JPS5819261A - Aromatic composition - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は、新規な芳香組成物に関する。さらに詳しくは
、芳香組成物として経時変化性が少なくしかも発散香の
マイルド性にすぐれた芳香組成物に係わるものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel fragrance compositions. More specifically, the present invention relates to an aromatic composition that has little change over time and has an excellent mild emitted aroma.

従来、香料の取扱いの簡便化を計るために、各種の吸着
担体に香料を吸着させる試みがなされてきたことは公知
である。例えば、古くは、合成珪酸マグネシウム粉末に
香料蒸気を吸着させた粉香剤（特公昭２５―１３３４号
公報）、無水珪酸のエロゲルを液状香料に添加して固化
せしめた粉末またはゲル状香料（特公昭３１―５１００
号公報）あるいは、結晶状ゼオライトの分子ふるいに香
料を吸着させた組成物（特公昭３５―１１８１７号公報
）など、また最近では、シリカゲル、沸石などの吸着担
体に液状香料を吸着させて用いる方法（特開昭５３―２
６３３５号公報）、活性アルミナまたはアルミナ・シリ
カ球に液状香料を含浸させた発香組成物（特開昭５３―
２９９４３号公報）、本発明者が先に出願した粉末アル
ミナなどに液状香料を吸着させて成形物とした芳香組成
物（特開昭５５−４０５６１号公報など）あるいは粉末
セルロースを保香担体とした芳香組成物（特開昭５５−
１０６１５９号公報）などがあげられる。しかし、これ
らの粉香剤または固形芳香剤は一部実用化されているも
のの、いづれも共通の欠点がありその改良が求められて
いるのが実情である。すなわち、吸着担体に液状香料を
吸着させたこれら既存の芳香組成物は、取扱いの便利さ
は向上したものの、香りの柔かさ、マイルド性が液状香
料にくらべて劣ること、保存中に香が経時変化して極端
な場合には不快臭がまじること、および担体の吸着容量
に限度があるため保香寿命が短かく香りの発散も弱いこ
となどが経験されていることである。It is known that attempts have been made to adsorb fragrances onto various adsorption carriers in order to simplify the handling of fragrances. For example, in the past, there were powdered fragrances made by adsorbing fragrance vapor to synthetic magnesium silicate powder (Japanese Patent Publication No. 1334/1983), and powdered or gel fragrances made by adding silicic anhydride erogel to liquid fragrances and solidifying them (Japanese Patent Publication No. 1334/1983). Kosho 31-5100
(Japanese Patent Publication No. 11817/1983), or a composition in which a fragrance is adsorbed on a molecular sieve of crystalline zeolite (Japanese Patent Publication No. 11817/1983), and recently, a method in which a liquid fragrance is adsorbed on an adsorption carrier such as silica gel or zeolite is used. (Unexamined Japanese Patent Publication No. 53-2
No. 6335), a fragrance composition in which activated alumina or alumina-silica spheres are impregnated with a liquid fragrance (Japanese Patent Application Laid-open No. 1983-
No. 29943), aromatic compositions made by adsorbing liquid fragrance to powdered alumina etc. which the present inventor previously applied for (Japanese Unexamined Patent Publication No. 55-40561, etc.), or powdered cellulose as a fragrance carrier. Aromatic composition (Japanese Patent Application Laid-open No. 1983-
106159). However, although some of these powdered fragrances or solid fragrances have been put into practical use, the reality is that they all have common drawbacks, and improvements are needed. In other words, although these existing fragrance compositions in which liquid fragrances are adsorbed onto adsorption carriers are more convenient to handle, they are inferior in softness and mildness to liquid fragrances, and the fragrance deteriorates over time during storage. In extreme cases, it has been experienced that unpleasant odors are mixed in, and that the adsorption capacity of the carrier is limited, resulting in a short fragrance retention life and weak fragrance release.

