against heat can be used, and the selection range of additives and the like is widened. Various transparent gel compositions using water-soluble polymers are known, but most of them have a heating process in their production process, and heat-sensitive additives cannot be used. . Therefore, if a method for producing a highly transparent gel that can form a uniform gel at room temperature and requires a certain amount of time for gelation can be developed, the selection range of additive types that can be added to the gel will be greatly expanded. It will be useful. For the above reasons, there is a demand for the emergence of an aqueous gel composition capable of adjusting the gelation speed and capable of forming a gel having an excellent balance between transparency and strength (shape retention) and a method for producing the same. It was.

Japanese Patent Application Laid-Open No. 2002-179935 (Patent Document 6) discloses a transparent aqueous gel containing two or more polyvalent metal compounds having different solubility in CMC and water and at least one acidic compound such as hydrochloric acid and lactic acid. ing. This aqueous gel is disclosed having a gel strength of 10 to 18 g / cm ² .

  According to this technique, a transparent and non-heated aqueous gel can be obtained. However, this technique needs to contain at least one acidic compound such as oxyacid. Then, the polyvalent metal compound reacts with the acidic compound to generate aluminum ions, which causes gelation due to the crosslinking reaction.

  When an acidic compound reacts with a polyvalent metal compound, a low-boiling acid such as acetic acid is produced, and the problem of odor caused by this low-boiling acid such as acetic acid is a problem immediately after the gel composition is produced. However, as the water contained in the aqueous gel evaporates over time and the concentration of low boiling acid such as acetic acid increases in the aqueous gel composition, the odor of these acids is generated. was there.

  These problems are caused by the evaporation of moisture with the passage of time. In particular, when used for applications such as fragrances, an irritating odor of the acid component is caused. Furthermore, a gel having a higher gel strength could not be obtained.

Japanese Patent Application Laid-Open No. 2003-276737 (Patent Document 7) discloses an aqueous gel composed of an aqueous solution of one or more anionic water-soluble polymers, a crosslinking agent, and fine fibrous cellulose. An aqueous gel with high gel strength is disclosed by adding microfibrous cellulose. However, transparency is lost when microfibrous cellulose is added. An aluminum compound is disclosed as a crosslinking agent. For example, in Comparative Examples 1 and 2, an aqueous gel having a gel strength of 156 g / cm ² to 250 g / cm ² is obtained by using sodium aluminate as a cross-linking agent without adding microfibrous cellulose. When sodium is used, there is a problem that the amount of water separation is large. For example, in Comparative Example 6, an aqueous gel having a gel strength of 3000 g / cm ² is obtained by using basic aluminum acetate as a cross-linking agent. However, when this cross-linking agent is used, the problem of odor is as described above. Occurs. On the other hand, in the examples, aqueous gels having excellent gel strength and water separation properties are disclosed, but these are added with fine fibrous cellulose. Microfibrous cellulose is a water-insoluble substance, which remains as a solid in an aqueous gel. For this reason, the aqueous gel described in the Example of patent document 7 had the fault that it was not transparent.
JP 59-110616 A JP 59-110617 A JP-A 61-043678 JP-A-2-311549 Japanese Patent Laid-Open No. 3-070707 JP 2002-179935 A Japanese Patent Laid-Open No. 2003-277737

  The problem to be solved is that the gel strength is large but the gel strength is large, the water separation and uniformity are excellent, there is no odor, the gel stability is excellent, the gelation time is adjustable, and the reaction at room temperature An object is to provide an aqueous gel composition that is less susceptible to the temperature at which a transparent gel can be formed, and a method for producing the same.

The present invention provides (1) an aqueous gel composition comprising a water-soluble polymer (component (A)) composed of one or more glucan derivatives and a water-soluble titanium compound (component (B)).

The present invention also provides
(2) The aqueous gel composition according to (1), wherein the component (A) comprises carboxymethyl cellulose and / or an alkali metal salt thereof.

The present invention also provides
(3) The aqueous gel composition according to (1) or (2), wherein the component (B) is titanium lactate (chemical formula [TiC ₆ H ₁₀ O ₇ ]).

The present invention also provides
(4) The aqueous gel composition according to any one of (1) to (3), wherein the molar ratio of the component (B) to the component (A) is 0.005 or more and 0.8 or less in the former / the latter.
(5) The molar ratio (M) of the component (B) to the component (A) (the former / the latter), the square root (SR) of the viscosity (mPa · s) of the 1% by weight aqueous solution of the component (A), and ( The aqueous gel composition according to (1) to (4), wherein the product of the weight ratio of component A) to water (the former / the latter) (C) is represented by the following formula:

(Formula) 1.5 ≦ M × SR × C × 100 ≦ 40

The present invention also provides
(6) Each component constituting the aqueous gel composition comprises 2.5 to 10 parts by weight of carboxymethyl cellulose and / or an alkali metal salt thereof as component (A), titanium lactate as component (B) TiC ₆ H ₁₀ O ₇ ]) is 0.3 to 5.0 parts by weight and water is 80 to 100 parts by weight, and the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of component (A) is 5 The aqueous gel composition according to (1) to (5), which is ˜1000 mPa · s.
(7) The molar ratio of the component (B) to the component (A) is from 0.1 to 0.75 in the former / the latter, the gel strength is from 10 g / cm to 700 g / cm, and the transparency is 10 cm. The aqueous gel composition described in (1) to (6) above is provided.
(8) Each component constituting the aqueous gel composition is composed of 0.5 to 10 parts by weight of carboxymethylcellulose and / or an alkali metal salt thereof as component (A), titanium lactate as a component (B) ₆ H ₁₀ O ₇ ]) is 0.02 to 3.0 parts by weight, and water is 80 to 100 parts by weight, and the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of component (A) is 4000 to 400. The aqueous gel composition according to (1) to (5) is 10,000 mPa · s.
(9) The molar ratio of the component (B) to the component (A) is 0.005 or more and 0.5 or less in the former / the latter, the gel strength is 10 g / cm or more and 700 g / cm or less, and the transparency is 10 cm. The aqueous gel composition described in (1) to (5) and (8) above is provided.

Furthermore, the present invention provides
(10) The aqueous gel composition according to any one of (1) to (9), including an additive and a fragrance that are weak against heat.
(11) The aqueous gel composition according to (1) to (11), comprising at least one additive selected from deodorants, deodorants, antibacterial agents, antifungal agents, bactericides, and repellents To do.

The present invention also provides
(12) The method for producing a gel composition according to (1) to (11), wherein the component (B) is added in a liquid state to the aqueous solution of the component (A).

