DE3602671A1 - HOT MOLDED PART FOR INSECTICIDES AND BACTERICIDES USE - Google Patents

Description

3602577

The invention relates to a thermoformed part for insecticidal and bactericidal Use.

Around molded parts made of high molecular weight material, such as resin and rubber, which are molded by hot processes, with insecticides and bactericides To provide effects, it is customary to knead in an active ingredient as an agrochemical before molding. But because such agrochemicals are generally not very heat-resistant and experience pyrolysis during the hot forming process thereby the insecticidal and bactericidal effect is reduced, and the duration of this effect is shortened. Such an approach can therefore can only be bought with economic disadvantages. It is also possible to use a film or paper on thermoformed parts are coated or impregnated with an ingredient active as an agrochemical, stick on or use adhesives that contain the active Contain ingredients. Such active ingredients, however, are easily separated, evaporated or eluted, reducing the duration the desired effect is shortened; in addition, they are harmful to human health.

The invention is based on the object of a thermoformed part for insecticides and to provide bactericidal use which avoids the above-mentioned deficiencies.

A thermoformed part for insecticidal and bactericidal use is characterized according to the invention by a high molecular weight material, at least one agrochemical with an insecticidal, bactericidal or similar effect, and at least one component from that of an ester of phthalic acid, an ester of phosphoric acid, an organic acid and an ester of an organic acid

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Acid existing group.

As used herein the term "hot-molding" a product is to be understood, which is constituted by a working process with application of heat (for example, about 100 ⁰ C or higher) formed. There are no particular restrictions on the molding method or the shaping. In principle, any desired molding process can be used, for example extrusion blow molding, calendering, extrusion, injection molding, pressing, blowing, vacuum molding, pressure hollow molding, pressure drawing molding, prefilling, die casting and die casting. The product can be in the form of a film, a sheet, a plate, a textile structure (fabric), a rod, a tube, a sphere, a hollow body, a layered body or laminate, a foam body or a composite body, or an irregular shape.

Under the term "high molecular weight material" used here a high molecular weight material (natural or synthetic) is to be understood, for example resin or rubber. Of the High molecular weight material can, if necessary, with a plasticizer, a crosslinking agent (vulcanizing agent or Hardener), a lubricant, an antioxidant, an ultraviolet ray absorbent, a filler (reinforcing agent), an antistatic agent, a flame retardant, a dye, a thermal stabilizer, a foaming agent or a reforming agent or mixed with other auxiliaries, such as those used in particular in the field of high polymer technology be used. In consideration of the original heat resistance of the ingredient used as an agrochemical However, the high molecular weight material used in the present case should preferably be a material that is used in a temperatures below about 200 ° c melt, soften, harden or foam. Such materials include aliphatic

-A-

Monoolefin polymers such as polyethylene and polypropylene, monoolefin polymers such as ethylene-vinyl acetate copolymer and ethylene-propylene rubber, diene polymers such as polybutadiene, butadiene-styrene rubber, polyisoprene, Acrylonitrile butadiene rubber and chloroprene rubber, chlorinated polymers such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene and their copolymers, aliphatic or aromatic polymers with vinyl groups, prepolymers of reactive Polymers and prepregs made from thermosets, such as phenolic resin.

If auxiliaries of the type mentioned are a high molecular weight material are added, the type and the mixing ratio of the auxiliaries with reference to the active ingredient as an agrochemical to consider. For example, alkali metals such as calcium carbonate and inorganic salts of alkaline earth metals have im general adverse effects on the stability of the agrochemical.

100 parts by weight of vinyl chloride resin were chosen as the high molecular weight material and mixed with 50 parts by weight of a plasticizer, 2.2 parts by weight of a stabilizer for vinyl chloride resin, 5 parts by weight of "white carbon" as an auxiliary and one part by weight of fenitrothion as an agrochemical and one part by weight of di-2-ethylhexyl azelainate as a heat stabilizer The composition thus obtained were added 45 to 200 parts by weight of calcium carbonate as a filler, to prepare a sample. The sample was heated by a hot roll at 100 ⁰ C 150 ⁰ C 180 ⁰ C and 2 00 ⁰ C and 3 0 minutes at any of these Table 1 shows the relationship between the content of calcium carbonate and the residual amount (%) of the agrochemical active ingredient. The residual amount can be kept above a certain value if the mixing ratio is appropriately selected, although the filler content should be as small as possible Table 1 shows that with e a content of calcium car-

carbonate, the residual amount of the active agrochemical ingredient at 100 ⁰ C or higher can be maintained at a value of more than about 20% of less than 200 parts by weight.

