JP2003253246A - Aqueous gel molded product and article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous gel molded product for decoration, produced by using a gelatinizing agent for an aqueous liquid and having a good design, and to provide an article using the molded product. <P>SOLUTION: The aqueous gel molded product for decoration is obtained by gelatinizing an aqueous liquid containing a gelatinizing agent for the aqueous liquid which is a reaction product or the like of (A) an ammonia-reacted product of a copolymer of an ethylenic unsaturated compound and maleic anhydride, with (B) a gelatin, in a dividable mold for forming a shape, and taking out the molded product to form the molded product into a specific shape which is a miniature of a geometric shape, character goods, animals, plants, geographical features, buildings, transportation equipment or the like. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative water-based gel molded article having a design property, which is produced by using a gelling agent for an aqueous liquid, and an article using the same. For more details,
TECHNICAL FIELD The present invention relates to a decorative water-based gel molded article to be used for articles having functions such as insect proof, deodorant / deodorant, antibacterial, and aromatic used in a room, a toilet, and a car, and an article using the same.

[0002]

2. Description of the Related Art Conventionally, deodorants and fragrances used indoors, toilets, cars, etc. are prepared by putting an aqueous solution or an aqueous emulsion of a substance having a deodorant property or a fragrance into a certain package (eg, , Patent Document 1), those obtained by immobilizing the above liquid with polysaccharides such as agar and carrageenan, and those obtained by gelating the above liquid with a water-absorbent resin powder, etc. are put to practical use (for example, Patent Documents 2 and 3).

[0003]

[Patent Document 1] JP-A-1-201261

[Patent Document 2] Japanese Patent Laid-Open No. 11-226103

[Patent Document 3] Japanese Patent Laid-Open No. 62-298361

[0004]

However, most of the above items (1) to (5) are provided with only deodorant and / or aroma functions. Is a liquid, and there is a problem that the contents are washed away when it moves or falls. , Had no fear of the contents being washed away when they moved or fell, but the deodorant and / or fragrance obtained had no design. Further, recently, such deodorant and / or fragrance is not satisfied only by the deodorant and / or fragrance function, and the demand as an interior accessory is increasing. However,~
The maximum number of products that can be handled is the design of the package or the design of the label on the package.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors to obtain an article having a design property which improves the above problems and having functions such as deodorant and aromatic properties, a gel for aqueous liquids is obtained. A water-based gel molding having a design property is obtained by adding an aqueous liquid containing an agent into a container that can be processed into a shape such as character goods having interior properties, and the water-based gel molding is put into a package. , The entire package is integrated by gelling with an aqueous liquid containing a gelling agent for an aqueous liquid, or the aqueous gel molded product is put into an aqueous liquid containing a deodorant and / or aromatic agent. The inventors have found that the designability can be significantly improved by doing so, and arrived at the present invention.
The design in the present invention refers to a shape, a pattern, or a color of an article (including a part of the article) or a combination thereof, which gives a aesthetic feeling through visual sense.

That is, the present invention provides (I) a decorative water-based gel molded article which is processed into a specific shape by taking out an aqueous liquid containing a gelling agent for an aqueous liquid in a mold for molding and then taking it out. (II) Article characterized by comprising the above water-based gel molding; (III) The above water-based gel molding, gelling agent for aqueous liquid, and insect repellent, deodorant / deodorant, antibacterial and An article obtained by gelling an aqueous liquid containing one or more agents selected from the group consisting of aromatic agents.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of gelling agents for aqueous liquids include gelling agents for natural aqueous liquids, gelling agents for semi-synthetic aqueous liquids, gelling agents for synthetic aqueous liquids, and others. An aqueous liquid gelling agent may be mentioned. The preferred weight average molecular weight of these gelling agents for aqueous liquids is 1,000 to 2,000.
It is 50,000. Specific examples include the following. As a gelling agent for natural aqueous liquid, starchy material (starch); animal protein (gelatin, collagen); vegetable protein (soy protein, ovalbumin, casein); fibrin (wood cellulose); seaweed extract (agar, Carrageenan); Plant seed mucilage (guar gum, locust bean gum, etc.); Plant tree mucilage (tragacanth gum); Plant fruit mucilage (pectin); Microbe-produced mucilage (xanthan gum, pullulan, dextran, julan gum, curdlan, hyaluronic acid Etc.); plant rhizome mucilage (konnyakunanman) and the like.

Examples of gelling agents for semi-synthetic aqueous liquids include cellulose derivatives (methyl cellulose, ethyl cellulose,
Carboxymethyl cellulose, etc.); Starch derivatives (carboxymethyl starch, etc.); and Alginic acid derivatives (Alginate, Propylene glycol alginate)
Etc.

As the gelling agent for synthetic aqueous liquid, polyoxyalkylene compound (a1); acrylic polymer (a2); vinyl polymer (polyvinyl alcohol,
Carboxyvinyl polymer and the like); isobutylene-maleic anhydride copolymer, polyvinyl alcohol and the like.

Examples of the polyoxyalkylene (preferably having 2 to 4 carbon atoms) compound (a1) include, for example, polyethylene oxide (high molecular weight polymer of ethylene oxide), alcohol (preferably having 1 to 30 valence, more preferably 2 to 2).
Hexavalent) or alkylene oxide (ethylene oxide, propylene oxide, etc.) adduct of phenols (monohydric or polyhydric phenol of 2 to 6), polyoxyethylene / oxypropylene glycol (block or random of ethylene oxide and propylene oxide) Copolymers) and the like, and derivatives in which the terminal is substituted with an alkyl (C 1 to C 30) ether, ester or the like. The number average molecular weight of these polyoxyalkylene compounds is preferably 1,000 to 2,000,000.

