JPS6289603A - Subliming fungistatic and insect-repellent composition - Google Patents
Subliming fungistatic and insect-repellent compositionInfo
- Publication number
- JPS6289603A JPS6289603A JP12429186A JP12429186A JPS6289603A JP S6289603 A JPS6289603 A JP S6289603A JP 12429186 A JP12429186 A JP 12429186A JP 12429186 A JP12429186 A JP 12429186A JP S6289603 A JPS6289603 A JP S6289603A
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- dimethyl fumarate
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- composition
- insect
- insect repellent
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Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は昇華性防かび・防虫剤組成物に関するものであ
る。さらに詳しくいえば、本発明は、人体に対する安全
性が高く、かつ糸状菌の発育阻止効果及び繊維害虫に対
する摂食阻害活性に優れ、かつその効果の持続性に優れ
た安価な実用的昇華性防かび・防虫剤組成物に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a sublimable fungicide/insect repellent composition. More specifically, the present invention provides an inexpensive practical sublimation preventive that is highly safe for the human body, has excellent growth inhibiting effects on filamentous fungi and antifeeding activity against textile pests, and has excellent long-lasting effects. This invention relates to a mold/insect repellent composition.
従来の技術
かびは自然界のいたるところに生存しており、温度、湿
度、栄養源などの環境要因が適当であれば、どこにでも
発生して、種々の被害をもたらしている。例えば、衣類
や皮革類はもちろんのこと、塩化ビニル樹脂などのプラ
スチックにおいても可塑剤を栄養源としてかびが発生し
、また最近では適温、気密性の高い住宅がふえ、その天
井、床、トイレ、浴室、台所、ときには居室壁面などに
もかびの発生がみられる。BACKGROUND OF THE INVENTION Molds exist everywhere in the natural world, and if environmental factors such as temperature, humidity, and nutrient sources are suitable, they can occur anywhere and cause various types of damage. For example, mold can grow not only in clothing and leather, but also in plastics such as vinyl chloride resin, using plasticizers as a nutrient source.In recent years, there has been an increase in the number of houses with moderate temperatures and high airtightness, such as ceilings, floors, toilets, etc. Mold can be found in the bathroom, kitchen, and sometimes even on the walls of living rooms.
このようなかびの発生は、外観を悪くしたシ、製品の品
質を劣化させたりし、さらには人体に対して悪影響を及
ぼす場合があり、特に医薬、食品工場では絶対にかびの
混入が許されず、徹底的な防かび対策が進められている
。このような背景から、近年防かび剤の必要性が増大し
、優れた防かび剤の開発研究が積極的に行われている。The occurrence of such mold can impair the appearance, deteriorate the quality of the product, and even have an adverse effect on the human body.Mold must never be allowed to enter, especially in pharmaceutical and food factories. , thorough anti-fungal measures are being taken. Against this background, the need for fungicides has increased in recent years, and research and development to develop excellent fungicides has been actively conducted.
ところで、これまで防かび剤としては、銅系、有機スズ
系、塩素化フェノール系、第四級アンモニウム塩系、チ
アゾール及びインチアゾール系。By the way, the fungicides so far include copper-based, organotin-based, chlorinated phenol-based, quaternary ammonium salt-based, thiazole and inthiazole-based.
有機ブロム系など数多くの薬剤が知られている。Many drugs are known, including organic bromine-based drugs.
しかしながら、これらの薬剤は、通常噴霧、塗布、注入
、混入などの表面処理又は内部処理により施されている
が、対象とする物体又は場所に対して直接処理すること
が困難であるし、ある種の物質。However, these drugs are usually applied by surface treatment or internal treatment such as spraying, coating, injection, or mixing, but it is difficult to treat the target object or location directly, and some substance.
例えば食品包装材料、医薬品包装材料、衣料などの繊維
製品、皮革原料及びその製品、農産物などに対しては、
汚染や毒性の間−を伴うため用いることができないとい
う欠点がある。For example, for food packaging materials, pharmaceutical packaging materials, textile products such as clothing, leather raw materials and their products, agricultural products, etc.
