JPS6144934A - Production of insect-repellent resin foam - Google Patents

Abstract

PURPOSE:To obtain a resin foam in which an insert repellent is uniformly dispersed, by incorporating the repellent in expandable beads and molding them by a bead expansion process. CONSTITUTION:An insect repellent is incorporated in expandable beads, and the beads are molded by a bead expansion process. The incorporation of the repellent is performed at a point of time selected from among (i) between the time of an 80% completion of the polymerization reaction and its completion in the production of expandable beads, (ii) after the polymerization reacton and (iii) after primary expansion. In the case (i), a method in which the repellent is dispersed or dissolved in a suspension of the resin is adopted and in the case (ii) or (iii), a method in which the beads are coated or impregnated with the repellent is adopted. As the foaming agents, aliphatic hydrocarbons, halohydrocarbons, air, argon, carbon dioxide, etc., are used. Although the mixing ratio of the repellent to the resin varies with the kind of a repellent, its specification of activity, the kind of a resin, production conditions of the beads, etc., it is generally about 0.0005-10pts.wt. per 100pts.wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a resin foam having insect repellent properties.

Conventional Technology and Problems Resin foam has many air bubbles inside, so it exhibits excellent insulation and cushioning properties, and is used as insulation material for ceilings, walls, floors, piping, etc., such as chairs, pinerests, beds, etc. furniture, etc.
It is widely used in various fields as cushioning material for bedding and as packaging material for various products.

However, since resin foams such as keratin have appropriate heat insulating properties, heat retaining properties, moisture absorbing properties, etc., pests such as mites and bacteria are likely to breed there, causing a series of damage.

In response to this, spray insecticides, disinfectants, etc., and incense regularly! l! However, in reality, it is extremely difficult to uniformly kill insects and disinfect young fruit in every corner of the resin foam.
Moreover, even these treatments are often not possible.

Means for Solving the Problems The present inventor has discovered a method for uniformly dispersing insect repellent, etc. into a resin foam obtained by molding it using a known foam bead method. The invention has been completed.

That is, the present invention relates to a method for producing an insect-repellent resin foam, characterized in that the foamed beads are impregnated with an insect repellent and then molded by a foamed bead method.

The resin foam of the present invention is produced using a well-known foam bead method.
It is molded in a t-shape. In the present invention, in order to uniformly contain the insect repellent in the resin foam, the insect repellent is added.薯) After the completion of the polymerization reaction, or ①) - Next foaming removal.

The type of base resin used is not particularly limited, and any resin normally used in the foamed bead method can be used, and examples include polystyrene, polyethylene, polypropylene, polyvinyl chloride, and copolymers thereof.

As blowing agents, commonly used propane, butane,
In addition to aliphatic hydrocarbons such as pentane, halogenated hydrocarbons such as methylene chloride, dichlorodifluoromethane, tricrylmonofluoromethane, and monochlorotrifluoromethane, air, nitrogen, argon, neon, helium, and dioxide. Inorganic gases such as carbon, azodicarbonamide, etc. can be used, and these can be used alone or in combination of two or more.

Expanded beads can be obtained by a suspension polymerization method using the above resin and a blowing agent according to a conventional method.