Table 1

A. Calcium carbonate content (parts by weight) 50 55 60 65 • 70 100 150 200 100 45 99 4 99.1 98.0 94.7 92.6 72.2 37.5 15.0 150 99.7% 95.4 93.5 87.7 84.4 70.4 35.9 23.3 8.1 180 96.8 91.1 90.6 84.1 76.0 64.5 29.4 9.8 7.2 200 92.4 42.7 33.2 26.5 15.9 10.8 3.1 1.8 0.4 57.2

As used herein, the term "agrochemical" is intended to mean an insecticide, bactericide, or similar chemical be understood. It can be an insecticide such as fenitrothion, fenthion, cyanophos, chloropyriphosmethyl, pyridaphention, Propoxyl, BPMC, Phenothrin, Propentanphos, or around a Bactericidal such as thiabentazole, O-phenylphenol, PCMX, isobutyl-paraoxybenzoate, Isopropyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, Diphenyl, allyl isothiocyanate and sorbic acid act. These substances can either be used alone or in combination be provided.

An ester of phthalic acid, an ester of phosphoric acid, an organic one Acid or an ester of an organic acid is useful as a heat stabilizer for the agrochemical. To suitable phthalic acid esters include butyl benzyl phthalate, dilauryl phthalate, dipeptyl phthalate, Dipropyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, Dioctyl phthalate, diisodecyl phthalate, di-2-ethylhexyl phthalate or benzyl n-butyl phthalate. Suitable phosphoric acid esters are including tricresol phosphate, triisopropylpheny! phosphate, tributylphosphate

phate, triethyl phosphate, trioctyl phosphate and triphenyl phosphate. Suitable organic acids and their esters are in particular oleic acid, palmitic acid, stearic acid, myristic acid, Adipic acid, azelaic acid, esters of glycerol monooleate, dioctyl adipate, Methyl palmate, dibutyl diglycol adipate, di-2-ethylhexyl azelate, Methyl myristate, ethyl myristate, methyl stearate, ethyl stearate, 2-ethylhexyl alcohol, n-butyl caprinate, di-2-ethylhexyl sebazate, Sorbitan fatty acid esters, methyl acetyl ricinoleate, methyl anthranate, Isoamyl isovalerate, ethyl isovalerate, ethyl enanthate, oxyethylene highly aliphatic Alcohol, ethyl caprylate, ethyl caprinate, allyl caproate, ethyl caproate, isoamyl formate, gelanyl formate and Benzyl propionate. These heat stabilizers for agrochemical can be provided alone or in combination.

As for the mixing ratio (in parts by weight) of high molecular weight Material, agrochemicals and heat stabilizer for the agrochemicals As far as the drug effect and the economy of the agrochemicals are concerned, 100 parts by weight can be used of the high molecular weight material expediently with 0.1 to 5.0 parts by weight of the agrochemical active ingredient and 0.1 to 10.0 parts of the heat stabilizer are mixed. As a mixing process Conventional processes in which additives are introduced during the processing of the resin or rubber are suitable will. Mixing can be done either prior to thermoforming or at the same time as the thermoforming process.

An ester of phthalic acid, an ester of phosphoric acid, an organic acid or an ester of such an organic acid, which are added to the high molecular weight material, stop the pyrolysis of the agrochemical at 100 ⁰ C or higher temperatures and fulfill the task of removing the remainder of the agrochemical to keep active ingredient in the thermoformed part at a high level.

Examples 1 to 4:

55 parts of vinyl chloride resin were used as the high molecular weight material. The resin was mixed with 27 parts of plasticizer, 14 parts of calcium carbonate, 1.2 parts of stabilizer for vinyl chloride resin, 0.55 parts of pigment and 1.25 parts of "white carbon" as auxiliaries and with 0.5 part of fenitrothion as an insecticide, in order to achieve a To maintain the basic composition. Then a phthalic acid ester, a phosphoric acid ester, an organic acid or an ester of an organic acid according to Table 2 were mixed. The mixture was mixed, while it was heated for 30 minutes at 160 ⁰ C and molded by means of a calender to a 0.5 mm-thick film. The residual amount (%) of fenitrothion was over 90% for each film, while it was only 6.3% for the control sample. The activity on Tyrophagus putrescentiae and German cockroaches was also measured. The results are shown in Table 2. To determine the effect on Tyrophagus putrecentiae, 200 to 300 insects were contacted with each 50 mm x 50 mm test sample and the number of dead insects was counted microscopically after 24 hours. To determine the effect on German cockroaches, 30 insects were kept on each test specimen 200 mm in diameter with free access to food and water, and the number of dead insects within 24, 48 and 72 hours was counted. The effectiveness is expressed as a percentage.