Examples of the acrylic polymer (a2) include (meth) acrylamide, (meth) acrylic acid (salt) [for example, sodium acrylate, etc.], 2-alkyl (1-10 carbon atoms) -2-acrylamidopropanesulfone. Acid (salt) [2-alkyl (1-10 carbon atoms) -2-
Sodium acrylamide propane sulfonate, etc.], (meth) acryloyloxyalkyl (C 1-10) trialkyl (C 1-4) ammonium quaternary salts [eg (meth) acryloyloxyethyltrimethylammonium chloride, etc.], (Meth) acryloyloxyalkyl (C1-10) dialkylamine salt [eg tertiary or quaternary salt of diethylaminoethyl methacrylate]
A water-thickening polymer having at least one kind of a vinyl-based monomer selected from the group consisting of as constituent units. Specific examples thereof include poly (meth) acrylamide, poly (meth) acrylic acid (salt), and acrylic acid. -Acrylic ester copolymer, partial hydrolyzate of poly (meth) acrylamide, (meth) acrylic acid (salt) and (meth) acrylamide and 2-acrylamido-2-methylpropanesulfonic acid (salt) or (meth) Acrylamide and (meth) acryloyloxyethyl trimethyl ammonium 4
Examples thereof include copolymers with graded salts. The weight average molecular weight of (a2) is preferably 1,000 to 2,000,000.

Other aqueous gelling agents include (b)
1) A mixture obtained by mixing a reaction product obtained by reacting ammonia with a copolymer of a vinyl compound or a vinylidene compound and maleic anhydride, a polyvalent amine, and water are subjected to gelation treatment in a water-containing state. The resulting hydrogel (Japanese Patent Publication Sho 61
No. 50493); (b2) An aqueous gelling agent and an aqueous gel comprising a reaction product of gelatin or collagen and an olefin-maleic anhydride copolymer (Patent No. 2616).
960); (b3) [number average molecular weight is 1,000.
~ 10,000 urethane compounds obtained by reacting hydrophilic polyol, polyisocyanate and imidazole or 2-methylimidazole 5-30%, perfume 1
10% by weight, surfactant 1 to 10% by weight, ultraviolet absorber 0.01 to 2% by weight, reducing agent 0.01 to 2% by weight, water
The balance], which is a transparent fragranced gel composition. (JP-A-63-79661); (b4) Copolymer of ethylenically unsaturated compound (eg, isobutylene) and maleic anhydride (weight average molecular weight of 2,000 to 5,000,0).
00) a reaction product of the ammonia reaction product (A) and gelatin (B), and a gelling agent for an aqueous liquid (JP-A 2000-1).
Details are described in Japanese Patent Publication No. 92011) and the like. Among these gelling agents for aqueous liquids, preferred are transparent gels such as carrageenan, xanthan gum, gellan gum, and other aqueous gelling agents (b4), and particularly preferred are transparent gels having gel strength. Is large and the water separation upon freeze-thawing is small (b4).

The gelling agent for an aqueous liquid is a gelling agent for an aqueous liquid, and the concentration in the aqueous liquid varies depending on the kind of the gelling agent for an aqueous liquid, but preferably the gelling agent is 0.05
˜15.0% by weight, more preferably 0.1 to 10.0
Used as an aqueous solution of wt%. In the case of the above other gelling agents for aqueous liquids [eg (b4)], the compounding ratio of the components is used in a specific ratio. For example, in the case of the above (b4), it is preferable to use 3 to 50 parts by weight of (A) with respect to 100 parts by weight of (B). And, this (A) is 0.5 mol of ammonia for 1 mol of maleic anhydride group in the copolymer.
It is preferred to use ~ 2 moles. In addition to the gelling agent for aqueous liquid, other additives and the like can be mixed as the aqueous liquid. Other additives include water-swelling water-absorbent resins, volatile chemicals and the like. The water absorbent resin is selected from, for example, a water-soluble monomer containing starch or cellulose (ii) and a hydrophilic group such as a carboxyl group and a sulfonic acid group and / or a monomer which becomes water-soluble by hydrolysis. A water-absorbent resin obtained by polymerizing at least one kind of monomer (b) and a cross-linking agent (c) as essential components and performing hydrolysis if necessary is mentioned. The ratios of (a), (b) and (c) used in the production of the water absorbent resin exemplified above, the production method and specific examples of the water absorbent resin are described in JP-A-52-25.
886, Japanese Patent Publication No. 53-46199, Japanese Patent Publication No. 53-4
No. 6200 and Japanese Patent Publication No. 55-21041.

Examples of the water absorbent resin other than those exemplified above are those obtained by polymerizing (a) and (b) (hydrolyzate of starch-acrylonitrile graft polymer,
Cellulose-hydrolyzate of acrylonitrile graft polymer, etc.); Cross-linked product of (a) (cross-linked product of carboxymethyl cellulose, etc.); Copolymer of (b) and (c) (partial hydrolyzed product of cross-linked polyacrylamide, Cross-linked acrylic acid-acrylamide copolymer, cross-linked sulfonated polystyrene, JP-A-52-14689 and JP-A-SHO-5
2-27455 Publication Saponified vinyl ester-unsaturated carboxylic acid copolymer, crosslinked polyacrylic acid (salt), crosslinked acrylic acid-acrylic acid ester copolymer, crosslinked isobutylene-maleic anhydride Acid copolymers and crosslinked carboxylic acid-modified polyvinyl alcohols); and polymers (b) having self-crosslinking properties (self-crosslinking polyacrylic acid salts, etc.). or,
You may use together 2 or more types of the water absorbent resin illustrated above.