There are no particular restrictions on the insect repellent used in the present invention, and the most suitable one may be selected by considering the use of the resin foam, the compatibility between the resin and the insect repellent, the balance during polymerization, etc. Specifically, pyrethrin, allethrin, 7talsulin, resmethrin,
Framethrin, 1-Zf=lug-methyl-2-pentenyl-2,2-dimethyl-8-(2'-methyl-1'-
propenyl)-cyclopropane-1-carboxylate, 1-x f = A/-2-methyl-2-pentenyl-2,2-dimethyl-8-(2'-methoxycarbonyl-1'-flebenyl)-cyclopropane -1-carboxylate, 1-ethynyl-2-methyl-2-pentenyl, 2,2,s, a-tetramethylcyclopropane-1-carboxylate, 1-ethynyl-2=methyl-2-pentenyl-2 ,2-dimethyl-8
pyrethroid insecticides such as -(2', 2'-diquarvinyl)-Schiftetrapropane-1-carboxylate;
DDVP, dianodine, 0.0-dimethyl-0-(8
- Organophosphorus insecticides such as methyl-4-nitronenyl) thiophostuate and pyridafenthione, carbamate insecticides such as propoxal and sevin, biperonyl butoxide, provilaim, and biperonal dimethyl acecoolant. repellents such as butylacetanilide, N,N-dimethyl-toluamide, N,N-diethyltoluamide, dioctyl phthalate, didodecyl heptatalate, ethylhexanediol, Su70-l, Isosa70-
Examples thereof include naphthalene, camphor, P-dichlorobenzene, cinnamic aldehyde, anisaldehyde, polychloroalkyl ether, boric acid, sodium borate, potassium borate, tributyl borate, and triphenyl borate. These insect repellents can be used alone, but more favorable results can be obtained by using several types in combination. For example, when non-volatile boric acid or boric acid salts are combined with other volatile insect repellents, the non-volatility of the boron compound provides a long-lasting medicinal effect, the slow-acting insect poison, the residual effect, and the volatile insect repellent. The fast-acting and volatile properties of this compound provide a complementary insect repellent effect. In this example, 1 to 10 parts of volatile insect repellent is added to 100 parts by weight of boric acid or borate.
It is preferable to use it in a range of 0.00 parts by weight.

The blending ratio of insect repellent to resin varies depending on the type of insect repellent, medicinal efficacy specifications, type of plum oil, foam bead manufacturing conditions, etc., but it is 0.0006 to 0.0006 parts by weight of insect repellent to 100 parts by weight of resin.
The amount is about 10 parts by weight, preferably about 5 parts by weight. If the amount of the insect repellent is less than 0.0005 parts by weight, the insect repellent effect will be insufficient, and if it exceeds 10 parts by weight, it may cause molding defects such as poor foaming, poor adhesion, and shrinkage/expansion of the resin.

In the case of 1) above, the insect repellent is added to the resin by dispersing or dissolving it in a suspension of the resin, and in the case of ii) (2), the insect repellent is added to the resin by coating or impregnating the foamed beads. Insect repellents are not permitted except when added alone.

If necessary, auxiliary agents such as a solvent, a dispersion medium, and a carrier may be added, and the amount of the auxiliary agent to be used can be determined as appropriate depending on the purpose. In the case of 1), if the foaming agent can act as a fg agent for the insect repellent, the two can be mixed and added in the form of a solution.

In the present invention, in addition to the above-mentioned insect repellents, benzoic acids,
Sorbates, parachloromethaxylenol, α-promosinamaldehyde, triazine, imidazole, benzimidazole, tetrachloroiso7talonitrile, 2
- Antibacterial and antifungal agents such as methoxycarbonyl amonobenzimidazole, young numbers of linalool, geraniol, limonene, citral, cytop-neral, plant extracts, etc.
Deodorant, butylhydroxyanisole, 2,6-di-t
In addition to antioxidants such as -butyl-P-cresol, tocopherol, and triphenylphostuate, and rust inhibitors such as benzotriazole, tolyltriazole, and 2-methyl-6-pyrazolone, quenyl sanicylate and 2-hydroxy - UV absorbers such as 4-methoxybenzophenone, antistatic agents such as polyoxyethylene alkyl acids, alkyl sulfonates, and alkyl phosphates, stabilizers such as lead salts, metal soaps, organotin compounds, and mercaptide compounds;
Appropriate amounts of inorganic fine powders such as mica powder, silicates, calcium carbonate, clay, asbestos, and silica, coloring agents such as various pigments, and other types of polymers can also be contained.

The foamed beads containing the insect repellent are molded into a desired shape by a normal foamed bead method. There are no particular restrictions on the foaming method, and in most cases, two-stage foaming with secondary foaming and secondary foaming is used, but it is also possible to use multi-stage foaming. You can get the magnification. There is no particular limit to the foaming ratio, and it ranges from several times to 100 times, and in most cases it is 20 times.
It is about 70 times to 70 times.

