JPH0312042B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a drug sustained release material. It has been known to mix drugs into resins to achieve sustained release of drugs, but the degree of drug release depends on the resin used, and it is difficult to achieve sustained release of highly volatile drugs. In many cases, the controlled release of drugs could not be controlled as expected.
In addition, it tends to cause a blooming phenomenon in which the chemical is pushed out to the outer surface during or after curing, which has fatal drawbacks in terms of chemical loss and wetting, as well as safety during use and impact on other materials. Ta. In view of the current situation, we have conducted extensive research into sustained release materials that can prevent drug loss and appropriately control drug volatilization, resulting in the present invention. That is, the present invention relates to a drug and a rosin ester, a hydrogenated rosin ester, an aliphatic saturated hydrocarbon resin, a polyterpene, a terpene/phenol copolymer, an ethylene/vinyl acetate copolymer, or a maleic acid resin (hereinafter referred to as "resin A"). After curing, the powder/granules are further mixed with polyvinyl acetate, polyvinylidene chloride, α-olefin resin, ionomer resin, polyurethane resin, vinyl acetate/acrylic copolymer, and polyvinyl acetate/acrylic copolymer. This is a drug sustained release material characterized by being mixed with chain polyethylene oxide homopolymer or SBR emulsion (hereinafter referred to as "resin emulsion") and hardened. In the present invention, as described above, the drug and resin A are mixed together, hardened, made into powder or granules, and further mixed into a resin emulsion and cured to prevent the loss of the drug and the blooming of the drug, and to prevent the drug from blooming. It has the characteristic that the volatility of the material can be controlled arbitrarily and extremely effectively depending on the purpose. In the present invention, the mixing ratio when mixing the drug and resin A to form powder or granules can be determined as desired depending on the properties of the drug and resin emulsion and the purpose, but preferably, 1 part by weight of the drug is mixed with resin A. A suitable amount is 1 to 100 parts by weight, and any commonly used methods can be used for powdering and granulating. Further, the mixing ratio of the resin emulsion with the resin emulsion can be arbitrarily determined according to the purpose as described above, but it is preferably 0.1 to 50 parts by weight of the resin emulsion per resin content per 1 part by weight of the powder/granules. The resin A used in the present invention is a rosin ester, a hydrogenated rosin ester, an aliphatic saturated hydrocarbon resin, a polyterpene, a terpene/phenol copolymer, an ethylene/vinyl acetate copolymer, or a maleic acid resin, and A mixture of two or more types may be used. Furthermore, the resin emulsion used in the present invention includes polyvinyl acetate, polyvinylidene chloride, α-
Olefin resin, ionomer resin, polyurethane resin, vinyl acetate/acrylic copolymer, linear polyethylene oxide homopolymer, or
It is an SBR emulsion, and two or more types may be used in combination. These resin emulsions can easily form a resin film on the powder or granules by simply curing, and can form a film suitable for sustained release of drugs. The drugs used in the present invention are not particularly limited, but include the following. Insecticides include pyrethrin, allethrin, phthalthrin, resmethrin, permethrin, huenvalerate, phenotrin, flamethrin, cypermethrin, cyphenotrin, 1-ethynyl-
2-Methyl-2-pentenyl 2,2-dimethyl-
3-(2'-methyl-1'-propenyl)-cyclopropane-1-carboxylate (hereinafter referred to as MA)
pyrethroid insecticides such as DDVP, diazinon, sumithion, marathon, dibrom, etc., carbamate insecticides such as pyridafentione, propoxal, sevin, etc. Synergists such as S-421, Pipe Ronyl butoxide, cinepirin 222, cinepirin 500, piperonal dimethyl acetal, etc. are used as repellents, N,N-diethyl-m-toluamide, butyryl acetanilide, ethylhexanediol, butylhydroxyanisole, p-t-butyl-m -cresol,
Insect repellents include naphthalene, camphor, paradichlorobenzene, etc.; fungicides include benzoic acids, sorbic acids, PCMX, BCA, thiophanate, triazine, Irgasan DP300, hinokitiol,
TBZ, Daconil, etc., and fragrances/deodorants include linalool, geraniol/cinnamic alcohol, anethole, citral, citronellal, cinnamaldehyde, lilyal, limonene, vanillin, musk ketone, cineol, lauric acid methacrylate, etc. These drugs can be used in any combination of one or more types depending on the purpose. The sustained release material of the present invention can be used as it is by forming it into a predetermined shape during curing, but it can also be used in the form of being held on a base material. The sustained-release material is used as a sheet-like member, furniture member, etc. that has pest repellent properties by utilizing the characteristics of its base material. Examples of the base material here include synthetic resin sheets such as polyethylene, polypropylene, polyamide, polyvinyl chloride, polyvinylidene chloride, and polyester, animal/vegetable or inorganic fiber sheets (paper,
(cloth, nonwoven fabric, leather, etc.), mixed sheets or blended fabrics of synthetic resins and inorganic fibers or powders, blended fabrics or nonwoven fabrics of the above synthetic resins and animal and plant fibers,
Examples include foils or films of metals such as aluminum, stainless steel, and zinc, and laminated sheets of the above various sheets. Further, as the above-mentioned base material, molded materials such as natural wood such as awn, pencil fern, oak, etc. and plastics such as vinyl chloride resin, chlorinated polyethylene, polyethylene, polypropylene, etc., which are used as furniture members, can also be effectively used. The means for holding the sustained release material of the present invention on the base material is as follows:
There are no particular restrictions, and the uncured mixture after mixing may be held by coating, impregnation, dropping, kneading, etc., and then cured, and placed on the target location in the form held by the base material. It can be used by bonding or bonding. The retained amount is not particularly limited and can be determined as appropriate, but it is preferably up to the saturation impregnated amount of the base material, etc. By changing the mixing ratio with resin A, the drug treated in this way can achieve the desired sustained release properties, and can be put to practical use as a product depending on the purpose and period of use of the drug. . The present invention will be explained in detail below based on examples. Example 1 The chemicals listed in Table 1 below were mixed with Resin A, formed into a plate, hardened or dried, and pulverized with an atomizer. After kneading 200 mesh powder with resin emulsion, 72 g/ ^m2 high quality paper (20 x 20
After applying an amount equivalent to 60 g/m ² to cm), dry at 100℃ for 5 minutes.
It was cured and used as a sheet. Test Example 1 Using the treated sheet of Example 1 and a sheet prepared by mixing only the drug and resin emulsion (comparison sheet), the sustained release effects were compared by analyzing the residual amount of the drug over time. The test results are shown in Table 1.