Among these water-absorbent resins, more preferable ones are, and among those exemplified as, crosslinked polyacrylamide copolymer, crosslinked polyacrylic acid (salt), crosslinked acrylic acid-acrylic acid ester. A copolymer, a crosslinked isobutylene-maleic anhydride copolymer, and a crosslinked carboxylic acid-modified polyvinyl alcohol. The absorption capacity of water or an aqueous liquid of the water-absorbent resin is preferably 10 to 1,000 times, more preferably 100 to 1,000 times, by weight. Further, the shape of the water-absorbent resin is preferably powder, granules, fibrous and pearl-like ones, and the pearl-like one is preferable because the swollen / gelled water-based molded article has a transparent appearance.
The particle size is not particularly limited, but the average particle size is preferably 100 to 5,000 microns, particularly preferably 200 to
It is 3,000 microns. If the average particle size exceeds 5,000 microns, the water absorption rate becomes slow, and a core of a water absorbent resin that does not swell when used as an aqueous gel may be formed. On the other hand, if the average particle size is less than 100 μm, the water-absorbent resin may be too dense, which may hinder the transparency of the water-based gel. The amount of the water absorbent resin used is preferably 0.05 to 3%, more preferably 0.1 to 2%, based on the total weight. If the amount of the water absorbent resin used exceeds 3%, the transparency of the water-based gel will decrease. On the other hand, if the amount of the water-absorbent resin used is less than 0.05%, the release property of volatile substances such as fragrances will decrease. In the present invention, the absorption capacity of the water absorbent resin is a value obtained by measurement by the method described below.

<Absorption capacity of water-absorbent resin> A sample of water-absorbent resin (sample amount; Eg) was placed in a nylon net bag (250 mesh), and the bag was immersed in an excess of water or aqueous liquid. After 60 minutes of the immersion, the whole bag was pulled up into the air, allowed to stand and drained for 15 minutes, and then the mass (Fg) was measured to obtain the absorption capacity from the following formula. [The same operation as above was performed using only the mesh bag, and the mass (Gg) of this portion was subtracted as a blank. ] Absorption capacity = (FG) / E

In the present invention, one or more agents selected from the group consisting of insect repellent agents, deodorant / deodorant agents, antibacterial agents and aromatic agents are insect repellent, deodorant / deodorant, antibacterial agents, There is no particular limitation as long as it is an aromatic drug. Preferably, it is one or more kinds of agents selected from the group consisting of insect repellent agents, deodorant / deodorant agents, antibacterial agents and aromatic agents, and agents having volatility. These may be drugs having one or more functions and are not particularly limited. Specific examples of these agents include the following. The amount of these used is slightly different depending on the kind thereof, but is preferably 0.1% of the total weight of the aqueous gel molding.
1 to 15%. Examples of insect repellents include synthetic pyrethroids, empesrins, hinokitiol, and hiba oil to prevent wool fabrics from being damaged by insects, and water and an emulsifier, if necessary, a solvent, etc., to prepare an aqueous emulsion or aqueous liquid. You can

Examples of the deodorant / deodorant agents include weak base salts of strong inorganic acids (aluminum sulfate, ammonium aluminum sulfate, ammonium chloride, alums, etc.),
Flavonoid compounds (for example, substances extracted from plants such as rice, pine, cypress, bamboo grass, etc., “Freshray pine” (Shiraimatsu Shinyaku Co., Ltd.), “Smeral” (Environmental Science Development Co., Ltd.), etc., cyclodextrin (α- Or β-cyclodextrin or a derivative thereof), an acid or alkaline aqueous liquid, zeolite, activated carbon, etc., which can be an aqueous liquid diluted with water or an aqueous solution containing a part of the solvent. As the antibacterial agent, a quaternary ammonium compound having at least one alkyl group having 6 to 30 carbon atoms (octyltrimethylammonium chloride, didecyldimethylammonium gluconic acid, etc.), polymethylene biguanidine compound (polyhexamethyleneguanidine salt) Compounds, polyoctamethylene guanidine salt compounds, etc.), chlorhexidine compounds (chlorhexidine, chlorhexidine gluconate, etc.) and the like. As an aromatic drug,
For example, natural flavors and synthetic flavors may be mentioned, and if they are water-soluble, they may be an aqueous solution thereof, and if they are water-insoluble, they may be an aqueous emulsion or an aqueous liquid containing water and an emulsifier, and optionally a solvent. . Here, since a substance having an aromatic property also has a masking effect, it may be said that it is practically deodorant.

Examples of the natural fragrances include animal fragrances such as musk, spirit cat scent, rye scent, etc., abies oil, ajyokun oil, almond oil, angelica root oil, basil oil, bergamot oil, birch oil, boa barose oil, kayabae. Oil, cananga oil, kabushicam, 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, funnel oil, garlic oil, ginger oil, grapefruit oil, hop oil, juniper berry oil, laurel leaf oil, lemon oil, lemongrass oil, lovage oil, mace oil, nutmeg oil Including vegetable flavors such as, mandarin oil, tanzelin oil, mustard oil, peppermint oil, lantern oil, onion oil, pepper oil, orange oil, sage oil, star anise oil, turpentine oil, warmwood oil, and vanilla bean extract. .

