JPS58210003A - Insecticidal resin composition - Google Patents

Abstract

PURPOSE:An insecticidal resin composition that is made by adding a fine particle powder of silicic acid or aluminosilicic acid substance, when fenitrothion, an insecticidal ingredient, is mixed with a resin such as ethylene polymer, thus causing no deterioration in film characteristics without blocking. CONSTITUTION:The objective insecticidal resin composition comprises O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate(fenitrothion), a low-toxicity insecticide, a fine-particle powder of silicic or aluminosilicic acid and an ethylene polymer or copolymer. The composition is obtained in the form of pellets, sheets or films, especially in case of films, it is preferred that the amount of fenitrothion is 0.1-2wt% based on the resin, the fine-particle powder is 1-20 microns in its size and added by such an amount as it can adsorb 100-300% of the phosphate ester according to the JIS method. EFFECT:The composition has residual effect and shows stabilized effect.

Description

Detailed description of the invention: 0,0-dimethyl O-(,
? - Insecticidal resin composition containing methyl-dernitrophenyl) phosphorothioate (hereinafter referred to as fenitrothion) and silica or aluminosilicate fine powder all-ethylene polymer sludge or ethylene copolymer. Can pesticides be added to the resin without reducing the properties of the pesticides? The overall object of the present invention is to provide an improved resin composition that provides a stable pest control effect.

Conventionally, it is well known that agrochemicals such as insecticides, bactericides, herbicides, etc. are dispersed or dissolved in a resin by some method to impart functions such as sustained release or residual effect to the agrochemicals.

Resin compositions containing pesticides have been molded into films for mulch cultivation, packaging, etc., insecticidal sheets, monograms of 1 gram size, or insecticidal powders, and have not been put to practical use.

Insecticide collars and insecticidal dispensers may be newly designed and molded for VC1 insecticidal purposes, but there are also products such as herbicide-containing mulch cultivation films, insecticide-containing packaging films, insecticides, and boxcide-containing bags for cultivation. As seen in the case of fruit tree bags for commercial use, in many cases, insecticidal, sterilizing, weeding, and other functions are added to the original purpose of use.

Therefore, especially in the case of films, the addition of new agricultural chemicals usually causes the film's original physical properties such as transparency, gloss, strength, and anti-blocking properties to deteriorate in many cases.

On the other hand, since fenitrothion is an insecticide that has a wide spectrum of insecticidal activity and has low toxicity to humans, it is highly preferred as an active ingredient to be added to resin compositions for this purpose. 'Unfortunately, however, as shown in the reference examples, in order to stably and fully maintain the effect of insecticidal films, it is necessary to mix fenitrothion in a ratio of 0.1 times or more to the resin, preferably o, s i (it is better to add more than 100%, but even with addition of this amount, fenitrothion will cause blooming in resins such as polyethylene), and there are problems such as blocking the force and making it difficult to open the IC. This results in the loss of product value.

This is because fenitrothion is a liquid at room temperature and has a weak ability to be retained by resins, except for some resins such as polyvinyl chloride, and it cannot be put to practical use unless this drawback is completely resolved. It tells the story.

Therefore, the present inventors have worked diligently to develop a method that will not cause blocking even when a practical amount of an insecticidal active ingredient is added to the resin, and will not reduce other film properties such as strength, and will exhibit sufficient insecticidal activity. As a result of investigation, it was confirmed that the addition of silica or aluminosilicate was effective in improving the above-mentioned drawbacks, and the present invention was completed.

That is, in the present invention, a total of 7 dispersible powders, which are silica or aluminosilicate powders and have a center particle size of 7 to 20μ, are used.
For the addition of enitrothion, Japanese Industrial Standards (JI)
It is characterized by an oil absorption capacity of 10 (・~, ?00%) calculated by the S) method.

-I-, I-time 300 section was set because it is meaningless in terms of anti-blocking effect in force B after this t1, and excessive inorganic substance filling significantly deteriorates the resin properties. be.