From Table 2 it follows that the control sample on German cockroaches had no effect at all, while the drug effect of fenitrothion in the case of Examples 1 to 4 was considerable Scope was maintained.

Table 2

- ■ Example
■ - ■ ~. Diisodecyl phthalate 24 hours 1 2 3 4th control 6.3 0 salary Trioctyl phosphate 48 h 0.5 - - - 0 0 0 (Parts) Dioctyl adipate 72 h - 0.5 - - 0 20 I 0 Di-2-ethylhexyl azelate - - 0.5 - 0 43 Residual amount of fenitrothion - - - o, s I ο 87 Effectiveness on Tyrophagus
pntrpscentiae in 24 h (%) 93.0 91.2 95, 4 94.8 effectiveness 100 100 100 100 on
German 17th 13th 10 Cockroaches 40 37 53 72 77 73

Examples 5 to 11:

50 parts of vinyl chloride resin were used as the high molecular weight material. This resin was made with 25 parts of plasticizer, 1.0 part of stabilizer for vinyl chloride resin, 30.0 parts of calcium carbonate, 7.2 parts White carbon and 0.55 parts pigment mixed to form a base composition. Then there was another mixing in of Calcium carbonate as a filler, fenitrothion as an insecticidal component and triphenyl phosphate as a stabilizer according to Table 3. Films were produced by thermoforming in the same manner as in Examples 1 to 4. The remaining amount of fenitrothion was measured for the foils. The results are given in Table 3. The addition of triphenyl phosphate had a significant impact Influence.

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Table 3

"" ——. example Fenitrothion 5 0 6th , 0 7th 0 8th 0 9 0 10 , 0 11th 0 control salary Triphenyl phosphate 1, 1 1 , 2 1, 35 Ir 0 1, 0 1 , 0 1, 0 l, 0 (Parts) Remaining quantity (%) 0, 5 0 , 4 0, 0 1, 8th 3, 3 6th , 5 10, 7th 0 33, 48 65, 74, 81 85 86 7.6

Examples 12 to 18:

The contents of vinyl chloride resin, plasticizer, stabilizer for vinyl chloride resin, The filler and pigment were the same as in Examples 5 to 11. Only the white carbon content was increased 6.7 parts reduced. The contents of fenitrothione and methyl myristate given in Table 4 were provided. Slides were manufactured in a similar manner. The residual amount of fenitrothion was determined in a similar manner. The results are in the Table 4 shown; the addition of methyl myristate has a significant influence

Table 4

- Example salary
(Parts) Fenitrothion 12th 13th 14th 15th 16 17th 18th control Methyl myristate 1.5 1.5 1.5 1.5 1.5 1.5 .1.5 1.5 Remaining quantity (%) 0.15 0.25 0.5 1.5 4.5 9.0 15.0 0 61.8 72.5 80.9 86.4 92.6 95.1 96.0 I 14.0

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Examples 19 to 25:

The same basic mixture as in the case of Examples 5 to 11 was used. Calcium carbonate was added to this mixture as a filler, Fenthion as an insecticidal component and tri-n-butyl phosphate as a stabilizer in the ratio given in Table 5 mixed in. Films were produced in the same manner as in Examples 1 to 4. The remaining amount of fenthion in these Foils were measured. The results are shown in Table 5; this leaves a significant effect of the addition of Recognize tri-n-butyl phosphate.

Table 5

~~ -—_____ J3example Fenitrothion 19th 20th 21 22nd 23 24 25th control salary
(Parts) Tri-n-butyl phosphate 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1, 0 Remaining quantity (%) 0.1 0.2 0.35 1.0 3.0 6.0 10.0 0 17.7 36.5 56.6 68.0 78.0 79.6 82, .O ff 4, 0

Examples 26 to 32:

Films were made in the same manner as in Examples 12-18 except that phenotrin was used in place of Fenitrothion was used as an insecticidal ingredient and that a mixture of trimethyl phosphate and methyl palmitate in place of Triphenyl phosphate was used as a stabilizer. The residual amount of phenothrin was measured as a percentage for the films in question. The results are given in Table 6. The table shows that the mixture of the ester of phosphoric acid and the ester

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of palmitic acid also leads to a remarkable thermal stability leads.

