JPH05163187A - New clathrate compound - Google Patents
New clathrate compoundInfo
- Publication number
- JPH05163187A JPH05163187A JP3350734A JP35073491A JPH05163187A JP H05163187 A JPH05163187 A JP H05163187A JP 3350734 A JP3350734 A JP 3350734A JP 35073491 A JP35073491 A JP 35073491A JP H05163187 A JPH05163187 A JP H05163187A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- clathrate compound
- fragrance
- essential oil
- tetrakis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fats And Perfumes (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は包接化合物に係り、更に
詳しくはテトラキス(ヒドロキシフェニル)エタンをホ
ストとしてなる徐放性の芳香剤、抗菌剤、殺虫剤、防虫
剤等として有用な新規包接化合物に関するものである.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inclusion compound, and more particularly to a novel package useful as a slow-release aromatic agent, antibacterial agent, insecticide, insect repellent, etc., which uses tetrakis (hydroxyphenyl) ethane as a host. It is related to contact compounds.
【0002】[0002]
【従来の技術】芳香剤は、家庭の居住空間、ホテルの客
室やロビー、車中、トイレなどに幅広く使用されてお
り、その形態からエアゾール、液体及び固体に大別され
る。エアゾール芳香剤は、スプレー方式で用いられるも
のが多く、効果が即効的であり、また芳香剤組成が一定
であることから香りの経時変化が少ない特長を有してい
る。液体の芳香剤は、ガラス瓶などの容器の口に取り付
けたスポンジやフェルトなどの多孔性の基体に吸い上
げ、この基体と容器のシャッターとの開閉度により、芳
香の強さや持続性を調節している。固体芳香剤として
は、香料を可塑剤、安定剤、多孔質担体に混合し、プラ
スチックに混練して成型したものがあり、玩具、インテ
リア商品などに使用されている。抗菌剤、殺虫剤、芳香
剤等をゲスト化合物とする包接化合物の例としては、特
開平2ー178243号等の記載が知られているが、テ
トラキス(ヒドロキシフェニル)エタンをホスト化合物
とする包接化合物は知られていない。BACKGROUND OF THE INVENTION Fragrances are widely used in living spaces of homes, guest rooms and lobbies of hotels, in cars, toilets, etc., and are roughly classified into aerosols, liquids and solids according to their forms. Most of the aerosol fragrances are used in a spray method, and the effect is immediate, and since the fragrance composition is constant, the fragrance has little change over time. Liquid fragrance is sucked up by a porous base such as sponge or felt attached to the mouth of a container such as a glass bottle, and the strength and duration of the fragrance are controlled by the degree of opening and closing of this base and the shutter of the container. .. As the solid fragrance, there is a fragrance mixed with a plasticizer, a stabilizer, and a porous carrier, and the mixture is kneaded and molded into plastic, which is used for toys, interior products and the like. As an example of an inclusion compound having a guest compound such as an antibacterial agent, an insecticide, and an aromatic agent, the description of JP-A-2-178243 is known, but the inclusion compound containing tetrakis (hydroxyphenyl) ethane as a host compound is known. No contact compound is known.
【0003】[0003]
【発明が解決しようとする問題点】上述した従前のエア
ゾールタイプ芳香剤は、化学変化や缶容器の腐食の原因
となる香料成分の使用は、殊に安全面での配慮が必要で
あり、これらの香料を用いると、香りの変化やエマルジ
ョンの不安定化によるバルブ詰まりの原因となる。従っ
て、香料の選定に大きな制約がある。また、液体タイプ
は開放系容器を用いることから、転倒による液漏れ事故
は避けられず、取り扱い性の点においても問題がある。
更に、固体のタイプは加熱成型工程が入るため、低沸点
香料の加工が困難であという欠点があった。本発明は、
このような実情からみてなされたものであり、効果の持
続性、安定性、取り扱い性、加工性等を改善し、更には
徐放性を有する新規な包接化合物を提供することを目的
とする。In the above-mentioned conventional aerosol type fragrance, the use of the fragrance component which causes the chemical change and the corrosion of the can container requires special consideration from the viewpoint of safety. If the fragrance is used, it will cause valve clogging due to change of fragrance and destabilization of emulsion. Therefore, there are great restrictions on the selection of fragrances. In addition, since the liquid type uses an open container, a liquid leakage accident due to a fall is unavoidable, and there is a problem in handleability.