The composition of the present invention is usually produced in a final form such as pellets, sheets, films, etc., such as leafhoppers (Hemiptera),
Adzuki bean weevil (Coleoptera), Spodoptera (Mf1 order), house fly (Diptera), German cockroach (Opiptera)
It is effective against a wide range of pests such as, and especially these pests. It can be used satisfactorily as a film for insect-proof fruit tree bags, etc.

It is a known low toxicity organophosphorus insecticide whose active ingredient is fenitrothion and is readily available.

A film prepared by adding a predetermined amount of an active ingredient to an ethylene polymer or ethylene copolymer and then heat forming the film has an active ingredient needle of 0.
Although it is effective even at 7% by weight, in order to be stably effective over a long period of time, the mackerel content is preferably 06.5% to 1% by weight. If the content exceeds λ, the blocking performance of the film will be poor, and this is not preferred in practice.

Some grades are used for sheet molding, blow molding, etc., and have a melt index of 7 g//.

Low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer containing ethylene as a main component, ethylene-acrylic acid ester copolymer, ethylene-propylene copolymer, These include ethylene-butene copolymers, which also include modified resins such as partially chlorinated polyethylene and ionomers.

The silicic acid or alumino-silicic acid fine powder of the present invention is an inorganic fine powder mainly composed of silicic acid and alumino-silicic acid,
Although it can be used by completely crushing naturally occurring ores, it is better to use synthetic products because the particle size is finer and more consistent, and the content of impurities such as iron components that cause decomposition of fenitrothion is extremely low, resulting in stable quality. It's convenient to be there. Further, powders obtained by firing these powders at a suitable temperature to reduce the amount of free water can also be used in the present invention.

On the other hand, when an undesirable inorganic powder is used, the effect of preventing blocking may be weak, or even if it exists, it has disadvantages such as accelerating the decomposition of fenitrothion and reducing the strength of the film.

Particularly, when manufacturing thin films using an inflatable mold or the like, the film breaks during molding due to a decrease in strength, making continuous and stable operation impossible.

To produce the composition according to the present invention, fenitrothion and silica or aluminosilicate fine powder are separately added to the ethylene polymer or ethylene copolymer and kneaded in a kneading machine or the like. However, the following method is preferable judging from the efficiency of uniform dispersion into the resin.

That is, a predetermined amount of fenitrothion and silicic acid or aluminosilicate fine powder are mixed in advance so that fenitrothion is mixed with the inorganic fine powder, and this fixed amount is sufficiently uniformly dispersed in the entire resin. Mix with a kneader or the like so that it dissolves into the desired composition, or prepare a masterbatch in advance with a concentration of 2 to 700 times that of the desired composition, and then mix it with the virgin resin that is not mixed in a predetermined ratio. and then molded using a total extruder. In the case of blown film molding, the temperature at the exit is approximately 7
A value between 20 and 10"Q is appropriate.

Even after heat treatment with Composition 2/go C of the present invention for 30 minutes, the loss of the insecticidal active ingredient due to heat is negligible.

In addition, colorants, antioxidants,
It is also possible to add ultraviolet absorbers and the like.

Next, the present invention will be explained by Examples and Test Examples07
However, these examples are not intended to limit the invention.

Example/a. Production of aluminosilicate gel fine powder Distilled water ysl
In advance, J-Konichi No. 3 water glass j? was charged into a SUS reaction tank adjusted to JOC. 4t during KP? Weight
1) JaOH aqueous solution, a solution completely mixed with 2 parts λ and 2 parts distilled water, and the sulfuric acid band 741! 11: simultaneously from separate charging ports while stirring at a speed of 3 ~ 1/2 min. I let it drip.

During the reaction, the pH of the system was [jxj.

After dropping the entire amount, stir for 7 hours under the same conditions and use a centrifugal filter to separate the solid content from the completely reacted slurry, then add distilled water several times to remove the water-soluble content. Removal and washing were repeated.