Table 6

"- ■ _____ ^ example Phenothrin 26th 27 28 29 30th 31 32 control salary
(Parts). Tr ime thy I phosphate 1.5 1.5 I, ⁵ 1.5 1.5 1.5 1.5 1.5 Methyl palmitate 0.1 0.17 0.33 1.0 3.0 6.0 10, 0 0 Residual volume (%) 0.05 ο, οε 0.17 0.5 1.5 3.0 5.0 0 11.3 24.7 37.1 46.1 53.3 55.2 58, 4 2.6

Examples 33 to 39:

Films were made in the same manner as in Examples 12-18 except that a mixture of fenitrothione and phenothrin was provided as an insecticidal ingredient in place of fenitrothion and dioctyl phthalate in place of Triphenyl phosphate was used as a stabilizer. The remaining amounts (%) of fenitrothion and phenothrin were determined for the respective Foils measured. The results are shown in Table 7. From this table it can be seen that dioctyl phthalate has both Fenitrothion as well as phenothrin gives an excellent heat resistance.

Table 7

- ■ Example salary
(Parts) Fenitrothion 33 34 35 36 37 38 29 control rest
lot
(%) Phenothrin IrO 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Dioctyl phthalate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Fenitrothion 0.15 0.25 0.5 1.5 4.5 9.0 15.0 0 Phenothrin 35.5 56.5 75.7 83.5 87.4 88.5 89.9 8.1 31.5 62.9 62.2 86.0 87.4 88.0 90.9 7.1

Examples 40 to 43:

Films were produced in the same manner as in Examples 1 to 4, except that as synthetic resin, filler, insecticidal component, bactericidal component and stabilizer the substances listed in Table 8 were used. The remaining quantities (%) of the insecticidal and bactericidal ingredients were measured for the foils in question. The results are shown in Table 8. It can be seen that the addition of a Esters of phthalic acid, stearic acid or adipic acid for the thermal stability of the insecticidal and bactericidal components regardless of the type of resin used. For Examples 40 to 4 3, control samples without a stabilizer were used produced in a corresponding manner. In all of these control samples, the active ingredient was significantly broken down.

- 13 Table 8

—________ ^ example
"~ - ■ salary
(Parts) resin Polyethylene White carbon Fenitrothion 40 41 '42 43 rest
lot
(%) Polypropylene insecticides
component Cyanophos 96 - 96 - Ethylene vinyl acetate
Copolymer Bactericidal
component Ethyl paraoxybenzoate - 96 - - Stabilisatoi Propyl paraoxybenzoate • - - - 96 Benzyl n-butyl phthalate 2 2 2 2 Di-n-butyl phthalate 1 1 - 1 Methyl stearate - - 1 - Dioctyl adipate - 0.5 0.3 Fenitrothion - - - 0.2 Cyanophos 1 - - - Ethyl paraoxybenzoate - 1 - - Propyl paraoxybenzoate - - 0.5 - - - - 0.5 74.6 71.2 - 86, 4 - - 88.4 - - 92.1 92.4 - - - 92.0

- 14 Example 44:

In order to investigate the stability of the insecticidal constituents in the surroundings as they exist in the practical use of the hot molded parts according to the invention for insecticidal and bactericidal use, sample A and control samples B, C were produced and placed in a desiccator at 35 ^° C. and 95% relative Moisture held.

Sample A corresponds to the film of Example 3. That is, 55 parts of vinyl chloride resin, 27 parts of plasticizer, 14 parts of calcium carbonate, 1.2 parts of stabilizer for vinyl chloride resin, 0.55 parts of pigment, 1.25 parts of white carbon, 0.5 parts Fenitrothion as an insecticidal component and 0.5 part of dioctyl adipate as a stabilizer were mixed and ^{heated to 160 °} C. for 30 minutes. The mixture was made into a 0.5 mm thick sheet by means of a calender, and the sheet was cut to a size of 50 mm x 50 mm.

