JPS6318561B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for maintaining the effectiveness of a heating volatilization agent that volatilizes components by heating. Conventionally, there are insecticides and fragrances as heating volatilization agents that volatilize components by heating.For example, as an insecticide, a pyrethroid insecticide is impregnated and absorbed into a porous substrate such as pulp, asbestos, or a clay plate, and an electric heating device is used. Fragrance agents are known in which the insecticidal component is volatilized by heating at 120 to 190°C, or the fragrance is impregnated and absorbed into the base material and then volatilized by heating. However, when these insecticides and fragrances are heated, the amount of volatilization is high initially and the efficacy is excellent, but the amount of volatilization decreases significantly in a short period of time, resulting in a decrease in efficacy. Various attempts have been made to improve this drawback, but an economically inexpensive and good method has not yet been found. The present invention aims to improve the above-mentioned drawbacks, and by changing the type and blending ratio of the thermosetting resin, the duration of efficacy can be arbitrarily changed. Sustained efficacy of a heating volatilization agent characterized by holding and curing the agent, one or more selected from thermosetting resins, and at least one curing agent in a porous base material. It is related to the method. As the chemicals used in the present invention, various fragrances for air fresheners, heat-volatile pyrethroid and organic phosphorus insecticides, repellents and fungicides for mosquitoes, flies, cockroaches, etc. can be used. . Typical drugs are listed below. 1 Insecticide Γ 3-allyl-2-methylcyclopentane-2-
En-4-one-1-yl chrysanthemate (generic name: allethrin, hereinafter referred to as allethrin), and the geometric and optical isomer Γ of this drug Optical isomer of allethrin (trade name Pinamin Fuorte: manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as allethrin) Γ Geometric and optical isomers of allethrin (trade name: Exrin; manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as Exrin) Γ Geometric and optical isomers of allethrin (trade name: Bioallethrin; manufactured by Roussel-Niclaus, hereinafter referred to as bioallethrin) Γ 0,0-dimethyl 0-(2,2-dichloro)vinyl phosphate (DDVP) 2 Insecticide Γ Salicylic acid Γ Parachloro-meta-xylenol (PCMX) 3 Repellent Γ N,N-diethyl-meta-toluamide (below)
DET) and various fragrances for fragrances, such as lemon-based, rose-based, green-based, and diasmine-based fragrances. Furthermore, various commonly used additives such as insecticide efficacy enhancers, deodorants, and pigments can be optionally added to the above-mentioned chemicals. Although various thermosetting resins and their curing agents can be used in the present invention, typical thermosetting resins (hereinafter referred to as resins) and their curing agents are exemplified. 1 Epoxy resin curing agent: aliphatic amine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m
- Aromatic amines such as phenylene diamine, 4,4'-diaminodiphenylmethane,
One or more types selected from acid anhydrides such as phthalic anhydride, maleic anhydride, and hexahydrophthalic anhydride. 2 Polyester resin curing agent: benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, ditertiary butyl peroxide, methyl ethyl ketone peroxide,
One or more types selected from peroxides such as cobalt naphthenate. 3. Methacrylic acid resin curing agent: 1 selected from peroxides such as benzoyl peroxide and lauroyl peroxide.
More than a species. 4 Phenol resin curing agent: Acids such as oxalic acid, hydrochloric acid, phosphoric acid, and sulfonic acid, or alkalis such as ammonia, barium caustic soda hydroxide, tetraethylhydroxylamine, and Sumilite HP-44 to 45 (product name manufactured by Sumitomo Bakelite Co., Ltd.) One or more types selected from the following types. 5 Urethane resin curing agent: diamines such as ethylenediamine, isopropyldiamine, hexamethylenediamine, hydrazine, diols such as ethylene glycol, propane-1,2-diol, butane-1,4-diol,
From triols such as glycerin, trimethylolethane and hexanetriol, diacids such as succinic acid and adipic acid, lactones such as caprolactone and pivalolactone, and isocyanates such as 2,6-tolylene diisocyanate and 2,4-tolylene diisocyanate. One or more selected types. In the present invention, the ratio of resin and curing agent is
It is used in a range of 0.5 to 100 parts of curing agent per 100 parts, and varies depending on the type of resin and chemical and the method of retention. In addition, the ratio of the chemical to the resin and hardening agent varies depending on the holding method, and in the case of holding the chemical in a porous substrate and then coating and holding and curing the resin and hardening agent, the ratio is 100 parts of the chemical. The total amount of resin and curing agent is relatively small at 1 to 50 parts, but for products that are mixed with chemicals and held at the same time, it is relatively large at 10 to 500 parts per 100 parts of chemicals. It requires a resin and a hardening agent. Also,
Regarding the curing conditions in the present invention, it is preferable to cure at room temperature, but curing can be accelerated and completed by heating, and the above resin and curing agent meet these conditions. . In the present invention, as a method for retaining a drug, a resin, and a curing agent in a porous substrate, a mixture or a single agent thereof can be dropped, applied, sprayed, or immersed.
Even when the holding process involves two or more steps, the holding process can be carried out by appropriately repeating or combining these methods. Furthermore, regarding the order of holding the chemical, resin, and curing agent, for example, one that holds a mixture of three types, one that holds the chemical, then holds a mixture of resin and a hardening agent, and one that holds a mixture of the chemical and resin, and then holds the mixture of the resin and curing agent, and It is possible to retain only the agent. They are characterized by a single holding process, and are porous when the drug is insoluble in the resin or curing agent, or when a small amount of resin is used for the drug to obtain a sustained effect. It is used when coating the front or back side of a substrate, and is used when the curing agent is particularly unstable. As the porous substrate that can be used in the present invention, heat-resistant substrates such as pulpy asbestos and unglazed plates are preferable.
Further, regarding the shape of the porous substrate, a flat plate shape is preferable in order to increase the heating evaporation surface of the drug. Furthermore, auxiliary means such as increasing the surface area by making the surface of the porous base material uneven, changing the heating distribution by making the back surface which is the heated surface uneven, or increasing the surface area by providing through holes. Of course, it is also possible to take the shape, and the planar shape can be any shape such as a circle, an ellipse, a triangle, a rectangle, or a polygon. However, a heating device (electric heater) suitable for these shapes, planar shapes, sizes, etc. is required. As mentioned above, the present invention is a method for sustaining the effectiveness of a heat-volatizing agent that can be obtained easily and inexpensively by varying the types of resins and curing agents and their ratios to the chemicals. Examples are given below to explain the present invention in more detail. However, Epoxy resin No. 1: average molecular weight 355, epoxy equivalent 182-194 Epoxy resin No. 2: average molecular weight 470, epoxy equivalent 225-280 Epoxy resin No. 3: average molecular weight 350, epoxy equivalent 180-200 Polyester resin No. .1; Polylite TC-141
(Product name, manufactured by Dainippon Ink and Chemicals Co., Ltd.) Polyester resin No. 2; Polylite TP-122
(Product name, manufactured by Dainippon Ink and Chemicals Co., Ltd.) Phenol resin No. 1; Sumilite PR-50202 (Product name, manufactured by Sumitomo Bakelite Co., Ltd.) Phenol resin No. 2; Sumilite PR-50087 (Product name, Sumitomo Bakelite Co., Ltd.) (manufactured by company) Urethane resin No. 1; Polyoxypropylene triol average molecular weight 3000 OH number; 56 Example 1 Pulp material as porous base material 3 cm x 2 cm x 0.25
cm size, one that uses fragrance as the drug and holds a mixture of the drug, resin, and curing agent in the holding order, one that holds the chemical and then holds a mixture of resin and curing agent, and one that holds the mixture of the drug and resin. One was selected from among those that retained a mixture of the above and only the post-curing agent, and was then cured at room temperature to obtain a heating volatilization agent according to the present invention. (Table 1)