Finally, the obtained wet cake was heated at 00C for 20
After drying for hours, the composition becomes Al2O3・&JSiO2-0,
An aluminosilicate gel of ♂Na2O.nH2O was obtained.

The refractive index of the aluminosilicate gel obtained as described above is 7.4t/3, and the equilibrium adsorbed water content under 5C 168% RH based on the weight after hot air drying at 250C for 2 hours is /, 2 It was Chi.

b. Manufacture of concentrate 1 part of fenitrothion, 2 parts of the aluminosilicate gel produced in a, and the whole super mixer ((to) Yoda Seisakusho S
MV-, 20 type) under SOC, zoo rotation conditions.
By stirring for a minute, fenitrothion was uniformly supported on the aluminosilicate gel to obtain a concentrate.

Production of C9 resin composition Low-density polyethylene (melt index 3.!, density 0.ri λ, trade name Sumirikisen F' qoti-H manufactured by Sumitomo Chemical) and the fenitrothion concentrate produced in b. Using a Banbury mixer (BR type small Banbury mixer made by Kobe Steel, Ltd.) / 7 at 50 c
○d, which obtained a uniform compound by kneading for 0 minutes, and the compound obtained in film molding C.
d Li2)=2a CR=3. Pass it through A Modern Machinery Hat 1 and get this 7! was introduced into a spiral die of had, and inflation molded at a temperature at the exit of /1tOc to a thickness of /,2. ．． Active ingredient IN of 5μ, medium 3za OUT
The Zengchi-containing film was completely molded.

Example-~S Example/2. The aluminosilicate gel was replaced with Carplexus 5ZO (trade name of Shionogi & Co., Ltd., synthetic hydrated silicon oxide B S 300 mesh passed), or the low-density composite polyethylene was replaced with ethylene-vinyl acetate copolymer (melt index: 5, density: 0). 3. Vinyl acetate content/S weight 1 part, trade name Evatate H-, 202/A manufactured by Sumitomo Chemical Co., Ltd.) was changed, and the ratio of fenitrothion and inorganic fine powder to the resin was varied. example/
Films having the compositions of Examples λ~S by the same method as ? Obtained.

The blending ratios of the actual Ldu examples/-- are shown in Table/.

Example 2 ~// Using Jilton pFot (@Powder Silicate Mizusawa Chemical Industry ■ trade name) and Carplex #go (described above) as an inorganic fine powder,
The concentrated powder of fenitrothion obtained in the same manner as Example /-1) was mixed with Sumikasen Ftioy-H (described above) and low density polyethylene Sumikasen L <to, 2 (melt index 3.j, density 0.J, 2 Sumitomo Chemical Nishi (trade name) was triblended in a polyethylene bag and placed directly in an extruder to form a film having the composition shown in Table 1 in the same manner as in Example 1-d.

Also, only fenitrothion without extracting the inorganic fine powder? Control example 4. Added control example/-3 film and inorganic fine powder, fenitrothio 7, both without additives. j film and inorganic fine powder, Aerosil coK-gt (synthetic anhydrous silica alumina, Nippon Aerosil 1 Kiku trade name), bentonite clay (Bentonite Myogi Seal, Toyojun Yoko Co., Ltd.) and synthetic zeolite) (A-4', 200 The films of Reference Examples/--3 using Metsushi, Toyo Soda Kogyo ■) were molded in the same manner, and all of the layer formations of 0 or more are shown in Table/.

In the system using Aerosil 0OK-ZAG, uniform dispersion was extremely difficult, and fish eyes occurred during inflation molding, making stable molding impossible.

Table / Composition ratio (formulation) table Test example / Film physical property test experimental example / Film of the present invention obtained in ~S and control example /, 4t
Table 1 shows the results of the blocking measurement at room temperature before washing the films of A and J, and shows that the blocking of the film of the present invention is significantly improved compared to the case where 90 fenitrothion was added alone. The haze was measured in accordance with the MuSTMD-/θθ3 standard, and the blocking was measured as follows.