  The water-soluble polymer comprising a glucan derivative referred to in the present invention may be a substantially water-soluble glucan derivative as its structure, including nonionic hydroxyethyl cellulose, including carboxymethyl cellulose and alkali metal salts thereof. Contains methylcellulose and the like. In addition, polysaccharides composed of α-glucoside bonds include all what are generally called water-soluble polymers or water-soluble polymers. A more preferable water-soluble polymer comprising the glucan derivative of the present invention is an anionic water-soluble polymer. A water-soluble polymer composed of β-glycoside bonds is more preferable.

  The water-soluble titanium compound in the present invention may be any titanium compound that is soluble in water or dilute acid aqueous solution, and is substantially about 0.0001 mol or more with respect to 1 L of pure water or dilute acid solution. Any one can be used as long as it exhibits a solubility of about 0.001 mol with respect to 1 L of pure water or dilute acid solution. More preferably, the solubility is 0.002 mol or more, still more preferably 0.01 mol or more, and particularly preferably 0.02 mol or more.

  The titanium lactate in the present invention is a lactic acid chelate of titanium.

  According to the present invention, an aqueous gel composition containing a water-soluble polymer, preferably an anionic water-soluble polymer, and a titanium compound, has no odor, and has gel strength, water separation, transparency and uniformity. A well-balanced aqueous gel composition that can be applied to a transparent gel using an additive that is easily affected by temperature because a transparent gel can be formed by reaction at room temperature. It is obtained and exhibits excellent practicality and convenience not found in conventional aqueous gel compositions.

  Therefore, the aqueous gel composition of the present invention includes fresh foods such as seafood, ham, and vegetables and juices, wine, blood, etc. It can be used as a fragrance used in toilets, a poultice or a cooling sheet that gives a refreshing feeling or cooling sensation to the part by applying it to the skin. Especially for those with low gel strength, as hair shampoo, hair conditioner and other hair gel, skin cream, skin care lotion, facial treatment agent, skin care gel such as body and face cleanser, ointment, toothpaste, gel soap, etc. Can be used.

Below, the aqueous gel composition of this invention and its manufacturing method are demonstrated in detail.
1. Raw Material for Aqueous Gel Composition The greatest feature of the aqueous gel composition of the present invention is an aqueous gel composition containing a water-soluble polymer (component (A)) and a water-soluble titanium compound (component (B)). . In order to produce the aqueous gel composition of the present invention, the following water-soluble polymer (component (A)) and water-soluble titanium compound (component (B)) are used as essential components.

Water-soluble polymer (component (A))
The water-soluble polymer (component (A)) contained in the aqueous gel composition of the present invention is a component that becomes a gelling substrate. As the component (A), a so-called general water-soluble polymer composed of a glucan derivative can be used. The water-soluble polymer is a polymer that contains many polar groups (ionic group, hydroxyl group, amino group, amide group, ether group, etc.) that interact strongly with water in the molecule and dissolves in water. Examples of such water-soluble polymers include starches, mannans, seaweeds, plant gums, natural polymers such as proteins, and semisynthetics such as carboxymethylcellulose and carboxymethyl starch. be able to. The component (A) in the present invention is most preferably one that dissolves in water, but does not exclude a polymer that dissolves in a hydrophilic solvent such as acid, alkali, or ethyl alcohol. In particular, natural polymers or derivatives thereof that can be dissolved in an acid solution can be included in the component (A) of the present invention. As the component (A), an acid solution or a hydrophilic solution can be used if it can be finally dissolved in a solution containing water at a concentration of 0.1 to 20% by weight. Examples of such natural polymers or derivatives thereof include chitin / chitosan and derivatives thereof.

  In the present invention, one or more kinds of such water-soluble polymers can be selected and used. From such water-soluble polymers, a plurality of types of water-soluble polymers can be combined according to the properties of the target gel. When used in combination, a combination of a semi-synthetic system and a natural system is preferably used. Among them, a water-soluble polymer composed of a plurality of types of glucan derivatives is combined to form an α-glucoside such as CMC and guar gum, starch or starch. A polysaccharide water-soluble polymer consisting of a bond or a water-soluble polymer is preferably used.

  Further, the component (A) in the present invention and a synthetic system such as sodium polyacrylate can be used in combination.

  Particularly preferable examples of the synthetic water-soluble polymer to be combined with the component (A) of the present invention include polyvinyl alcohol and sodium polyacrylate. However, the water-soluble polymer in the present invention is preferably selected from water-soluble polymers having biodegradability. Therefore, polyvinyl alcohol is particularly preferable.

  Among the components (A), as the semi-synthetic water-soluble polymer, a semi-synthetic water-soluble polymer composed of a glucan derivative can be preferably used. Semi-synthetic water-soluble polymers composed of glucan derivatives include water-soluble polymers of cellulose-based cellulose derivatives based on cellulose and water-soluble polymers of starch-based starch derivatives based on starches. In the present invention, a water-soluble polymer of a cellulose derivative having a cellulose as a skeleton can be more preferably used from the viscous behavior of an aqueous solution of the water-soluble polymer. Water-soluble polymers of these cellulose derivatives are roughly classified into anionic CMC and nonionic methylcellulose (MC), ethylcellulose (EC), and hydroxyethylcellulose (HEC). In the present invention, among these water-soluble polymers of cellulose derivatives, cellulose derivatives that are anionic water-soluble polymers can be preferably used. CMC can be illustrated as a cellulose derivative which is an anionic water-soluble polymer.

  CMC preferable as the component (A) has a specific degree of substitution (sometimes referred to as etherification degree or DS) and molecular weight. The degree of substitution (degree of etherification = DS) is generally a numerical value indicating how much the hydroxyl group of cellulose has been etherified (carboxymethylated), and therefore there are numerical values of 0 to 3, The CMC used as the component (A) to be used has a degree of substitution of 0.5 to 2.0, preferably 0.5 to 1.5, more preferably 0.7 to 1.0. Is desirable. At that time, if the degree of substitution is lower than 0.5, the water solubility is insufficient and a uniform gel cannot be obtained. On the other hand, when the degree of substitution is higher than 2.0, crosslinking with the water-soluble titanium compound (B) ions proceeds in the molecule and may settle without forming a uniform gel. Two or more CMCs having different degrees of substitution can be used in combination.

  In addition, the molecular weight of CMC as the component (A) was determined by adding 60 wt. p. Those having a viscosity at 25 ° C. measured in m of 5 to 10,000 mPa · s are suitable. It is preferably 10 to 8000 mPa · s, more preferably 10 to 200 mPa · s. At this time, if the viscosity is less than 5 mPa · s, the three-dimensional crosslinking does not proceed effectively, and the gel strength is lowered. On the other hand, if the viscosity is greater than 10,000 mPa · s, the viscosity before gelation becomes very high, which causes problems such as poor injection into a container and workability.