【table】

[Table] The heated volatilizing agent obtained according to the above-mentioned formulation of the present invention was heated with a heater having a surface temperature of about 150°C.
A comparative test was conducted to compare comparative examples and their effects on the duration of efficacy. (Table 2) Note that the effective volatilization rate was measured by gas chromatography by volatilizing in a closed container, collecting the air in the container with benzene.

【table】

[Table] When No. 1.8. and Comparative Example 1 of this Example are illustrated, the result is as shown in FIG. 1, and the excellent durability of the effect of the Example of the present invention is clearly shown. <Test Example 1> Formulations Nos. 1 and 8 in Example 1 and Comparative Example were compared in a sensory test. (Number of panelists: 10 men and women each) Strength of sensory test: (5) Very strong (2) Weak (4) Strong (1) Very weak (3) Moderate

[Table] Example 2 In the same manner as in Example 1, a heating volatilization agent according to the present invention for insecticides and repellents was obtained. (Table 4)

[Table] The heating volatile agent obtained according to the above-mentioned formulation of the present invention was heated with a heater with a surface temperature of about 150°C,
A comparative test was conducted on comparative examples and their effects on the duration of efficacy. (Table 5) The effective volatilization rate is determined by volatilizing in a closed container, capturing the air in the container with benzene per unit time, and measuring it by gas chromatography. The rate was calculated.

[Table] As is clear from Table 5, the formulation of the present invention exhibits stable volatilization for 0 to 10 hours, and
While transpiration continued even after 10 hours, in the comparative example, most of the drug was evaporated within 0 to 4 hours. <Test Example 2> A comparative test of the insecticidal efficacy against Culex Culex adults was conducted over time for Practical Formulation No. 13 and Comparative Example 3. Insecticidal efficacy test method 1 Test insect: Culex Culex adult 2 Test method (aeration device method) The test device was a cylinder with an inner diameter of 20 cm and a height of 43 cm, with Saran net placed over it, and a cylinder with an inner diameter of 20 cm and a height of 20 cm in two stages. Put it on your eyes. Furthermore, place a net and stack the third cylinder (inner diameter 20cm, height 20cm).
Place it on a glass disk (with a 5cm circular hole in the center) and set it on a 30cm high stand. In the test, the heating volatilization agent according to the present invention is brought into close contact with a heating plate and heated. Approximately 20 test insects are released into the third cylinder, a heating plate is placed in the center of the lower disk, and the number of insects knocked down is recorded over time by contacting the heating plate with the heated volatile paper. . 1, 2,
Tests were conducted after use for 4, 6, 8, and 10 hours. The results of the insecticidal efficacy test are shown in Figure 2. In Comparative Example 3, the efficacy decreased sharply from around 4 to 5 hours, but in Inventive Formulation No. 13, the efficacy decreased even after 10 hours. The efficacy was almost the same as that of .

[Brief explanation of the drawing]

Figure 1 shows formulations No. 1 and 8 of the present invention and comparative example 1.
Fig. 2 shows the results of a comparative test of the insecticidal efficacy of the present invention formulation No. 13 and Comparative Example 3 against Culex Culex adults.

Claims (1)

[Claims] 1. In a heating volatilization agent that volatilizes a chemical by heating, one or more selected from the chemical, a thermosetting resin, and at least one curing agent are held in a porous base material, A method for maintaining the effectiveness of a heating volatile agent characterized by curing it. 2. The method for maintaining the effectiveness of a heating volatilization agent according to claim 1, wherein the thermosetting resin is selected from epoxy resins, polyester resins, methacrylic acid resins, phenolic resins, and urethane resins.