In other words, with one film overlapping /θθX J
, cut out a 2-jm test piece, and store it at room temperature (-0°C).
Place a 7 Kl load plate on it.1. ! After leaving for a period of time/θθX
The blocking value is defined as the load when 1.2 films are completely peeled off by peeling off at a constant speed in the direction perpendicular to the film surface with only the part /θθ■ being raised.

Table 2 Film physical property test results measurement method Total light transmittance ASTM D-10
To 0G.

Test example Example of measuring fenitrothion content/~//
Table 3 shows the results of measuring the fenitrothion content in the film immediately after production and the content after storage at room temperature for several years by gas chromatography using chloroform as an extraction solvent. Since almost the predetermined amount is recovered, there is no loss of fenitrothion due to volatilization, decomposition, etc. during production, and it can be seen that stability over time is superior compared to the fragile reference example.

Table 3 Fenitrothion Recovery Rate Test Example 3 The insecticidal activity of the films was evaluated using the films of Biological Test Examples/- and Control Examples/-. It can be seen from the caps shown in Tables 11 to 7 that the insecticide-containing film has sufficient activity, and its effectiveness does not decrease even when inorganic fine powder is added.

For the surface test, send the sample film to the inside! , a bag-like shape on the θ side, and inside it, 3 to 4 instar larvae (
/ku/θ head), adzuki bean weevil adult (/ku-θ head), leafhopper adult (/ku/θ head), house fly adult (7
Ward/θ head), German cockroach male and female adult (/ Ward/θ head)
were released into each bag, and the mortality rate was determined after 1.2 q hours. However, for house flies only, the bag contains approximately /Nrφ
Small holes were made at gu θ locations, and the mortality rate was determined 5 hours after release.

As bait, we used absorbent cotton soaked in 0.5% sugar water for houseflies, five collection sheaths tied together for leafhoppers, and Chinese cabbage leaves for armyworms when released. I put it in a bag at the same time.

In the tests shown in Tables j to 7, a polyethylene cup with a diameter of /θcrn was covered with a film, test insects were released inside, and the test insects were placed upside down on the film. The number of insects knocked down at intervals of j~/θ was investigated. The number of writhing insects was investigated for Spodoptera larvae.

Procedural amendment (spontaneous) January 1982 Commissioner of the Patent Office Kazuo Wakasugi 1 Indication of the case 1988 Patent application No. 98788 2 Name of the invention Insecticidal resin composition 3 Person making the amendment Relationship to the case Patent Applicant Address: 5-15 Kitahama, Higashi-ku, Osaka, Column 6 of Detailed Description of the Invention in Specification 1, Contents of Amendment (11 Specification, page 9, 3rd to 2nd line from the bottom, "25
℃ x 2 hours'' is 25℃, 2 o'clock + 171 and lunar pressure.

(2) At the 18th stroke of the same 1st lR [synthetic hydrated silicon oxide BS]
J is corrected to [synthetic hydrated silicon oxide BSJ].

(3) In the table on page 14, in the column for the resin used in Comparative Example 2, "Sumiyokusen (F2O3-H)" is corrected to "〃".

(4) In the table on page 20, the column for the adzuki bean weevil of the film of Control Example 4 has ro, 0(100)J, and l'-
Correct it to 0,0(0,0)J.

Below

Claims (1)

[Claims] (1) Zero in ethylene polymer or ethylene copolymer
．． Insecticidal resin composition (2) 0.0, characterized in that it is made entirely of 0-dimethyl 0-(3-methyluda-nitrophenyl) phosphorothioate and silica or aluminosilica fine powder. -Dimethyl〇-(3-methyl-t-nitrophenyl)phosphorothioate content is 0.0% relative to the resin. The amount of silicic acid or alumino-silicic acid fine powder is /~20μ in particle size, and the amount added is equal to the oil absorption capacity specified in the JIS method for the above phosphorus [12 ester]. The insecticidal resin composition according to claim 1, which is in film form and has a conversion % of 100 to aoo qb.