  When preparing an aqueous gel composition, when CMC is used as the component (A), it is water-soluble, so it is usually dissolved in water and used in the form of an aqueous solution. At that time, the content of CMC is usually 0.5 to 10% by weight on the basis of the concentration of the aqueous solution, preferably 1.0 to 5.0% by weight, more preferably 1.5 to 3.5%. It is desirable to set the weight%. If the aqueous solution concentration is lower than 0.5% by weight, sufficient gel strength cannot be obtained. On the other hand, if the aqueous solution concentration is higher than 10% by weight, the viscosity before gelation becomes very high, and injection into a container or processing is performed. This causes problems such as inferiority. Further, when preparing an aqueous solution of CMC, it is easy to disperse and dissolve easily by once dispersing in glycerin and adding the dispersion to water. In addition, the aqueous solution of (B) component can be prepared and (A) component can be added and used.

  Here, the content of the component (A) in the aqueous gel composition needs to be 0.2% by weight or more as a water-soluble polymer composed of a glucan derivative typified by carboxymethyl cellulose and / or an alkali metal salt thereof. . Moreover, the required amount of (A) component correlates with the viscosity of (A) component. When the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 5 to 1000 mPa · s, the content of the component (A) is 0.5% by weight or more. In addition, when the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 4000 to 10,000 mPa · s, the content of the component (A) is 0.2% by weight or more. .

  For example, if the component (A) is an alkali metal salt of carboxymethyl cellulose, it is 0.2% by weight or more, and the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 5 to 1000 mPa · s. In some cases, it is preferably 0.5% by weight or more, more preferably 0.5 to 10.0% by weight, still more preferably 2.5 to 10.0% by weight. Moreover, when the 1 weight% aqueous solution viscosity (mPa * s) in 25 degreeC of (A) component is 4000-10000 mPa * s, Preferably it is 0.2 weight% or more, More preferably, it is 0.5-10. It is 0% by weight, more preferably 0.5 to 3.0% by weight.

  When 80 to 100 parts by weight of water is used, the content of the component (A) in the aqueous gel composition is a water-soluble polymer comprising a glucan derivative typified by carboxymethyl cellulose and / or an alkali metal salt thereof. 0.2 parts by weight or more is necessary. Moreover, the required amount of (A) component correlates with the viscosity of (A) component. When the (A) component has a 1 wt% aqueous solution viscosity (mPa · s) at 25 ° C of 5 to 1000 mPa · s, the content of the component (A) is 0.5 parts by weight or more, and more Preferably 0.5 to 10.0 parts by weight, more preferably 2.5 to 10.0 parts by weight are required. In addition, when the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 4000 to 10,000 mPa · s, the content of the component (B) is 0.2 parts by weight or more. More preferably, it is 0.5-10.0 weight%, More preferably, it is 0.5-3.0 weight%.

Water-soluble titanium compound (component (B))
The water-soluble titanium compound (component (B)) contained in the aqueous gel composition of the present invention is a component that three-dimensionally crosslinks the component (A) in the aqueous gel composition. In the present invention, the component (B) includes an alkyl (or aryl) titanium compound. These (B) components also include alkoxide titanium compounds. Moreover, a titanium chelate compound is also contained as (B) component in this invention. Titanium chelate compounds and those represented by the general formula Ti (OR) _n (X) _4-n are used. Specific examples of the compound include titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, and titanium ethylacetoacetate.

  (B) As a component, peroxotitanate, a titanium organic acid chelate compound, a titanium alkylamine chelate compound, etc. can be mentioned. These components (B) preferably have an aqueous solution having a pH of 7 or less. That is, when the pH of the aqueous solution of the component (B) is 10 or more, it comprises a glucan derivative suitable as the component (A) contained in the aqueous gel composition when the component (B) and the component (A) are mixed. This is because the molecular weight of the semi-synthetic water-soluble polymer is lowered, which may adversely affect the viscosity and gel strength of the aqueous solution before gelation.

From this point of view, the most suitable component (B) is a titanium organic acid chelate compound, for example, a titanium lactic acid chelate compound. The chemical abbreviated name of the titanium lactic acid chelate compound is titanium lactate, and the chemical formula can be shown as [TiC ₆ H ₁₀ O ₇ ].

  Such a titanium lactic acid chelate compound can be obtained as ORGATICS (registered trademark) TC-310 from Matsumoto Pharmaceutical Co., Ltd. The component (B) in the present invention may contain an acid component such as an organic acid or an organic solvent.

  In the present invention, it is not preferable to use a material such as titanium alkoxide or polyhydroxy titanium stearate as the component (B). These titanium alkoxysides and the like are hydrolyzed and polycondensed under acidic conditions. In the present invention, components (A) and (B) are used without using gelation with such an inorganic polymer as a main gelled product. A gel can be produced by the crosslinking reaction or chelate formation.

  In addition, when (B) component is water-soluble, it can maintain transparency irrespective of the addition amount, and can obtain a required gel strength and easily obtain a transparent material. However, it is not excluded that it is not water-soluble as follows.

  Even when the component (B) does not exhibit water solubility, it can be easily used when it is dissolved in an acid or the like. In that case, before adding (B) component to (A) component, (B) component can be added after melt | dissolving in an acid component. Even if the component (B) is not water-soluble and does not dissolve in the acid component, it can be used as long as it can be dissolved in a hydrophilic organic solvent. However, in this case, since it contains an organic solvent, it may not be a complete aqueous gel.

  Here, the content of the component (B) in the aqueous gel composition needs to be 0.01% by weight or more as the titanium chelating agent, and the molar concentration needs to be 0.001 or more. Moreover, the required amount of (B) component correlates with the viscosity of (A) component. When the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 5 to 1000 mPa · s, the content of the component (B) is 0.3% by weight or more. As the molar concentration, 0.01 molar concentration or more is necessary. In addition, when the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 4000 to 10,000 mPa · s, the content of the component (B) is 0.02% by weight or more. . As the molar concentration, 0.001 molar concentration or more is necessary.

  For example, if the component (B) is titanium lactate, it is 0.02% by weight or more, and when the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 5 to 1000 mPa · s. , Preferably 0.5% by weight or more, more preferably 0.5 to 5.0% by weight, still more preferably 0.5 to 2.0% by weight. Moreover, when the 1 weight% aqueous solution viscosity (mPa * s) in 25 degreeC of (A) component is 4000-10000 mPa * s, Preferably it is 0.04 weight% or more, More preferably, it is 0.04-3. It is 0% by weight, more preferably 0.05 to 1.0% by weight.