保香寿命と香りの発散性向上の目的で、吸油性の比較的
大きい吸着担体、たとえば合成ケイ酸カルシウムあるい
はアエロジルのごとき合成シリカを用いる試みもなされ
ているが、これらはいづれも微細な粉末状のために液状
香料の吸着混合作業中に微粉末の飛散の問題があり、さ
らにかさ高いため成型性が劣る欠点がある。例えば、特
開昭５６―３８３７３号公報には、花弁状を呈するケイ
酸カルシウムなどに液状香料を吸着させて錠剤に成形す
る例が記載されているが、かかる組成物は、工業的規模
の打錠成形機で量産する場合、材料がかさ高いために一
度仮成形した後粉砕してか粒物とし、これをさらに成形
するという工程が必要であり経済的に不利である。また
、これらの吸油性の比較的大きい吸着担体を使用した場
合も、前述の香りの経時変化および香りのマイルド性が
劣る欠点は解決できないことが明らかになった。For the purpose of improving fragrance retention life and scent dispersion, attempts have been made to use adsorption carriers with relatively high oil absorption properties, such as synthetic calcium silicate or synthetic silica such as Aerosil, but these are all in the form of fine powder. Therefore, there is a problem of scattering of fine powder during adsorption and mixing of liquid fragrances, and furthermore, it has the disadvantage of poor moldability due to its bulk. For example, Japanese Patent Application Laid-Open No. 56-38373 describes an example in which a liquid fragrance is adsorbed onto petal-shaped calcium silicate and formed into a tablet. When mass-producing the tablet using a tablet molding machine, since the material is bulky, it is necessary to temporarily form the material and then crush it into granules, which are then further molded, which is economically disadvantageous. Furthermore, it has become clear that even when these adsorption carriers with relatively high oil absorption properties are used, the above-mentioned disadvantages of change in fragrance over time and poor fragrance mildness cannot be solved.

本発明者は、先に粉末状セルロース誘導体に香料と水と
をそれらが分離滲出しないような組成化で混合すること
によって、発生香のマイルド性が改良できることを見出
した（特開昭５５−１０６１５９号公報）が、この芳香
組成物にしても、保存中の香りの経時変化の欠点が完全
に克服されたものではなく、しかもペースト状であるた
めその使途が限られているのが現状である。The present inventor discovered that the mildness of the odor generated could be improved by first mixing a powdered cellulose derivative with a fragrance and water in a composition that would prevent them from separating and exuding. However, even with this aromatic composition, the drawback of odor change over time during storage has not been completely overcome, and furthermore, its use is currently limited because it is in the form of a paste. .

本発明者は、多年にわたって香料吸着用担体の種類、そ
の吸着能、発生香のマイルド性および香りの経時変化性
について鋭意研究を重ねてきたが、驚くべきことに、吸
着担体中に微量含まれる不純物のうち、とくに鉄化合物
が香りの経時変化の大きい要因となっていること、およ
び、吸着担体のＰＨは酸性側より中性〜弱塩基性の範囲
内にあることが、とくに香りの経時変化性に関してその
影響が少ない事実を見出した。さらに、合成珪酸カルシ
ウム粉末のスラリー状物を成形乾燥してえられる成形物
が、香料と水とを任意の割合で分離をおこすことなく吸
着することができること、および担体成形物重量の１．
５〜２．０倍の吸着量を保持しても、なおその形状と強
度が劣化しない特徴をもつことを見出して本発明を完成
させるに至った。The present inventor has spent many years conducting intensive research on the types of fragrance adsorption carriers, their adsorption capacity, the mildness of the fragrance generated, and the change in fragrance over time. Among impurities, iron compounds in particular are a major factor in the change in fragrance over time, and the pH of the adsorption carrier is in the range of neutral to weakly basic rather than the acidic side. We found that there is little effect on gender. Furthermore, the molded product obtained by molding and drying a slurry of synthetic calcium silicate powder is capable of adsorbing fragrance and water at any desired ratio without separation, and the weight of the carrier molded product is 1.
The present invention was completed based on the discovery that the shape and strength do not deteriorate even when the adsorption amount is maintained at 5 to 2.0 times.

本発明の目的は、その発散香の経時変化が少なく、しか
も液状香料の香りに近いマイルド性をもち、かつ保香寿
命の長い特徴をもった固形状の芳香組成物を提供するこ
とにある。An object of the present invention is to provide a solid fragrance composition whose emitted fragrance changes less over time, has a mildness similar to that of a liquid fragrance, and has a long fragrance retention life.