As the synthetic fragrance, hydrocarbons such as pinene and limonene, linalool, geraniol, citroneol, menthol, borneol, benzyl alcohol,
Alcohols such as anis alcohol and β-phenylethyl alcohol, phenols such as anenol and eugenol, n-butyraldehyde and isobutyraldehyde,
Hexyl aldehyde, heptyl aldehyde, n-nonyl aldehyde, nonadienal, citral, citronellal, benzaldehyde, aldehydes such as cinnamic aldehyde, heliotropin, vanillin, methyl amyl ketone, methyl nonyl ketone, diacetyl, acetylpropionyl, acetylbutyrin, Ketones such as carvone, menthone, camphor, acetophenone, P-methylacetophenone and ionone, amyl butyrolactone, ethyl methylphenylglycidate, γ-nonyl lactone,
Coumarin, lactones or oxides such as cineol, methyl formate, isopropyl formate, linalyl formate, 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 verahagonate,
Methyl octynecarboxylate, isoacyl caprate, methyl laurate, ethyl myristate, ethyl benzoate, benzyl benzoate, methyl phenylacetate, phenylacetate, methyl cinnamate, cinnamyl cinnamate, methyl saltinate, ethyl anisate, anthranil Methyl acid,
Esters such as ethyl bilbate and ethyl α-butyl butyrate are included.

The fragrance may be only one kind, or a mixed fragrance prepared by mixing two or more kinds. Along with the fragrance, a volatilization retention agent such as butchery oil, a modulator such as eugenol, and other various components used in the fragrance industry may be added. The amount of the fragrance used varies slightly depending on its type, but is preferably 0.1 to 15% of the total weight. In the present invention, the aqueous liquid may further contain other additives, if necessary. The blending amount is somewhat different depending on the kind, but is preferably 0.001 to 30% of the total weight. Examples of the additives include colorants [pigments (including fluorescent pigments and phosphorescent pigments), dyes, pigments (food additives pigments, etc.); stabilizers [antiaging agents, ultraviolet absorbers, defoaming agents, defoaming agents]. Oxygen agents, antioxidants, etc.], surfactants, alcohols and the like.

As a method for producing the aqueous gel molding of the present invention, an aqueous liquid containing a gelling agent for an aqueous liquid is poured into a mold for molding, and after gelling in the mold, a specific shape is obtained. There is a method of taking out the gel molded body processed into the above. In order to produce an aqueous solution containing a gelling agent, an aqueous solution of the gelling agent may be prepared in advance and the above additives may be mixed, or the additives may be coexisted from the beginning and mixed. The order of mixing is not limited. The viscosity of the gelling agent for an aqueous liquid may be such that it can be poured into a container,
It is preferably used as an aqueous solution of 1 to 10,000 cPs, and more preferably 1 to 5,000 cPs. The viscosity measurement temperature is 60 ° C. The gelling conditions differ depending on the type of gelling agent for aqueous liquid. For example, in the case of agar and pectin, after the gelling agent is dissolved by boiling, when the temperature of the aqueous solution drops to about 70 ° C, an aqueous solution containing a volatile drug is added and gelled at room temperature. Let gelatin,
In the case of carrageenan, the gelling agent for an aqueous liquid is dissolved at a temperature of 50 ° C. or higher, an aqueous liquid containing a volatile drug is added at a temperature of 70 ° C. or lower, and gelled at room temperature. In the case of other gelling agents for aqueous liquids (b4), liquid A (preparing a gelatin aqueous liquid in the same manner as), liquid B (ammonium neutralized product of a copolymer of isobutylene and maleic anhydride is dissolved at room temperature). (A volatile drug is added to the prepared aqueous liquid) in advance, and then the liquid A and the liquid B are mixed at an appropriate mixing ratio,
Examples thereof include gelation at room temperature, but are not limited to the above conditions.

The mold for molding which is the container used in the present invention is not particularly limited as long as the mold can be molded.
A structure that can be divided is preferable. The size, location, number of divisions, etc. of the division are not particularly limited. A mold that can be divided into upper and lower two stages is preferable. As long as the mold has a structure capable of being divided, even a mold having a complicated shape can be divided, so that the water-based gel molded body can be easily taken out. The shape of the mold is a geometric body (for example, spherical,
Cubes, star shapes, etc., character goods (eg, Disneyney dolls, cartoon characters, etc.), animals and plants (eg, dogs,
Animals such as cats, squirrels, elephants; flowers such as tulips, cherry blossoms, etc.),
It is preferable to use a miniature object such as a terrain (mountain etc.), a building (National Diet Building, Tokyo Tower etc.) and a transportation device (car, train, ship, airplane etc.), which is excellent in decorativeness. As the material of the container, glass, metal (for example, SUS, etc.), synthetic resin (for example, polyethylene, epoxy resin, etc.), rubber or the like is used. When using a synthetic resin or rubber, it is necessary to use one having a melting point higher than the operating temperature. The size (capacity) is not particularly limited and can be arbitrarily selected as long as it can be stored in the package.

