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

【発明の詳細な説明】 産業上の利用分野 本発明は、防虫性を有する樹脂発泡体の製造方法に関す
る。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.

従来の技術及び問題点 樹脂発泡体は、内部に多くの気泡を有するために、優れ
た断熱性、緩衝性を示し、例えば天井、壁、床、配管等
の断熱材として、椅子、マツトレス、ベッド等の家具、
寝装品のクッション材として、また各種製品の梱包材と
して各分野に幅広く利用されている。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.

しかし、仁のような樹脂発泡体は、適度の断熱性、保温
性、吸湿性等を有するため、ダニ類等の害虫や細菌類が
繁殖しやすく、これらにより梯々の被害が生じている。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.

これに対して、殺虫剤、消毒剤等の散布、薫じよう等を
定期的に！ｌ！施することが最も実用的な対策であると
されているが、実際には、樹脂発泡体の隅々まで、一様
に殺虫、消毒の幼果を及ばずことは極めて困難であり、
更に、これらの処置さえ実施不可能な場合が多い。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.

問題点を解決するための手段 本発明者捻、公知の発泡ビーズ法により、成形して得ら
れる樹脂発泡体について、該発泡体に均一に防虫剤等を
分散することのできる方法を見出しここに本発明を完成
した。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.

即ち、本発明は、発泡ビーズに防虫剤を含有せしめた後
、発泡ビーズ法によシ成形することを特徴とすゐ防虫性
樹脂発泡体の製造方法に係る。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.

本発明の樹脂発泡体とは、公知の発泡ビーズ法によりｕ
ｔ成形されるものである。本発明で杜、樹脂発泡体に均
一に防虫剤を含有せしめるために防虫剤の添加を １）発泡ビーズ製造時において、重合反応が鈴−程度進
行した後、重合反応が完了するまでの間、 薯）重合反応完了後、または ■）−次発泡抜、 のいずれかの時点で行なう。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.

使用する基材樹脂の種類には、特に制限はなく、通常発
泡ビーズ法で用いる樹脂は、いずれも使用でき、ポリス
チレン、ポリエチレン、ポリプロピレン、ポリ塩化ビニ
ル及びこれらの共重合体が例示できる。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.

発泡剤としては、一般に用いられるプロパン、ブタン、
ペンタン等の脂肪族炭化水素類の他、メチレンクロライ
ド、ジクロルジフルオルメタン、トリクリルモノフルオ
ルメタン、モノクロルトリフルオルメタン等のハロゲン
化炭化水素類、空気、窒素、アルゴン、ネオン、ヘリウ
ム、二酸化炭素等の無機ガス類、アゾジカルボンアミド
等が使用でき、これらを一種または二種以上混合して用
いる。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.

発泡ビーズは、上記樹脂及び発泡剤を用いて、懸濁重合
法によシ常法に従って得ることができる。Expanded beads can be obtained by a suspension polymerization method using the above resin and a blowing agent according to a conventional method.

本発明で用いる防虫剤には特に制限はなく、樹脂発泡体
の用途、樹脂と防虫剤との相溶性、重合時のバランス等
を検討し最適なものを選択すれば良い。具体的には、ピ
レトリン、アレスリン、７タルスリン、レスメトリン、
フラメトリン、１−Ｚｆ＝ルーｇ−メチル−２−ペンテ
ニル−２，２−ジメチル−８−（２’−メチル−１′−
プロペニル）−シクロプロパン−１−カルボキシレート
、１−ｘ　ｆ　＝　Ａ／　−２−メチル−２−ペンテニ
ル−２，２−ジメチル−８−（２’−メトキシカルボニ
ル−１′−フレベニル）−シクロプロパン−１−カルボ
キシレート、１−エチニル−２−メチル−２−ペンテニ
、ルー　２　、２　、　ｓ　、　ａ　　−テトラメチル
シクロプロパン−１−カルボキシレート、１−エチニル
−２＝メチル−２−ペンテニル−２，２−ジメチル−８
−（２’　、　２’−ジクヮルビニル）−シフ四プロパ
ンー１−カルボキシレート等のピレスロイド系殺虫剤、
ＤＤＶＰ、ダイアノジン、０．０−ジメチル−０−（８
−メチル−４−二トロンエニル）チオホスツエート、ピ
リダフェンチオン等の有機燐系殺虫剤、プロポキサール
、セビン等のカーバメイト系殺虫剤、ビペロニルブトキ
サイド、プロビルアインム、ビペロナールジメチルアセ
クール醇の共力剤、ブチルアセトアニリド、Ｎ、Ｎ−ジ
メチル−トルアミド、Ｎ、Ｎ−ジエチルトルアミド、ジ
オクチルフタレート、ジドデシル７タレート、エチルヘ
キサンジオール等の忌避剤、す７０−ル、イソサ７０−
ル、ナフタリン、樟脳、Ｐ−ジクロルベンゼン、シンナ
之ツクアルデヒド、アニスアルデヒド、シ（ポリクロロ
アルキル）エーテル、硼酸、硼酸ナトリウム、硼酸カリ
ウム、硼酸トリブチル、硼酸トリフェニル等を例示でき
る。これらの防虫剤は、単独でも使用可能であるが、数
種類を併用することにより更に好ましい結果を与えるこ
とができる。例えは、不揮発性の硼酸または硼酸塩と他
の揮散性防虫剤とを組み合わせると、硼素化合物の有す
る不揮発性がもたらす薬効の永続性、昆虫毒としての遅
効性、残効性と揮散性防虫剤の速効性、揮散性とが相剰
的な防虫効果を発揮する。この例の場合には、硼酸また
は硼酸塩１００重量部に対して揮散性防虫剤を１〜１０
００重量部の範囲で用いることが好ましい。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.

