JP2000192011A - Gelling agent for aqueous liquid and article prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gelling agent which can form an aqueous gel without using a compound toxic to humans, is easily dissolved in water for forming an aqueous gel, and can form an aqueous gel excellent in clarity and shape retention by combining gelatine with a reaction product of ammonia and an ethylenically unsaturated compound/maleic anhydride copolymer. SOLUTION: An aqueous gel is formed by the gelling reaction of (B) gelatine with (A) a reaction product of ammonia and an ethylenically unsaturated compound/maleic anhydride copolymer. Ingredient B in an amount of 100 pts. mass is reacted with ingredient B in an amount of about 3-50 pts.mass. Preferably, respective aqueous solutions of both the ingredients are prepared first, and then both the solutions are mixed and reacted with each other. Isobutylene and methyl vinyl ether are each especially preferable as the ethylenically unsaturated compound for ingredient A. An aqueous solution containing a substance having deodorant and/or fragrant properties is gelatinized with the gelling agent to give a deodorant and/or fragrant agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gelling agent for aqueous liquids and an aqueous gel or gel-like deodorant and / or fragrance gelled thereby.

[0002]

2. Description of the Related Art Conventionally, as a water-based gel type deodorant and / or fragrance, those using carrageenan as a gelling agent occupy the mainstream, but water separation phenomenon after freezing and thawing, gel deterioration, fragrance, etc. However, when the water-insoluble compound was blended, uniform gelation could not be formed. As a solution to the above problems, a reaction product (a) obtained by reacting ammonia with a copolymer of a vinyl compound or a vinylidene compound and maleic anhydride, a polyamine (b), and water (c) A gel obtained by subjecting a mixture obtained by mixing the above to a gelation treatment in a water-containing state (see Japanese Patent Publication No. 61-50493). It is a reaction product of gelatin or collagen and an olefin-maleic anhydride copolymer. An aqueous gelling agent and an aqueous gel (see Japanese Patent No. 2616960) are introduced.

[0003]

However, the above-mentioned method uses a polyvalent amine at the time of producing a hydrogel, and thus has a problem in the influence on the human body. The solubility was poor, and the transparency of the resulting aqueous gel was not satisfactory.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to obtain a gelling agent or deodorant and / or fragrance for aqueous liquid which has improved the above-mentioned problems. It was found that a reaction occurs when the ammonia reactant of the copolymer of the compound and maleic anhydride is combined with gelatin, and as a result of further developing the invention,
A water-based gel having good solubility in water of the raw material at the time of preparation without using a compound toxic to the human body at the time of preparation of the gel and having transparency and shape-retaining property was found. . The ammonia reactant of the above-mentioned copolymer becomes a water-based gel excellent in transparency and shape retention by performing a gelling reaction with gelatin. Furthermore, if desired, a molded article of a water-swellable resin which has been swollen in advance with water and / or an aqueous solution is added to the aqueous gel, and the molded article of the water-swellable resin is shaped like a character goods having interior properties. The present invention has been found to be easy to mold and to be able to enjoy the state of reduction while maintaining the shape together with the surrounding aqueous gel when used. That is, the present invention relates to a gelling agent for aqueous liquids comprising, as an essential component, a reaction product of an ammonia reactant (A) of a copolymer of an ethylenically unsaturated compound and maleic anhydride and a gelatin (B), Water-based gel, gel-like deodorant and / or fragrance, and articles thereof.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an ammonia reactant (A) of a copolymer of an ethylenically unsaturated compound and maleic anhydride was prepared as a copolymer of an ethylenically unsaturated compound and maleic anhydride. The product may be reacted with ammonia later, or a product obtained by copolymerizing a reaction product of maleic anhydride and ammonia with an ethylenically unsaturated compound may be used.
The former is obtained by reacting a copolymer obtained by copolymerizing an ethylenically unsaturated compound and maleic anhydride in a solvent with ammonia, and the latter is obtained in the presence or absence of a solvent. It is obtained by copolymerizing a reaction product of maleic acid and ammonia with an ethylenically unsaturated compound. Preferably the former. The ethylenically unsaturated compound used here is not particularly limited as long as it is an unsaturated compound capable of copolymerizing maleic anhydride, and specifically, for example,

(1) Olefin-based unsaturated compounds Linear or branched olefins having 2 to 24 carbon atoms [ethylene, propylene, butene-1, butene-2, isobutylene, n-pentene, isoprene, 2-methyl −
1-butene, n-hexane, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-pentene, 2-ethyl-1-butene, diisobutylene, 2-methyl-4-dimethyl-1 -Pentene, 2-methyl-4-
Dimethyl-2-pentene, dodecene, tetradecene, hexadecene, octadecene, vinylidene (vinylidene chloride, vinylidene fluoride, etc.)]; aromatic olefins (styrene, α-methylstyrene, α-methylstyrenesulfonic acid, etc.); halogen-containing olefins (Vinyl chloride, vinyl fluoride, ethylene tetrafluoride, etc.); nitrogen-containing olefins (nitroethylene, acrylonitrile, etc.); other olefins (allylamine, vinyl sulfonic acid, etc.);

(2) Non-olefinic unsaturated compound vinyl ether [methyl vinyl ether, polyoxyalkylene (n = 2 to 200) monoallyl monoalkyl (C1 to C24) ether, etc.]; carbon of alkyl group and hydroxyalkyl group Number is 1-2
2, alkyl (meth) acrylates or hydroxyalkyl esters (methyl acrylate, methyl methacrylate, n-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hexyl acrylate, behenyl acrylate, etc.) Carboxyl group-containing (meth) acrylic acid ester [(meth) acrylic acid, monoalkyl maleate, fumaric acid, itaconic acid, glycol itaconate monoether, etc.]; unsaturated compound containing sulfonic acid group [3-sulfopropyl (Meth) acrylates and the like]; phosphoric acid group-containing unsaturated compounds [hydroxyalkyl (meth) acrylate monoester, 2-hydroxyethyl (meth) acryloyl phosphate and the like];