本発明芳香組成物に用いる合成珪酸カルシウムの成形物
としては、その形状にとくに制限はないが、固形芳香剤
として取扱いの簡便性から円形または四角形などの板状
が好ましい。この成形物は次の方法によって製造できる
。合成珪酸カルシウムの製造過程で乾燥粉化する前のス
ラリー状合成珪酸カルシウム、あるいは粉末状合成珪酸
カルシウムに水を加えてスラリー状にしたものを所望の
形の型枠内に流し込み圧力１０〜１４ｋｇ／ｃｍ２で圧
縮して脱水した後乾燥する。The shape of the synthetic calcium silicate molded product used in the aromatic composition of the present invention is not particularly limited, but a circular or square plate shape is preferred for ease of handling as a solid aromatic agent. This molded article can be manufactured by the following method. In the manufacturing process of synthetic calcium silicate, slurry-like synthetic calcium silicate before drying and powdering, or powdered synthetic calcium silicate with water added to form a slurry, is poured into a mold of the desired shape at a pressure of 10 to 14 kg/ It is compressed in cm2, dehydrated, and then dried.

こうしてえられる成形物のＰＨは９．０〜９．４（５％
スラリー液で測定）の範囲にあり、香料の吸着担体とし
て用いて実用上問題にならないＰＨ値であるが、用いる
合成珪酸カルシウムの１〜３０重量％の硫酸ばん土をス
ラリー中に添加して同様に成形物としてＰＨを７．６〜
８．６に低下させた方が好ましい。また、上述の方法で
えられる合成珪酸カルシウム成形物は、香料の吸着担体
として取扱うのに実用上差支えない強度をもつが、さら
に成形物の強度（もろさ）を改善し同時に香料の発散を
抑制する効果をもつ添加剤として粉末状セルロース誘導
体の使用が好ましい。粉末状セルロース誘導体としては
、結晶セルロース、アルカリ　セルロースにメトキシ基
、ヒドロキシプロポキシ基を導入したメチルセルロース
、ヒドロキシプロピルメチルセルロースなどのセルロー
スエーテル類、あるいはカルボキシメチル化したカルボ
キシメチルセルロースなどの粉末があげられ、合成珪酸
カルシウムの１〜３０重量％をスラリー中に混合して用
いればよい。The pH of the molded product thus obtained is 9.0 to 9.4 (5%
The pH value is within the range (measured with a slurry liquid) and does not pose a practical problem when used as a fragrance adsorption carrier. As a molded product, the pH is 7.6~
It is preferable to lower it to 8.6. In addition, the synthetic calcium silicate molded product obtained by the above method has a strength that is practically acceptable for handling as a fragrance adsorption carrier, but it is also possible to improve the strength (brittleness) of the molded product and suppress the release of fragrance at the same time. Preference is given to using powdered cellulose derivatives as effective additives. Powdered cellulose derivatives include crystalline cellulose, cellulose ethers such as methyl cellulose and hydroxypropyl methyl cellulose in which methoxy groups and hydroxypropoxy groups have been introduced into alkali cellulose, and powders such as carboxymethyl cellulose that has been carboxymethylated. Synthetic calcium silicate It may be used by mixing 1 to 30% by weight of the above into the slurry.

本発明で、成形物の構成主材料となる合成珪酸カルシウ
ム粉末としては、吸着容量の大きい、たとえば液状香料
を少なくとも５０重量％、好ましくは約１００〜２５０
重量％吸着しうるような合成珪酸カルシウムが好ましい
。さらに、合成珪酸カルシウム粉末の表面積は９０ｍ２
／ｇ以上、好ましくは約１００〜１５０ｍ２／ｇ、その
粒度は平均粒子経で１０μｍ以下、好ましくは約１〜５
μｍの範囲が望ましい。先述のごとく、吸着担体中に不
純物として含まれる鉄分が吸着香料の経時変化の大きな
要因となっていることから、本発明で用いる合成珪酸カ
ルシウム中の鉄分はＦｅ２Ｏ５として、０．０９重量％
以下に制限されねばならない。したがって、スラリー液
から成形物をうる際に用いる型枠などからの鉄さびの混
入をさけるための配慮が必要である。In the present invention, the synthetic calcium silicate powder, which is the main constituent material of the molded product, contains at least 50% by weight of a liquid fragrance having a large adsorption capacity, preferably about 100 to 250% by weight.
Synthetic calcium silicate is preferred, such that it can adsorb % by weight. Furthermore, the surface area of the synthetic calcium silicate powder is 90 m2.
/g or more, preferably about 100 to 150 m2/g, and the particle size is 10 μm or less in average particle size, preferably about 1 to 5
A range of μm is desirable. As mentioned above, the iron content contained as an impurity in the adsorption carrier is a major factor in the change over time of the adsorbed fragrance, so the iron content in the synthetic calcium silicate used in the present invention is 0.09% by weight as Fe2O5.
Must be limited to: Therefore, consideration must be given to avoid contamination of iron rust from the formwork used to obtain molded articles from the slurry liquid.