It has the disadvantage that it cannot be used because it involves pollution and toxicity.
そのため、汚染や毒性が問題とされる場合には、通常昇
華性防かび剤が用いられ、これまで、p−ジクロロベン
ゼンやこれと他の防かび性物質、例えばp−クロロ−m
−キシレノールとの混合物が最も広く用いられている(
特公昭55−2403号公報)。Therefore, when contamination or toxicity is a concern, sublimation fungicides are usually used, and until now, p-dichlorobenzene and other fungicides, such as p-chloro-m
- mixtures with xylenol are most widely used (
(Special Publication No. 55-2403).
しかしながら、p−ジクロロベンゼンは有機塩素系薬剤
の1種であって、生物体内に蓄積して害を与えるおそれ
があり、また眼粘膜と結合して水晶体の混濁を起すおそ
れがある(実業中毒便覧)ため、その使用については規
制される方向にある。However, p-dichlorobenzene is a type of organic chlorine drug that can accumulate in living organisms and cause harm, and can also combine with the ocular mucosa and cause clouding of the lens (Industrial Poisoning Handbook). ), its use is likely to be regulated.
したがって、近年p−ジクロロベンゼンに代わるべき昇
華性防かび剤として、多くの化合物やその組合せが提案
されている。例えば、アダマンタン、昇華性炭化水素及
び昇華性又は揮発性を有する防かび物質を配合して成る
昇華性防かび剤(%開昭55−4313号公報)、t−
ブチルフェノール系化合物を有効成分とし、かつ共力剤
としてナフタレン、ジクロロベンゼン、シーt−7”チ
ルベンゼン、アセトアルデヒド三量体、プロピルアルデ
ヒド三量体及びイソブチルアルデヒド三量体の中から選
ばれた少なくとも1種の昇華性化合物を含有して成る揮
発性防かび剤(特公昭59−29161号公報)などが
提案されている。Therefore, in recent years, many compounds and combinations thereof have been proposed as sublimable fungicides to replace p-dichlorobenzene. For example, a sublimating fungicide containing adamantane, a sublimable hydrocarbon, and a sublimating or volatile fungicidal substance (%Kokai No. 4313/1983), t-
A butylphenol compound is used as an active ingredient, and at least one type selected from naphthalene, dichlorobenzene, sheet t-7'' methylbenzene, acetaldehyde trimer, propylaldehyde trimer, and isobutyraldehyde trimer is used as a synergist. A volatile fungicide containing a sublimable compound (Japanese Patent Publication No. 59-29161) has been proposed.
しかしながら、これらの防かび剤はいずれもp−ジクロ
ロベンゼンに比べて高価である上に、防かび効果も劣り
、実用上必ずしも満足しうるものとはいえない。However, all of these fungicides are more expensive than p-dichlorobenzene and have inferior fungicidal effects, so they cannot be said to be practically satisfactory.
他方、衣料用防虫剤としては、従来ナツタリスショウノ
ウ、p−ジクロロベンゼンなどが知られており、なかで
も高濃度下での殺虫効果が強く安価であるという点でp
−ジクロロベンゼンが最も広く大量に使用されていた。On the other hand, as insect repellents for clothing, so far known are camphor camphor, p-dichlorobenzene, and p-dichlorobenzene.
-Dichlorobenzene was the most widely used in large quantities.