Acrylamide [(meth) acrylamide, N-methyl (meth) acrylamide, etc.]; tertiary amine or quaternary ammonium base-containing unsaturated compound [dimethylaminoethyl (meth) acrylate, quaternized product thereof (methyl chloride, Quaternized with a quaternizing agent such as dimethyl sulfate, benzyl chloride or dimethyl carbonate), etc.]: an epoxy group-containing unsaturated compound [glycidyl (meth) acrylate, etc.]; other (N-vinylpyrrolidone, propionic acid) Vinyl, vinyl alcohol obtained by saponifying vinyl acetate, etc.); Of these, linear or branched olefins having 2 to 24 carbon atoms and vinyl ethers, preferably isobutylene, methyl vinyl ether and polyoxyalkylene monoallyl monoalkyl ether, and particularly preferably isobutylene and methyl Vinyl ether. These monomers may be used alone or in combination of two or more.

In the polymerization, the above ethylenically unsaturated compound and maleic anhydride can be polymerized in the presence or absence of a solvent by a known method such as thermal radical polymerization, photoradical polymerization, or anionic polymerization. The polymerization is carried out, for example, at 0 to 200 ° C. under normal pressure or under pressure. In the case of thermal radical polymerization, an azo compound (such as azobisisobutyronitrile), a peroxide (t-
Butyl peroxybenzoate, etc.), and in the case of photoradical polymerization, a photoradical initiator (benzoin alkyl ether, etc.) and a sensitizer (anthraquinone, etc.)
In the case of anionic polymerization, a Ziegler-Natta catalyst, a metallocene catalyst or the like is used in combination. The obtained copolymer may be used after removing the solvent, or may be used in the presence of the solvent. Preferably, the solvent is removed. The composition ratio of the ethylenically unsaturated compound and maleic anhydride in the polymer may be any as long as the ammonia reactant of the produced copolymer is soluble in water. The composition ratio of maleic anhydride to the ethylenically unsaturated compound is usually from 100: 1 to 1: 100, preferably from 10: 1 to 1:10, and particularly preferably from 5: 1 to 1: 5 in molar ratio. It is. The molecular weight of the produced copolymer is generally 2,000 to 5,000,000, preferably 3,000 to 3,000,000.

Various methods can be adopted for the reaction between the copolymer and ammonia. The solid powder of the copolymer is dispersed in a slurry in a solvent, and the ammonia gas is brought into contact with the solvent while bubbling. A method or a method of dissolving the copolymer powder in aqueous ammonia is preferably employed. The reaction ratio of the copolymer to ammonia is 0.5 to 2 moles, preferably 0.8 to 2 moles of ammonia per mole of maleic anhydride groups contained in the copolymer. The viscosity of the aqueous solution of the reaction product (at a concentration of 5% by weight) at 25 ° C. is usually from 5 to 100,000 cps, preferably from 10 to 10,000 cps, particularly preferably from 15 to 5,000.

In the present invention, gelatin (B) includes
In addition to alkali-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate can also be used.
What is necessary is just to have at least one free amino group.
For example, after removing bovine bone minerals to make ossein,
It is immersed in a suspension of slaked lime, the cowhide is cut to a suitable size, washed with water and then immersed in a lime solution for usually 2 to 3 months. Gelatin obtained by performing such pretreatment with a lime solution is called alkali-treated gelatin. On the other hand, gelatin obtained by immersing pig skin in diluted hydrochloric acid or diluted sulfuric acid for several tens of hours is called acid-treated gelatin. Gelatin may be in the form of granules, powders or sheets, and the molecular weight is preferably from 3,000 to 30,000. In particular, in order to obtain the transparency and shape retention of the gel, the molecular weight is 50,000.
00 to 20,000 is preferred.

The reaction between the ammonia reactant (A) of the copolymer of the ethylenically unsaturated compound and maleic anhydride and the gelatin (B) is as follows: Presumed. When ammonia reacts with the copolymer of the ethylenically unsaturated compound and maleic anhydride, the maleic anhydride portion in the copolymer is cleaved to form a mixture of partial amide and ammonium salt.
This structure is (A), and this amide group reacts with the amino group of the lysine residue of gelatin (B), NH3 is eliminated and a new amide bond is formed. As a result, a three-dimensional structure (gel) is formed. Is presumed to be formed.

[0013]

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In the reaction of the ammonia reactant (A) of the copolymer of the ethylenically unsaturated compound and maleic anhydride with the gelatin (B), the proportion used cannot be specified unconditionally by the number of free amino groups of the gelatin. In order to obtain transparency and shape retention, it is preferable to react (A) with 3 to 50 parts by mass, preferably 5 to 40 parts by mass, per 100 parts by mass of (B). Examples of the reaction method of (A) and (B) include a method of directly mixing (A) and (B), a method of mixing (B) with an aqueous solution of (A), and a method of mixing (A) with an aqueous solution of (B). There is a method of mixing (A) and (B) before preparing each aqueous solution, and then mixing both. However, a preferable method is that a uniform gel is easily obtained.