Hereinafter, specific examples of the mold for molding which can mold the water-based gel molded article of the present invention will be described with reference to the accompanying drawings, but the invention is not limited to these descriptions. Here, FIG. 1, FIG. 3, FIG. 9, FIG. 10, FIG. 12, FIG.
FIG. 20 is a schematic drawing of the mold. Of these, FIG.
15 to 18 and 20 show examples of molds having a dividable structure. 2, FIG. 4, FIG. 11, FIG. 14, FIG.
Reference numeral 1 is an aqueous gel molded product taken out from the mold. 5 to 8 show the water-based gel molded product taken out from the mold and further cut by a cutting machine such as a cutter knife.

(C1) In the case of producing a product having a flat surface on one side, an aqueous liquid containing an aqueous gelling agent in a mold having a concave shape as shown in FIGS. 1, 3, 9 and 10. Then, the mixture is put into a gel, and then it is demolded to obtain a water-based gel molded article (FIG. 2, FIG. 4, FIG. 11). (C2) First, after forming a large block (FIG. 4) of a water-based gel molded body, it is cut with a cutter such as a cutter knife as shown in FIGS. ) Can also be created. (C3) As shown in FIGS. 12 and 13, two molds are prepared in which the flat surfaces of FIG. 9 can be matched with each other, and one concave portion and the other concave portion can at least partially coincide with each other. First, the same procedure as in (c1) above is performed to prepare a water-based gel molded product that has been contained in the mold before the mold is removed, and then the surface of the water-based gel molded product exposed on the surface of one or both molds. Then, an aqueous liquid containing the same water-based gelling agent is applied by a coating machine such as a brush, and the concave portions are made to coincide with each other as shown in FIGS. 12 and 13 before the surface gels. After the bonding surface gels,
It is possible to obtain a water-based gel molded product as shown in FIG. 14 in which the flat surfaces of FIG.

(C4) A method for producing the water-based gel molded article as shown in FIG. 14 obtained in (c3) in one gelling step will be described. Two types similar to FIG. 9 (FIGS. 16 and 17)
To prepare. The molds of FIG. 16 and FIG. 17 have a concavo-convex relationship with each other, and FIG. 18 is a form in which FIG. 17 is fitted. FIG. 17 has an outlet port through which bubbles can escape and an excess aqueous liquid can flow when the water-based gel molded body is produced. After pouring an aqueous solution containing a gelling agent for an aqueous solution, which is slightly larger than the total volume of the concave portion (hemisphere) of FIG. 16, the mold of FIG. 17 is slowly fitted into the mold of FIG. At the time of fitting, the air sandwiched between FIG. 16 and FIG. 17 escapes from the outlet of FIG. 17, and the aqueous liquid containing the gelling agent for aqueous liquid of FIG. 16 is the concave portion (hemisphere) of FIG. The filling,
An excessive amount of liquid flows out from the outlet shown in FIG. The inside of the sphere of FIG. 18 is filled with an aqueous liquid containing a gelling agent for an aqueous liquid,
After gelling, the mold can be demolded to obtain an aqueous gel molding as shown in FIG.

(C5) In order to prepare a water-based gelled body having a complicated shape as shown in FIG. 21, a shape to be processed (which is the source of FIG. 21) is prepared and vacuum casting of silicon rubber is performed. A rubber mold (FIG. 20) is created by. This rubber mold can be divided into two or more parts, and has an input port at the top for pouring an aqueous liquid containing a gelling agent for an aqueous liquid. After firmly fixing the divided rubber molds so that the aqueous liquid does not leak, the aqueous liquid containing the gelling agent for the aqueous liquid is charged and gelled, and then the mold is removed to obtain the desired shape (FIG. 21). Obtainable. The spherical water-based gel molded body shown in FIG. 19 can also be prepared in the same manner as in FIG.

The shape of the water-based gel molded article of the present invention is not particularly limited, but in consideration of the case of being used in the room, the toilet, the inside of a car, etc., a geometrical body, a character goods, Miniature shapes of objects such as animals and plants, terrain, buildings and transportation equipment are preferable. The size is not particularly limited and can be arbitrarily selected as long as it can be stored in the package.

There is no particular limitation on the method of using and using the water-based gel molding of the present invention. For example, the water-based gel molding may be put in a packaging container as it is, or the water-based gel molding and volatility may be used. The drug may be contained in an aqueous liquid, or as described below, the gelling agent for an aqueous liquid may be used again or may be used in combination with another gelling agent. The proportions of the water-based gel molded product, the volatile drug, and the aqueous liquid are not particularly limited, and they can be blended in any proportions. In this case, the gelling agent for the aqueous liquid and the aqueous liquid may be the same as those described above (used for the molded product) or may be different. The different ones include those mentioned above. For example, an article obtained by adding an aqueous liquid containing a gelling agent for an aqueous liquid to the above water-based gel molded article to cause gelation; a gelling agent for an aqueous liquid and a volatile agent are further added to the above water-based gel molded article. An article obtained by adding an aqueous liquid contained therein and gelling it; an article in which the aqueous liquid further contains a water-absorbing resin, and the like can be mentioned. These may be put in a packaging container after being produced, or in a packaging container. Gelling may be carried out to produce the above article. The latter is preferable. Also,
The liquid or gel molded article containing the volatile drug can be used as a drug-volatile article. About the mixing ratio