樹脂に対する防虫剤の配合比は、防虫剤の種類、薬効の
仕様、梅脂の種類、発泡ビーズ製造条件等により異なる
が、樹脂１００重量部に対して、防虫剤０．０００６〜
１０重量部好ましくはｏ、ｏ　ｏ　ｔ〜５重量部程度で
ある。防虫剤が０．０００５重量部より少ないと防虫効
果が不足し、１０重量部をこえると樹脂の発泡不良、接
着不良、収縮膨張等の成形不良の原因と女シ易す。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.

防虫剤の樹脂への添加は、上記１）の場合は、樹脂の懸
濁液中に分散、溶解せしめる方法、ｉｉ）■）の場合は
、発泡ビーズに塗布或輻含浸せしめる方法で行なう。防
虫剤は、単独で添加する以外Ｋ。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.

必要に応じて溶媒、分散媒、担体等の助剤を用いて添加
してもよく、助剤の使用量は、目的に応じて適宜法める
ことができる。また、１）の場合には、発泡剤が防虫剤
のｆｇ謀となり得るならば、両者を混合して、溶液の形
態で添加することもできる。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.

本発明に於ては、上記した防虫剤の他に、安息誉酸類、
ソルビン酸類、パラクロロメタキシレノール、α−プロ
モシナモアルデヒド、トリアジン、イミダゾール、ベン
ゾイミダゾール、テトラクロロイソ７タロニトリル、２
−メトキシカルボニルア文ノベンゾイミダゾール等の抗
菌、防黴剤、リナロール、ゲラニオール、リモネン、シ
トラール、シトｐネラール、植物抽出エキス等の若番、
消臭剤、ブチルヒドロキシアニソール、２．６−ジーｔ
−ブチル−Ｐ−クレゾール、トコフェロール、トリフェ
ニルホスツエイト等の酸化防止剤、ベンゾトリアゾール
、トリルトリアゾール、２−メチル−６−ピラゾロン等
の防錆剤の他、クエニルサニシレート、２−ヒドロキシ
−４−メトキシベンゾフェノン等の紫外線吸収剤、ポリ
オキシエチレンアルキルアシド、アルキルヌルホネート
、アルキルホスフェート等の帯電防止剤、鉛塩、金属石
鹸、有機錫化合物、メルカプタイド化合物等の安定剤、
マイカ粉、硅酸塩、炭酸カルシウム、クレー、アスベス
ト、シリカ等の無機質微粉末、各種顔料等の着色剤、他
種のポリマーなどを適量含有せしめることもできる。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.

防虫剤を含有せしめた発泡ビーズは、通常の発泡ビーズ
法により所望する形状に成型される。発泡方法としては
、特に制限はなく、多くの場合−次発泡、二次発泡によ
る二段発泡を採用するが、多段発泡を採用するとともで
き、またポリエチレンなどは、一段発泡によシ所望の発
泡倍率を得ることができる。発泡倍率についても特に制
限はなく、数倍〜１００倍程度であり、多くの場合２０
倍〜７０倍程度である。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.

防虫剤を樹脂の重合時に含有せしめる場合には、重合後
または一次発泡後に発泡ビーズに防虫剤を塗布する場合
と比べて、防虫剤は、発泡体中に拘−に分散される。一
方、重合後または一次発泡後に発泡ビーズに防虫剤を塗
布する場合には、複雑な作業条件を選ぶ必要がないとい
う利点がある。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.

本発明樹脂発泡体は、含有する防虫剤及び各種薬剤を徐
放するという性質を有する。徐放性は、薬剤の種類、薬
剤の添加量、薬剤の含有部分、樹脂の発泡倍率等を変え
ることによりコントロールできる。薬剤を混入、含浸に
より添加する場合には、比較的長期間効果を持続でき、
塗布によシ薬剤を添加する場合には、短期間の使用に適
する。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.