吸着担体中の鉄化合物が、吸着された香料の経時変化に
どう作用するかの反応機構については学問的解明はまだ
なされていないが、微量の鉄が、香料分子中の官能基（
アルデヒド基、水産基、エステル基など）の反応、分解
などに触媒的作用をもつため、その変質（経時変化）の
促進原因になるのではないかと推考されている。Although the reaction mechanism of how iron compounds in adsorption carriers affect the time-course changes in adsorbed fragrances has not yet been scientifically elucidated, a trace amount of iron may affect the functional groups (
Because it has a catalytic effect on reactions and decomposition of aldehyde groups, aquatic groups, ester groups, etc., it is speculated that it may be the cause of accelerating their deterioration (change over time).

本発明芳香組成物は、上述の合成珪酸カルシウム成形物
に香料含有液体を吸着させることによってえられるが、
ここで香料含有液体とは、液状香料、香水あるいは固体
香料を液状香料、アルコールなどの溶剤に溶解した香料
など香料を含有した液状物を称する。要するに香料を含
んだ液体であれば、その組成、濃度にかかわらず用いう
る。成形物に対する香料含有液体の量化は、要求される
商品の態称によって成形物１００重量部に対し、香料含
有液体の５０〜２５０の重量部を用いる。５０重量未満
は保香期間が短いことで、また、２５０重量部を超える
量は吸着容量を超えることで本発明の範囲外である。The aromatic composition of the present invention can be obtained by adsorbing a fragrance-containing liquid to the synthetic calcium silicate molded article,
Here, the perfume-containing liquid refers to a liquid perfume containing a perfume, such as a liquid perfume, a perfume, or a solid perfume dissolved in a solvent such as alcohol. In short, any liquid containing a fragrance can be used regardless of its composition or concentration. The amount of perfume-containing liquid for the molded article is determined by using 50 to 250 parts by weight of the perfume-containing liquid per 100 parts by weight of the molded article, depending on the desired product name. If the amount is less than 50 parts by weight, the fragrance retention period will be short, and if it exceeds 250 parts by weight, the adsorption capacity will be exceeded, which is outside the scope of the present invention.

吸着担体に香料を吸着させた従来の固形状芳香剤は、そ
の香りが液状香料からの発生香りにくらべて、柔らかみ
、マイルド性に欠けることは先述の通りであるが、本発
明芳香組成物においてはこの欠点を解決するために、吸
着さすべき香料含有液体の４〜６０重量％を水と代替し
、両液を混合することなく担体の成形物に吸着さす方法
が効果的であることを見出した。水と香料含有液体との
吸着させる順序はとくに問わないが、吸着させる量が多
い場合、水の吸着を後にすると、まれに担体からの香料
の滲出現象がみられるので、水、香料含有液体の順で吸
着させるのが好ましい。４重量％未満はその効果が少な
いこと、６０重量％を超えると香料量の減少に伴って保
香寿命が短かくなることの理由で本発明より除外される
。用いる水は脱イオン水または蒸留水が好ましい。As mentioned above, conventional solid fragrances in which fragrances are adsorbed on adsorption carriers lack softness and mildness compared to the fragrance generated from liquid fragrances, but the fragrance composition of the present invention In order to solve this drawback, we have found that an effective method is to replace 4 to 60% by weight of the fragrance-containing liquid to be adsorbed with water, and to adsorb both liquids onto a molded carrier without mixing them. I found it. The order in which the water and the perfume-containing liquid are adsorbed is not particularly important, but if a large amount is adsorbed, if the water is adsorbed later, the perfume may ooze out from the carrier in rare cases. It is preferable to adsorb them in this order. If the amount is less than 4% by weight, the effect is small, and if it exceeds 60% by weight, the fragrance retention life will be shortened due to the decrease in the amount of fragrance, and therefore, it is excluded from the present invention. The water used is preferably deionized water or distilled water.

合成珪酸カルシウム成形物への香料含有液体の吸着は、
噴霧または浸漬などの方法を用いてなされる。吸着物は
３〜５分間、自然乾燥すれば乾燥状態の本発明芳香組成
物とすることができる。The adsorption of fragrance-containing liquids onto synthetic calcium silicate moldings is
This is done using methods such as spraying or dipping. By naturally drying the adsorbed material for 3 to 5 minutes, the aroma composition of the present invention can be obtained in a dry state.