As the reaction between (A) and (B) progresses, the viscosity of the system increases. It gels as it proceeds further. The end point of the reaction can be confirmed by the gel strength. The method for measuring the gel strength is described below. The temperature at which (A) and (B) are reacted is not particularly limited. For example, when the reaction is performed at 40 to 60 ° C., the reaction is completed within several hours, and when the reaction is performed at room temperature, one day and night are required. . The gel strength of the reaction product of (A) and (B) is usually from 3 to 1,000 g, preferably from 5 to 600, particularly preferably from 10 to 500. (Measurement method of gel strength) After the temperature of the gel was adjusted to 25 ° C, a rod having a metal ball having a diameter of 15.7 mm was connected to a Shimadzu autograph (AGS-500B, manufactured by Shimadzu Corporation). 5cm metal ball
/ Min was pressed into the gel, and the stress (g) immediately after the metal sphere completely entered the gel was measured. This is the gel strength (g). After the reaction between (A) and (B), an aqueous gel having high transparency is obtained. Transparency can be measured by transmittance (%). The transmittance (%) of the aqueous gel is usually 70 to 10
0, preferably 80-100, particularly preferably 90-1
00. (Measurement method of transmittance) After leaving the gel in a 10 mm thick glass cell at room temperature for 1 day to adjust the temperature to 25 ° C, a spectrophotometer (UV-1200, manufactured by Shimadzu Corporation)
, The transmittance of visible light (700 nm) was measured.

As the aqueous liquid used here, other additives and the like can be mixed in addition to (A) and (B). There are no particular restrictions on what can be mixed, as long as it is water-soluble or water-insoluble, but examples thereof include solvents (alcohol, acetone, etc.), pigments, dyes, antioxidants, ultraviolet absorbers, surfactants, preservatives and the like. Any concentration of these compounds can be used according to the purpose. However, if a water-insoluble additive is blended, the transmittance is reduced. Therefore, in order to obtain the transparency that is a feature of the article of the present invention, the water-insoluble one is blended in a small amount so that the transmittance becomes 70% or more. There is a need to. Prepare these aqueous solutions in advance (A)
It may be mixed with the aqueous solution of (B) or from the beginning (A)
You may make it coexist and mix with (B). (A) (B)
In mixing, the necessary additives must be mixed. Further, the water-based gel of the present invention can be used as an article having a specific purpose by including a deodorant and / or aromatic substance (C) or a molded article of a water-swellable resin.

In the present invention, the substance (C) having a deodorant property and / or an aromatic property may be a substance generally used as a substance having a deodorant property, an aromatic property or a deodorant and aromatic property. , Is not particularly limited. Examples of substances having deodorant properties include, for example, extracted substances from plants such as rice, pine, hinoki, bamboo grass, and acidic or alkaline aqueous liquids, which were diluted with water or an aqueous solution partially containing a solvent. It can be an aqueous liquid. Examples of the substance having an aromatic property include natural flavors and synthetic flavors. These are aqueous solutions of water-soluble substances, and water-emulsifiers of non-water-soluble substances, and aqueous emulsions of solvents and the like as necessary. Alternatively, it can be an aqueous liquid. Here, since the substance having an aromatic property has a masking effect, it may be said that the substance has a deodorizing property in practical use.

Examples of natural flavors include animal flavors such as jasper, spirit cat and dragon fragrant, avies oil, aziyokun oil, almond oil, angelica root oil, basil oil, bergamot oil, birch oil, boa rose oil, kayabute Oil, cananga oil, turnip oil, caraway oil, cardamom oil,
Cassia oil, celery oil, cinnamon oil, citronella oil,
Cognac oil, Coriander oil, Cubeb oil, Cumin oil, Camphor oil, Jill oil, Estgolan oil, Eureka oil, Fuennel oil, Garlic oil, Ginger oil, Grapefruit oil, Hop oil, Juniper berry oil, Laurel leaf oil, Lemon oil, Lemongrass oil, robe oil, mace oil, nutmeg oil, mandarin oil, tangerine oil, mustard oil, seaweed oil, lantern oil, onion oil, pepper oil, orange oil, sage oil, star anise oil, turpentine oil, warmwood oil And vegetable flavors such as crocodile bean extract.

Examples of the synthetic fragrance include hydrocarbons such as pinene and limonene, alcohols such as linalool, geraniol, citroneol, menthol, borneol, benzyl alcohol, anis alcohol and β-phenylethyl alcohol, and phenols such as anenol and eugenol. , N-butyraldehyde, isobutyraldehyde, hexyl aldehyde, heptyl aldehyde, n
Aldehydes such as nonylaldehyde, nonadienal, citral, citronellal, benzaldehyde, cinamic aldehyde, heliotropin, varnish,
Ketones such as methyl amyl ketone, methyl nonyl ketone, diacetyl, acetyl propionyl, acetyl butyrine, carvone, menthone, camphor, acetophenone, P-methyl acetophenone, ionone, amyl butyrolactone, ethyl methyl phenyl glycidate, γ-nonyl lactone Lactones or oxides such as coumarin, cineol, methylformate, isopropylformate, linaloolformate, ethyl acetate, octyl acetate, menthyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate,
Isoamyl acetate, isopropyl isobutyrate, geranyl isovalerate, allyl caproate, butyl heptylate, octyl caprylate, methyl heptine carboxylate, ethyl berahagonate, methyl octyne carboxylate, isoacyl caprate, methyl laurate, ethyl myristate , Ethyl benzoate, benzyl benzoate, methyl phenylacetate,
Includes esters such as butyl phenylacetate, methyl cinnamate, cinnamyl cinnamate, methyl sarinate, ethyl anisate, methyl anthranilate, ethyl bilbate, and ethyl α-butyl butyrate.

The fragrance may be only one kind or two or more kinds. Along with the fragrance, a volatile retention agent such as batchuri oil, a modulator such as eugenol, and other various components used in the fragrance industry may be added. The amount of the fragrance used depends on the type thereof, but is usually 0.1 to 15% of the total mass. In the present invention, other additives can be blended into the aqueous liquid of the substance (C) having a deodorant property and / or an aromatic property, if necessary. Examples of the additive include a pigment (including a fluorescent pigment and a luminous pigment), a dye, an antioxidant, an ultraviolet absorber, a preservative,
Examples include fungicides, defoamers, oxygen absorbers, antioxidants, surfactants, alcohols, fillers, extenders, and the like.