Examples of the drug-volatile article using the above-mentioned water-based gel molded article include the articles manufactured by the following method. (D1) A drug-volatile product, which is obtained by charging an aqueous gel molded product into a packaging container, then charging an aqueous liquid containing a gelling agent for an aqueous liquid and a volatile drug, and gelating and integrating them. ) A drug-volatilizable article in which an aqueous liquid containing a gelling agent for an aqueous liquid and a volatile drug is put into a packaging container and gelated, and then an aqueous gel molding is added thereto (d3) packaging A drug-volatile article obtained by adding an aqueous liquid containing a volatile drug to the container and then adding an aqueous gel molding; (d4) a water-absorbent resin and an aqueous liquid containing the volatile drug in a packaging container. In addition, after gelling, a drug-volatile article to which an aqueous gel molding is added; (d5) After the aqueous gel molding is put into a packaging container, an aqueous solution containing a gelling agent for an aqueous solution is put. , After gelling and integrating, an aqueous liquid containing a water-absorbent resin and a volatile chemical is added, And the like, which are gelled drug-volatile articles;

The packaging container used in the present invention is not particularly limited as long as it is made of a material other than water-soluble, such as a sheet, a film, a tray, etc., but the internal volume is the size of the water-based gel molding to be filled. It is preferably from 2 to 100 times the length. Examples of the packaging container include a cylindrical shape, a prismatic shape, a conical shape, a pyramidal shape, and a spherical bottom surface. The material of the package may be glass or synthetic resin. As the synthetic resin, all those other than the water-soluble substances that are included in the general category of synthetic resins are used and are not particularly limited. The synthetic resin may be thermoplastic or thermosetting, and may be soft or hard. For example, ethylene-vinyl acetate copolymer or a saponified product thereof, polyvinyl chloride, vinyl chloride. Examples thereof include copolymers, polyethylene, polypropylene, polyethylene-acrylic acid salt copolymers, acrylonitrile-butadiene copolymers, styrene-butadiene copolymers, polyesters, polyamide resins, acrylic resins, styrene resins and the like. Furthermore, it is preferable that at least a part of the packaging container is transparent so that the inside can be viewed and enjoyed from the side through the packaging body.

In the present invention, inorganic materials, metals, glass,
One or more decorative solids selected from the group consisting of rubber, synthetic resins and composites thereof may be contained in either or both of the molded body and the article. The shape is not particularly limited, but in order to enhance the decorative property of the water-based gel molded article, it is preferable that the shape is powdery, granular, pearl-like, pellet-like, fibrous or three-dimensional. The size of the solid is
The size is not particularly limited as long as it is smaller than the size of the water-based gel molded article, but the particle diameter (major axis) of these powdery, granular and pearl-like particles is preferably 1 to 10,000 μm, more preferably 100 to 5,000 μm. The fibrous size is usually 0.001 to 50 mm, preferably 0.1 to 30 m
m. The pellet shape is preferably 1 to 50 mm, more preferably 2 to 30 mm. The solid matter may or may not be colored, but is preferably colored from a visual effect, and at least the additive is colored in a color different from that of the water-based gel molding. Is particularly preferable. The amount of solid used is preferably 0.05 to 90%, and more preferably 0.1 to 5%, based on the total weight.
It is 0%. If the amount of solids used exceeds 90%, the integrally moldability of the water-based gel will deteriorate, and the water-based gel as a whole tends to fall apart. On the other hand, if the amount of solids used is less than 0.05%, the visual effect is reduced, and conversely, it is mistaken for foreign matter such as dust, which is a negative effect.

In the present invention, as the solid material for decoration, which is made of inorganic material, metal and glass, those which are generally used may be used. Examples of solid materials made of inorganic materials include ceramics, porcelain, pottery, and artificial zeolite. Examples of solids made of metal include iron and iron alloys (stainless steel, austenite, etc.)
Examples thereof include copper, copper alloys (bronze, brass, etc.), aluminum, aluminum alloys (duralumin, etc.) zinc, nickel and the like. Examples of solids made of glass include soda lime glass, soda lime aluminum glass, borosilicate crown glass, borosilicate flint glass, borate flint glass, phosphate crown glass, quartz glass, and glass containing rare elements such as neodymium, Colored glass etc. are mentioned.

The solid substance using rubber as a raw material carrier may be one that is generally used. For example, in addition to ordinary natural rubber (NR), styrene butadiene rubber (SB) may be used.
R), butadiene rubber (BR), isoprene rubber, butyl rubber (IIR), ethylene propylene rubber, ethylene propylene non-conjugated diene rubber, polypropylene rubber (C
R), nitrile rubber, acrylonitrile-butadiene rubber and the like.

Solids made of synthetic resins other than water-soluble, whether soft or hard, include, for example, ethylene-vinyl acetate copolymers or saponified products thereof, ethylene-acrylic acid salt copolymers, ethylene-acrylics. Examples thereof include acid ester copolymers, chlorosulfonated polyethylene, chlorinated polyethylene, urethane resins, styrene resins, vinyl chloride resins, olefin resins, polyester resins and polyamide resins.

In the present invention, as the solid composite, the synthetic resin films or sheets are stuck together and cut into an appropriate shape, and the synthetic resin film or sheet is vapor-deposited with metal (copper, aluminum, etc.). Alternatively, a laminate, a laminate obtained by cutting these laminates or the like into an appropriate size, a laminate of metal and glass, a laminate of glass and a metal melt-bonded, and the like can be given.

