JPS6348905B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field) The present invention relates to a technique for preventing a decrease in the viscosity of a gel produced using a highly water-absorbing synthetic resin as a gelling agent. From another point of view, the present invention relates to a technique for preventing a decrease in the viscosity of a transpiration agent formed by blending a transpiration agent such as a fragrance, a repellent, or an insecticide into the above-mentioned gel. (Prior Art) Transparent gels manufactured using some of the highly water-absorbing synthetic resins described below as gel agents exhibit irradiation depending on the intensity of the rays when irradiated with light from the sun, fluorescent lights, incandescent lights, etc. It is known that the viscosity gradually decreases, although there are differences. However, no technique is known to prevent such a decrease in viscosity. (Purpose of the Invention) The inventors have developed a method to prevent viscosity reduction over a long period of time even when a gel manufactured using a highly water-absorbing synthetic resin as a gel agent is exposed to various types of visible light including ultraviolet rays. As a result of repeated research and development of technology to achieve this goal, the present invention has achieved that goal. (Structure of the Invention) The present invention provides a transparent gel produced using a highly water-absorbing synthetic resin such as modified sodium polyacrylate as a gel agent, and the addition of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, and ethylenediaminetetraacetic acid as viscosity reduction inhibitors. Decreasing the viscosity of a gel characterized by adding one or more selected from tetrasodium acetate, triisopropanolamine, ethanolamine, gallic acid n-propyl ester, nickel dibutyldithio carbamate, phenyl-α-naphthylamine, and benzophenone derivatives. This is a prevention method. From a different perspective, the present invention provides a transparent gel produced using a highly water-absorbing synthetic resin such as modified sodium polyacrylate as a gel agent, and a viscosity reduction inhibitor such as ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, or ethylenediaminetetraacetic acid. Non-reducing viscosity characterized by the addition of one or more selected from tetrasodium acetate, triisopropanolamine, ethanolamine, n-propyl gallic acid, nickel dibutyldithio carbamate, phenyl-α-naphthylamine, and benzophenone derivatives. It's a gel. A detailed explanation of the constituent elements of the present invention is as follows. (Highly water-absorbing synthetic resin) The highly water-absorbing synthetic resin used as a gel agent in the present invention includes, for example, a polymerizable monomer that is water-soluble in polysaccharides such as starch and cellulose, or that becomes water-soluble by hydrolysis. For example, acrylic acid, methacrylic acid, acrylate, methacrylate, acrylic ester, methacrylic ester, acrylic amide, methacrylic amide, acrylonitrile, methacrylonitrile, maleic acid, sulfonated styrene, vinylpyridine, etc.
Or a hydrophilic polymer obtained by graft polymerizing these oligomers or cooligomers and hydrolyzing them as necessary, or polyethylene oxide, polypropylene oxide, polyvinylpyrrolidone, sulfonated polystyrene, polyvinylpyridine, polyacrylate, polyacrylic acid amide Hydrophilic polymers such as polymethacrylate, polymethacrylic acid amide, etc., which are three-dimensionally polymerized using a crosslinking agent, are used. Examples of the crosslinking agent include esters of di- or tri-acrylic acid or methacrylic acid of polyols such as ethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, and polyoxypropylene glycol; Unsaturated polyesters obtained by reacting unsaturated acids such as acids, bisacrylamides such as N,N-methylene-bisacrylamide, and di- or tri-acrylic acids obtained by reacting polyepoxide with acrylic acid or methacrylic acid. - esters of acrylic acid or methacrylic acid, carbamyl esters of diacrylic acid or dimethacrylic acid obtained by reacting polyisocyanates such as tolylene diisocyanate and hexamethylene diisocyanate with hydroxyethyl acrylate or hydroxyethyl methacrylate; Bifunctional compounds that can be crosslinked under certain reaction conditions include allylated starch, allylated cellulose, etc., but optionally methylolated acrylamide, methylolated methacrylamide, glyoxal, phthalic acid, adipic acid, ethylene glycol, etc. Polyvalent metal compounds such as calcium oxide and zinc diacetate can also be used. These highly water-absorbent synthetic resins can be used in amounts ranging from 0.5 to 20% of the gel, depending on the desired hardness of the finished gel. (Additives) In the present invention, additives include ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, triisopropanolamine, ethanolamine (monoethanolamine, diethanolamine, triethanolamine), n-gallic acid. One or more compounds selected from propyl esters, nickel dibutyl dithiocarbamates, phenyl-α-naphthylamine and benzophenone derivatives can be used. In the present invention, the benzophenone derivatives include 2,4-hydroxybenzophenone, 2,2'-
Dihydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid, etc. Can be done. Care must be taken, since using more additives than necessary may cause coloring, cloudiness in the transparent gel, or generation of an unpleasant odor. Since the suitable proportion of the viscosity reduction inhibitor varies depending on the type thereof, it can be divided into several groups and explained as follows. That is, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, and tetrasodium ethylenediaminetetraacetate are 0.001 to 3% by weight, triisopropanolamine, ethanolamine, and nickel.
Dibutyl dithiocarbamate and phenyl-α
-Naphthylamine is preferably in the range of 0.1 to 5% by weight, benzophenone derivatives are in the range of 0.01 to 3% by weight, and gallic acid n-propyl ester is preferably in the range of 0.001 to 5% by weight. (Auxiliary Components) Water-soluble substances such as alcohols and polyols may be added to the gel of the present invention as dispersants. ,