発明の効果 ■　本発明防虫性樹脂発泡体は、その発泡体としての性
質に影響を受けることなく、均一に防虫剤を含有するも
のであり、優れた防虫性を有する。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.

■　防虫剤として揮散性薬剤を使用する場合は、周囲の
環境にまで効果を及ぼすことができる。■ When using volatile chemicals as insect repellents, they can also have an effect on the surrounding environment.

■　他の薬剤を併用することにより、その薬剤に応じた
効果、例えは抗囚、防□黴醇の効果を付加することがで
きる。■ By using other drugs in combination, it is possible to add effects depending on the drug, such as anti-convict and anti-mildew effects.

■　防虫剤として、硼酸または硼酸塩のような不揮発性
薬剤と他の揮散性防虫剤とを併用することにより相剰的
な防虫効果を発揮し、長期間防虫効果を持続できる。■ 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.

■　発泡倍率や薬剤の添加量等を調整することＫよシ所
望の徐放性を有する発泡体とすることができる。(2) By adjusting the foaming ratio, the amount of drug added, etc., it is possible to obtain a foam with desired sustained release properties.

実施例 次に実施例を示して本発明を更に詳細に説明する。Example Next, the present invention will be explained in more detail by showing examples.

実施例１ １−エチニル−２−メチル−２−ペンテニル−２，２−
ジメチル−８−（２’−メチル−１１−プロペニル）シ
クロプロパン−１−カルボキシレート２０重量部及びホ
ウ酸トリブチル８０重′＃、ｑＩｊからなる防虫剤２０
重量部をブタノール１００重量部に溶解した。これを発
泡剤ベンタフ８Ｍ量チを含むポリスチレン発泡ビーズ表
面に塗布した後、ブタノールを完全に乾燥した。なお塗
布量は、発泡ビーズ１００重量部に対して防虫剤５Ｎ量
部であった。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.

この発泡ビーズを予備発泡機にて、約２分間加熱し、予
備発泡倍率が５０倍となるように予備発泡した。この予
備発泡粒を室温で１２時間熟成し、ブロック用金型（８
００Ｘ４００　Ｘ　１４０ｍｍ）中に充填して通常の加
熱法によシ発泡させた。金型中での発泡体の面圧が０と
なり、成型体が取り出し得る状態まで冷却した後離型し
た。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.

得られた樹脂発泡体を用いて、５００　Ｘ　５００　Ｘ
　５００ｆｆｉ気の立方体で内部にａｏｏ　ｘ　ａｏｏ
　ｘ　ａｏｏｍｍの空洞を有する容器を作り、その容器
中にチャバネゴキブリ成虫雌雄６５０頭を放ち、４８時
間放置後の死虫数を計数した（試Ｍｌ）。更にこの容器
と同様の容器を屋内にて５年間放置し、容器中にチャバ
ネゴキブリ成虫雌雄６６０頭を放ち４８時間放置後の死
虫数を計数した（試験■）。結果を第１表に示す。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.

実施例２ １−エチニル−２−メチル−２−ペンテニル−２，２−
ジメチル−８−（２’−メチル−１′−プロペニル）シ
フ党プロパノー１−カルボキシレート２０重量部をブタ
ノール１０．０重量部に溶解した。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.

以下実施例１と同様に塗布、乾燥、発泡、成形を行なっ
た。得られた樹脂発泡体を用いて実施例１と同様の試験
を行なった。結果を第１表に示す。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.

比較例Ｉ 発泡剤ペンタン８重量％を含むポリスチレン発泡ビーズ
を用いて実施例１と同様にして、発泡成形を行なった。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.

得られた樹脂発泡体を用いて実施例１と同様の試験を行
なった。結果を第１表に示す。The same test as in Example 1 was conducted using the obtained resin foam. The results are shown in Table 1.

第　　１　　表 第１表から本発明防虫性樹脂発泡体は、防虫作用を有す
ことが明らかであり、更に実施例１の場合には防虫作用
を長期間持続できることが明らかである。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.

実施例８ プロピレンーエチレンランダムコホリマー（密度０．９
０Ｊ／／ｃｍｌｌエチレン含有率４．８％）ペレット１
００重量部をジクロロシフ０ロメタン飽和蒸気中に６Ｇ
℃、５ｋＩｉ／ｃｍ！にて６時間置き、ジクロロジツロ
田メタン８０重量部を含浸した。この発泡ビーズをり、
Ｓ　ｋ　＆／ｃｍｌの水蒸気で１分間予備発泡させ、発
泡倍率１０倍の予備発泡ビーズを得た。この予備発泡ビ
ーズを常温で２４時間熟成した後、窒素；ジクロロシフ
０ｐメタン（モル比）＝ｌ：１の混合ガス中に８０℃、
２０ｋｇ／ｃｍ２　　で４時間保持した。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.

