JPS61176502A - Thermally molded article for insecticidal and fungicidal use - Google Patents

Abstract

PURPOSE:To provide the titled molding material stable to thermal molding, by compounding a polymeric material, an active pesticidal component and a heat stabilizer consisting of a phthalic acid ester, phosphoric acid ester, an organic acid or its ester, or their mixture. CONSTITUTION:A polymeric material such as polyethylene, polybutadiene, polyvinyl chloride, etc., is mixed with an active posticidal component such as insecticide, fungicide or other agent, and the mixture is subjected to the thermal molding. In the above process, the molding mixture is incorporated with a heat stabilizer consisting of a phthalic acid ester, a phosphoric acid ester, an organic acid or its ester, or their mixture. The amounts of the active pesticidal component and the heat stabilizer are preferably 0.1-5.0pts. and 0.1-10.0pts. per 100pts. of the polymeric material, respectively. EFFECT:The heat-decomposition of the active pesticidal component can be suppressed and the retention of the component can be meintained at a high level.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] This invention relates to a heat-molded product for insect repellent and antibacterial use.

[Conventional technology]

Conventionally, in order to impart insect repellent and antibacterial effects to molded products of polymeric materials such as resin or rubber that are molded through a heating process, a method has been used in which active pesticide ingredients are kneaded into molded products before molding. However, active pesticide ingredients are generally sensitive to heat and undergo thermal decomposition during the heat molding process, significantly reducing their insecticidal, insect repellent, bactericidal or antibacterial efficacy or shortening their duration, resulting in economic disadvantages. It was difficult to adopt such a method unless the Therefore, instead of this, a sheet, film, paper, etc. coated or impregnated with an agrochemical active ingredient may be applied to the molded product after heat molding, and these may be laminated together, or an adhesive containing an agrochemical active ingredient may be used. These active ingredients easily fall off,
Such a method cannot be said to be satisfactory, since it is not preferable from the viewpoint of human safety as well as the persistence of the medicinal effect due to diffusion or dissolution.

[Problem that the invention seeks to solve]

Therefore, this invention is an attempt to solve the various problems in the prior art, such as the agrochemical active ingredients mixed in through thermoforming causing thermal decomposition, resulting in decreased efficacy, shortened duration, and economic disadvantage. Measures to solve the problem] Combining one or more of phthalate esters, phosphate esters, or organic acids or their esters as a heat stabilizer for the active ingredients of agricultural chemicals. We adopted the method of using a composition that 12 is detailed below.

First, the heat-molded product in this invention is a product that is molded through a heating process (for example, at around 100° C. or higher), and the molding method and shape thereof are not particularly limited.

In other words, the molding method is, for example, an inflation method,
Calender method, extrusion method, injection method, press method, blow method,
Other so-called thermoforming methods such as vacuum forming, pressure forming, drawing, pre-stretching, and matt molding may also be used, and the shapes include films, sheets, plates, fibers (cloth), rods, etc. It may be any of a tube, a sphere, a deformed body, a hollow body, a multilayer (laminated) body, a foam, a composite, and the like.

In addition, the polymeric material of this invention is a polymeric substance (natural or synthetic) such as resin or rubber, and if necessary, a plasticizer, a crosslinking agent (a vulcanizing agent, a curing agent), etc. , lubricants, antioxidants, ultraviolet absorbers, fillers (strengthening agents, reinforcing agents), antistatic agents, flame retardants (flame retardants), colorants,
Although auxiliary materials commonly used in the polymer chemical industry such as heat stabilizers, blowing agents, and other modifiers may be added, considering the inherent heat resistance of the agricultural chemical active ingredients described below,
At present, the polymer material of this invention has a melting temperature, softening temperature, temperature of various reactions such as hardening and foaming, etc. of about 2.
00''C or less, for example, aliphatic monoolefin polymers such as polyethylene and polypropylene, monoolefin polymers such as ethylene-vinyl acetate copolymer, ethylene-propylene rubber, polybutadiene, butadiene-styrene rubber, Diene polymers such as polyisoprene, acrylonidonal-butadiene rubber, chloroprene rubber, chlorine-containing polymers such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene or their copolymers, and other aliphatic or vinyl group-containing polymers. It may be an aromatic polymer, an initial polymer (prepolymer) of a reactive polymer, a prepreg of a thermosetting resin such as a phenolic resin, or the like.

When adding the above-mentioned auxiliary material to such a polymeric substance, the type and amount of the auxiliary material should be considered in relation to the agricultural chemical active ingredient.