Further, the solid type has a drawback that it is difficult to process a low boiling point fragrance because a heat molding step is included. The present invention is
The present invention has been made in view of such circumstances, and an object thereof is to provide a novel clathrate compound having improved effect persistence, stability, handleability, processability and the like, and further having sustained release. ..
【0004】[0004]
【問題点を解決するための手段】本発明者らは上記の問
題点を解決するため、鋭意研究を重ねた結果、精油又は
香料をゲスト分子とし、テトラキス(ヒドロキシフェニ
ル)エタンをホスト分子としてなる新規な包接化合物を
提供することで所期の目的を達成することを見出し、本
発明を完成した。本発明は、精油又は香料と、下記一般
式〔1〕で示されるテトラキス(ヒドロキシフェニル)
エタンとからなることを特徴とする包接化合物である。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, use essential oils or fragrances as guest molecules and tetrakis (hydroxyphenyl) ethane as host molecules. The present invention has been completed by finding that the intended object can be achieved by providing a novel inclusion compound. The present invention comprises an essential oil or fragrance and tetrakis (hydroxyphenyl) represented by the following general formula [1].
It is an inclusion compound characterized by comprising ethane.
【0005】[0005]
【化2】 [Chemical 2]
【0006】以下、本発明を詳細に説明する。本発明に
おいて、ゲスト化合物である精油又は香料は、天然若し
くは合成のもが用いられる。精油としては、主に天然精
油のシネオール、ヒノキチオール、メントール、テルピ
ネオール、ボルネオール、ノポール、シトラール、シト
ロネロール、シトロネラール、ゲラニオール、リナロー
ル、ジメチルオクタノール等が挙げられる。一方、香料
としてはキンモクセイ、ジャスミン、レモン等が挙げら
れる。これらはいずれも香料として有用であるが、精油
の場合には、更に殺菌作用、殺虫作用、防虫作用等を併
せて有するものである。これらの化合物は単独で、若し
くは必要に応じて二種以上を混合して使用することがで
きる。The present invention will be described in detail below. In the present invention, as the guest compound, the essential oil or fragrance may be natural or synthetic. Examples of the essential oil mainly include natural essential oils such as cineol, hinokitiol, menthol, terpineol, borneol, nopol, citral, citronellol, citronellal, geraniol, linalool and dimethyloctanol. On the other hand, examples of the fragrance include oyster wax, jasmine, lemon and the like. All of these are useful as fragrances, but in the case of essential oils, they further have bactericidal action, insecticidal action, insecticidal action and the like. These compounds may be used alone or in admixture of two or more, if necessary.
【0007】本発明において、ホスト化合物である下記
一般式〔1〕で示されるテトラキス(ヒドロキシフェニ
ル)エタンが用いられる。In the present invention, the host compound tetrakis (hydroxyphenyl) ethane represented by the following general formula [1] is used.
【0008】[0008]
【化3】 前記一般式 [1] で示される化合物の具体例として、
1,1,2,2−テトラキス(p−ヒドロキシフェニ
ル)エタン(以下「TEP−DF」と略記) 、1,1,
2,2−テトラキス(m−ヒドロキシフェニル)エタン
等が挙げられる。中でもTEP−DFは、得られる包接
化合物が常温で固体であり、取り扱いが容易なことから
特に好んで用いられる。[Chemical 3] Specific examples of the compound represented by the general formula [1] include:
1,1,2,2-tetrakis (p-hydroxyphenyl) ethane (hereinafter abbreviated as “TEP-DF”), 1,1,
2,2-tetrakis (m-hydroxyphenyl) ethane and the like can be mentioned. Among them, TEP-DF is particularly preferably used because the clathrate compound obtained is a solid at room temperature and is easy to handle.
【0009】本発明の包接化合物は、溶媒を用い、若し
くは溶媒なしで容易に製造することができる。溶媒を用
いる場合には、ホスト化合物をメタノール、エタノー
ル、イソプロパノール、メチルエチルケトン等の溶媒に
溶解し、次いでこの溶液に液体化した精油又は香料を加
え反応させる。反応後、必要に応じて溶媒を蒸発留去す
るか、冷却すると包接化合物が析出する。この析出物を
常法により濾過分離し、目的とする包接化合物を得る。
溶媒を用いない場合には、精油や香料の液中にテトラキ
ス(ヒドロキシフェニル)エタンを直接添加して反応さ
せる。その後は前述の方法と同様に、析出した固形物を
分離すればよい。両者の場合、反応温度は0〜100
℃、好ましくは10〜60℃であり、反応時間は5分〜
24時間である。上記のようにして得られる包接化合物
は、通常粉末状であり、粒度を変えたり、形状の異なる
成形体にすることにより、使用目的に応じた包接化合物
を得ることができる。The inclusion compound of the present invention can be easily produced with or without a solvent. When a solvent is used, the host compound is dissolved in a solvent such as methanol, ethanol, isopropanol or methyl ethyl ketone, and then liquefied essential oil or fragrance is added to this solution for reaction. After the reaction, if necessary, the solvent is evaporated off or the clathrate compound is precipitated by cooling. This precipitate is separated by filtration by a conventional method to obtain the target clathrate compound.