For example, propylene glycol, ethanol, glycerin, etc. can be used up to a maximum of about 50% by weight. Furthermore, depending on the intended use of the gel, insecticides, repellents, fragrances, deodorants, etc. can be added. If such auxiliary ingredients are water-soluble, they can be added as is, but if they are not water-soluble, nonionic surfactants, cationic surfactants, anionic surfactants, and zwitterionic surfactants are used. It is also possible to use the above-mentioned dispersants together. Since the gel of the present invention is transparent, it can be used for ornamental purposes such as fresh flowers, insects, fish, shellfish, artificial flowers, imitation animals, imitation plants, imitation fruits, sequins, hair powder, aurora film, or various toys. The ornamental quality and decorativeness can be improved by charging the objects. (Operations and Effects of the Invention) In the present invention, although the mechanism of action of the viscosity reduction inhibitor has not yet been elucidated, it is clear that the transparent gel does not cause viscosity reduction over a long period of time even when exposed to sunlight or other rays. It is reliable and has a completely unexpected effect. Furthermore, the present invention has made it possible to put into practical use a transparent gel using a highly water-absorbing synthetic resin as a gel agent, so the present invention is a very useful invention. (Examples) Next, the present invention will be explained in detail by describing examples of the present invention, but the present invention is not limited in any way by the following examples. Example 1 (Triisopropanolamine) Modified sodium polyacrylate (manufactured by Showa Denko K.K.)
Mix 1.5g of ethanol and 10g of propylene glycol, and separately add 2.5g of ethanol, 7.5g of glycerin, 2.0g of triisopropanolamine, and NITSUKOL NP-
1.0 g of 18TX (manufactured by Nikko Chemicals Co., Ltd.) and 1.5 g of Fragrance Hydrangea No. 100 (manufactured by Kobayashi Perfume Co., Ltd.) are mixed, added to the above mixture, and stirred well. 76 ml of water was added to this to obtain a transparent aromatic gel that prevents viscosity from decreasing. Example 2 (Triisopropanolamine) Starch-acrylic acid graft polymer Sunwet 1M-300 (manufactured by Sanyo Chemical Co., Ltd.) 3 g, propylene glycol 20 g, water-soluble fragrance rose oil No. 5-
A (manufactured by Kobayashi Fragrance Co., Ltd.) 3g, glycerin 20g, triisopropanolamine 2.0g, Nitsukor NP-
After adding 1.0 g of 18TX and stirring well, 51 ml of water was added to obtain a stable transparent aromatic gel. Example 3 (Triisopropanolamine) Acrylic polymer Aqua Keep 4S (manufactured by Steel Chemical Industry Co., Ltd.) 0.8g, propylene glycol 20g, triisopropanolamine 2.0g, Nitsukol NP
11.0 g of -18TX and 1.5 g of the fragrance Osmanthus M2852 (manufactured by Kobayashi Perfume Co., Ltd.) were thoroughly stirred and mixed, and 75 ml of warm water was added to obtain a transparent aromatic gel. Example 4 (Triisopropanolamine) 40 g of propylene glycol to 0.6 g of acrylic polymer Aqua Keep 10SH (manufactured by Steel Chemical Industry Co., Ltd.),
2.4 g of Nitsukor NP-18TX, 1.6 g of the water-soluble fragrance Osmanthus M-2851-S (manufactured by Kobayashi Perfume Co., Ltd.) and 2.0 g of triisopropanolamine were well added.
After stirring thoroughly, 54 g of warm water was added to obtain a transparent aromatic gel. Example 5 (Monoethanolamine) 0.8 g of starch-acrylic acid graft polymer Sunwet SAP-300 (manufactured by Sanyo Chemical Co., Ltd.), 40 g of propylene glycol, and 1.0 Nitzkol NP-18TX.
g, 2.4 g of water-soluble fragrance Lila No. 1 (manufactured by Kobayashi Perfume Co., Ltd.) and 0.5 g of monoethanolamine were added, and after stirring well, 55 ml of water was added to obtain a transparent aromatic gel. Example 6 (Triisopropanolamine) 2.0 g of vinyl alcohol-acrylate copolymer Sumikagel (manufactured by Sumitomo Chemical Industries, Ltd.), 40 g of polyethylene glycol-300 (manufactured by Sanyo Chemical Industries, Ltd.), and Nitzkol NP-18TX2. After adding 4 g of the water-soluble fragrance Osmanthus M-2851-S (manufactured by Kobayashi Perfume Co., Ltd.) and 3.0 g of triisopropanolamine and stirring well, 51 ml of warm water was added to obtain a transparent aromatic gel. Example 7 (Monoethanolamine) Sodium polyacrylate cross-linked aquarium
1.2 g of CA (manufactured by Nippon Shokubai Chemical Co., Ltd.), 40 g of polyethylene glycol-400 (manufactured by Sanyo Chemical Industries, Ltd.),
Add 1.0 g of Nitsukor NP-18TX, 3.0 g of water-soluble fragrance rose oil No. 5-A (manufactured by Kobayashi Fragrance Co., Ltd.) and 1.0 g of monoethanolamine, stir well, and then add 55 g of water.
ml was added to obtain a clear fragrance. Example 8 (Triisopropanolamine) Sodium polyacrylate-Aquarik 1H
(manufactured by Nippon Shokubai Chemical Co., Ltd.) 2.8 g, propylene glycol 40 g, Nitsukor NP-18TX 2.4 g, water-soluble fragrance Osmanthus M-2851-S (manufactured by Kobayashi Fragrance Co., Ltd.)
1.6 g and 1.0 g of triisopropanolamine were added, stirred well, and 52 ml of water was added to obtain a transparent aromatic gel. Example 9 (Triisopropanolamine) Isoprene maleic acid copolymer K1 gel Kuraraisoban GH (manufactured by Kuraraisoprene Chemical Co., Ltd.)
1.6g, propylene glycol 40g, Nitsukor NP-18TX 1.0g, water-soluble fragrance rose oil No.
Add 3.0 g of 5-A (manufactured by Kobayashi Fragrance Co., Ltd.) and 1.0 g of triisopropanolamine, stir well, and add 53 ml of water.
was added to obtain a transparent aromatic gel. Example 10 Modified sodium polyacrylate (manufactured by Showa Denko K.K.)
1.5g with 10g of propylene glycol and ethanol
2.5g, glycerin 7.5g, Nitsukor NP-
18TX1.0g, Fragrance Hydrangea No.100 (manufactured by Kobayashi Fragrance Co., Ltd.)
1.5 g was added thereto, and the following viscosity reduction inhibitors (as shown in Table 18) were added thereto, mixed well, and 78 ml of water was added to each to obtain a transparent aromatic gel.