  When 80 to 100 parts by weight of water is used, the content of the component (B) in the aqueous gel composition needs to be 0.01 parts by weight or more as a titanium chelating agent. Moreover, the required amount of (B) component correlates with the viscosity of (A) component. When the (A) component has a 1 wt% aqueous solution viscosity (mPa · s) at 25 ° C of 5 to 1000 mPa · s, the content of the component (B) is 0.3 parts by weight or more. Moreover, when the 1 weight% aqueous solution viscosity (mPa * s) in 25 degreeC of (A) component is 4000-10000 mPa * s, as content of (B) component, 0.02 weight part or more is required. .

  If the component (B) is titanium lactate, it is 0.02 parts by weight or more, and when the 1 wt% aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 5 to 1000 mPa · s, 0.3 parts by weight or more, preferably 0.5 parts by weight or more, more preferably 0.5 to 5.0 parts by weight, still more preferably 0.5 to 2.0 parts by weight. Further, when the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of component (A) is 4000 to 10,000 mPa · s, it is 0.02 parts by weight or more, preferably 0.04 parts by weight or more, more preferably. Is 0.04 to 3.0 parts by weight, more preferably 0.05 to 1.0 parts by weight.

  In addition, when each component which comprises an aqueous gel composition is 80-100 weight part of water, and the 1 weight% aqueous solution viscosity (mPa * s) in 25 degreeC of (A) component is 5-1000 mPa * s, it is. CMC as component (A) is 2.5 to 10 parts by weight, preferably 2.5 to 5.0 parts by weight, and titanium lactate as component (B) is 0.3 to 5.0 parts by weight, preferably Is 0.5 to 2.0 parts by weight.

  In addition, when the 1% by weight aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 4000 to 10,000 mPa · s, the CMC as the component (A) is preferably 0.5 to 10 parts by weight, 0.5 to 3.0 parts by weight, and titanium lactate as component (B) is 0.02 to 3.0 parts by weight, preferably 0.04 to 1.5 parts by weight.

  The amount of component (B) used in the present invention is important because it affects the physical properties of the resulting aqueous gel composition. Therefore, the component (B) used as the gelling agent has a molar ratio in the aqueous gel composition when CMC is used as the component (A), and the molar ratio between the component (B) and the component (A). The following formula is preferred.

0.005 ≦ mol of component (B) / mol of component (A) ≦ 0.8

In the present invention, the gel strength of the aqueous gel composition obtained can be adjusted by the molar ratio of the component (B) and the component (A).
At that time, when the ratio of “mol of component (B) / mol of component (A)” is less than 0.005, gelation as an aqueous gel composition is not sufficient, and gel strength required as a gel is obtained. There is no problem.

  Furthermore, the required range of the ratio of “mol of (B) component / mol of (A) component” also correlates with the concentration of component (A). (B) molar ratio of component to component (A) (former / latter) (M), square root (SR) of viscosity (mPa · s) of 1% by weight aqueous solution of component (A), and component (A) It is necessary that the product of the ratio of water to water (the former / the latter) (C) is within the range represented by the following formula.

(Formula) 1.5 ≦ M × SR × C × 100 ≦ 40

On the other hand, in the case of an aqueous gel composition that does not depend on chelate formation as in the present invention, that is, an aqueous gel composition with a metal salt of the prior art, “equivalent of metal salt / number of moles of water-soluble polymer” When the value is larger than 1.0, there is a problem that the amount of water separation increases. The present invention does not mainly use a phenomenon in which a metal salt of a cationic water-soluble polymer is replaced from a monovalent metal salt to a polyvalent metal salt, such as gelation with a metal salt. In the invention, the ion equivalent ratio (in the present invention, the ratio of “mole of component (B) / mole of component (A)”) is greater than 1.0. No water separation phenomenon is observed. Therefore, in the present invention, even if the ratio of “(B) component mole / (A) component mole” exceeds 1.0, it can be used without water separation phenomenon, and the gel strength can be increased without concern for water separation phenomenon. I can go.

  Naturally, it is possible that a part of the titanium compound of the component (B) can be replaced with a part of the CMC sodium salt of the component (A) of the present invention. A) The water-soluble polymer of the component forms a three-dimensional network structure.

  For this reason, in this invention, the aqueous gel composition with a large gel strength can be obtained easily. However, if the ratio of “mol of component (B) / mol of component (A)” increases, there is an advantage that the gel strength is increased, but the gelation time, so-called pot life (pot life) is shortened. Is inferior.

  In the present invention, an aqueous gel composition having a gel strength exceeding 600 g / cm can be obtained by adjusting the ratio of “mol of component (B) / mol of component (A)”, but it is too hard. The use of gels is also limited. Accordingly, the ratio of “mol of component (B) / mol of component (A)” is preferably 0.8 or less.

  As described above, the ratio of “mol of component (B) / mol of component (A)” directly affects the gel strength in the present invention. When the 1% aqueous solution viscosity (mPa · s) at 25 ° C. of the component (A) is 5 to 1000 mPa · s, preferably 0.1 or more and 0.75 or less, more preferably 0.1 or more. And 0.5 or less, more preferably 0.2 or more and 0.45 or less. Moreover, when the 1 weight% aqueous solution viscosity (mPa * s) in 25 degreeC of (A) component is 4000-10000 mPa * s, Preferably, it is 0.005-0.5, More preferably, 0.01 ~ 0.45.

  Furthermore, the preferred gel strength varies depending on the use in which the aqueous gel is used, and is not generally determined. However, when used in applications such as fragrances, “(B) component mol / (A) component mol” Is preferably 0.005 to 0.6.

  In addition, a harder gel may be preferred depending on the use of the aqueous gel. This case can be dealt with by increasing the ratio of “(B) component mole / (A) component mole”. Specifically, 0.4 to 0.75 can be preferably used, and 0.4 to 0.6 can be preferably used. Thus, when using the thing of 0.4-0.75, the high gel intensity | strength and transparency which were not able to maintain transparency with the conventional aqueous gel composition can be made compatible.

  Here, “mole of the component (A)” is obtained by dividing the mass of the component (A) contained in the aqueous gel composition by the molar mass per repeating unit of the water-soluble polymer. “Mole of component (B)” is obtained by dividing the mass of component (B) contained in the aqueous gel composition by the formula amount of the titanium compound of component (B). The molar ratio of the component (B) to the component (A) is “the mole of the component (B)” divided by the “mol of the component (A)”, and the numerator is “the mole of the component (B)”. Becomes “mol of component (A)”.

When carboxymethyl cellulose sodium salt is used as the component (A), the molar mass of the glucose ring is 162.12. Therefore, the molar mass of the substituent may be added thereto.
Since the molar mass of the H group is 1.01 and the molar mass of the CH2COONa group is 81.02, the substitution degree is DS.
(A) molar mass per repeating unit of CMC as component
= 162.12 + (81.02-1.01.) X DS
It is. For example, when using CMC with a substitution degree of 0.9,
(A) molar mass per repeating unit of CMC as component
= 162.12 + (81.02-1.01.) X 0.9
= 234.13
It is. Therefore, the mole of component (A) in this case = mass of CMC / 234.13
It becomes.
The moles of component (B) are simply the molar mass of component (B) divided by the weight of component (B).
As the component (B), when ORGATICS TC-310 (titanium lactate content, about 46%) is used, the molar mass of titanium lactate is 242.02.
Component (B) mole = (mass of Orgatics TC-310 × 0.46 / 242.02
It becomes.