しかしながら、とのp−ジクロロベンゼンは前記したよ
うに衛生上の問題を有するため、近年p−ジクロロベン
ゼンに代わる人体に無害な防虫剤の開発研究が広く行わ
れ、多くの新しい化合物や組合せ薬剤などが提案されて
いる。例えばトリイソプロピル−8−トリオキサン又は
トリ第三ブチル−5−1リオキサントリナロール、アネ
トール、メントール、ケイ皮アルデヒド、チモール、オ
イゲノール又はこれらの誘導体との組合わせを有効成分
とした羊毛用防虫剤(特開昭50−24436号公報)
、エーテル結合を有する炭素数10個の環式化合物を有
効成分とする防虫剤(特開昭52−110823号公報
)、アダマンタン、昇華性炭化水素及び昇華性又は揮発
性を有する極性化合物を配合して成る昇華性防虫剤(特
開昭53−121936号公報)、ナフタリンとチモー
ルとの組合わせを有効成分とする防虫剤(特開昭53−
109938号公報)、ナフタリンと2−イソプロピル
−5−メチルフェノールとの組合わせを有効成分とする
衣料用防虫剤(特開昭54−32620号公報)、アセ
トキシムを主成分とする衣料用防虫剤(特開昭54−1
01425号公報)、α−位に分枝を有する炭素鎖など
の置換基をもった芳香族化合物を活性成分として含有し
ている防虫剤(特開昭54−110321号公報)、l
−カルボンを有効成分とする芳香性防虫剤(特開昭55
−19229号公報)などが提案されている。However, p-dichlorobenzene has hygienic problems as mentioned above, and in recent years, research has been widely conducted to develop insect repellents that are harmless to the human body in place of p-dichlorobenzene, and many new compounds and combination drugs have been developed. is proposed. For example, insect repellents for wool containing as active ingredients triisopropyl-8-trioxane or tritert-butyl-5-1rioxanthantolinalool, anethole, menthol, cinnamaldehyde, thymol, eugenol, or a combination of these derivatives ( (Japanese Patent Application Laid-Open No. 50-24436)
, an insect repellent containing a cyclic compound having 10 carbon atoms and an ether bond as an active ingredient (Japanese Unexamined Patent Application Publication No. 110823/1982), which contains adamantane, a sublimable hydrocarbon, and a sublimable or volatile polar compound. (Japanese Unexamined Patent Publication No. 53-121936), an insect repellent containing a combination of naphthalene and thymol as active ingredients (Japanese Unexamined Patent Publication No. 53-121936)
No. 109938), an insect repellent for clothing containing a combination of naphthalene and 2-isopropyl-5-methylphenol as an active ingredient (Japanese Patent Application Laid-open No. 1983-32620), an insect repellent for clothing containing acetoxime as the main ingredient ( JP-A-54-1
01425), an insect repellent containing as an active ingredient an aromatic compound having a substituent such as a carbon chain having a branch at the α-position (Japanese Unexamined Patent Publication No. 110321/1983), l
- Aromatic insect repellent containing carvone as an active ingredient (Unexamined Japanese Patent Publication No. 55
19229) and the like have been proposed.
しかしながら、これらの防虫剤はいずれもp −ジクロ
ロベンゼンに比べて高価である上に、防虫効果やその持
続性に問題があり、実用上十分満足しつるものとはいえ
ない。However, all of these insect repellents are more expensive than p-dichlorobenzene and have problems with their insect repellent effects and their sustainability, and cannot be said to be fully satisfactory in practice.
発明が解決しようとする問題点
本発明の目的は、このような事情のもとで、人体に対し
て極めて安全で、防かび及び防虫効果に優れ、かつその
効果の持続性が良好である上に安価な実用的昇華性防か
び・防虫剤を提供することにある。Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to provide a method that is extremely safe for the human body, has excellent fungicidal and insect repellent effects, and has good sustainability of its effects. The objective is to provide an inexpensive and practical sublimation fungicide/insect repellent.
問題点を解決するための手段
本発明者は鋭意研究を重ねた結果、フマル酸ジメチルと
ガンファーとの混合物は、その蒸気が糸状菌発育阻止効
果及び繊維害虫に対する摂食阻害活性に優れ、かつ人体
に対する安全性が高く、化学的にも安定である上に、融
点が高く、しかも昇事件を有することを見出し、この知
見に基づいて本発明を完成するに至った。Means for Solving the Problems As a result of intensive research, the present inventor has found that the vapor of a mixture of dimethyl fumarate and gunfer has an excellent effect of inhibiting the growth of filamentous fungi and an antifeeding activity against textile pests, and is harmful to the human body. The inventors have discovered that they have a high safety profile, are chemically stable, have a high melting point, and have a melting point, and have completed the present invention based on this knowledge.
すなわち、本発明は、フマル酸ジメチル及びガンファー
から成る昇華性防かび・防虫剤組成物を提供するもので
ある。That is, the present invention provides a sublimable fungicide/insect repellent composition comprising dimethyl fumarate and gunfer.