【table】

[Table] Experiment 1 The eight types of fragrances obtained in Example 10 were placed in a transparent 200 ml glass container, left in a room with scattered light, and the state of the gel was observed every 5 days. As a control, a gel containing no viscosity reduction inhibitor was used for comparison, and the number of days in which the viscosity of the gel significantly decreased (to the same level as water) was recorded. The results are shown in the following table (Table 2), and the viscosity lowering effect was remarkable.

【table】

[Table] Note that the water and fragrance evaporated in 27 days.

Claims (1)

[Claims] 1. A transparent gel produced using a highly water-absorbing synthetic resin such as modified sodium polyacrylate as a gel agent, and ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid as additives.
Addition of one or more selected from disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, triisopropanolamine, ethanolamine, n-propyl gallic acid, nickel dibutyldithio carbamate, phenyl-α-naphthylamine, and benzophenone derivatives. A gel that does not reduce viscosity. 2. The non-viscosity reducing gel according to claim 1, which contains 5% by weight or less of an additive. 3 Add ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid as additives to a transparent gel made from a highly water-absorbing synthetic resin such as modified sodium polyacrylate as a gel agent.
Adding one or more selected from disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, triisopropanolamine, ethanolamine, n-propyl gallic acid, nickel dibutyldithio carbamate, phenyl-α-naphthylamine, and benzophenone derivatives. A method for preventing gel viscosity reduction, characterized by: 4. The method for preventing a decrease in viscosity of a gel according to claim 3, wherein the content of the additive is 5% by weight or less.