  In addition, in this invention, gel strength means the force (shape retention strength) which maintains the shape of a gel, and the measuring method is as follows. Using a food rheometer (manufactured by Sun Kagaku), a cylindrical gel having a diameter of 50 mm and a height of 30 mm is placed in a container and evaluated using a gel that has been allowed to stand for 24 hours or more. Using a rod-shaped adapter having a diameter of 11 mm, measurement was performed at 10 points located inside the middle distance from the center to the end of the gel composition, and the average was calculated as the weight per surface area. g / cm2).

  The gel strength in the present invention is 4 to 1000 g / cm 2, preferably 5 to 1000 g / cm 2, more preferably 10 to 700 g / cm 2, and still more preferably 10 to 600 g / cm 2.

  In the present invention, transparency refers to the degree to which the gel composition can be seen through, and the measurement method is as follows. Evaluation is made using a columnar gel composition having a diameter of 50 mm and a height of 50 mm in a transparent container and allowed to stand for 24 hours or more. Evaluation is made by placing a gel test piece on a black and white 1 mm wide slit striped mount, looking into the gel composition from 25 cm above the top surface of the gel, and separating the gel composition upward from the striped mount. The distance (cm) between the gel composition and the striped mount that cannot be identified is used as an index of transparency.

  The transparency of the preferable gel composition in the present invention is 10 cm or more, more preferably 15 cm or more. More preferably, it is 20-100 cm.

2. Method for Producing Aqueous Gel Composition The aqueous gel composition of the present invention can be basically produced by various methods based on the aqueous solution of component (A). Not. Hereinafter, the typical manufacturing method will be listed and described mainly.

  In the present invention, an aqueous gel composition is produced according to the following steps using the above-described components (A) to (B) and other optional components as required. In addition, in the aqueous gel composition of the present invention, a gel can be formed after a lapse of a predetermined time just by mixing the aqueous solution of component (A) and component (B), and it is necessary to take measures such as heating. There is no. In addition, although the method to add (B) component and other components to the aqueous solution of (A) component is demonstrated concretely below, the method to add (A) component to solutions (or aqueous solution) other than (A) component. Are also included in the present invention.

(1) Preparation of water-soluble polymer (component (A)) solution At room temperature, water is added to the acid solution, alkali solution or hydrophilic solvent solution of component (A) or component (A). An aqueous solution of 1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, particularly preferably 1 to 5% by weight, in which the component (A) is completely dissolved is prepared. At this time, in the case of CMC, MC, HEC, etc. where the component (A) is a glucose derivative, the component (A) is once dispersed in glycerin, propylene glycol, etc., and then the dispersion is added to water for easy dispersion and dissolution. To do. Depending on the composition, structure and degree of polymerization of component (A), it may be difficult to dissolve. In such a case, dissolution by adding an acid component may be promoted. In particular, in the case of a polymer composed of a glucan derivative containing an amino group such as chitin or chitosan as the component (A), the aqueous solution can be prepared after dissolving in lactic acid or phosphoric acid aqueous solution.

(2) Addition of acidic compound (acid component) In the present invention, an acid component may be added for the purpose of adjusting the gelation reaction pot life and the gel strength. The addition of the acid component may be performed at any stage, but it is preferably performed in a step before adding the component (B). That is, it is preferable to add after completion of the above (1), or to add an acid component in the stage before the following step (3).

(3) Addition of water-soluble titanium compound (component (B)) Component (B) is added to the aqueous solution of component (A) obtained above at room temperature under stirring. At this time, when the component (B) is dispersed in glycerin or the like and then added to the above aqueous solution, the component compound (B) is easily dispersed and dissolved, so this method may be used. Further, the component (B) dispersed and dissolved in the acid solution of (2) may be dispersed in glycerin or the like and then added to the aqueous solution. Further, a component obtained by dispersing and dissolving the component (B) in an acid solution may be directly added to the aqueous solution of the component (A). Further, the acid component (2) may be added to the aqueous solution of the component (A), and the component (B) may be further added thereto.

(4) Gelation After completion of the step (3), the solution obtained as described above is stirred and put into a container as quickly as possible, preferably within 1 hour, and gelation is allowed to proceed. By leaving it to stand at room temperature for 1 day, a uniform and transparent aqueous gel composition can be obtained. The gelation speed in the present invention, that is, the pot life, varies depending on the molar ratio of the component (B) and the component (A). That is, when the mole of the component (B) / the mole of the component (A) is increased, the strength of the produced aqueous gel composition is increased, but at the same time, the gelation rate is increased. At the same time, the gel strength can be adjusted in the production method of the present invention.

  The aqueous gel of the present invention contains an acidic compound acid (hereinafter simply referred to as an acid component) as necessary.

  One of the acid components contained in the present invention is contained in the component (B), maintains the pH of the solution of the component (B) in the acidic region, and keeps the component (B) in a stable solution. . On the other hand, the acid component may be added to the (A) component solution or the gel solution (for example, the (A) component solution containing ethylene glycol) before the addition of the (B) component. In this case, the acid component is a component for causing gelation by causing cross-linking to the component (B) contained in the gel solution by a chelate bond. The addition of such an acid component is preferable from the viewpoints of adjusting the gelation reaction pot life and adjusting the gel strength.

  Examples of the acid component include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as acetic acid, succinic anhydride, maleic anhydride, fumaric acid, maleic acid, phthalic acid, phthalic anhydride, and aspartic acid; Examples thereof include oxyacids such as lactic acid, tartaric acid, malic acid, citric acid, gluconic acid, and glucuronic acid, and one or more acid components selected from these are used. In the present invention, oxyacids are preferably used from the viewpoint of adjusting the gelation reaction pot life (pot life) and gel strength, and lactic acid is particularly preferably used.

  In the aqueous gel composition of the present invention, in addition to the above-mentioned components, other components such as a fragrance, a deodorant, a deodorant, an antibacterial agent, a fungicide, a disinfectant, and a repellent are added as long as the object of the present invention is not impaired. Additives such as agents can be blended. In addition, since the aqueous gel composition of the present invention also has antibacterial performance, the antibacterial agent may be added as necessary.

  Among these, heat-sensitive components (additives) that have been difficult to use in the past can be easily used in the present invention. A heat-sensitive component means a component that loses its original function by evaporating or decomposing at a temperature higher than room temperature (1 to 30 ° C.).