In the present invention, the molded article (D) of the water-swellable resin may be one or more, and may be present anywhere in the container, but is fixed to at least a part of the container. It is preferred that By being fixed, when gelling is performed using the gelling agent for an aqueous liquid, movement is prevented. When (D) is fixed, it is particularly preferable that it is fixed to the bottom surface of the container from the viewpoint of stability. The fixing position when fixed to the bottom surface may be the entire bottom surface or a part of the bottom surface, and if it is a part, the fixing position is not particularly limited to a central portion, a peripheral portion, or the like. The method of fixing is not particularly limited, and may be any method such as adhesion with an adhesive or insertion into a pin protruding from the bottom of the container.

In the present invention, the water-swellable resin molded article (D) includes (D1) a rubber and / or a synthetic resin into which a hydrophilic group is introduced, and (D2) a rubber and / or a synthetic resin (1). Kneaded product with water-thickening polymer (2), (D3)
A kneaded product of rubber and / or synthetic resin (1) and water-absorbing resin (3) is exemplified. (D1), (D2), (D3)
As the rubber and / or synthetic resin (1) used in the above, all those included in the category of ordinary rubber or synthetic resin are used and are not particularly limited. For example, as rubber, other than normal natural rubber, styrene butadiene rubber, butadiene rubber, isoprene rubber, butyl rubber, ethylene propylene rubber, ethylene propylene non-conjugated diene rubber, chloroprene rubber, nitrile rubber, urethane rubber, acrylic rubber, chlorosulfonated polyethylene And various synthetic rubbers such as chlorinated polyethylene.

The synthetic resin may be either thermosetting or thermoplastic, and may be either soft or hard. For example, ethylene-vinyl acetate copolymer or its saponified product, polychlorinated Vinyl, vinyl chloride copolymer, polyethylene, polypropylene, polyethylene-acrylate copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, polyester, polyamide resin, acrylic resin, styrene resin, etc. It is preferable that the material has such flexibility that the volume can be expanded by water absorption. When a hard material is used, it is preferable to use a suitable plasticizer to impart flexibility.

Examples of the hydrophilic group (D1) include polyethylene oxide blocks, carboxyl groups and salts thereof, sulfonic acid groups and salts thereof, and hydroxyl groups. Compounds containing these blocks and functional groups are used for producing rubber and synthetic resins. It is sometimes blended or reacted and incorporated. For example, as a synthetic resin into which a hydrophilic group has been introduced, a urethane resin using a polyether polyol obtained by addition polymerization of ethylene oxide as a raw material may be used. (D1) preferably has a rubber and / or synthetic resin (1) content of 20 to 95% by mass and a hydrophilic group portion of 5 to 80% by mass. If the content of the hydrophilic group in (D1) is less than 5% by mass, the amount of water or aqueous liquid absorbed decreases. On the other hand, when the amount of the hydrophilic group is more than 80% by mass, molding may be difficult.

Examples of the water-thickening polymer (2) include natural water-thickening polymers, semi-synthetic water-thickening polymers and synthetic water-thickening polymers. Natural water-thickening polymers include starch (starch); animal proteins (gelatin, casein, collagen); plant proteins (soy proteins, wheat proteins); fibrin (wood cellulose); seaweed extracts (agar, carrageenan) Plant seed mucilage (guar gum, locust bean gum, etc.); plant tree leaf mucilage (gum arabic, tragacanth gum); plant fruit mucilage (pectin); Mucilage (konnyakunanman)
And the like.

The semisynthetic water-thickening polymer includes cellulose derivatives (methyl cellulose, ethyl cellulose,
Carboxymethylcellulose); starch derivatives (soluble starch, carboxymethyl starch, etc.); and alginic acid derivatives (alginate, propylene glycol alginate). As the synthetic water-thickening polymer, a polyoxyalkylene compound (b
1), acrylic water thickening polymer (b2), vinyl water thickening polymer (polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, etc.), isobutylene-maleic anhydride copolymer and the like. Examples of the polyoxyalkylene compound (b1) include polyethylene glycol, polyethylene oxide (high-molecular-weight polymer of ethylene oxide), alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts of polyhydric alcohols, polyoxyethylene oxypropylene glycol ( Block or random copolymer of ethylene oxide and propylene oxide). The molecular weight of the polyoxyalkylene compound is usually from 1,000 to 2,000,000.

Examples of the acrylic water-thickening polymer (b2) include (meth) acrylamide, (meth) acrylic acid (salt) [eg, sodium acrylate], and 2-alkyl-2-acrylamidopropanesulfonic acid (salt). [2
-Alkyl-2-acrylamidopropanesulfonic acid sodium salt], (meth) acryloyloxyalkyltrialkylammonium quaternary salt [for example, methacryloyloxyethyltrimethylammonium chloride], (meth) acryloyloxyalkyldialkylamine salt [for example,
Tertiary or quaternary diethylaminoethyl methacrylate
Water-thickening polymer having at least one vinyl monomer selected from the group consisting of
Specific examples thereof include poly (meth) acrylamide, poly (meth) acrylic acid (salt), acrylic acid-acrylate copolymer, partially hydrolyzed poly (meth) acrylamide, and (meth) acrylic acid (salt). ) And (meth) acrylamide and 2-acrylamido-2-methylpropanesulfonic acid (salt) or a copolymer of (meth) acrylamide and (meth) acryloyloxyethyltrimethylammonium quaternary salt.