For example, inorganic salts of alkali metals or alkaline earth metals, such as calcium carbonate, generally have a negative effect on the stability of pesticide active ingredients, but as polymeric substances, vinyl chloride resin 100! Add auxiliary materials such as 50 parts by weight of plasticizer, 2.2 parts by weight of vinyl chloride resin stabilizer, 5 parts by weight of white carbon, 1 part by weight of agricultural chemical active ingredient fenitrothion, and heat stabilizer azelaic acid di-2. A sample was prepared by adding 45 to 200 parts by weight of calcium carbonate as a filler based on a composition containing 1 part by weight of ethylhexyl, and the sample was mixed at ioo°C, 150°C, 180°C and 20°C.
It is clear from Table 1 illustrating the relationship between the amount of calcium carbonate blended and the residual rate (%) of pesticide active ingredients when heated (using a hot roll) to 0°C (holding time at each temperature is 30 minutes). As is obvious, it is desirable that the amount of the filler to be blended is small, but if the blending ratio is appropriately selected, the residual rate of the agricultural chemical active ingredient can be maintained above a certain level. In other words, from the example in Table 1, the carbonation power is
1 Table 10 if the amount of lucium blended is within 2001 parts
The residual rate of agricultural chemical active ingredients at temperatures above 0°C can be maintained at about 20% or more.

Next, the agricultural chemical active ingredients of this invention include insecticides, fungicides, and other drugs, including but not limited to fenitrothion, fenthion, cyanophos, chlorpyrifos-methyl, pyridafenthione, propoxur, and BP.
In addition to insecticidal ingredients such as MC, phenothrin, propentaphos, thiabentazole, O-phenylphenol, P
CMX.

Examples include bactericidal components such as isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, diphenyl, allyl inthiocyanate, and sorbic acid.
It may be either a single component or a mixture of these components.

The phthalate esters, phosphate esters, organic acids, or esters thereof used as heat stabilizers for these agricultural chemical active ingredients are not particularly limited, but examples of phthalate esters include butylbenzyl phthalate, dilauryl phthalate, and phthalate. diheptyl acid, dipropyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisodecyl phthalate,
7p phosphoric acid')-2: r-tylhexyl, benzyl n-butyl phthalate, etc., and phosphoric acid esters include tricresyl phosphate, phosphoric acid (trisisopropylphenyl), tributyl phosphate, triethyl phosphate, phosphoric acid Trioctyl, triphenyl phosphate, etc., as organic acids or their esters such as oleic acid, palmitic acid, stearic acid, myristic acid, adipic acid, azelaic acid, glycerin monooleate, dioctyl adipate, methyl palmitate, dibutyl adipate Diglycol, di-2-ethylhexyl azelaate, methyl myristate, ethyl myristate, methyl stearate, ethyl stearate, 2-ethylhexyl alcohol, n-phthyl caprate, di-2-ethylhexyl sebacate, sorbitan fatty acid ester, acetyl ricinol Methyl acid, methyl anthranilate, isoamyl isovalerate,
Examples include ethyl isovalerate, ethyl enanthate, oxyethylene higher aliphatic alcohol, ethyl caprate, ethyl caprate, allyl caproate, ethyl caproate, isoamyl formate, geranyl formate, and benzyl propionate. There is no problem whether the heat stabilizer for these agricultural chemical active ingredients is used alone or in combination of two or more.

The mixing ratio (weight) of the above-mentioned polymeric material, agricultural chemical active ingredient, and heat stabilizer for the agricultural chemical active ingredient should be determined by considering the medicinal efficacy and economical efficiency of the agricultural chemical active ingredient. Active ingredient 0.1-5.0 parts, heat stabilizer 0.
1 to 10.0 parts may be used as a practical guideline. In addition, the method for blending these can be applied directly to the method of adding various additives in ordinary resin processing or rubber processing, and it is possible to mix them before heat molding or at the same time as heat molding. do not have.

[Effect]

As in the present invention, the phthalate ester, phosphate ester, or organic acid or a mixture of two or more thereof added to the polymer material suppresses the thermal decomposition of the agricultural chemical active ingredient at temperatures above 100°C. , shows the effect of maintaining a high residual rate of agricultural chemical active ingredients in the heat-molded product.