  The fragrance | flavor (aqueous gel composition containing a fragrance | flavor) of this invention is obtained by making a fragrance | flavor contain in the aqueous gel composition of this invention.

  About a fragrance | flavor, it does not restrict | limit in particular, What was used conventionally can be used. In addition to various fragrances, there are essential oils. For example, grapefruit oil, costas oil, citronella oil, jasmine oil, sweet orange oil, spearmint oil, pine oil, patchouli oil, bran oil, bitter orange oil, hiba oil, peppermint oil, bergamot oil, mandarin oil Eucalyptus oil, lavender oil, lemon oil, lemongrass oil, rose oil, rosemary oil, peppermint white oil, plant extractant as a deodorant, etc., and alpha-pinene, beta-pinene, limonene as synthetic fragrance Terpene hydrocarbons such as terpene, terpene alcohols such as linalool, geraniol, and nerol, other alcohols such as benzyl alcohol, phenethyl alcohol, and γ-phenylpropyl alcohol, and diphenyl ethers, isosafluoroeugenol, and p-methylanisole Derivatives, heptanal, octanal, nonanal and other aliphatic aldehydes, citral, citronellal, hydroxycitronellal and other terpene aldehydes, benzaldehyde, phenylacetaldehyde, 3-phenylpropionaldehyde and other aromatic aldehydes, citral dimethyl acetal, citral Acetals such as diethyl acetal, aliphatic ketones such as 2-heptanone, 3-octanone and 2-octanone, terpene ketones such as carvone, menthone and pregon, aromatic ketones such as p-methylacetophenone, benzophenone and benzylideneacetone, Macrocycles such as alicyclic ketones such as α-, β-, and γ-ionone, theaspirane, jasmine lactone, ethers, lactones, muscone, and ambridolide Synthetic musks such as ketones, lactones, musk xylenes, musk ketones, musk ambrets, cyclic ethers such as rose oxide, 1,8-cineol, bicyclodihydrohomofarnesyl oxide, indoles, 6-methylquinoline, 2-furylmethanethiol, etc. Heterocyclic compounds, esters of aliphatic acids such as benzyl formate, ethyl acetate, ethyl propionate, esters of aromatic acids such as methyl benzoate, ethyl benzoate, ethyl phenylacetate, ethyl cinnamate, isobutyl salicylate, γ- So-called aldehydes such as heptylbutyrolactone and allyl hexanoate are used alone or in appropriate mixture.

  As deodorant and deodorant, amphoteric surfactants such as plant extract, alkyldimethylaminoacetic acid betaine, alkylglycine salt, N-acylaminoethyl-N-2-hydroxyethylglycine salt, glyoxal, methacrylate ester, Unsaturated ester compounds such as maleate esters, etc., as antifungal agents, bactericides, as volatile compounds such as thymol, stabilized chlorine dioxide, allylisothiothionate, etc., as repellents natural fragrances, Examples include plant extracts and wood vinegar.

  These additives (drug components) are preferably 0.001 to 15% by weight of the aqueous gel composition, and more preferably 0.01 to 5.0% by weight. If it is less than 0.001% by weight, a sufficient additive (drug) effect cannot be obtained. On the other hand, if it exceeds 15% by weight, the gel strength tends to be weakened.

  Water is used as the medium of the aqueous gel composition, but the amount of water is a ratio excluding the above-mentioned components constituting the aqueous gel composition and components such as solvents, surfactants and various compounding agents described later. Usually, it becomes 60 to 99% by weight.

  In addition to water as a medium, alcohol, glycols such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,3-butanediol, hexylene glycol, glycerin, etc. are blended as needed to prevent freezing and as a low temperature stabilizer Is done.

  Furthermore, surfactants such as anionic surfactants, amphoteric surfactants, and nonionic surfactants are used as emulsifiers and solubilizers of additive components as necessary. Specifically, examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt and α-olefin sulfonate. Also, amphoteric surfactants include alkyl betaines, fatty acid amidopropyl betaines, and nonionic surfactants include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylenes. Oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid alkanolamide ethylene oxide adduct, fat ethylene oxide adduct, ethylene oxide / propylene oxide block copolymer, glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol Sorbitan fatty acid ester, sucrose fatty acid ester, polyhydric alcohol alkyl ether, alkanolamine fatty acid ester Such as soil and the like. Of these, alkyl sulfate ester salts, alkyl betaines, and higher alcohol ethylene oxide adducts are preferred from the viewpoint of emulsification and solubilization power.

  When using surfactant, the compounding quantity is preferably 0.001 to 10% by weight, more preferably 0.005 to 4.0% by weight, based on the entire aqueous gel composition.

  Furthermore, a coloring agent, an antioxidant, an ultraviolet absorber, and a chelating agent may be blended with the aqueous gel composition and the fragrance of the present invention as necessary.

  In the aqueous gel composition of the present invention, the pH of the aqueous solution is preferably 1.0 to 6.0, and particularly preferably 3.0 to 6.0.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The aqueous gel compositions obtained in Examples and Comparative Examples were evaluated as follows. Odor and gel transparency were measured even when the aqueous gel composition did not gel completely.

(Water separation (R))
A cylindrical gel composition having a diameter of 50 mm and a height of 50 mm is put in a container, and the upper part of the gel composition after 1 month is visually observed at 25 ° C., and after confirming whether water is floating on the surface of the gel composition, Tilt the container and measure the amount collected. The case where the amount of exploitation was 0 mg and no water separation was observed visually was rated as “◎”, and the case where the amount of exploitation was 0 mg and water separation was visually observed was rated as “◯”. Moreover, when there was water separation, the amount of exploitation was described. At this time, it is considered that the smaller the water separation, the better the water retention and the better the gel properties.

(Odor)
The gel composition (200 g) immediately after preparation is put into a 1 l container, the upper lid is closed, and it is cured until the next day (to create a completely gelled sealed state). After gelling, 24 hours later, the lid on the top of the container is removed and sensory evaluation is performed. The case where no odor was felt was marked with ◎, the level where the odor was felt but not noticeable with a fragrance, etc., the level where the odor was felt subtlely, and the level where the odor was felt was marked as x. Further, the above gel is stored at room temperature for 60 days with the lid on the top of the container removed, and then the lid is capped and stored for 24 hours. The lid on the top of the container is removed, and sensory evaluation is performed. The case where no odor was felt was marked with ◎, the case where it felt slightly, ○, and the degree where odor was felt was marked with ×.