(D2) is a water-thickening polymer (2) containing 20 to 95% by mass of rubber and / or synthetic resin (1).
Is preferably 5 to 80% by mass. When the content of (2) in (D2) is less than 5% by mass, the amount of water or aqueous liquid absorbed decreases. On the other hand, when (2) is more than 80% by mass,
Molding may be difficult. The water-absorbing resin (3) is selected from, for example, a water-soluble monomer containing starch or cellulose (A) and a hydrophilic group such as a carboxyl group or a sulfonic acid group and / or a monomer that becomes water-soluble by hydrolysis. The water-absorbing resin obtained by polymerizing one or more kinds of the monomers (b) and the crosslinking agent (c) as essential components and performing hydrolysis as required is mentioned. The proportions of (a), (b) and (c) used in the production of the water-absorbing resin exemplified above, the production method and specific examples of the water-absorbing resin are described in JP-A-52-25886 and JP-B-53-46199. And JP-B-53-46200 and JP-B-55-21041.

Examples of the water-absorbing resin other than those exemplified above include, for example, those obtained by polymerizing (a) and (b) (hydrolyzate of starch-acrylonitrile graft polymer,
A crosslinked product of (a) (such as a crosslinked product of carboxymethyl cellulose); a copolymer of (b) and (c) (a partially hydrolyzed product of crosslinked polyacrylamide, Crosslinked acrylic acid-acrylamide copolymer, crosslinked sulfonated polystyrene, saponified vinyl ester-unsaturated carboxylic acid copolymer described in JP-A-52-14689 and JP-A-52-27455, crosslinked Polyacrylic acid (salt), crosslinked acrylic acid-acrylate copolymer, crosslinked isobutylene-maleic anhydride copolymer, and crosslinked carboxylic acid-modified polyvinyl alcohol); and self-crosslinking (B) a polymer (e.g., a self-crosslinkable polyacrylate)
Further, two or more of the above-described water-absorbing resins may be used in combination.

Among these water-absorbing resins, more preferred are, among those exemplified above, a crosslinked polyacrylamide copolymer, a crosslinked polyacrylic acid (salt), a crosslinked acrylic acid-acrylate ester A copolymer, a crosslinked isobutylene-maleic anhydride copolymer, and a crosslinked carboxylic acid-modified polyvinyl alcohol. The absorption capacity of water or aqueous liquid with respect to the mass of the water-absorbent resin (3) is preferably 10 to 1,000.
It is 0 times, and more preferably 100 to 1,000 times. As the shape of the water-absorbent resin (3), powder or granular one can be used, but one having a uniform particle size is preferable because the shape of the water-absorbent resin after swelling becomes uniform. In the present invention, the absorption capacity of the water-absorbent resin is a value obtained by measuring by the following method.

<Absorbency of Water Absorbent Resin> A sample (sample amount: Eg) of a water absorbent resin was placed in a nylon mesh bag (250 mesh), and this bag was immersed in excess water or aqueous liquid. After 60 minutes of immersion, the bag was pulled up into the air, allowed to stand and drained for 15 minutes, and then the mass (Fg) was measured to determine the absorption capacity from the following formula. [The same operation as above was performed using only the net bag, and the mass (Gg) for this was subtracted as a blank. Absorbency = (FG) / E Among (D1) to (D3), the water-absorbent resin (3) is used (D3), but the swelling speed is high and the aqueous liquid dissolves even after swelling. This is preferable because the shape is maintained without being projected.

The absorption capacity of water or aqueous liquid with respect to the mass of the water-absorbent resin (3) is preferably from 10 to 1,000 times, more preferably from 100 to 1,000 times. or,
The water-absorbent resin (3) is preferably in the form of powder or granules, and particularly preferably those having an average particle size of 200 μm or less. If the average particle size is larger than 200 μm, when the molded body swells, it may have a distorted shape, and the falling off from the molded body may be increased. (D3) is a rubber and / or
Alternatively, it is preferable that the synthetic resin (1) is 20 to 95% by mass and the water absorbent resin (3) is 5 to 80% by mass. When the content of (3) in (D3) is less than 5% by mass, the amount of water or aqueous liquid absorbed decreases. On the other hand, when the content of (3) is more than 80% by mass, molding becomes difficult, and even if molding can be performed, the water-absorbing resin may fall off. In the present invention, the water-swellable resin molded article (D) may optionally contain other additives. Examples of the additive include a pigment (including a fluorescent pigment and a phosphorescent pigment), a dye, an antioxidant, an ultraviolet absorber, a preservative, a surfactant, a plasticizer, and a filler. Molded product (D) of the water-swellable resin
Absorbs water or an aqueous liquid [for example, the above-mentioned aqueous liquid of the substance (C) having deodorant and / or aromatic properties], and preferably 5 to 200 times, more preferably 5 to 200 times the mass of (D). Preferably, it has the property of swelling 10 to 100 times.