When a solvent is not used, tetrakis (hydroxyphenyl) ethane is directly added to the liquid of essential oil or fragrance to react. After that, the precipitated solid matter may be separated in the same manner as the above method. In the case of both, the reaction temperature is 0-100.
℃, preferably 10 to 60 ℃, the reaction time is 5 minutes ~
24 hours. The clathrate compound obtained as described above is usually in the form of powder, and the clathrate compound can be obtained according to the intended use by changing the particle size or forming a molded product having a different shape.
【0010】また、本発明のテトラキス(ヒドロキシフ
ェニル)エタンをホストとする包接化合物は、ホスト化
合物に対して、通常、2倍モルから4倍モルのゲスト化
合物を包接することが出来る。The inclusion compound of the present invention having tetrakis (hydroxyphenyl) ethane as a host can usually include 2 to 4 moles of guest compound with respect to the host compound.
【0011】本発明の包接化合物は、次に記載したよう
な態様で使用することができる。 粉末状の本剤を、開孔を有する容器に入れて使用 本剤を適当な形状に成型して使用 塗料、樹脂等に混練りして部材等に塗布 物体の表面に適当な手段により付着させる 具体的には次のような用途に適用できる。 室内及び車内の芳香性、殺虫性、防虫性装飾品 芳香性、殺虫性、防虫性又は防黴性建材や床材 芳香性、殺虫性、防虫性又は防黴性家具類 芳香性、殺虫性、防虫性寝具類 トイレタリー商品(化粧品、浴用剤、洗剤等) 芳香性玩具 芳香性装身具 芳香性アクセサリー類 芳香性文具事務用品類The clathrate compound of the present invention can be used in the following modes. Use this agent in powder form by putting it in a container with open holes. Use this agent by molding it into an appropriate shape. Knead it with paint, resin, etc. and apply it to members etc. Specifically, it can be applied to the following uses. Indoor and vehicle aromatic, insecticidal, insect-proof ornaments Aromatic, insecticidal, insect-proof or mildew-proof building materials and floor materials Aroma, insecticidal, insect-proof or mildew-proof furniture Aromatic, insecticidal, Insect-proof bedding Toiletry products (cosmetics, bath agents, detergents, etc.) Aromatic toys Aromatic accessories, Aromatic accessories, Aromatic stationery Office supplies
【0012】[0012]
【作用】本発明では、精油又は香料が、テトラキス(ヒ
ドロキシフェニル)エタンと包接化合物を形成してお
り、従って、ゆっくりと精油や香料が放出される。その
揮散速度は、適宜粒度を変えたり、成形体の形状を変え
たりすることによって容易に制御される。本発明で用い
られるゲスト化合物の精油又は香料は香料として用いら
れるが、精油を用いた場合には、更に殺虫、殺菌作用を
も発揮する。In the present invention, the essential oil or fragrance forms an inclusion compound with tetrakis (hydroxyphenyl) ethane, so that the essential oil or fragrance is slowly released. The volatilization rate can be easily controlled by appropriately changing the particle size or changing the shape of the molded body. The essential oil or fragrance of the guest compound used in the present invention is used as a fragrance. When the essential oil is used, it also exhibits insecticidal and bactericidal effects.
【0013】以下、本発明を実施例及び比較例により、
更に詳細に説明する。ただし、本発明の範囲は、これら
の実施例により何等制限を受けるものではない。The present invention will be described below with reference to Examples and Comparative Examples.
Further details will be described. However, the scope of the present invention is not limited by these examples.
【0014】実施例1 メタノール5ml中にTEP−DF(旭有機材工業製)1.