〔Example〕

Examples 1 to 4: Table 2 55 parts of vinyl chloride resin was selected as the polymer material, and to this was added 27 parts of plasticizer, 14 parts of calcium carbonate, 1.2 parts of vinyl chloride resin stabilizer, 0.55 part of pigment, and white. carbon 1
．． Based on a product containing 25 parts of auxiliary materials and 0.5 part of the insecticidal ingredient fenitrothion, 7-talate ester, phosphate ester, and organic acid ester were added as shown in Table 2. and each at 160℃, 3
After heating and mixing for 0 minutes, the mixture was molded into a sheet with a thickness of 0.5 mm using a calendar molding machine. The residual rate (%) of fenitrothion in each sheet obtained was 6% for the control product.
．． Even though it was only 3%, it was more than 90% in all cases. The efficacy against woolly mites and German cockroaches was also determined, and the results are also listed in Table 2. Here, the efficacy against woolly mites is 50mm x 50mm
200 to 300 woolly mites were brought into contact with each test sample, and after 24 hours, the number of dead woolly mites was measured using a microscope.
Thirty German cockroaches were reared on each test specimen of 00 mm for 24 hours with free access to food and water.

The number of deaths after 48 and 78 hours was counted and the number was expressed as a percentage.

From Table 2, it is clear that although no effect on cockroaches was observed when the control product was used, the remarkable medicinal effects of fenitrothion remained in all cases in Example IN4.

Examples 5 to 11: Table 3 Polymer - 50 parts of vinyl chloride resin as material, 25 parts of plasticizer
parts, vinyl chloride resin stabilizer 1.0 parts, calcium carbonate 3 parts
0.0 part, white carbon 7.2 parts and pigment 0.5
Based on 5 parts, calcium carbonate as a filler,
Fenitrothion as an insecticidal ingredient and triphenyl phosphate as a stabilizer were blended in the proportions shown in Table 3, and Examples 1-
It was made into a sheet by the same heat forming as in 4. The residual rate of fenitrothion in the obtained sheet was determined, and the results are also listed in Table 3. The effect of adding triphenyl phosphate was significant.

Examples 12 to 18: The blending standards of vinyl chloride resin, plasticizer, vinyl chloride resin stabilizer, filler, and pigment in Examples 5 to 11 remained the same, and only the white carbon in Table 4 was reduced to 6.7 parts. Sheets were prepared by performing the same heat treatment as in Examples 1 to 4, except that the amounts of fenitrothion and methyl myristate were changed to the proportions shown in Table 4, and the residual rate of fenitrothion in the obtained sheets was determined. . The results are also shown in Table 4, and the effect of adding methyl myristate was also significant.

Examples 19 to 25: Calcium carbonate as a filler, fenthion as an insecticidal ingredient, and tri-n-butyl phosphate as a stabilizer were mixed in the ratio shown in Table 5 to the standard mixture with the same blending ratio as Examples 5 to 11. A sheet was molded by performing the same treatment as in Examples 1 to 4 except for the following. The residual rate of fenthion in this sheet was determined, and the results are also listed in Table 5, and the effect of adding tri-n-butyl phosphate was also significant.

Table 5 Examples 26 to 32: Phenothrin was used in place of the insecticidal ingredient fenitrothion used in Examples 12 to 18, and a mixture of trimethyl phosphate and methyl palmitate was used in place of the stabilizer triphenyl phosphate. Except for the above, sheets were produced by performing exactly the same operations as in Examples 12 to 18, and the residual rate (%) of phenothrin in the obtained sheets was determined. The results are also shown in Table 6, and it was found that the mixture of phosphoric acid ester and palmitic acid ester also showed remarkable thermal stability.

Table 6 Examples 33 to 39: A mixture of fenitrothion and phenothrin was used instead of the insecticidal ingredient fenitrothion in Examples 12 to 18.
In addition, sheets were prepared by carrying out exactly the same operations as in Examples 12 to 1.8, except that dioctyl phthalate was used instead of the stabilizer triphenyl phosphate, and the respective residual amounts of fenitrothion and phenothrin in the obtained sheets were The rate (season) was calculated.The results are also listed in Table 7,
Table 7 Dioctyl phosphate was found to exhibit remarkable thermal stability against both insecticidal ingredients, fenitrothion and phenothrin.

Examples 40 to 43: Table 8 Sheets were prepared by carrying out exactly the same operations as Examples 1 to 4, except that the synthetic resin, filler, insecticidal component, bactericidal component, and stabilizer as shown in Table 8 were blended. Then, the residual rate (%) of the insecticidal component and bactericidal component in the obtained sheet was determined. The results are listed in Table 8, and it was found that when any resin was used, the insecticidal and fungicidal components exhibited remarkable thermal stability by adding esters of phthalic acid, stearic acid, or adipic acid. Ta. In addition, control products were prepared in which no stabilizer was added to each of Examples 40 to 43, but in all cases, the active ingredients were significantly decomposed.

Example 44: In order to examine the stability of the insecticidal component under the environmental conditions during actual use of the insect repellent and antibacterial heat molded product of the present invention, the following sample A and sample B as a control product were prepared. Each sample was stored in a desiccator at 35° C. and 95% humidity.

