JPS62212302A - Resin molded article for repelling insect pest, having durability - Google Patents

Abstract

PURPOSE:The titled resin molded article capable of surely keeping improved preventing or repelling effects on insects on the surface of the molded article for a long period by a simple means, consisting of a composition comprising a chlorine-containing polymer, an insecticide against insect pests, etc., and a transfer promoter. CONSTITUTION:A chlorine-containing compound such as polyvinyl chloride, etc., is blended with an insecticide such as pyrethroid insecticide, etc., or a repellent and a transfer promoter such as phosphorus oxy acid mono- or diester type, e.g. compound shown by formula (R is H, cationic group or <=20C monofunctional hydrocarbon group; R is <=20C monofunctional hydrocarbon group) by an extruder, etc., and used as furniture in kitchens, structural materials for building construction, wall materials, wall frame part materials, containers for electronic devices, underlays, etc., or for preventing cockroaches and other insect pests from coming. The amounts of the components blended are 0.05-5wt% insecticide and 0.05-3wt% transfer promoter based on the chlorine-containing polymer.

Description

[Detailed description of the invention] (Industrial application field) TECHNICAL FIELD The present invention relates to a pest repellent resin molded article with excellent durability.

Conventional technology) Conventionally, various insect repellents and pest repellents have been widely used to prevent pests from entering living spaces. One of the known uses is to mix insect repellent or repellent into a resin and mold it into a sheet, etc. (Japanese Patent Laid-Open No. 60-1
46805).

In this pest repellent, the mixed repellent migrates to the surface of the resin molding, thereby obtaining the pest repellent effect.

(Problems to be Solved by the Invention) However, the molded sheet 1. It was found that the molded product F was still unsatisfactory in its insect repellent and repellent performance against pests.

One of the reasons for this is that the chemicals used have heat resistance, which tends to cause decomposition and volatilization under the resin melt molding conditions, and second, even if the heat resistance of the chemicals can be met, the molded product It is thought that the transfer of the medicinal ingredients to the surface is still insufficient, and the higher efficacy and durability cannot be obtained.

Therefore, an object of the present invention is to provide an insect repellent resin molded article that has an excellent insect repellent or repellent effect on insect pests and the sustainability of the effect.

(Means for solving the problem) In the present invention, a molded article is produced from a composition containing a chlorine-containing polymer, an insecticide or repellent for pests, and a migration accelerator represented by a phosphorus oxyacid ester. By manufacturing it, an insect repellent or repellent effect against pests and a sustainability of the effect can be obtained.

(Function) The present invention provides that the combination of a chlorine-containing polymer and a migration accelerator
The insecticide or repellent blended into the chlorine-containing polymer gradually but reliably transfers (bleeds out) to the surface of the molded product over a long period of time, and as a result, the insect repellent or repellent effect is reliably and over a long period of time. This is based on the knowledge that

Migration is generally known as a phenomenon in which compounding agents blended into rubber or plasticized plastic move from the higher concentration side to the lower concentration side (surface) within the compound. The extent to which this is formed is also related to properties such as the compatibility between the plastic and the compounding agent.In the chlorine-containing polymer of the present invention, stable insect repellent or repellent effects against pests occur because of the presence of the chlorine-containing polymer in the chlorine-containing polymer. This is due to the fact that the insecticide or repellent blended into the molded product effectively migrates to the surface of the molded product. This seems to be because the accelerator acts to reduce the degree of compatibility of the insecticide or repellent with the chlorine-containing polymer, and as a result promotes the migration of the insecticide or repellent. In any case,
In the present invention, the migration accelerator is blended in a significantly smaller amount than the amount of insecticide or repellent against pests, and the insect repellent or repellent effect is more reliable and the effect lasts longer than when it is not blended. What we obtained was truly surprising knowledge. Also,
In the present invention, the product containing the migration accelerator has an excellent initial insect repellent or repellent effect immediately after molding.
It is also inferred that the migration accelerator described above has the effect of stabilizing the insecticide or repellent against the heat applied during kneading and molding.

(Operations and Effects of the Invention) According to the present invention, by a simple means of blending a chlorine-containing polymer with an insecticide or repellent for harmful insects and a phosphorus oxyacid ester transfer accelerator, the surface of the molded product can be improved. It can be used as an insect repellent or repellent effect and has a long-term sustainability, for example, it can be used as kitchen furniture, architectural structural materials, wall materials or window frame members, electronic instrument containers or mats, etc. to prevent cockroaches and other insects. It is effectively used to prevent the invasion of pests.