本発明で用いるフマル酸ジメチルは、融点102℃、沸
点88.5℃7121111Hgの無色結晶状固体で、
ラットに対する急性経口毒性LD50値は2240■/
に9、ウサギに対する皮膚毒性LD5Q値は1250■
/句であって、安全性が高く、かつ安定な化合物である
。Dimethyl fumarate used in the present invention is a colorless crystalline solid with a melting point of 102°C and a boiling point of 88.5°C and 7121111 Hg.
Acute oral toxicity LD50 value for rats is 2240■/
9. The skin toxicity LD5Q value for rabbits is 1250■
/phrase, and is a highly safe and stable compound.
このフマル酸ジメチルと組み合わせて用いるガンファー
は、衣料用の昇華性防虫剤として広く用いられている化
合物であるが、フマル酸ジメチルと組み合わせた場合著
しくその効果が向上する上に、防かび作用も発揮される
。Ganfer, which is used in combination with dimethyl fumarate, is a compound that is widely used as a sublimation insect repellent for clothing, but when combined with dimethyl fumarate, its effectiveness is significantly improved and it also exhibits a fungicidal effect. be done.
本発明組成物におけるフマル酸ジメチルとガンファーと
の配合割合は重量比で10:90ないし2.98の範囲
で選ばれる。これよシもフマル酸ジメチルの量が少ない
と防虫、防かび効果が不十分になる。また、これよシも
フマル酸ジメチルの量を増加させても効果の点では特に
不都合を生じないがコスト高になるので不利である。The mixing ratio of dimethyl fumarate and gunfer in the composition of the present invention is selected in a weight ratio of 10:90 to 2.98. Again, if the amount of dimethyl fumarate is small, the insect and fungal effects will be insufficient. Furthermore, even if the amount of dimethyl fumarate is increased, there is no particular disadvantage in terms of effectiveness, but it is disadvantageous because it increases the cost.
本発明組成物には、これらの必須成分に加えてシリカゲ
ルや塩化カルシウムなどの防湿剤を含ませることもでき
る。In addition to these essential components, the composition of the present invention can also contain a moisture-proofing agent such as silica gel or calcium chloride.
本発明の昇華性防かび・防虫剤組成物は、フマル酸ジメ
チル及びガンファーの組合せを有効成分とするものであ
って、人体に対する安全性が高い上に、防かび及び防虫
効果に優れ、かつその効果の持続性に優れた安価な実用
的薬剤である。The sublimation mold/insect repellent composition of the present invention contains a combination of dimethyl fumarate and gunfer as active ingredients, and is not only highly safe for the human body but also has excellent fungicidal and insect repellent effects. It is an inexpensive and practical drug with excellent long-lasting effects.
このものを防かび剤として用いる場合、昇華性を有して
いるので、特に表面処理や内部処理などの薬剤による直
接処理が適さない物体や場所、例えば食品包装材料、医
薬品包装材料、衣料などの繊維製品、皮革原料及びその
製品、農産物など、あるいは家屋内では戸棚、引出し、
押入れ、浴室、家具内、衣裳ケースなど、屋外では倉庫
、ビニルハウスのような温室などの防かびに有用である
。When using this product as a fungicide, it has sublimation properties, so it can be applied to objects or places where direct treatment with chemicals such as surface treatment or internal treatment is not suitable, such as food packaging materials, pharmaceutical packaging materials, clothing, etc. Textile products, leather raw materials and their products, agricultural products, etc., or in the house, such as cupboards, drawers, etc.
It is useful for preventing mold in closets, bathrooms, inside furniture, clothing cases, and outdoors in warehouses and greenhouses such as vinyl houses.
−万、防虫剤として用いる場合、繊維害虫に対する優れ
た摂食阻害活性を有することから、衣類やカーペットの
ような絹、羊毛などの繊維製品の防虫に有用である。- When used as an insect repellent, it is useful for insect repelling textile products such as silk and wool, such as clothing and carpets, because it has excellent feeding inhibiting activity against textile pests.