0 g (2.51 mmol) を加え、TEP−DFが完全に溶解す
るまで加温しながら攪拌する。これに1,8−シネオー
ル 1.55 g (10.04 mmol)を徐々に滴下し、60℃で10分間
攪拌しながら反応させた後、直ちに濾過し、この濾液を
室温で放置して結晶を析出させた。この析出物を濾別
後、室温にて真空乾燥して白色結晶物の試料A−1を得
た。Example 1 TEP-DF (manufactured by Asahi Organic Materials Co., Ltd.) in 5 ml of methanol 1.
Add 0 g (2.51 mmol) and stir while warming until TEP-DF is completely dissolved. 1.58 g (10.04 mmol) of 1,8-cineole was gradually added dropwise thereto, and the mixture was reacted at 60 ° C. for 10 minutes while stirring, then immediately filtered, and the filtrate was left at room temperature to precipitate crystals. This precipitate was separated by filtration and then vacuum dried at room temperature to obtain a white crystalline sample A-1.
【0015】実施例2 メタノール5ml中にTEP−DF 1.0 g (2.51 mmol)を
加え、TEP−DFが完全に溶解するまで加温しながら
攪拌した。これにヒノキチオール 1.65g(10.04mmol)を
徐々に滴下し、60℃で10分間攪拌しながら反応させた
後、直ちに濾過し、この濾液を室温で放置して結晶を析
出させた。この析出物を濾別後、室温にて真空乾燥して
白色結晶物の試料A−2を得た。Example 2 1.0 g (2.51 mmol) of TEP-DF was added to 5 ml of methanol, and the mixture was stirred with heating until TEP-DF was completely dissolved. 1.65 g (10.04 mmol) of hinokitiol was gradually added dropwise to this, and after reacting at 60 ° C. for 10 minutes while stirring, it was immediately filtered and the filtrate was left at room temperature to precipitate crystals. This precipitate was separated by filtration and then vacuum dried at room temperature to obtain a white crystalline sample A-2.
【0016】実施例3 ベンゼン5ml中にTEP−DF 1.0 g (2.51 mmol)を加
え、攪拌しながら懸濁分散させた。ここへl−メントー
ル 1.57 g (10.04 mmol)を添加し、40℃で30分攪拌しな
がら反応させた後、室温まで放冷した。この懸濁物を濾
別後、室温にて真空乾燥して白色粉末の試料A−3を得
た。Example 3 1.0 g (2.51 mmol) of TEP-DF was added to 5 ml of benzene and suspended and dispersed while stirring. To this, 1.57 g (10.04 mmol) of 1-menthol was added, reacted at 40 ° C. for 30 minutes with stirring, and then allowed to cool to room temperature. After the suspension was filtered off, it was vacuum dried at room temperature to obtain a white powder sample A-3.
【0017】実施例4 α−テルピネオール 1.55 g (10.04 mmol)にTEP−D
F 1.0 g (2.51 mmol)を加え、60℃で攪拌しながら反応
させて固形物を得た。この固形物を粉砕した後、室温に
て真空乾燥して白色粉末の試料A−4を得た。Example 4 TEP-D was added to 1.55 g (10.04 mmol) of α-terpineol.
F 1.0 g (2.51 mmol) was added, and it was made to react at 60 degreeC, stirring, and the solid substance was obtained. After crushing this solid substance, it vacuum-dried at room temperature and obtained the white powder sample A-4.
【0018】前記で得られた各試料(A−1〜A−4)
の製造条件、得られた包接化合物のゲスト/ホスト mol
比及びゲストの再放出温度を表1に示した。Each sample (A-1 to A-4) obtained above
Production conditions, guest / host mol of the obtained inclusion compound
The ratios and the re-emission temperature of the guest are shown in Table 1.
【0019】[0019]
【表1】 [Table 1]
【0020】前記方法で得られたA−1〜A−4試料
は、IRスペクトル、X線回折、DTAにより、包接化
合物であることが確認された。The A-1 to A-4 samples obtained by the above method were confirmed to be clathrate compounds by IR spectrum, X-ray diffraction and DTA.
【0021】実施例5 実施例1、2で得られた試料A−1、A−2及び比較試
料1,8−シネオール(R−1)、ヒノキチオール(R
−2)単独のそれぞれを、ゲスト化合物換算で0.6g
となるようにシャーレに採り、25℃及び40℃に保持
したデシケーター中にセットした。これに乾燥空気を2
50ml/分で導入し、経時的に重量減少を測定した。そ
の結果を表2に示した。また、その放出曲線を図8及び
図9に示した。Example 5 Samples A-1 and A-2 obtained in Examples 1 and 2 and comparative sample 1,8-cineole (R-1), hinokitiol (R
-2) 0.6 g of each of the single compounds in terms of guest compound
It was taken in a Petri dish so that it would become, and set in a desiccator kept at 25 ° C and 40 ° C. 2 dry air to this
It was introduced at 50 ml / min, and the weight loss was measured over time. The results are shown in Table 2. The release curves are shown in FIGS. 8 and 9.