(Description of Embodiments of the Invention) In the present invention, various types of migration accelerators are used, such as phosphorus oxyacid esters, silicone-based, carboxylic acid-based, alcohol-based, carboxylic ester-based, and epoxy-based ones. However, typical phosphorus oxyacid ester transfer accelerators include those based on phosphites or phosphates. As a phosphite-based migration promoter, in the following formula, R is a hydrogen atom, a cationic group, or a monovalent hydrocarbon having 20 or less carbon atoms, such as an alkyl group, an aryl group, an aralkyl group, or an alkaryl group, R1 is a monovalent hydrocarbon group having 20 or less carbon atoms, or in the following formula, R1 and R2 have the meanings described above, and R3 is a divalent hydrocarbon group.

Compounds represented by; for example, triphenyl phosphite, tricresyl phosphite, diphenyl tridecyl phosphite, phenyl ditridecyl phosphite, trinonylphenyl phosphite, diphenyl phosphite, 2,2-bis(4-dioctoxy) Examples include phosphinoxyphenyl)propane. Further, as a phosphate transfer promoter, in the following formula, R is a hydrogen atom, a cationic group, or a monovalent hydrocarbon group having 20 or less carbon atoms.

R1 is a monovalent hydrocarbon group having 20 or less carbon atoms. Esters 1 represented by the following include, for example, triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, dioctyl phosphate, monoisopropyl phosphate, calcium monoisopropyl phosphate, etc. can.

Among these, mono- or diesters of phosphorus oxyacids, such as diphenyl phosphite, diphenyl phosphate, mono-inpropyl phosphate, calcium heptad-twinpropyl phosphate, etc., are particularly preferred for the purposes of the present invention.

Examples of the silicone migration accelerator include organosiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methyl/hydrodiene polysiloxane, dimethylpolysiloxane-polyalkylene oxide copolymer; or alkyltrialkoxysilane, aminoalkyl Examples include trialkoxysilane, hydroxyalkyltrialkoxysilane, epoxyalkyltrialkoxysilane, and homo or co-oligomers thereof.

Examples of the carboxylic acid transfer accelerator include saturated fatty acids, unsaturated fatty acids, and aromatic carboxylic acids having 20 or less carbon atoms, and these may be basic acids or polybasic acids, such as acetic acid. , propionic acid, lauric acid,
Mention may be made of glutamic acid, phosphoric acid, benzoic acid, tartaric acid, etc. Alcohol transfer promoters include alcohols having 20 or less carbon atoms, particularly polyols 1 such as pentaerythritol, mannitol, xylitol, sorbitol, glycerin, Examples include polyethylene glycol, diglycidyl, dipentaerythritol, and the like.

Examples of the carboxylic acid ester transfer accelerator include the aforementioned esters of carboxylic acid and alcohols, such as glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester,
Butyl stearate and the like can be mentioned.

Examples of the epoxy migration accelerator include epoxidized soybean oil, epoxidized linseed oil, epoxidized poly-1,2-butadiene, and bisphenol A diglycidyl ether.

Of course, these migration accelerators can be used alone or in combination.

As the insecticide or repellent, any insecticide or repellent that has an insecticidal effect and/or a repellent effect on pests such as cockroaches and has been conventionally used for this type of application can be used. Examples of suitable insecticides or repellents include, but are not limited to, pyrethroid insecticides and pyrethrin insecticides. Pyrethrins are insecticidal components contained in the ovary of pyrethrum flowers, while pyreth-Aide insecticides are insecticides synthesized based on pyrethrum components, and these have extremely low toxicity to humans and animals.

It has the characteristics of being less irritating to the skin and being highly effective. As the pyrethroid insecticide, ethofenbrox (chemical name: 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether, manufactured by Mitsui Tsuka L Kagaku ■) can be suitably used.

Examples of chlorine-containing polymers include vinyl chloride resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinyl chloride-acrylic copolymers, 11X vinyl-butadiene copolymers, or blends of these polymers; Vinylylene resin: post-chlorinated polyethylene; chlorinated polypropylene; chlorinated polyvinyl chloride; polychloroprene or a blend of two or more of these; It is highly effective when applied to resins.

Of course, the chlorine-containing polymer used in the present invention can be blended with known compounding agents according to known formulations. Suitable examples of such additives include plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sepatate, polypropylene glycol adipate; calcium stearate, magnesium stearate, zinc stearate, dioctyltin maleinate polymer, dioctyltin Heat stabilizers such as laurate; lubricants such as higher fatty acid amide, polyethylene wax, microcrystalline wax; fillers such as calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined lay - titanium dioxide,
Pigments such as carbon black, red iron, and ocher; anionic pigments.

These include cationic, nonionic, or amphoteric antistatic agents.

In the present invention, based on a chlorine-containing polymer, the insect repellent or repellent is preferably used in an amount of 0.05 to 5% by weight, particularly 0.5 to 4% by weight, while a phosphorus oxyacid ester The system transfer accelerator is 0.05 to 3% by weight, especially 0.
．． It is preferably used in an amount of 1 to 1% by weight.

