JPH0313201B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a drug sustained release material. Conventionally, it has been known to mix a drug into a resin to achieve sustained release of the drug, but since the degree of sustained release of the drug is determined by the resin used, it is not possible to control the release of the drug as desired. There are many things. In addition, the phenomenon of blooming, in which the chemical is extruded during or after curing, is likely to occur, which has fatal drawbacks in terms of chemical loss and wetting, as well as safety during use and impact on other materials. . Therefore, in view of the current situation, the present inventors have conducted extensive research into a sustained release method that can prevent drug loss and appropriately control drug volatilization, resulting in the present invention. That is, in the present invention, after holding a layer made of resin A mixed with a drug on a base material, a layer made of resin B having a different composition from resin A is held on the layer, This is a sustained release material for drugs that is cured. Further, examples of the drug include one or more of insecticides, synergists, repellents, insect repellents, fungicides, fragrances, and deodorants. As described above, the present invention involves mixing a drug and a resin A, and controlling the amount of the resin A or the resin B to be laminated.
By adjusting the amount of resin A and resin B, and by selecting the respective compositions of resins A and B, plumping can be prevented and volatilization of chemicals can be extremely effectively controlled depending on the intended purpose. has. In the present invention, the above-mentioned mixing is a general term for retaining in the resin by kneading, impregnation, etc. In the present invention, when mixing resin A and a drug, the mixing ratio can be arbitrarily determined depending on the properties and purpose of the drug and resin A, but it is preferable to mix resin to 1 part by weight of drug. By uniformly mixing 0.1 to 100 parts by weight of A, the drug-containing resin A used in the present invention is obtained. The present invention can be produced by holding this resin A on a suitable base material and curing a sustained release composition obtained by laminating coating resin B on the resin A. Note that the amount of resin B to be laminated can be arbitrarily determined depending on its properties and purpose. Specific examples of the resins used in the present invention include the following. Cellulose derivatives include nitrocellulose,
Acetylcellulose, acetylbutyrylcellulose, methylcellulose, ethylcellulose, acetylpropionylcellulose, benzylcellulose, hydroxypropylcellulose and phosphorylated cellulose, etc. Examples of vinyl resins include polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, vinyl acetate, vinyl chloride copolymer, polyvinyl acetal, polyvinyl butyral, polystyrene, and polymethyl acrylate resin. Examples of alkyd resins include condensed resins made by modifying condensates of polyhydric alcohols such as glycerin and pentaerythritol and polybasic acids such as phthalic acid with oil or fatty acids to make them soluble. Acid-curing urea resins include urea with a low degree of etherification or urine/melamine cocondensation resins, etc. Epoxy resins include halogenated bisphenol type, resorcinol type, bisphenol F type, tetrahydrophenylethane type, novolac type, and polyalcohol.・
Polyglycol type, glycerin triether type,
Polyolefin type, epoxidized soybean oil or epoxy resin amine, etc. are available, and if necessary, amine curing agents such as diethylenetriamine, triethylenetetramine, m-phenylenediamine, diaminodiphenylsulfone polyamide, or phthalic anhydride, hexahydrophthalic acid are used. Organic acid anhydride curing agents such as acid anhydrides, pyromellitic anhydride, and maleic anhydride mixtures can be used. Examples of polyester resins include unsaturated dibasic acids such as maleic anhydride and phthalic acid, saturated dibasic acids such as adipic acid, phthalic anhydride, isophthalic acid, tetrachlorophthalic anhydride, and nethylene glycol, propylene glycol, and 1,3-butylene. glycol,
There are polyester resins made by condensing dihydric alcohols such as diethylene glycol, dipropylene glycol, and neopentyl glycol, and urethane resins are resins that have urethane bonds, and have isocyanates and at least two hydroxyl groups at the ends of the molecule. It is a reaction product with polyols, and the isocyanates include hexamethylene diisocyanate, naphthalene-1,5-diisocyanate, 4,4'-diphenylmethane diisocyanate, polymers of the above diisocyanates,
Reaction products of the above diisocyanates and trimethylolpropane, etc., polyols include ethylene glycol, propylene glycol, butylene glycol (1,3-butanediol), 1,2,
Polyhydric alcohols such as 6-hexanetriol, trimethylolpropane, glycerin, and sorbitol, polyethers that are polymers of the above polyhydric alcohols, and reaction products of the above polyhydric alcohols and their polymers with dibasic organic acids. Examples include certain polyester polyols, acrylic polyols, and alkyd polyols obtained by modifying the above polyester polyols with coconut oil or castor oil. Examples of polysaccharides include vegetable gums such as gum arabic, chitin, xatone, pectin, starch, and inulin, and examples of proteins include gelatin, casein, peptone, and albumin. Natural resins include sumac, cassieurosin or rosin methyl, monoethylene glycol,
Examples include esters such as diethylene glycol and glycerin, rosin derivatives such as hydrogenated rosin, dehydrogenated rosin, and polymerized rosin, amber, copal, cowri gum, dammer mastic, sandarac, shellac, and oleo resin. As the resin A, a resin having high affinity with the drug additive used is suitable, and a resin having a property that the drug does not bleed after mixing is preferable.
Preferred examples include aliphatic saturated hydrocarbon resins such as polyα-olefin and polyterpene, terpene/phenol copolymer resins, polyurethane resins, and vinyl acetate resins such as vinyl acetate/acrylic copolymer resins. B has properties that do not release from the sheet of drug additive-retaining resin A;
Resins having different resin properties are preferred, and examples thereof include cellulose resins such as methyl cellulose and hydroxyethyl cellulose, polyvinyl alcohol resins, polyvinyl acetate resins, polyethylene oxide resins, and rubber resins such as SBR.
Further, the combination of resins A and resins B is selected depending on the type of drug contained in resins A and the like. The drugs used in the present invention are not particularly limited, but include the following. Insecticides include pyrethrin, allethrin, phthalthron, resmethrin, permethrin, fuenvalerate, phenothrin, 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, pyridafentione, marathon, diprom, and carbamate insecticides such as propoxal and sevin; synergists such as S-421 and 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, etc. are used as insect repellents, naphthalene, camphor, paradichlorobenzene, etc. are used as insecticides, benzoic acids, sorbic acids, PCMX, BCA, thiophanate, triazine, Irgasan DP300, hinokitiol, etc. are used as fungicides.
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 depending on the purpose. The sustained-release material of the present invention can be used as a sheet-like member, furniture member, etc. that has sustained-release properties by utilizing the characteristics of the 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 metal foils or films 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. There are no particular limitations on the means for retaining the sustained release material of the present invention on the base material, for example, by coating, impregnating, dropping, kneading, etc., and applying it to the desired location in the form retained on the base material. It can be used by placing or pasting. The retained amount is not particularly limited and can be determined as appropriate, but it is sufficient to retain up to approximately 1 times the saturated impregnated amount of the base material, etc. By changing the mixing ratio of the drug and resin A, the drug treated in this way can obtain the desired controlled release properties and can be put to practical use as a product depending on the purpose and period of use of the drug. becomes. The present invention will be specifically described below based on examples. Example 1 Pure fat A mixed with the chemicals shown in Table 1 below
An amount equivalent to 75 g/m ² was uniformly coated on high-quality paper (80 g/m ² , 20×20 cm) with one side laminated with aluminum film and then cured. On top of the drug-containing resin A applied to this sheet, resin B shown in Table 1 below was applied uniformly in an amount equivalent to 100 g/m ² and heated to 100°C.
It was dried and cured for 5 minutes before use. Test Example 1 The remaining amount of the drug was analyzed over time using the treated sheet of Example 1 and, for comparison, a sheet treated with the same amount of the resin B used for the above lamination on a sheet treated with the same amount of the drug. The sustained release effects were compared. The test results are shown in Table 1.