In the present invention, the absorption capacity of the water-swellable resin is a value obtained by measurement according to the following method.
<Absorption capacity of water-swellable resin> Nylon mesh bag (250
A sample of water-swellable resin (sample amount; H)
g) was put, and the bag was immersed in excess water or aqueous liquid. Pull the bag up into the air every 24 hours and let it stand still for 1 hour.
After draining for 5 minutes, the mass (Ig) was measured, and the absorption capacity was determined by the following formula. [The same operation as above was performed using only the net bag, and the mass (Jg) of this was subtracted as a blank. However, the point at which the absorption capacity at each measurement time reached equilibrium (the rate of change of mass was within 3%) was defined as the absorption capacity of the water-swellable resin. Absorption magnification = (I-J) / H

As a typical example of the method for producing the water-swellable resin molded article (D), a water-swellable resin (D) using a water-absorbent resin (3) is used.
As an example of the method for producing a molded article of 3), (1)
Except for kneading (3) and the like using a kneader such as a roll mixer, a Banbury mixer, a kneader, a general method of producing rubber and / or synthetic resin may be used. In the case of a vulcanized rubber product, for example, It comprises a mastication step, a mixing step, a molding step, a vulcanization step and the like. In particular, a method for producing a mold product is preferable. For example, in a molding and vulcanizing step, it can be produced by a press vulcanization method, a transfer vulcanization method or an injection molding vulcanization method. In the case of the water-swellable resin (D2), a molded article can be produced in the same manner as described above except that the water-absorbing resin (3) is replaced with the water-thickening polymer (2). Here, in the mixing step,
In addition to (1) and (3), rubber chemicals generally used in rubber processing as required, such as vulcanizing agents or crosslinking agents,
Vulcanization accelerators, vulcanization accelerators and the like are used.

The shape of the molded article of (D) of the present invention is not particularly limited. However, in consideration of the case where the molded article is used in a room, a toilet, a car, and the like, a character goods, a moving object, a moving object, etc. A miniature shape of an object such as a plant, a terrain, a building, or a transportation device is preferable. The container used in the present invention is not particularly limited, and examples thereof include a cylinder, a prism, a cone, a pyramid, and a sphere having a flat bottom. Further, the material of the container may be glass or synthetic resin. As the synthetic resin, all that are included in the category of ordinary synthetic resins are used and are not particularly limited. Regardless of thermoplastic or thermosetting as synthetic resin,
Any of soft and hard materials can be used. For example, ethylene-vinyl acetate copolymer or a saponified product thereof, polyvinyl chloride, vinyl chloride copolymer, polyethylene, polypropylene, polyethylene-acrylate copolymer can be used. Polymer, acrylonitrile-butadiene copolymer,
Styrene-butadiene copolymer, polyester, polyamide resin, acrylic resin, styrene resin and the like can be mentioned. Further, it is preferable that at least a part of the container is a transparent container so that the inside of the container can be enjoyed through the container from the side. Molded product (D) of the water-swellable resin
May be colored or uncolored, but is preferably colored from the viewpoint of visual effect, and at least (D) is particularly preferably colored differently from the aqueous gel.

[0036]

EXAMPLES Hereinafter, deodorizing and / or using the aqueous gel of the present invention will be described.
Alternatively, the present invention will be described with reference to the drawings showing examples of the fragrance.
1 and 2 are perspective views showing one embodiment of the deodorant and / or fragrance of the present invention. FIG. 3 is a cross-sectional view showing a state after an aqueous liquid of a substance having a deodorant property is charged into the container of FIG. 1 and uniformly stirred. 1 to 3, reference numeral 1 denotes a molded product of a water-swellable resin, 2 denotes an aqueous liquid of a deodorant substance, 3 denotes a glass container, 4 denotes a cap, and 5 denotes an adhesive. FIG.
, The water-swellable resin (D) has a mushroom shape, and the bottom surface is fixed to the center of the bottom of the container with an adhesive. In FIG. 2, the water-swellable resin (D) has a mountain shape of Mt. Fuji type, and is fixed to the entire bottom surface of the container with an adhesive. As described above, the shape of the molded body of (D) is not limited to this, and may be any of character goods, animals and plants, terrain, buildings, transportation equipment, etc., and the number of molded bodies is not limited to one but may be plural. There may be. Further, the position fixed to the bottom surface of the container is not limited. As examples of the shape of the molded body (D) other than those shown in FIGS. 1 and 2, there are a plurality of horseshoe-shaped ones and a toy train-shaped one round around the container. And so on.

FIG. 4 is a sectional view showing the state after FIG. 3 has been left for four days. In FIG. 4, reference numeral 1 'denotes a water-swellable resin molded article (D) which has absorbed a part of the deodorant liquid and the gelatin solution and swelled about 40 times. Reference numeral 2 denotes an aqueous liquid of a deodorant substance, 3 denotes a glass container, 4 denotes a cap, and 5 denotes an adhesive. FIG. 5 shows that an aqueous solution of gelatin and an aqueous solution of a reaction product obtained by reacting ammonia with a copolymer of methyl vinyl ether / succinic anhydride are further added to the container of FIG. It is sectional drawing which showed the state of the aqueous | water-based gel produced | generated around the molded object of 1 'by leaving. 3 is a glass container, 4 is a cap, 5 is an adhesive, and 6 is an aqueous gel. A water-swellable resin molded article was contained in the aqueous gel in the course shown in FIGS. 3 to 5. When used as a deodorant, of course, the lid is opened and used, and over time, the molded body of the water-swellable resin becomes smaller with the surrounding water-based gel, and after two months, the state shown in FIG. Return to Since the shape of the mushroom changes as described above, the process of reducing the mushroom can be enjoyed, and the indicator also functions as an indicator for indicating the remaining amount of the deodorant. Hereinafter, the present invention will be further described with reference to Examples showing Production Examples and Use Examples, but the present invention is not limited thereto. The following parts represent parts by mass.