There is no particular restriction on the order in which they are added to the chlorine-containing polymer; the insecticide or repellent and the phosphorus oxyacid ester transfer accelerator may be added together with other ingredients, or the chlorine-containing polymer may be added to the chlorine-containing polymer at the same time. The other components may be blended together, and finally the insecticide or repellent and the phosphorus oxyacid ester transfer agent may be blended in this order, in the reverse order, or at the same time.

The resin is blended after so-called dry blending.

It may also be carried out by supplying it to a molding machine.

Blending may be performed by kneading in advance by supplying the mixture to a Banbury mixer, a twin-screw extruder, rolls, etc.
Molding of the resin is easily performed by extrusion molding, sheet molding using calender rolls, injection molding, etc., and sheets, panels, PL frames, other structural materials, etc. can be easily obtained.

(Example) In the examples shown below, efficacy tests were conducted as follows.

(1) Forced contact test method A test piece (width 40 mm x thickness 1 am) with a size of 100 m
The test piece was pasted onto a 5 + The number of fatalities was determined by contacting the animals. still,
The test piece was left at 40°C and the number of deaths was examined for 6 months.

(2) Repellent test method Test tank (length 10100Os width 1000+u+X height 50
A partition wall was provided at the center of the room (0 am) to divide the room into chambers A and B, and a passage having a width of 1001 mm between the chambers A and B was provided at the center of the partition wall. A width of 40 mm is placed on the side of one of the chambers A.
A single layer of test pieces was pasted, food was placed approximately in the center of chambers A and B, and American cockroaches toW4 were placed therein. I checked the number of cockroaches in room A.

Example l A composition with the following formulation was prepared.

Sample 1 Vinyl chloride resin (degree of polymerization 1350) 1000% by weight g/
Zn-based heat stabilizer B // Insecticide repellent MTI-500・1 3 // Diphenyl phosphite ° Q, 3 tr test 'J42 Vinyl chloride resin (degree of polymerization 1350) 100 parts by weight Mg/
Zn-based heat stabilizer 13 //Insecticide repellent MTI-5003/1 Sample 3 Vinyl chloride resin (degree of polymerization 820) 100 parts by weight Heat stabilizer 5 //Insecticide repellent MTI
-5003 parts by weight diphenyl phosphite 0.1 // Sample 4 Vinyl chloride resin (degree of polymerization 820) 100 parts by weight Heat stabilizer 5 Insecticide repellent MTI-
5003// Insecticide repellent MTI-500 is 2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether with the following structural formula. 3
In the case of No. 4 and 4, extrusion molding was performed at 160° C. to form a sheet with a width of 40 m and a thickness of 1 liter.

The efficacy test described above was conducted using each of these sheets.

The results of the forced contact test are shown in Table 1 below.8 The test in Table 1 is 4.
This is an accelerated test conducted at a temperature of 0°C, and the values indicate the number of dead animals 24 hours after the start of the test.

Table 1 The results shown in Table 1 above indicate that significant lethality and long-lasting effects can be obtained by using a phosphite-based migration promoter in combination.

Next, the results of the repellent test are shown in Table 2.

Table 2 The results in Table 2 above show that by using a bosphite transfer agent together with an insecticide repellent, a remarkable repellent effect can be obtained, and that the agent gradually bleeds onto the surface of the test piece due to the action of the transfer agent. It can be seen that a stable repellent effect can be obtained over the i period.

Example 2 A molded sheet was produced in the same manner as in Example 1 except that the following migration accelerator was used in place of diphenylphosphite in the formulation of Sample 1 of Example 1.

Sample 5 Dimethylpolysiloxane oil sample 6 Succinic acid sample 7 Dipentaerythritol sample 8 Propylene glycol fatty acid ester sample 9 Epoxidized soybean oil A forced contact test and a repellency test were conducted on each of these samples, and the results are shown below. Shown in 3.

Claims (5)

[Claims] (1) A durable pest repellent resin molded article comprising a composition containing a chlorine-containing polymer, an insecticide or repellent for pests, and a migration accelerator. (2) 0.05 insecticide or repellent per chlorine-containing polymer
Molded article according to claim 1, wherein the molded article is present in an amount of from 0.05 to 3% by weight and the migration promoter is present in an amount of from 0.05 to 3% by weight. (3) The molded article according to claim 1, wherein the migration promoter is a phosphorus oxyacid ester, silicone, carboxylic acid, alcohol, carboxylic ester, or epoxy migration promoter. (4) The molded article according to claim 1, wherein the migration accelerator is a mono- or diester of phosphorus oxyacid. (5) The molded article according to claim 1, wherein the insecticide or repellent is a pyrethroid insecticide.