【table】

[Table] Example 2 N, N-
Add and mix 0.25 parts by weight of diethyl-m-toluamide. Spread this mixture into raw fabric (15 x 15 cm) for 400 min.
After uniformly applying an amount equivalent to g/ ^m2 , drying and curing
SBR packing agent (manufactured by Numata Chemical Products Co., Ltd.)
An amount equivalent to 1400 g/m ² was applied, and jute was bonded and dried (100° C., 30 minutes) to obtain the sustained release material of the present invention in the form of 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, place one sugar cube, which has been weighed in advance, in the center of the insect-proof carpet, and place it in a container (40 x 30 x
25cm). (As a blank, an untreated carpet with sugar cubes placed on it was placed next to the insect-proof carpet as well.) Release 100 adult German cockroaches into this container and place it in a dark place at 25°C for 48 hours. Thereafter, the remaining amount of each sugar cube was measured, the amount of decrease was calculated, and the repellency rate was determined using the following formula. Repellency rate (%) = Reduction in blank sugar cubes - Reduction in insect-proof carpet top sugar cubes / Reduction in blank sugar cubes x 100 (Repellency of 80% or more is judged to be practically effective.) For comparison, N, N- 1 part by weight of diethyl-m-toluamide and 16.5 parts by weight of SBR backing agent are mixed uniformly, and this mixture is made into a raw fabric (15 x 15 cm).
An insect-proof carpet coated with an amount equivalent to 1400 g/m ² was used. In addition, the repellent efficacy test was conducted on the front and back sides of the insect repellent carpet. The test results are shown in Table 2.