【table】

[Table] Example 2 0.25 parts by weight of N-diethyl-m-toluamide was added and mixed with 1 part by weight of a molten aliphatic saturated hydrocarbon resin (manufactured by Arakawa Chemical Co., Ltd., trade name Alcon P-70). After cooling and solidifying, it is crushed to form a powder. Add and mix 4 parts by weight of SBR-based packing agent SBR-based emulsion (manufactured by Numata Chemical Products Co., Ltd.) to 1 part by weight of this powder, and apply the mixture to raw fabric (30 x 30 cm) in an amount equivalent to 1.4 kg/ ^m2 . After coating, jute was laminated and dried (100°C, 30 minutes), the sustained release material of the present invention was obtained as an insect repellent carpet. Test Example 2 The efficacy of the insect repellent carpet shown in Example 2 was tested over time to compare the sustainability of the efficacy and confirm the sustained release effect. That is, transplant 10 g of a saturated medium on the back side of a 60 x 60 cm tatami overlay, apply adhesive around the overlay, seal the back side of the tatami with a 60 x 60 cm vinyl sheet, and transfer to the overlay surface only through the holes in the overlay. It was set to move. When the movement of woolly mites onto the surface of the overlay was observed, an insect-proof carpet was placed on the overlay and the specimen was placed indoors at 28°C and 90% humidity. The results were determined by counting the number of woolly mites on nine sheets of black high-quality paper (5 x 5 cm) placed on the carpet after 48 hours. In addition, by the method of Example 2, N,N-diethyl m-
An insect repellent carpet with an equal amount of toluamide only was used as a comparison. The test results are shown in Table 2.