The present invention will be further described with reference to Examples showing production examples and usage examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of Solution A To a 1 L beaker, 45 g of gelatin SE-1 (alkali-treated gelatin; manufactured by Nippi Gelatin Industry Co., Ltd.), 5 g of sugar, and 750 g of ion-exchanged water were added, and heated to 60 to 70 ° C. It was then stirred and dissolved uniformly. (2) Preparation of Solution B To a 500 mL beaker, 50 g of floral fragrance and 50 g of nonipol 120 (a nonionic surfactant of 12 mol adduct of nonylphenyl etheroxyethylene; manufactured by Sanyo Chemical Industry Co., Ltd.), 30 g of ethanol and 20 g of propylene glycol were added. It was stirred and dissolved uniformly. (3) Preparation of Solution C In a 200 mL beaker, Gantrez AN-119
(Methyl vinyl ether / maleic anhydride copolymer; weight average molecular weight 2.13 × 10 6; manufactured by ISPE Japan Ltd.) To 10 g, ion-exchanged water 84 g and ammonia aqueous solution (ammonia content; 29%) 6 g were added at room temperature. Gantrez with 80% ammonia neutralization rate
An aqueous solution of AN-119 was obtained. (4) Preparation of water-based gel molded body Solution A 40 g in a 200 mL beaker, solution B 9 g,
Solution C 2g, Food Blue No. 1 (Food Additive) 0.00
1 g and ion-exchanged water (49 g) were added to prepare a uniform and transparent aqueous solution. The aqueous solution thus obtained is shown in FIG.
6 into the mold of FIG.
The mold of FIG. 7 was placed on the mold, the aqueous solution was spilled through the hole in the head of the mold of FIG. 17, and then the mold of FIGS. 16 and 17 was fixed so as not to move. The gelation reaction was carried out by leaving it at room temperature for 1 day, and the mold was divided into upper and lower parts and taken out to obtain a uniform and transparent decorative water-based gel molded product having a shape shown in FIG.

Example 2 (1) Preparation of Solution E Isovan-04 (isobutylene /
Maleic anhydride copolymer; molecular weight 6 × 10 4; manufactured by Kuraray Co., Ltd.) To 10 g, ion-exchanged water 84 g and aqueous ammonia solution (ammonia content; 29%) 6 g were added, and stirred at room temperature to uniformly dissolve for 1 hour. An evenly dissolved aqueous solution of isoban-04 having an ammonia neutralization ratio of 80% was obtained. (2) Preparation of Aqueous Gel Molded Body In addition to 79 g of the solution A prepared in Example 1, 9 g of solution B similarly prepared in Example 1, 8 g of solution E, 0.001 g of food yellow No. 5 (food additive) and ion-exchanged water 4 g was added to prepare a uniform and transparent aqueous solution. The aqueous solution thus obtained was put into the mold shown in FIGS. 9 and 10 and left at room temperature for 1 day to carry out the gelation reaction. 9 and 1
An aqueous solution prepared in the same manner as described above was applied on the surface of the water-based gel of the No. 0 mold in such an amount that it did not flow out from the water-based gel surface, and the molds of FIG. 9 were combined as shown in FIG. Further, it was left at room temperature for 1 day to carry out gelation reaction, and then taken out.
A transparent water-based gel molded article having a uniform shape and having a shape shown in (1) was obtained.

Example 3 (1) Preparation of an article using a water-based gel molded article A blue water-based gel molded article (FIG. 19) prepared in Example 1 (4) was placed in a 300 mL transparent polyester wide-mouth container. Solution A prepared in Example 1 by throwing in pieces (7 g / piece)
After a transparent aqueous solution was prepared by adding 80 g, solution B 18 g, solution C 4 g and ion-exchanged water 98 g, the solution was allowed to stand at room temperature for 1 day for gelation reaction, and then taken out.
An article using the decorative water-based gel molded article having a transparent shape as shown in (3) was obtained.

Example 4 (1) Preparation of Article Using Water-based Gel Molded Body 12 blue water-based gel molded bodies (FIG. 19) prepared in Example 1 (12 g, 7 g) were placed in a 300 mL transparent polyester wide-mouth container. Solution / B18 prepared in Example 1
g and 182 g of ion-exchanged water were added to prepare a transparent aqueous solution to obtain an article using the transparent decorative water-based gel molding shown in FIG.

Example 5 (1) Preparation of Article Using Aqueous Gel Molded Body In a 300 mL transparent polyester wide-mouth container, 15 g of the solution B prepared in Example 1 and 150 ion-exchanged water were prepared.
After adding g to prepare a transparent aqueous solution, Sunfresh S
T-620 (acrylic water-absorbent resin, average particle size 280 microns or more, water absorption performance 250 g / g, Sanyo Chemical Industries)
8 g was added to cause gelation, and on the gel surface, the blue decorative water-based gel molded body prepared in Example 1 (see FIG. 1).
Six pieces (7 g / piece) of 9) were applied to obtain an article using the decorative water-based gel molding shown in FIG.

[0043]

The decorative water-based gel molding of the present invention has the following effects. It can be easily processed into any shape and color and can be arbitrarily selected from opaque to transparent. Therefore, it becomes a molded article with a rich design. It has excellent shape retention and is easy to handle without being damaged during transportation. By combining one or more agents selected from the group consisting of conventional insect repellent agents, deodorant / deodorant agents, antibacterial agents and aromatic agents with the water-based gel molding of the present invention, the decorative property is easily improved. Articles such as insect repellents, deodorants / deodorants, antibacterial agents and fragrances can be obtained. During use, the water-based gel molding will gradually become smaller, so when applied to the above deodorant and fragrance products, it will function as an indicator showing the remaining amount of the deodorant and fragrance products. It also has.