When the insect repellent is incorporated during polymerization of the resin, the insect repellent is more tightly dispersed in the foam than when the insect repellent is applied to the foamed beads after polymerization or primary foaming. On the other hand, when applying insect repellent to foamed beads after polymerization or primary foaming, there is an advantage that there is no need to choose complicated working conditions.

The resin foam of the present invention has the property of slowly releasing the insect repellent and various drugs it contains. Sustained release properties can be controlled by changing the type of drug, the amount of the drug added, the portion containing the drug, the foaming ratio of the resin, etc. When adding drugs by mixing or impregnating them, the effect can be maintained for a relatively long period of time.
If the drug is added to the application, it is suitable for short-term use.

Effects of the Invention ■ The insect repellent resin foam of the present invention uniformly contains an insect repellent without being affected by its properties as a foam, and has excellent insect repellent properties.

■ When using volatile chemicals as insect repellents, they can also have an effect on the surrounding environment.

■ By using other drugs in combination, it is possible to add effects depending on the drug, such as anti-convict and anti-mildew effects.

■ As an insect repellent, by using a non-volatile agent such as boric acid or a borate together with another volatile insect repellent, a complementary insect repellent effect can be exerted and the insect repellent effect can be maintained for a long period of time.

(2) By adjusting the foaming ratio, the amount of drug added, etc., it is possible to obtain a foam with desired sustained release properties.

Example Next, the present invention will be explained in more detail by showing examples.

Example 1 1-ethynyl-2-methyl-2-pentenyl-2,2-
Insect repellent 20 consisting of 20 parts by weight of dimethyl-8-(2'-methyl-11-propenyl)cyclopropane-1-carboxylate and 80 parts by weight of tributyl borate, qIj
Part by weight was dissolved in 100 parts by weight of butanol. This was applied to the surface of polystyrene foam beads containing a blowing agent of Bentuff in an amount of 8M, and then the butanol was completely dried. The applied amount was 5N parts of the insect repellent per 100 parts by weight of the foamed beads.

The foamed beads were heated in a pre-foaming machine for about 2 minutes to pre-foam to a pre-expansion ratio of 50 times. The pre-expanded grains were aged at room temperature for 12 hours, and the block mold (8
00 x 400 x 140 mm) and foamed by a conventional heating method. After cooling to a state where the surface pressure of the foam in the mold became zero and the molded product could be taken out, it was released from the mold.

Using the obtained resin foam, 500 x 500 x
500ffi cube with aoo x aoo inside
A container having a cavity of x aoomm was made, 650 male and female German cockroaches were released into the container, and the number of dead insects was counted after being left for 48 hours (trial M1). Furthermore, a container similar to this container was left indoors for 5 years, and 660 male and female German cockroaches were released into the container, and the number of dead insects was counted after 48 hours of standing (Test ■). The results are shown in Table 1.

Example 2 1-ethynyl-2-methyl-2-pentenyl-2,2-
20 parts by weight of dimethyl-8-(2'-methyl-1'-propenyl) Schiff's propano-1-carboxylate were dissolved in 10.0 parts by weight of butanol.

Thereafter, coating, drying, foaming, and molding were performed in the same manner as in Example 1. The same test as in Example 1 was conducted using the obtained resin foam. The results are shown in Table 1.

Comparative Example I Foam molding was carried out in the same manner as in Example 1 using polystyrene foam beads containing 8% by weight of pentane as a blowing agent.

The same test as in Example 1 was conducted using the obtained resin foam. The results are shown in Table 1.

Table 1 From Table 1, it is clear that the insect repellent resin foam of the present invention has an insect repellent effect, and furthermore, in the case of Example 1, it is clear that the insect repellent effect can be maintained for a long period of time.

Example 8 Propylene-ethylene random copolymer (density 0.9
0J//cmll ethylene content 4.8%) pellet 1
00 parts by weight of 6G in dichloromethane saturated vapor
℃, 5kIi/cm! The sample was left for 6 hours, and then 80 parts by weight of dichloromethane was impregnated therein. This foam beads,
Pre-foaming was carried out for 1 minute with water vapor of S k &/cml to obtain pre-foamed beads with an expansion ratio of 10 times. After aging the pre-foamed beads at room temperature for 24 hours, the beads were heated at 80°C in a mixed gas of nitrogen: dichlorosif 0p methane (molar ratio) = 1:1.
It was maintained at 20 kg/cm2 for 4 hours.