[Table] Example 3 0.25 parts by weight of DDVP was added and mixed with 1 part by weight of molten hydrogenated rosin ester (manufactured by Arakawa Chemical Co., Ltd., trade name: Ester Gum H), cooled and solidified, and then pulverized. Powder and eggplant. This powder 1
parts by weight, urethane resin emulsion (solids content 20
%, manufactured by Nippon Soflan Kako Co., Ltd.) was uniformly mixed with 4 parts by weight and 100 g/m2 was added to 120 g/ ^m2 of high-quality paper.
After applying an amount equivalent to m ² , it was dried and cured at 100°C for 5 minutes. This sheet was cut into 5×10 cm pieces to obtain the sustained release material of the present invention as an insecticidal sheet. Test Example 3 The efficacy of the insecticidal sheet shown in Example 3 was tested over time to compare the sustainability of the efficacy and confirm the sustained release effect. That is, a pillow containing about 1.7 kg of buckwheat moths was used, three insecticidal sheets were placed inside the buckwheat moths, and then, over time, a 60 mesh nylon bag containing 25 adult moths and fishmeal was placed inside the buckwheat moths. After sealing the pillow in a polyethylene (30μ) bag, it was left in a dark place at 25°C. The number of deaths was counted 7 days after the establishment of the adult Kokunus moths, and the mortality rate was determined. For comparison, insecticidal sheets treated with the same amount of DDVP were used. The test results are shown in Table 3.

[Table] Example 4 0.3 parts by weight of PCMX was added to 1 part by weight of a molten aliphatic saturated hydrocarbon resin (manufactured by Arakawa Chemical Co., Ltd., trade name Alcon P-70), and the mixture was cooled and mixed.
After solidification, it is crushed to form a powder. 1 part by weight of this powder and vinyl acetate resin emulsion (solid content)
A homogeneous mixture of 4 parts by weight of 50% (manufactured by Aica Kogyo Co., Ltd.) was applied to both sides of a board of red lauan (100 x 100 x 0.7 mm) in an ^amount equivalent to 100 g/m2 on each side. The plates were bonded together and, after crimping, the sustained release material of the present invention was obtained as a mold-proof plywood. Test Example 4 An efficacy test was conducted on the mold-proof plywood shown in Example 4 according to the mold resistance test method (JISZ2911), and the sustainability of the efficacy was compared to confirm the sustained release effect. That is, a potato decoction was attached to a mold-proof plywood board, and after air-drying, a mixed suspension of test bacterial spores was spray-inoculated every month, and cultured for 14 days in a thermostat at 30°C and 90-95% RH. The extent of mold outbreak was investigated. The strain is
Penicillium citrnum ATCC 9849 Rhizopus
nigricans SN32 Chaetomium globosum
ATCC 6205.Aapergillus oryzae IFO 4075-4
I tried the seeds. For comparison, a mold-resistant plywood treated with the same amount of PCMX was used. The test results are shown in Table 4.

[Table] Example 5 1 part by weight of MA was added to 5 parts by weight of melted terpene-phenol copolymer resin (manufactured by Yasushi Oil Industries Co., Ltd., trade name YS Polyster T#130) and mixed, then cooled, solidified, and pulverized. , powder and eggplant. 3 parts by weight of this powder and linear polyethylene oxide homopolymer (manufactured by Union Carbide, trade name:
Mix 1 part by weight of Polyox WSR N-10) and 9 parts by weight of water to give 75g/ ^m2 .
Spread evenly on ^m2 high-quality paper (15 x 20 cm) and heat at 100℃25
The material was dried and cured for several minutes to obtain a sustained release material of the present invention as an insect repellent sheet. Test Example 5 Using a 50-capacity drawer filled with clothes, three insect-proof sheets manufactured in Example 5 were placed in the middle of the clothes, and then 20 35-day-old burr larvae and a 2 x 2 cm muslin cloth were placed between the clothes over time. A 60-mesh polyamide bag containing (approximately 50 mg) was placed, and the lethal dose of larvae was counted two weeks after the larvae were placed, to determine the mortality rate. (Storage conditions: 25℃ in the dark). As a comparison, an insect repellent sheet was used in which high-quality paper was treated with only the same amount of the chemical used in Example 5 and coated with the same amount of the resin emulsion. As a blank, a drawer containing no chemicals was used, and larvae were placed between clothes. The test results are shown in Table 5 below.

【table】

[Table] Shows the average value of two series

[Claims]

1 The main constituents are silica and at least one metal oxide selected from the group consisting of groups of the periodic table, groups of the same group, groups of the same group, and groups of the same group that can be combined with silica, and the particle size is A dental composite filling material made of a vinyl polymer containing an inorganic oxide with a size of 0.1 to 1.0 μm and a spherical shape. 2. The dental composite filling material according to claim 1, wherein the inorganic oxide has a specific surface area of 4.0 to 40 m ² /g. 3. The dental composite filling material according to claim 1, wherein the particle size of the composite filling material is in the range of 0.1 to 150 μm. 4 The proportion of inorganic oxide in the composite filler is 50%.
90% by weight of the dental composite filling material according to claim 1.