実施例 次に実施例によシ本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail by way of examples.
実施例1
1tの広口びんの底にフマル酸ジメチル1重量部とガン
ファー9重量部の混合物100■を置き、その上方にイ
ガ(Tinea pellionella L、 )
幼虫10頭と羊毛標準試験布を入れたカゴを固定した。Example 1 100 μ of a mixture of 1 part by weight of dimethyl fumarate and 9 parts by weight of camphor was placed at the bottom of a 1 ton wide-mouth bottle, and above it was placed a burr (Tinea pellionella L, ).
A cage containing 10 larvae and a wool standard test cloth was fixed.
次にびんを密閉し、温度30℃、湿度65チの恒温恒湿
庫内に7日間放置したのち、虫を取シ出して死亡頭数を
数えた。Next, the bottle was sealed and left in a constant temperature and humidity chamber at a temperature of 30°C and a humidity of 65°C for 7 days, after which the insects were removed and the number of dead insects was counted.
また、比較のために、ガンファー単独、フマル酸ジメチ
ル単独のものも同様に試験した。試験は3@行い、その
平均値を第1表に示した。For comparison, Ganfer alone and dimethyl fumarate alone were also tested in the same way. Three tests were conducted, and the average values are shown in Table 1.
第 1 表
この表から7マル酸ジメチルとガンファーt−併用した
ときに相乗効果が奏されていることが分る。Table 1 From this table, it can be seen that a synergistic effect is produced when dimethyl 7malate and Ganfer t- are used together.
実施例2
加熱液化させたポテト・デキストロース寒天培地を直径
5cn1のガラスシャーレに流し込み、放冷して平面培
地とした。次に、その中央一点にのみアスペルギルス・
ニゲル(Aspergil’lus nigerATC
C6275)の胞子懸濁液を接種する。このシャーレを
1tのガラスびんに入れ、そのそばにガンファーとフマ
ル酸ジメチルの混合物をおき、密閉し、・温度25℃、
湿度65%の培養器にて一定期間培養してかびの生育状
態を観察した。また、比較として無薬剤のもの、ガンフ
ァー単独のもの、フマル酸ジメチル単独のものについて
同時に実験を行った。Example 2 A heated and liquefied potato dextrose agar medium was poured into a glass Petri dish with a diameter of 5 cn1, and allowed to cool to form a flat medium. Next, Aspergillus can be found only in one point in the center.
Aspergil'lus nigerATC
C6275). Place this petri dish in a 1 ton glass bottle, place a mixture of gunfer and dimethyl fumarate next to it, seal it tightly, and keep it at a temperature of 25°C.
The mold was cultured for a certain period of time in an incubator with a humidity of 65%, and the state of mold growth was observed. In addition, for comparison, experiments were conducted simultaneously with no drug, with only gunfer, and with only dimethyl fumarate.
防かび効果の判定は、次のようにかびの発育状態を5段
階に分けて行い、その結果を第2表に示した。The mold-preventing effect was evaluated by dividing the mold growth into five stages as shown below, and the results are shown in Table 2.
判定基準
−かびの発生が認められず
+ わずかに認められる
+1− 晃程度認められる
一H−1−殆程度認められる
千生 全面に認められる
手続補正書(自発)
昭和62年 2月]7日
特許庁長官 黒 1)明 雄 殿
昭和61年特許願第124291号
2、発明の名称
昇華性防かび・防虫剤組成物
3、軸)正をする者
事件との関係 特許出願人
住 所 東京都千代田区霞が関1丁目3番1号氏名
(114)工業技術院長 飯塚幸三4、指定代理人
自 発
6、補正により増加する発明の数 08、補正の内容
(1) 明細書第10頁第1表の次に以下の文章を加
入します。Judgment criteria - No mold growth + Slightly found +1 - Moderately found - H-1 - Mostly seen Chiu Procedural amendment fully accepted (voluntary) February 1988] 7th Commissioner of the Japan Patent Office Kuro 1) Yu Akira, Patent Application No. 124291, filed in 1986, 2, Name of the invention: Sublimated fungicide/insect repellent composition 3, Axis) Relationship with the person who makes the right decision Patent applicant's address: Tokyo 1-3-1 Kasumigaseki, Chiyoda-ku Name
(114) Director of the Agency of Industrial Science and Technology Kozo Iizuka 4, Designated Agent Voluntary 6, Number of inventions increased by amendment 08, Contents of amendment (1) The following sentence is added after Table 1 on page 10 of the specification. .