(Gel transparency (T))
The gel transparency is measured by using a cylindrical gel composition having a diameter of 50 mm and a height of 50 mm placed in a transparent container and allowed to stand for 24 hours or more. Evaluation is made by placing a gel test piece on a black and white 1 mm wide slit striped mount, looking into the gel composition from 25 cm above the top surface of the gel, and separating the gel composition upward from the striped mount. The distance (cm) between the gel composition and the striped mount that cannot be identified was used as an index of transparency.

(Gel strength (G) (shape retention strength))
The measurement of gel strength is evaluated using a food rheometer (manufactured by Sun Science). Evaluation is performed using a cylindrical gel having a diameter of 50 mm and a height of 30 mm placed in a container and allowed to stand for 24 hours or more. Using a rod-shaped adapter having a diameter of 11 mm, measurement was performed at 10 points located inside the middle distance from the center to the end of the gel composition, and the average was calculated as the weight per surface area. g / cm2). In the table, “NG” indicates that no gel was formed.

(Aroma persistence evaluation test)
To evaluate the gel air freshener, remove the top lid and leave it in a room where there is no wind at 25 ° C for a certain period of time. Then put each sample in a stainless steel container (5 L) with a lid without odor and open the lid after 1 hour. The sensory test of the intensity of fragrance and odor was conducted. In the sensory evaluation of the intensity of the scent, ◎ was given when the scent was strong, ◯ when it was slightly strong, △ when it was normal, and x when it was weak.

[Example 1]
(MC) Sodium salt of CMC having a degree of etherification of 0.9 as a water-soluble polymer as component (A) and a viscosity of 35% by weight of a 1% by weight aqueous solution (CMC Daicel (registered trademark) product number manufactured by Daicel Chemical Industries, Ltd.) 1240) 8.75 g of propylene glycol (hereinafter referred to as PG) was dispersed in 21 g of the propylene glycol, and the dispersion was added to 320 g of water and stirred to be completely dissolved. (A) 0.7g of lactic acid was added as an acid component to the above solution in which the component was completely dissolved.

Next, 2.4 g of Orgatix (registered trademark) product number TC-310, which is titanium lactate, was added to the aqueous solution as the water-soluble titanium compound of component (B) and stirred. This ORGATICS (registered trademark) product number TC-310 contained 46% by weight of titanium lactate [TiC ₆ H ₁₀ O ₇ ]. Further, 45% by weight of 2-propanol was contained, and the balance was water. Therefore, titanium lactate, which is an active ingredient, is obtained by multiplying the addition amount of organics by 0.46. Hereinafter, this sample was used for ORGATICS (registered trademark) product number TC-310 in Examples of the present specification.

  The aqueous solution was transferred to a container with stirring. When allowed to stand at room temperature for 1 day, a transparent and uniform gel composition (gel strength: 4.8 g / cm 2) was obtained. Table 1 shows the amount of the gel component and the evaluation results of the obtained aqueous gel composition.

[Examples 2 to 6]
An aqueous gel composition was produced in the same manner as in Example 1 except that the amount of the component (B) was changed as shown in Table 1. Table 1 shows the types and amounts of the gel components and the evaluation results of the obtained aqueous gel composition.

[Comparative Example 1]
Evaluation was conducted in the same manner as in Example 1 except that 1.4 g of ORGATICS (registered trademark) product number TC-310, which is titanium lactate, was added as the water-soluble titanium compound of component (B). The evaluation results are shown in Table 1.

［実施例７〜８］
（Ａ）成分の水溶性高分子としてエーテル化度が０．９であり、１重量％水溶液の粘度が３５ｍＰａ・ｓであるＣＭＣのナトリウム塩（ダイセル化学工業株式会社製 ＣＭＣダイセル（登録商標）品番１２４０）８．７５ｇを、ＰＧ２１ｇ中に分散し、該分散液を水３２０ｇ中に添加し攪拌することにより完全に溶解させた。

[Examples 7 to 8]
CMC sodium salt (CMC Daicel (registered trademark) product number manufactured by Daicel Chemical Industries, Ltd.) having a degree of etherification of 0.9 as a water-soluble polymer (A) and a viscosity of 1% by weight aqueous solution of 35 mPa · s. 1240) 8.75 g was dispersed in 21 g of PG, and the dispersion was added to 320 g of water and stirred to completely dissolve.

  Next, without adding any acid component, 2.8 g (Example 7) or 5.6 g (Orgatix (registered trademark) product number TC-310), which is titanium lactate, is used as the water-soluble titanium compound of component (B). Example 8) Added to the above aqueous solution and stirred. Thereafter, an aqueous gel composition was produced in the same manner as in Example 1. Table 2 shows the types and amounts of the gel components and the evaluation results of the obtained aqueous gel composition.

[Comparative Examples 2 to 4]
An aqueous gel composition was produced in the same manner as in Example 7 except that the amount of the component (B) was changed as shown in Table 2. Table 2 shows the types and amounts of the gel components and the evaluation results of the obtained aqueous gel composition.

［実施例９〜１４］
（Ａ）成分の水溶性高分子としてエーテル化度が０．９であり、１重量％水溶液の粘度が４８００ｍＰａ・ｓであるＣＭＣのナトリウム塩（ダイセル化学工業株式会社製 ＣＭＣダイセル（登録商標）品番２２６０）８．７５ｇを、ＰＧ２１ｇ中に分散し、該分散液を水３２０ｇ中に添加し攪拌することにより完全に溶解させた。

[Examples 9 to 14]
CMC sodium salt (CMC Daicel (registered trademark) product number manufactured by Daicel Chemical Industries, Ltd.) having a degree of etherification of 0.9 as the water-soluble polymer (A) and a viscosity of 4800 mPa · s in a 1% by weight aqueous solution 2260) 8.75 g was dispersed in 21 g of PG and the dispersion was added to 320 g of water and stirred until completely dissolved.

  About the other component, the quantity shown in Table 3 was used, and it carried out similarly to Example 1, and manufactured the aqueous gel composition. Table 3 shows the types and amounts of the gel components and the evaluation results of the obtained aqueous gel composition.

[Comparative Example 5]
An aqueous gel composition was produced in the same manner as in Example 9 except that the amount of the component (B) was changed as shown in Table 3. Table 3 shows the types and amounts of the gel components and the evaluation results of the obtained aqueous gel composition.

［比較例６］
アルミン酸ナトリウム２.９ｇを９６４ｇの水に溶かした水溶液に、エーテル化度が０．７ 、１重量％水溶液粘度７５ｍＰａ・ｓのＣＭＣのナトリウム塩（ダイセル化学工業株式会社製 ＣＭＣダイセル（登録商標）品番１１３０）を２９．０ｇ溶解し、さらに攪拌した。この溶液に、無水コハク酸５ｇをグリセリン（ＧＬと記載する。）１２ｇに分散させて添加し、水性ゲル組成物を調整した。その結果得られた水性ゲル組成物の特性を表３に示す。

[Comparative Example 6]
A sodium salt of CMC having an etherification degree of 0.7 and a 1% by weight aqueous solution viscosity of 75 mPa · s in an aqueous solution obtained by dissolving 2.9 g of sodium aluminate in 964 g of water (CMC Daicel (registered trademark) manufactured by Daicel Chemical Industries, Ltd.) 29.0 g of product number 1130) was dissolved and further stirred. To this solution, 5 g of succinic anhydride was added after being dispersed in 12 g of glycerin (described as GL) to prepare an aqueous gel composition. The properties of the aqueous gel composition obtained as a result are shown in Table 3.