To prepare Sample B, a sheet of paper was immersed in an acetone solution of fenitrothion was immersed, and acetone was evaporated so that the content of fenitrothion was 1.5 g / m 2. The insecticidal Paper sheet was cut to a size of 50 mm x 50 mm.

Sample C was commercially available fenitrothion in the form of a powder with a concentration of 1.5% (W / W). The remaining amount (%) of fenitrothion became after 1 month, 3 months and 6 months for each sample stored in a desiccator measured and expressed as a percentage, the content being immediately was set at 100 after molding. The results are shown in Table 9.

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Table 9

Residual amount (%) 1 month sample
_ 99 A. 91 B. C. To 3 Months 97 , 3 70 , 7 66, 2 To 6th Months 94 ,8th 43 ,8th 16.5 To ,1 , 6 8.7

From Table 9 it follows that the insecticidal component of the invention Thermoformed part (sample A) had an excellent residual amount, which neither did the conventional products is approximately reached.

Example 45:

A composition of 100 parts of vinyl chloride resin, 50 parts of plasticizer, 2.2 parts of vinyl chloride resin stabilizer, 50 parts of calcium carbonate and 5 parts of white carbon and one part of thiabentazole as an antifungal component and one part of di-2-ethylhexyl azelate as a heat stabilizer was heated to 160 ^{0 for 30 minutes} C and formed into a 0.5 mm thick film by means of a calender, which was then cut to a size of 50 mm x 50 mm. As control samples, the same vinyl chloride resin sheet but without the antifungal component (Sample D), a paper sheet coated with an antifungal component (Sample E), and a normal filter paper (Sample F) were used. The molding according to the invention and the control samples were placed in a medium; they turned blue

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and black molds cultivated; their growth was observed. The criteria were as follows:

no growth

mold-grown area 1/10 or

fewer

mold-grown area 1/5 or

fewer

mold-grown area 1/3 or

fewer

mold-grown area 1/2 or

fewer

Mold-grown area over 1/2.

As can be seen from Table 10, was for the invention A noticeable antifungal effect was observed. No such effect was found for the antifungal paper sheet and the filter paper a. On the vinyl chloride resin sheet having no antifungal ingredient, the growth of mold was compared with that bad on paper; however, the antifungal effect was small.

Table 10

species according to the invention 15th 30th 60 Bluer
Shame
Tielpilz D. - + + Black
zer
Shame
üielpilz
i E. +++ ++++ +++++ F. +++++ +++++ +++++ according to the invention +++++ +++++ +++++ D. - + + E. +++ ++++ +++++ F. +++++ +++++ +++++ +++++ +++++ ++++ - 4-

The ingredients active as an agrochemical, e.g. insecticides and bactericidal components, the thermoformed parts according to the invention have a large residual amount, although they have a heating process have gone through.

They are kneaded into the high molecular weight material and within its uniformly dispersed. As a result, the active ingredients hardly precipitate, evaporate or elute from the surface of the molding; the durability of the drug effect is improved. At the same time is security increased for humans. For the production of the invention Thermoformed parts are suitable devices, as they are currently normally be used on a large scale. This represents a significant economic advantage. If the thermoformed part Produced according to the invention in sheet or foil form, it can easily be provided where pests live or hide. There are no problems with powder or liquid dripping off, as occur when active Components are sprayed. The duration of the effect of the drug is very long compared with that of conventional preparations in the form of powders, emulsions or aerosols. There is also no risk of accidental inclusion as a Food. As a result, the thermoformed part can easily be used to control pests and molds, not only in use in warm and damp kitchens, but also on floor mats, carpets, furniture, toilets and the like.

Claims (1)

PATENT ADVERTISER DlTL.-ING GERHARD SCHWAN ' ELFENSTRASSE 32 ■ D-SOOO MÜNCHFN 83 '"^' Yamade Kosan Co., Ltd. 24-10, Enoki-cho, Suita-shi, Osaka, Japan Thermoformed part for insecticidal and bactericidal use Claim Thermoformed part for insecticidal and bactericidal use, characterized by a high molecular weight material, at least one agrochemical with an insecticidal, bactericidal or similar effect, and at least one component that of an ester of phthalic acid, an ester of phosphoric acid, an organic acid and an ester of an organic acid Acid existing group. TELEPHONE: nS9 / 6C12339 T E LEX ·. 522589 dpa dKABEL: ELECTIUCPATENT MUNICH