Example 1 (1) Preparation of Solution A Deionized water (750 parts) was added to gelatin SE-1 (45 parts) and sugar (5 parts), and the mixture was heated to 60 to 70 ° C. and uniformly dissolved. . Note) Gelatin SE-1: alkali-treated gelatin, manufactured by Nippi Gelatin Kogyo Co., Ltd. (2) Preparation of Solution B Nonipol 120 (50 parts) was added to floral flavor (50 parts).
Parts), ethanol (30 parts) and propylene glycol (20 parts) were added and uniformly dissolved. Note) Nonipol 120: polyoxyethylene nonyl phenyl ether-based nonionic surfactant, manufactured by Sanyo Chemical Industry Co., Ltd. (3) Preparation of solution C Ion-exchanged water (84 parts) and ammonia content 29 in GantazAN 119 (10 parts) % Ammonia solution (6 parts) and stirred at room temperature to dissolve uniformly in 1 hour. G uniformly dissolved with an ammonia neutralization rate of 80%
An aqueous solution of anterzAN119 was obtained. Note) Ganterz AN119: methyl vinyl ether / maleic anhydride copolymer, weight average molecular weight 2.13
× 10 ⁶ , manufactured by ASP Japan Co., Ltd. (4) Preparation of gel-like fragrance Solution A (40 parts) was mixed with solution B (9 parts), solution C (2 parts) and ion-exchanged water (49 parts). In addition, a uniform and transparent aqueous solution was prepared. The aqueous solution obtained in this way is treated at room temperature with 1
After standing for a day, a gelation reaction was performed to obtain a uniform and transparent aqueous gel.

Example 2 (1) Preparation of Solution D Ion-exchanged water (82.5 parts) and aqueous ammonia solution (7.5 parts) containing 29% ammonia were added to Gantaz AN 119 (10 parts) and stirred at room temperature. Then, it was uniformly dissolved in 30 minutes. A uniformly dissolved aqueous solution of GanterzAN119 having an ammonia neutralization ratio of 100% was obtained. (2) Preparation of gel-like fragrance Example 1 was prepared in the same manner as in solution A (79 parts) prepared in Example 1.
The solution B (9 parts) and the solution D (12 parts) prepared in the above were added to prepare a uniform and transparent aqueous solution. The aqueous solution thus obtained was allowed to stand at room temperature for one day to perform a gelling reaction, thereby obtaining a uniform and transparent aqueous gel.

Example 3 (1) Preparation of Solution E To Isovan-04 (10 parts), ion-exchanged water (84 parts) and an aqueous ammonia solution having an ammonia content of 29% (6 parts) were added and stirred at room temperature to obtain 1 Dissolved uniformly over time. Isovan-04 uniformly dissolved with an ammonia neutralization ratio of 80%
Was obtained. Note) Isoban-04: isobutylene / maleic anhydride copolymer, molecular weight 6 × 10 ⁴ , manufactured by Kuraray Co., Ltd. (2) Preparation of gel-like fragrance Example 1 was prepared in the same manner as solution A (79 parts) prepared in Example 1.
The solution B (9 parts), the solution E (8 parts) and the ion-exchanged water (4 parts) prepared in the above were added to prepare a uniform and transparent aqueous solution. The aqueous solution thus obtained was allowed to stand at room temperature for one day to perform a gelling reaction, thereby obtaining a uniform and transparent aqueous gel.

Example 4 (1) Preparation of Solution F Deionized water (82.5%) was added to Isovan-04 (10 parts).
Parts) and an aqueous ammonia solution (7.5 parts) having an ammonia content of 29% were added and stirred at room temperature to dissolve uniformly in 30 minutes. A homogeneously dissolved aqueous solution of Isovan-04 having an ammonia neutralization ratio of 100% was obtained. (2) Preparation of gel-like fragrance Example 1 was prepared in the same manner as in solution A (40 parts) prepared in Example 1.
The solution B (9 parts), the solution F (6 parts) and ion-exchanged water (45 parts) prepared in the above were added to prepare a uniform and transparent aqueous solution. The aqueous solution thus obtained was allowed to stand at room temperature for one day to perform a gelling reaction, thereby obtaining a uniform and transparent aqueous gel.

Example 5 (1) Preparation of Solution G As a substance having a deodorizing property, Eporion N-1000 was used.
(4 parts) and ion-exchanged water (52 parts) were added and uniformly dissolved. Note) Eporion N-1000: vegetable organic acid and organic acid salt, manufactured by Eporion Co. (2) Preparation of gel deodorant Solution G (56 parts) was added to solution A (40 parts) prepared in Example 1.
Parts) and the solution C prepared in Example 1 (4 parts) were added to prepare a uniform and transparent aqueous solution. The aqueous solution thus obtained was allowed to stand at room temperature for one day to perform a gelling reaction, thereby obtaining a uniform and transparent aqueous gel.

Example 6 (1) Preparation of Molded Product of Water-Swellable Resin A mixture of the following blending ratio was mixed at 150 ° C. with a kneader at 1 ° C.
The mixture was kneaded for 5 minutes and pressed into a mushroom-shaped mold with an expanded umbrella. The molded product was taken out to obtain a 1.8 g mass of the water-swellable resin of the present invention. The molded product thus obtained was combined with the solution B (9 parts) prepared in Example 1 and ion-exchanged water (1).
21 parts) was added to the uniformly dissolved aqueous liquid. Four days after immersion at room temperature, the molded product of the water-swellable resin in the aqueous liquid had greatly swollen. The molded body of the water-swellable resin was taken out and weighed 72 g. The shape of the swollen water-swellable resin molded article was large while maintaining the shape before swelling without distortion. Sunfresh ST-500MPS 53 parts Elastran ET1040 43 parts Phthalocyanine pigment 4 parts Note) Sunfresh ST-500MPS: acrylic water-absorbent resin, average particle size 20-50 microns, water absorption performance 40.
0 g / g, manufactured by Sanyo Chemical Industries, Ltd. Elastran ET1040: thermoplastic urethane resin, manufactured by Takeda Birdish Urethane Industries

(2) Preparation of gel-like fragrance containing molded article of water-swellable resin Prepared in Example 1 in an aqueous liquid containing a molded article of water-swellable resin swelled in the above aqueous liquid. A uniform and transparent aqueous liquid was prepared by adding the solution C (2 parts) prepared in Example 1 in the same manner as the solution A (40 parts). The aqueous solution thus obtained was allowed to stand at room temperature for one day to perform a gelling reaction, thereby obtaining a uniform and transparent aqueous gel containing a molded article. This was left indoors. The shape of the swollen water-swellable resin molded article gradually decreased with the water-based gel while maintaining the initial shape due to volatilization of the aromatic liquid, and returned to the size almost before the swelling after two months.