[Comparative Example 7]
Disperse 25 g of carboxymethylcellulose sodium salt Daicel Chemical Industries, Ltd. CMC Daicel (registered trademark) No. 1240) having a degree of etherification of 0.9 and a viscosity of 35 wt. The dispersion was added to 850 g of water and dissolved by stirring. Next, 1.5 g of basic aluminum acetate was dispersed in 20 g of GL, the dispersion was added to the aqueous solution, and stirring was continued.
Further, an aqueous solution prepared by dissolving 1.5 g of potassium alum and 2.0 g of lactic acid in 40 g of water was immediately added to the aqueous solution obtained above and transferred to a container with stirring. When allowed to stand at room temperature for 1 day, a transparent and uniform gel composition (gel strength: 13 g / cm 2) was obtained. Table 4 shows the amount of the gel component and the evaluation results of the obtained aqueous gel composition.

［実施例１５〜１６］
（Ａ）成分の水溶性高分子を溶解する水を、水３１０ｇに香料（香水系）１０ｇ、界面活性剤０．３ｇを加えたものに代えたこと意外は実施例２および実施例１０と同様にして水性ゲル組成物（水性ゲル芳香剤）を得た。ゲル成分の種類および量並びに得られた水性ゲル芳香剤の評価結果を表５に示す。

[Examples 15 to 16]
(A) The water which melt | dissolves the water-soluble polymer of a component is the same as Example 2 and Example 10 except having replaced with the thing which added perfume (perfume type) 10g and surfactant 0.3g to 310g of water. Thus, an aqueous gel composition (aqueous gel fragrance) was obtained. Table 5 shows the types and amounts of the gel components and the evaluation results of the obtained aqueous gel fragrance.

[Comparative Example 8]
A carboxymethylcellulose sodium salt Daicel Chemical Industries, Ltd. CMC Daicel (registered trademark No. 1240) 8.75 g having a degree of etherification of 0.9 and a 1 wt% aqueous solution viscosity of 35 mPa · s in 14 g of PG And the dispersion was added to 300 g of water and dissolved by stirring. Further, 10 g of a fragrance (perfume type) and 0.3 g of a surfactant were added and dissolved. Next, 0.5 g of basic aluminum acetate was dispersed in 7 g of PG, the dispersion was added to the aqueous solution, and stirring was continued.

  Further, an aqueous solution obtained by dissolving 0.5 g of potassium alum and 0.7 g of lactic acid in 10 g of water was immediately added to the aqueous solution obtained above and transferred to a container with stirring. When allowed to stand at room temperature for 1 day, a transparent and uniform gel composition (gel fragrance) (gel strength: 11 g / cm 2) was obtained. The evaluation results of the obtained aqueous gel fragrance are shown in Table 5.

Since the aqueous gel composition of the present invention gels without heating, it can produce a gel product including those that decompose by heating and a transparent aqueous gel composition even when heating is impossible in the process. And can be applied to various gel compositions.

Claims (13)

  An aqueous gel composition comprising a water-soluble polymer comprising one or more glucan derivatives (hereinafter referred to as component (A)) and a water-soluble titanium compound (hereinafter referred to as component (B)).   The aqueous gel composition according to claim 1, wherein the component (A) is carboxymethylcellulose and / or an alkali metal salt thereof. The aqueous gel composition according to claim 1 or 2, wherein the component (B) is titanium lactate (chemical formula [TiC ₆ H ₁₀ O ₇ ]).   The aqueous gel composition according to any one of claims 1 to 3, wherein a molar ratio of the component (B) to the component (A) is 0.005 or more and 0.8 or less in the former / the latter. (B) molar ratio of component to component (A) (former / latter) (M), square root (SR) of viscosity (mPa · s) of 1% by weight aqueous solution of component (A), and component (A) The aqueous gel composition according to any one of claims 1 to 4, wherein a product of a weight ratio of water and water (the former / the latter) (C) is represented by the following formula.

(Formula) 1.5 ≦ M × SR × C × 100 ≦ 40
Each component constituting the aqueous gel composition comprises 2.5 to 10 parts by weight of carboxymethyl cellulose and / or its alkali metal salt as component (A), titanium lactate as component (B) (chemical formula [TiC ₆ H ₁₀ O ₇ ]) is 0.3 to 5.0 parts by weight and water is 80 to 100 parts by weight, and the viscosity of the 1% by weight aqueous solution (mPa · s) at 25 ° C. of component (A) is 5 to 1000 mPa · s. It is s, The aqueous gel composition of any one of Claims 1-5 characterized by the above-mentioned.   The molar ratio of the component (B) to the component (A) is 0.1 or more and 0.75 or less in the former / the latter, the gel strength is 10 g / cm or more and 700 g / cm or less, and the transparency is 10 cm or more. The aqueous gel composition according to any one of claims 1 to 6. Each component constituting the aqueous gel composition comprises 0.5 to 10 parts by weight of carboxymethyl cellulose and / or its alkali metal salt as component (A), titanium lactate as component (B) (chemical formula [TiC ₆ H ₁₀ O ₇ ]) is comprised of 0.02 to 3.0 parts by weight and water is 80 to 100 parts by weight, and the viscosity of the 1% aqueous solution (mPa · s) of component (A) at 25 ° C. is 4000 to 10,000 mPa · s. It is s, The aqueous gel composition of any one of Claims 1-5 characterized by the above-mentioned.   The molar ratio of the component (B) to the component (A) is 0.005 or more and 0.5 or less in the former / the latter, the gel strength is 10 g / cm or more and 700 g / cm or less, and the transparency is 10 cm or more. The aqueous gel composition according to any one of claims 1 to 5 and claim 8.   The aqueous gel composition according to any one of claims 1 to 9, comprising an additive that is weak against heat.   The aqueous gel composition according to any one of claims 1 to 10, comprising a fragrance.   The aqueous solution according to any one of claims 1 to 11, comprising at least one additive selected from deodorants, deodorants, antibacterial agents, antifungal agents, bactericides, and repellents. Gel composition. The method for producing an aqueous gel composition according to any one of claims 1 to 12, wherein the component (B) is added in a liquid state to the aqueous solution of the component (A).