After applying 1 part by weight of 0゜0-dimethyl-0-(8-methyl-4-nitro7-denyl)thiophosphate and 4 parts by weight of boric acid to the surface of 100 parts by weight of the pre-foamed beads, 1 part by weight of boric acid was applied. .5, heat foaming was carried out for 1 minute with water vapor of Ii//cm''.

The same test as in Example 1 was conducted using the obtained resin foam. The results are shown in Table 2.

Example 4 0 was applied to the surface of 100 parts by weight of the pre-foamed beads obtained in Example 8.
．． After collecting 1 part by weight of 0-dimethyl-〇-(8-methyl-4-nitrophenyl)thiophosphate, 1.5k
Foaming was carried out by heating with water vapor at p/cm2 for 1 minute.

The same test as in Example 1 was conducted using the obtained resin foam. The results are shown in Table 2.

Comparative Example 2 A resin foam was obtained by heating and foaming in the same manner as in Example 8 without applying an insect repellent.

Table 2 shows the results of the same tests as in Example 1.

Table 2 It is clear from Table 2 that the foam of the present invention has an insect repellent effect, and especially in Example 8, this can be maintained for a long period of time.

! I! Example 5 After adding 1 part by weight of Saralol and 4 parts by weight of triphenyl borate to 100 parts by weight of high-pressure polyethylene, the mixture was crosslinked to obtain crosslinked polyethylene particles having a gel content of 49.4%. Next, the impregnated crosslinked polyethylene particles were placed in a pressure vessel p, dichlorosifuromethane was added as a blowing agent, impregnated with the blowing agent for 60 minutes at 66° C., and then cooled and returned to normal pressure. The beads were immediately heated with steam in an autoclave to obtain pre-expanded beads with an expansion ratio of 251 and a closed cell ratio of 87q6.

Store the pre-expanded granules in a pressure-resistant container and dichlorosift 0p.
Methane was added and the foaming agent was impregnated for 85 hours at 66°C. After returning this to normal pressure, 580 x 855 with small holes
The mixture was filled into a closed mold of X50fflf7+, heated with steam to a steam pressure of 2.5 kg/cm'', and foamed in the mold.

The resulting resin foam was made into the shape of ioxtoxBoomm and placed in the center of a waist-high petri dish with a diameter of 11 cm. Approximately 1 g (approximately 10
(adjusted so that there are 0 woolly mites),
The total number of dead insects after 48 hours was F<L (test ii). Furthermore, a resin foam similar to the one used was heated indoors for 5 minutes.
After leaving it for a year, a test similar to the above test ■ was conducted (
Exam ■). The results are shown in Table 8.

Example 6 100 parts by weight of the same raw material as in Example 6 was impregnated with 6 parts by weight of sub rolls, and then molded and foamed in the same manner as in Example 5. The same test as in Example 5 was conducted using the obtained resin foam. The results are shown in Table 8.

Comparative Example 8 A test was conducted in the same manner as in Example 5 except that the same raw material as in Example 5 was not impregnated with an insect repellent. The results are shown in table vg8.

Table 8 □ From Table 8, it is clear that the insect repellent resin foam of the present invention has a strong insecticidal effect, and especially in the case of Dormitory Example 6, it is clear that the insecticidal effect lasts for a long time. be.

(that's all)

Claims (2)

[Claims] (1) A method for producing an insect repellent resin foam, which comprises impregnating foam beads with an insect repellent and then molding them by a foam bead method. (2) The insect repellent is added i) after the polymerization reaction has progressed to about 80% during foamed bead production until the polymerization reaction is completed, ii) after the polymerization reaction is completed, or iii) after the primary foaming. 2. The method for producing an insect repellent resin foam according to claim 1, wherein the process is carried out at any point in time to cause the foamed beads to contain an insect repellent.