「実施例2
1Qの広口びんの底にフマル酸ジメチル1重量部とガン
ファー9重量部の混合物400mgを置き、その上方に
一頭あたりの平均体重9II1gのヒメ力ッオブシムシ
(Attagenus piceus 01iv、)幼
虫10−と羊毛標準試験布を入れたカゴを固定した。次
に、びんを密閉し、温度25℃、湿度65%の恒温恒湿
庫内に20日間放置したのち、虫の死亡頭数を数え、布
の食害量を測定した。Example 2 400 mg of a mixture of 1 part by weight of dimethyl fumarate and 9 parts by weight of camphor was placed at the bottom of a 1Q wide-mouth bottle, and above it were 10 larvae of Attagenus piceus (Attagenus piceus 01iv) with an average weight of 9II1 g per head. The basket containing the wool standard test cloth was fixed.Next, the bottle was sealed and left in a constant temperature and humidity chamber at 25℃ and 65% humidity for 20 days.The number of dead insects was counted, and the number of dead insects was counted. The amount of feeding damage was measured.
また、比較のために、フマル酸ジメチル単独、ガンファ
ー単独のものも同時に試験した。試験−は3回行いその
平均値を第2表に示した。For comparison, dimethyl fumarate alone and gunfer alone were also tested at the same time. The test was conducted three times and the average value is shown in Table 2.
第 2 表
」
(2)明細書第10頁下から111行目この表から」を
「第1表及び第2表から」に訂正します。"Table 2" (2) Line 111 from the bottom of page 10 of the specification, "From this table" is corrected to "From Tables 1 and 2."
(3)明細書第10頁下から9行目[実施例2」を「実
施例3」に訂正します。(3) On the 9th line from the bottom of page 10 of the specification, [Example 2] will be corrected to "Example 3."
(4)明細書第10頁下から6行目「第2表」を「第3
表Jに訂正します。(4) ``Table 2'' in the 6th line from the bottom of page 10 of the specification is changed to ``Table 3''.
Corrected Table J.
(5)明細書第12頁「第2表」を[第3表」に訂正し
ます。(5) "Table 2" on page 12 of the specification will be corrected to "Table 3."
Claims (1)
かび・防虫剤組成物。1. A sublimable fungicide/insect repellent composition comprising dimethyl fumarate and gunfer.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12879585 | 1985-06-12 | ||
JP60-128795 | 1985-06-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6289603A true JPS6289603A (en) | 1987-04-24 |
Family
ID=14993628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12429186A Pending JPS6289603A (en) | 1985-06-12 | 1986-05-28 | Subliming fungistatic and insect-repellent composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6289603A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63277281A (en) * | 1987-05-08 | 1988-11-15 | Kanebo Ltd | Coating pigment and production thereof |
CN1049798C (en) * | 1996-11-26 | 2000-03-01 | 中国科学院上海昆虫研究所 | Moth roof and mildew-proof mixture |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6160602A (en) * | 1984-08-30 | 1986-03-28 | Kao Corp | Volatile fungicidal and insecticidal agent |
-
1986
- 1986-05-28 JP JP12429186A patent/JPS6289603A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6160602A (en) * | 1984-08-30 | 1986-03-28 | Kao Corp | Volatile fungicidal and insecticidal agent |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63277281A (en) * | 1987-05-08 | 1988-11-15 | Kanebo Ltd | Coating pigment and production thereof |
JP2568481B2 (en) * | 1987-05-08 | 1997-01-08 | 鐘紡株式会社 | Coated pigment and method for producing the same |
CN1049798C (en) * | 1996-11-26 | 2000-03-01 | 中国科学院上海昆虫研究所 | Moth roof and mildew-proof mixture |
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