この予備発泡ビーズ１００重量部の表面に、０゜０−ジ
メチル−０−（８−メチル−４−二トロ７工二ル）チオ
ホスフェート１重量部及びホウ酸４重量部を塗布した後
、１．５に、Ｉｉ／／ｃｍ”の水蒸気で１分間加熱発泡
させた。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''.

得られた樹脂発泡体を用いて、実施例１と同様の試験を
行なった。結果を第２表に示す。The same test as in Example 1 was conducted using the obtained resin foam. The results are shown in Table 2.

実施例４ 実施例８で得た予備発泡ビーズ１００重量部の表面に０
．０−ジメチル−〇−（８−メチル−４−二トロフェニ
ル）チオホスフェート１重量部を珍重した後、１．５ｋ
ｐ／ｃｍ２の水蒸気で１分間加熱発泡させた。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.

得られた樹脂発泡体を用いて、実施例１と同様の試験を
行なった。結果を第２表に示す。The same test as in Example 1 was conducted using the obtained resin foam. The results are shown in Table 2.

比較例２ 実施例８と同様の方法により、防虫剤を塗布することな
く加熱発泡を行ない樹脂発泡体を得た。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.

実施例１と同様の試験を行なった結果を第２表に示す。Table 2 shows the results of the same tests as in Example 1.

第　　２　　表 第２表から本発明発泡体は防虫作用を有し、特に実施例
８では、これを長期間持続できることが明らかである。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！施例５ 高圧法ポリエチレン１００重量部にサラロール１重量部
及びホウ酸トリフェニル４重量部を添加した後、架橋し
て、ゲル含有率４９．４％を有する架橋ポリエチレン粒
子を得た。次いで、この含浸処理した架橋ポリエチレン
粒子を耐圧容ｐに入れ、発泡剤としてジクロロシフ０ロ
メタンを加え、６６℃で６０分発泡剤含浸を行なった後
、冷却し、常圧に戻した。このビーズを直ちにオートク
レーブ内でスチーム加熱して発泡倍率２５１独立気泡率
８７ｑ６の予備発泡粒を得た。! 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.

この予備発泡粒を耐圧容器に収容し、ジクロロシフ０ｐ
メタンを加え、６６℃にて発泡剤を８５俤含浸した。こ
れを常圧に戻した後、小孔を有する５８０　Ｘ　８５５
　Ｘ　５０ｆｆｌｆ７＋の閉鎖金型に充填し、水蒸気圧
力２．５ｋｇ／ｃｍ”となるように水蒸気加熱し、型内
発泡成形を行なった。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.

得られた樹脂発泡体をｉｏｘｔｏｘＢｏｏｍｍ　　の形
状とし、直径１１　ｃｍの腰高シャーレの中央に置いた
後、シャーレにケナガコナグニ飼育粉末約１ｇ（約１０
０頭のケナガコナダニが存在するように調整）を置き、
４８時間後の死虫数を計Ｆ＜　Ｌ、た（試験ｉｉ）。更
に使用した樹脂発泡体と同様の樹脂発泡体を屋内にて５
年間放置した後、上記試験■と同様の試験を行なった（
試験■）。結果を第８表に示す。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.

実施例６ 実施例６と同様の原料１００重量部に６重量部のサブロ
ールを含浸した後、実施例５と同様の方法にて成形発泡
した。得られた樹脂発泡体を用いて実施例５と同様の試
験を行なった。結果を第８表に示す。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.

比較例８ 実施例５と同様の原料に防虫剤を含浸せず、他は実施例
５と同様にして試験を行なった。結果をｖｇ８表に示す
。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.

第　　８　　表 □ 第８表から本発明防虫性樹脂発泡体は、強い殺虫作用を
有すことが明らかであり、特に寮施例６の場合には、殺
虫作用を長期間持続することが明らかである。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.

（以上）(that's all)

Claims (2)

【特許請求の範囲】[Claims] （１）発泡ビーズに防虫剤を含有せしめた後、発泡ビー
ズ法により成形することを特徴とする防虫性樹脂発泡体
の製造方法。(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）防虫剤の添加を ｉ）発泡ビーズ製造時において、重合反応が８０％程度
進行した後、重合反応が完了す るまでの間、 ｉｉ）重合反応完了後、または ｉｉｉ）一次発泡後、 のいずれかの時点に行なうことにより発泡ビーズに防虫
剤を含有せしめる特許請求の範囲第１項記載の防虫性樹
脂発泡体の製造方法。(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.