【0022】[0022]
【表2】 [Table 2]
【0023】本発明で得られた包接化合物試料A−2、
及びゲスト化合物であるヒノキチオールのDTAチャー
トを図1に示した。また、試料A−2のIRスペクトル
を図2に示した。この図2から明らかなように、包接化
に伴うヒドロキシル基吸収が 3182 cm-1付近に認めら
れ、更にカルボニル基吸収が 1594 cm-1に認められる。
更に図5に示す試料A−2のX線回折図から、試料A−
2は結晶性物質であることが判る。従って、本発明で得
られた試料A−2は、包接化合物であることが確認され
た。The inclusion compound sample A-2 obtained in the present invention,
A DTA chart of hinokitiol which is a guest compound is shown in FIG. The IR spectrum of Sample A-2 is shown in FIG. As is clear from FIG. 2, absorption of a hydroxyl group associated with inclusion is observed at around 3182 cm -1 , and further absorption of a carbonyl group is observed at 1594 cm -1 .
Furthermore, from the X-ray diffraction pattern of the sample A-2 shown in FIG.
It turns out that 2 is a crystalline substance. Therefore, it was confirmed that the sample A-2 obtained in the present invention was an inclusion compound.
【0024】[0024]
【発明の効果】本発明のゲスト化合物として精油又は香
料を、テトラキス(ヒドロキシフェニル)エタンのホス
ト化合物に包接させることにより得られる包接化合物
は、徐放性、有効成分の安定性に優れ、徐放速度も容易
に調節することができ、長期間に亘って芳香効果や殺
虫、殺菌効果が持続することができる。本発明の包接化
合物はホスト化合物に対し、4倍モル以上のゲストとな
る精油又は香料を包接することができる、極めて包接効
率の高いものである。また、本発明の包接化合物は固形
状を有し、常温下で任意の形状に適宜成形でき、低沸点
の香料も変性させずに加工できるため、取り扱い性、加
工性に優れている。The inclusion compound obtained by including the essential oil or fragrance as the guest compound of the present invention in the host compound of tetrakis (hydroxyphenyl) ethane is excellent in sustained release and stability of the active ingredient, The sustained release rate can be easily adjusted, and the aroma effect, insecticidal and bactericidal effect can be maintained over a long period of time. The clathrate compound of the present invention is capable of clathrating 4 times or more moles of guest essential oil or fragrance with respect to the host compound, and has extremely high clathrate efficiency. Further, the clathrate compound of the present invention has a solid state, can be appropriately molded into an arbitrary shape at room temperature, and can be processed without modifying a low-boiling-point fragrance, and therefore is excellent in handleability and processability.
【0025】[0025]
【図1】包接化合物試料A−2のDTAチャートを示
す。FIG. 1 shows a DTA chart of a clathrate compound sample A-2.
【図2】包接化合物試料A−2のIRスペクトル図を示
す。FIG. 2 shows an IR spectrum of inclusion compound sample A-2.
【図3】ホスト化合物であるTEP−DFのIRスペク
トル図を示す。FIG. 3 shows an IR spectrum diagram of TEP-DF which is a host compound.
【図4】ゲスト化合物であるヒノキチオールのIRスペ
クトル図を示す。FIG. 4 shows an IR spectrum diagram of hinokitiol which is a guest compound.
【図5】包接化合物試料A−2のX線回折図を示す。FIG. 5 shows an X-ray diffraction pattern of clathrate compound sample A-2.
【図6】ホスト化合物であるTEP−DFのX線回折図
を示す。FIG. 6 shows an X-ray diffraction pattern of TEP-DF which is a host compound.
【図7】ゲスト化合物であるヒノキチオールのX線回折
図を示す。FIG. 7 shows an X-ray diffraction pattern of hinokitiol, which is a guest compound.
【図8】包接化合物試料A−1と1,8−シネオール単
独について、放出試験を行い、放出量を測定して得た放
出曲線を示す。FIG. 8 shows a release curve obtained by performing a release test on the inclusion compound samples A-1 and 1,8-cineole alone and measuring the release amount.