Sample A was the same as the sheet of Example 3, including 55 parts of vinyl chloride resin, 27 parts of plasticizer, 14 parts of calcium carbonate, 1.2 parts of vinyl chloride resin stabilizer, and 0.0 parts of pigment.
55 parts of white carbon, 1.25 parts of white carbon, 0.5 parts of fenitrothion as an insecticidal ingredient, and 0.5 parts of dioctyl adipate as a stabilizer were heated and mixed at 160°C for 30 minutes. The sheet was formed into a 5 mm sheet and cut to a size of 50 mm><50 mm.

Sample B is a 50 mm paper insect repellent sheet with an added amount of fenitrothion of 1.5 g per 1 m2 by immersing paper in an acetone solution of fenitrothion and then evaporating the acetone.
It was cut into a size of 50mm x 50mm.

Sample C is a commercially available fenitrothion powder with a concentration of 1.5.
% (w/w).

When the residual percentage of fenitrothion in each sample stored in a desiccator was determined after 1 month, 3 months, and 6 months, taking the content of fenitrothion immediately after molding as 100, the results were as shown in Table 9. The results were obtained.

Table 9 As is clear from Table 9, the insecticidal component in the thermoformed product of the present invention (Sample A) exhibited an extremely excellent persistence that had not been seen before.

Example 45: 100 parts of vinyl chloride resin, 50 parts of plasticizer, 2.2 parts of vinyl chloride resin stabilizer, 50 parts of calcium carbonate, 5 parts of white carbon and other auxiliary materials, 1 part of anti-mold ingredient thiaventazole, and heat stabilizer. A composition consisting of 1 part of di-2-ethylhexyl azelaate was heated on a heating table at 160°C for 30 minutes, and then formed into a sheet with a thickness of Q and 5 mm using a calendar molding machine.
It was cut into a size of 0mm x 5Qmm. In addition, as control products, the vinyl chloride resin sheet of previous B which does not contain anti-mildew ingredients (this is called Sample Ri), paper coated with anti-mildew ingredients (this is called Sample E), and ordinary filter paper (this is called Sample E) were used. This will be referred to as sample F). The molded sheet of the present invention and the control product were placed on a medium, blue mold and black mold were cultured, and the state of growth thereof was observed. The judgment criteria at that time are as follows. That is, -No growth at all+ The area of the growing part of hyphae is 1/10 or less.

] t 115 or less.

−Touge← Same 1/391
under.

→Beef 1/2 or less.

1,000, 1, 2 or more.

As is clear from Table 10, the judgment results are as follows:
Although a remarkable anti-mildew effect was observed in the sample based on this invention, no anti-mildew effect was observed on paper anti-mildew sheets and filter paper, and no anti-mildew effect was observed on paper products made of vinyl chloride resin sheets that do not contain anti-mildew components. The growth was poor compared to that of the other plants, but no antifungal effect was observed.

〔effect〕

As mentioned above, the active pesticide ingredients such as insecticidal ingredients and bactericidal ingredients, which the heat-molded product of the present invention has, show a high residual rate despite being subjected to heat treatment, and are not mixed into the polymeric material. It is dispersed uniformly within the tissue. Therefore, the active ingredient will not unnecessarily fall off, diffuse, or elute from the surface of the molded product, and the durability of the medicinal effect will be increased, and at the same time, the safety for humans will be improved in a favorable direction. Moreover, the apparatus for molding the molded article of the present invention is economically advantageous because it is sufficient to use the apparatus that has been widely used in the past as is. Now, if the heat-molded product of this invention is in the form of a sheet, it is extremely easy to spread it over the habitat or hiding place of insect pests, and it is also possible to spread it over the habitat or hiding place of insect pests, and it is also possible to spread it in the form of powder or droplets, as when spraying active ingredients. There is no scattering, and compared to conventional powders, emulsions, or aerosols, the drug's efficacy lasts much longer.
There is no danger of accidental ingestion or ingestion. Therefore, it is extremely easy to control pests and fungi that occur in hot and humid kitchens, cooking areas, tatami mats, carpets, furniture, closets, etc., so the significance of this invention is very great.

Patent originator: Yamade Kosan Co., Ltd. Aritsune Pharmaceutical Industry Co., Ltd. Agent: Kama 1) Bun 2

Claims (1)

[Claims] An insect repellent or repellent comprising a composition of a polymeric material, an active pesticide ingredient, and a mixture of one or more of phthalic acid esters, phosphoric acid esters, or organic acids or their esters. Heat molded product for bacteria.