[0044]

[Brief description of drawings]

FIG. 1 is a perspective view of a molding container for producing a decorative water-based gel molding of the present invention.

FIG. 2 is a perspective view of a decorative water-based gel molded body created from FIG.

FIG. 3 is a perspective view of a molding container for producing the decorative water-based gel molding of the present invention.

FIG. 4 is a perspective view of the decorative water-based gel molded body prepared from FIG.

FIG. 5 is a perspective view showing a state in which a cut is made with a cutter knife in FIG.

FIG. 6 is a perspective view showing a state where one of FIG. 5 is taken out.

FIG. 7 is a perspective view showing a state where a cut is made with a cutter knife in FIG.

FIG. 8 is a perspective view showing a state where one of FIG. 7 is taken out.

FIG. 9 is a perspective view of a molding container for producing the decorative water-based gel molding of the present invention.

FIG. 10 is a schematic front view of a molding container for producing the decorative water-based gel molding of the present invention.

FIG. 11 is a perspective view of a decorative water-based gel molded body created from FIG.

FIG. 12 is a perspective view showing a state where FIGS. 9A and 9B face each other.

FIG. 13 is a schematic front view of FIG.

FIG. 14 is a perspective view of the decorative water-based gel molded body prepared from FIG.

FIG. 15 is a perspective view of a molding container for producing the decorative water-based gel molding of the present invention.

FIG. 16 is a schematic front view of a molding container for producing the decorative water-based gel molding of the present invention.

FIG. 17 is a schematic front view of a molding container for producing the decorative water-based gel molding of the present invention.

FIG. 18 is a schematic front view of the state in which FIG. 17 is superimposed on FIG. 16.

FIG. 19 is a perspective view of the decorative water-based gel molded body created from FIG. 18.

FIG. 20 is a schematic front view of a molding container for producing the decorative water-based gel molding of the present invention.

FIG. 21 is a perspective view of the decorative water-based gel molded body created from FIG. 20.

FIG. 22 is a schematic front view showing a state in which the decorative water-based gel molding of the present invention is put into a package.

FIG. 23 is a schematic front view showing a state in which an aqueous liquid is further added after the decorative water-based gel molding of the present invention has been put into the package.

FIG. 24 is a schematic front view of a state where the decorative water-based gel molding of the present invention is put into a package, and then an aqueous liquid is further added to cause gelation.

FIG. 25 is a schematic front view of a state in which the decorative water-based gel molding of the present invention is put into the packaging body after the pearly water-absorbent resin and the aqueous liquid are put into the packaging to gel.

FIG. 26 is a schematic front view showing a state in which a pearly water-absorbent resin and an aqueous liquid are put on the top of FIG. 24 to cause gelation.

[Explanation of symbols]

1 molded container 2 Decorative water-based gel molding 3 Aqueous liquid 4 Aqueous liquid containing gelling agent for aqueous liquid 5 packaging 6 Aqueous liquid gelled with a gelling agent for aqueous liquids 7 Pearl-like water-absorbent resin that gels by absorbing aqueous liquid

Claims (14)

[Claims] 1. An aqueous liquid containing a gelling agent for an aqueous liquid,
A decorative water-based gel molded product that is processed into a specific shape and is taken out after gelling in a mold for molding. 2. The decorative water-based gel molded article according to claim 1, wherein the molding mold has a structure that can be divided. 3. The water-based gel molding according to claim 1, wherein the water-based gel molding is further processed into a specific shape. 4. The gelling agent for aqueous liquids comprises agar, carrageenan, xanthan gum, gellan gum, and an ammonia reaction product (A) of an ethylenically unsaturated compound and a copolymer of maleic anhydride with gelatin (B). It contains one or more kinds selected from the group consisting of reactants.
The water-based decorative gel molding according to any one of 3 above. 5. The gelling agent for an aqueous liquid is a reaction product of an ammonia reaction product (A) of a copolymer of an ethylenically unsaturated compound and maleic anhydride and gelatin (B). 4. The decorative water-based gel molding according to any one of 4 above. 6. The aqueous liquid further comprises an insect repellent agent, deodorant,
2. A composition containing one or more agents selected from the group consisting of deodorant agents, antibacterial agents and aromatic agents.
5. A decorative water-based gel molded article according to any one of to 5. 7. The aqueous liquid further contains one or more kinds of decorative solid substances selected from the group consisting of inorganic substances, metals, glasses, rubbers, synthetic resins and composites thereof. The decorative water-based gel molded article according to any one of 1. 8. The shape of the water-based gel molding is a geometric body,
A miniature selected from the group consisting of character goods, animals and plants, terrain, buildings and transportation equipment.
A water-based gel molded article for decoration according to any one of 1 to 7. 9. An article comprising the water-based gel molded article according to any one of claims 1 to 8. 10. The water-based gel molded article further comprises:
7. An article obtained by adding an aqueous liquid containing the gelling agent for an aqueous liquid according to any one of to 7 to gel. 11. The aqueous solution further contains one or more agents selected from the group consisting of insect repellent agents, deodorant / deodorant agents, antibacterial agents and aromatic agents. Or the article according to 10. 12. The article according to claim 9, wherein the aqueous liquid further contains a water absorbent resin. 13. The article according to claim 9, wherein the gelling is performed in a packaging container. 14. One or more agents selected from the group consisting of insect repellent agents, deodorant / deodorant agents, antibacterial agents, and aromatic agents, and the water-based gel molded article according to claim 1. An article comprising an aqueous liquid containing the article.