【図9】包接化合物試料A−2とヒノキチオール単独に
ついて、放出試験を行い、放出量を測定して得た放出曲
線を示した図である。 (以下余白)FIG. 9 is a diagram showing a release curve obtained by performing a release test on the inclusion compound sample A-2 and hinokitiol alone and measuring the release amount. (Below margin)
Claims (1)
されるテトラキス(ヒドロキシフェニル)エタンとから
なることを特徴とする包接化合物。 【化1】 1. An inclusion compound comprising an essential oil or a fragrance and tetrakis (hydroxyphenyl) ethane represented by the following general formula [1]. [Chemical 1]
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35073491A JP3175252B2 (en) | 1991-12-12 | 1991-12-12 | New clathrate compound |
EP92924909A EP0589044B1 (en) | 1991-12-12 | 1992-12-11 | Novel inclusion compound comprising tetrakisphenol as host |
DE69214814T DE69214814T2 (en) | 1991-12-12 | 1992-12-11 | NEW INCLUSION COMPOUNDS WHICH CONTAIN TETRAKISPHENOL AS A HOST |
KR1019930702410A KR960004883B1 (en) | 1991-12-12 | 1992-12-11 | Novel inclusion compound comprising tetrakisphenol as host |
PCT/JP1992/001620 WO1993012060A1 (en) | 1991-12-12 | 1992-12-11 | Novel inclusion compound comprising tetrakisphenol as host |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35073491A JP3175252B2 (en) | 1991-12-12 | 1991-12-12 | New clathrate compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05163187A true JPH05163187A (en) | 1993-06-29 |
JP3175252B2 JP3175252B2 (en) | 2001-06-11 |
Family
ID=18412495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP35073491A Expired - Lifetime JP3175252B2 (en) | 1991-12-12 | 1991-12-12 | New clathrate compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3175252B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002145808A (en) * | 2000-09-28 | 2002-05-22 | Rohm & Haas Co | Delivery system of cyclopropene compounds |
-
1991
- 1991-12-12 JP JP35073491A patent/JP3175252B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002145808A (en) * | 2000-09-28 | 2002-05-22 | Rohm & Haas Co | Delivery system of cyclopropene compounds |
Also Published As
Publication number | Publication date |
---|---|
JP3175252B2 (en) | 2001-06-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4722815A (en) | Process of making a synthetic resin product containing a molecular inclusion compound in cyclodextrin | |
JP7034097B2 (en) | Profragrance composition | |
JP5403062B2 (en) | Durable pest repellent and pest repellent resin composition | |
KR102564753B1 (en) | Insect Repellents, and Insect Repellent Products | |
JP2018102866A (en) | Bactericidal agent | |
JP2004538342A (en) | Compounds for controlled release of active compounds | |
EP1483966A1 (en) | Method of controlling acarian and device for use in the same | |
TWI271432B (en) | Thermal evaporation preparation and method of thermal evaporating chemicals using the same | |
JP3175252B2 (en) | New clathrate compound | |
AU615395B2 (en) | Clathrate compound and a method of producing the same | |
EP0287342A2 (en) | A sustained release aromatic and a process for manufacturing thereof | |
US9968096B2 (en) | Process for preparing antimicrobial microcapsules | |
JPS5977859A (en) | Gel like aromatic deodorant composition | |
KR100626825B1 (en) | Functional microcapsule and the preparation method thereof | |
JP3052364B2 (en) | Host compounds and clathrates | |
JP4224175B2 (en) | Transparent gel fragrance / deodorant composition | |
JPH0564071B2 (en) | ||
CN103781890B (en) | Perfuming acetal | |
KR102612839B1 (en) | A method for manufacturing fragrances with high performance deodorizing power | |
JP2005289941A (en) | Sustained-release agent | |
JP2019104696A (en) | Mosquito-repellent incense | |
JP2004337219A (en) | Deodorant and deodorization device | |
JPH08188513A (en) | Antimicrobial agent for wall paper, furniture and miscellaneous goods | |
JP6700926B2 (en) | Antifungal and antifungal agent, volatile space antifungal and antifungal agent, solid antifungal and antifungal material, and method for suppressing generation of fungi or fungi | |
JP2002035101A (en) | Deodorant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080406 Year of fee payment: 7 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090406 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090406 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100406 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100406 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110406 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120406 Year of fee payment: 11 |
|
EXPY | Cancellation because of completion of term | ||
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120406 Year of fee payment: 11 |