Comparative Example 1 (1) Preparation of Solution H Ion-exchanged water (90 parts) was added to Gantaz AN119 (10 parts) and stirred for 6 hours.
N119 was not dissolved in water, and a dispersed aqueous solution of GanterzAN119 was obtained. (1) Preparation of gel-like fragrance Example 1 was prepared in the same manner as in solution A (40 parts) prepared in Example 1.
The solution B (9 parts), the solution H (2 parts) in a uniformly dispersed state, and the ion-exchanged water (49 parts) were added and stirred for about 1 hour. Was not obtained. The aqueous liquid thus obtained was allowed to stand at room temperature for one day to perform a gelling reaction, but did not gelate.

Comparative Example 2 (1) Preparation of Solution I Nonipol 120 (50 parts) was added to a floral flavor (50 parts).
Parts), ethanol (30 parts), propylene glycol (20 parts) and GantazAN119 (4 parts) were added and stirred for 6 hours. However, GantazAN119 was not dissolved, and an aqueous solution of GantazAN119 was obtained. (1) Preparation of gel-like fragrance Solution I (9.3 parts) uniformly dispersed in solution A (40 parts) prepared in Example 1 and ion-exchanged water (50.7)
Part) and stirred for about 1 hour.
119 precipitated and a uniform aqueous solution was not obtained. The aqueous solution thus obtained was allowed to stand at room temperature for one day to perform a gelling reaction, but did not gelate. Example 1
Table 1 shows the evaluation results of Comparative Example 5 and Comparative Examples 1 and 2.

[0047]

[Table 1]

The evaluation method is as follows. (1) Appearance of gel (1) The appearance of the gel prepared by being left at room temperature for one day is visually judged,
The evaluation was as follows. ○: Transparent △: Slightly cloudy ×: Cloudy (2) Appearance of gel (2) Appearance of gel The gel used in (1) was frozen at -20 ° C for 16 hours and left at room temperature for 8 hours. The appearance of the gel when thawed and reconstituted was visually judged and evaluated as follows. ○: No change △: Slight change ×: Change

(3) Transmittance The transmittance was measured according to the evaluation method described above. (4) Low-temperature stability The gel used in the appearance of the gel (1) was placed in a thermostat at 0 ° C. for 24 hours.
After leaving for a time, the presence or absence of the separated material was examined. ○: No change △: Slight water separation ×: Water separation (5) High temperature stability The gel used in the appearance of gel (1) was placed in a 70 ° C.
After leaving for 4 hours, it was examined whether the gel was broken and became liquid. …: No change Δ: Slightly broken and liquid X: Liquid (6) Gel strength The gel strength was measured according to the method described above.

[0050]

The deodorant and / or fragrance of the present invention has the following features. Since the deodorant and / or fragrance of the present invention has good shape retention,
When the container is moved or dropped, it is easy to handle without deformation or spillage. Since the deodorant and / or fragrance of the present invention has a transparent feeling,
Excellent aesthetics. During use, you can enjoy the state where the molded body of the water-swellable resin gradually becomes smaller while maintaining its shape,
In addition, it also functions as an indicator that shows the remaining amount of the deodorant. Since the solubility of the raw material in water is good, the gelling agent for an aqueous liquid of the present invention and the article thereof can be easily obtained. From the above, the deodorant and / or fragrance of the present invention is useful as a deodorant and / or fragrance having excellent interior properties.

[0051]

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of the deodorant and / or fragrance of the present invention.

FIG. 2 is a perspective view showing an example of the deodorant and / or fragrance of the present invention.

FIG. 3 is a cross-sectional view showing a state immediately after an aqueous liquid of a substance having a deodorant property is introduced into FIG.

FIG. 4 is a cross-sectional view showing a state four days after the molded article of the water-swellable resin of the present invention has absorbed the aqueous liquid of the deodorant substance.

FIG. 5 is a cross-sectional view showing a state of a water-based gel formed around a water-swellable resin molded article of the present invention.

[Explanation of symbols]

Reference Signs List 1 molded product of water-swellable resin 1 'molded product of water-swellable resin absorbs and swells aqueous liquid of deodorant substance 2 aqueous liquid of deodorant substance 3 glass container 4 cap 5 Adhesive 6 Water-based gel

Claims (6)

[Claims] An aqueous liquid gelling agent comprising, as an essential component, an ammonia reactant (A) of a copolymer of an ethylenically unsaturated compound and maleic anhydride and a reactant of gelatin (B). 2. The gelling agent for aqueous liquid according to claim 1, wherein (A) is a reaction product obtained by reacting a copolymer of an ethylenically unsaturated compound and maleic anhydride with ammonia. 3. The gelling agent for an aqueous liquid according to claim 1, wherein the ethylenically unsaturated compound (A) is isobutylene or methyl vinyl ether. 4. An aqueous gel obtained by gelling an aqueous liquid with the aqueous liquid gelling agent according to claim 1. 5. An aqueous liquid containing a substance (C) having a deodorizing property and / or an aromatic property, which is gelled with the gelling agent for aqueous liquid according to any one of claims 1 to 3, and And / or fragrance. 6. The deodorant and / or fragrance article according to claim 5, wherein the aqueous liquid containing the water-swellable resin molded article (D) is gelled with the aqueous liquid gelling agent.