[Table] Example 3 After uniformly mixing 1 part by weight of MA-108 and 9 parts by weight of a molten aliphatic saturated hydrocarbon resin (manufactured by Arakawa Chemical Co., Ltd., trade name Alcon P-70),
Apply an amount equivalent to 80 g/m ² evenly onto a high-quality paper (15 x 20 cm) of 80 g/m ² . A mixture of 1 part by weight of linear polyethylene oxide homopolymer (manufactured by Union Carbide, trade name: Polyox WSR N-10) and 9 parts by weight of water was evenly applied to both sides of this sheet in an amount equivalent to 100 g/m ² . This was dried and cured at 100° C. for 25 minutes to obtain the sustained release material of the present invention in the form of an insect repellent sheet. Test Example 3 An efficacy test of the sheet insect repellent shown in Example 3 was conducted over time to compare the sustainability of the efficacy and confirm the sustained release effect. In other words, using a 50-capacity drawer filled with clothing, place three sheets of insect repellent in the middle of the clothing, and then place 20 35-day-old burr larvae and 2 x 2 cm muslin cloth (approximately 50 mg) between the clothing over time. Place a 60-mesh nylon bag containing it, cover it, and place it in a dark place at 25°C. Two weeks after the larvae were placed, the number of dead larvae was counted to determine the mortality rate. In addition, 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 3 and then the same amount of the same resin was laminated thereon. Note that a drawer containing no drug was used as a blank, and larvae were placed between clothes. (Two tests each, 1,
This was done after 2, 4, 6, 9, and 12 months. ) The test results are shown in Table 3.

[Table] Example 4 α-olefin resin emulsion (solid content 49
%, manufactured by Aica Kogyo Co., Ltd.) 0.25 part of Sumithion is added and mixed to 1 part by weight. This mixture was evenly applied in an amount equivalent to 50 g/m ² to high-quality paper (80 g/m ² , 20 x 20 cm) laminated with aluminum film on one side, dried (100°C, 5 minutes), cured, and then coated with polyurethane. Resin emulsion (solid content 20
%, manufactured by Nippon Soflan Kako Co., Ltd.) in an amount equivalent to 75 g/m ² was uniformly applied, dried (100° C., 5 minutes) and cured to obtain the sustained release material of the present invention in the form of an insecticidal sheet. Test Example 4 The efficacy test of the insecticidal sheet shown in Example 4 was conducted over time to compare the sustainability of the efficacy and confirm the sustained release effect. In other words, place the insecticidal sheet in a container (40 x 30 x 25
cm), release 50 adult German cockroaches, and leave in a dark place at 25°C. Twenty-four hours after the installation of adult German cockroaches, the number of deaths was counted to determine the mortality rate. For comparison, an insect repellent sheet was used in which the same amount of Sumithion was applied to high-quality paper laminated with aluminum on one side and the same amount of the same resin was applied. The test results are shown in Table 4.

[Table] Example 5 1 part by weight of citronellol and molten polyterpene resin (manufactured by Yasushi Oil Industries Co., Ltd., trade name: YP)
After uniformly mixing 0.3 parts by weight of resin A#800)
An amount equivalent to 80 g/m ² is uniformly applied to 120 g/m ² high-quality paper and cured. Hydroxyethyl cellulose (manufactured by Union Carbide,
A solution obtained by adding 15 parts by weight of water to 1 part by weight (trade name: HEC QP-3L) was uniformly applied in an amount equivalent to 150 g/m ² , and dried and cured at 100° C. for 25 minutes. This sheet was cut into 20×30 cm pieces to obtain a sustained release material of the present invention in the form of an aromatic plate. Test Example 5 A sensory test of the fragrance plate shown in Example 5 was conducted over time to compare the persistence of the fragrance and confirm the sustained release effect. That is, two fragrance plates were hung from the ceiling in a four-and-a-half tatami Japanese-style room, and the level of fragrance was sensually examined. For comparison, an aromatic plate treated with only citronellol in the same amount was used. The test results are shown in Table 5.

【table】

Claims (1)

[Claims] 1. After holding a layer made of resin A mixed with a drug on a base material, a layer made of resin B having a different composition from resin A is held on the layer. , a sustained release material for drugs that is cured. 2. The sustained release material for a drug according to claim 1, wherein the drug is one or more of insecticides, synergists, repellents, insect repellents, fungicides, fragrances, and deodorants.