本発明芳香組成物は、任意の形、大きさの成形物として
えられ、経時による発生香の変化がないために長期保存
に耐えること、香りがこの種の従来品芳香剤にくらべマ
イルドで液状香料の香りに近いこと、保持香料量が多い
ため発散する香りが強くしかも長持ちすること、および
取扱いが便利であることなどの多くの特徴をすべて具備
することから、固形の芳香発生源として従来品芳香剤に
みられない巾広い応用面が期待できる。たとえば通気性
袋、容器に収納した芳香具、ファンなどの通風装置と組
合わせた芳香発生器、枠に収納して人形などの飾物の台
としての利用、あるいは造花への付香部品などに使用し
てその有用性は大きい。The aromatic composition of the present invention can be obtained as a molded product of any shape and size, and can withstand long-term storage because the odor generated does not change over time. It is a conventional product as a solid fragrance source because it has many characteristics such as the scent is close to that of fragrances, the scent is strong and long-lasting because it retains a large amount of fragrance, and it is convenient to handle. It can be expected to have a wide range of applications not found in air fresheners. For example, it can be used as a breathable bag, a fragrance device stored in a container, a fragrance generator combined with a ventilation device such as a fan, used as a stand for decorations such as dolls when stored in a frame, or as a component for adding fragrance to artificial flowers. Its usefulness is great.

以下、実施例を示すがとくに明記しない限り部および％
はすべて重量部および重量％を表わす。Examples are shown below, but unless otherwise specified, parts and %
All represent parts and percentages by weight.

実施例１． Ｆｅ２Ｏ３として鉄分を０．０３％含む合成珪酸カルシ
ウム粉末（表面積、１３０ｍ２／ｇ、吸油量６〜８ｍｌ
／ｇ、ＰＨ９．２〜９．４、粒子径１〜５μｍ、商品名
フローライト、徳山曹達株式会社製）の約２０％スラリ
ー液を用意する。１００ｍ／ｍ×７５ｍ／ｍ×５０ｍ／
ｍの鉄製型枠の底面と上面に■布をおき、上記スラリー
液を流し込み１２ｋｇ／ｃｍ２の圧力で約２分間圧搾し
た後とり出して約１００℃で２時間乾燥する。こうして
えられた合成珪酸カルシウムの成形板を５０ｍ／ｍ×５
０ｍ／ｍ×７ｍ／ｍ（重量４．４ｇ）に切断して、シャ
ネル＃５調香料（牛田香料株式会社製）１１部（吸着担
体の２５０％）を吸着させた。この本発明芳香組成物を
通気性の不織布の袋に入れた発香具は、開放雰囲気下で
保香期間が約８０日間であった。Example 1. Synthetic calcium silicate powder containing 0.03% iron as Fe2O3 (surface area, 130m2/g, oil absorption 6-8ml)
/g, pH 9.2 to 9.4, particle size 1 to 5 μm, product name Fluorite (manufactured by Tokuyama Soda Co., Ltd.) about 20% slurry liquid is prepared. 100m/m x 75m/m x 50m/
(2) Place a cloth on the bottom and top of an iron formwork, pour the slurry into it, squeeze it for about 2 minutes at a pressure of 12 kg/cm 2 , take it out, and dry it at about 100° C. for 2 hours. The molded plate of synthetic calcium silicate thus obtained was 50 m/m x 5
It was cut into pieces of 0 m/m x 7 m/m (weight 4.4 g), and 11 parts (250% of the adsorption carrier) of Chanel #5 fragrance (manufactured by Ushida Perfume Co., Ltd.) was adsorbed thereon. A fragrance device containing the aromatic composition of the present invention in a breathable nonwoven fabric bag had a fragrance retention period of about 80 days in an open atmosphere.

比較例１． Ｆｅ２Ｏ３として、鉄分が０．１％とした合成珪酸カル
シウムを用いて実施例１同様の方法で芳香組成物をうる
。Comparative example 1. An aromatic composition was obtained in the same manner as in Example 1 using synthetic calcium silicate containing 0.1% iron as Fe2O3.

実施例１と本例との芳香組成物を密閉保存して香りの経
時変化をチェックしたところ、３０日間は差が認められ
なかったが、６０日後に本例の芳香組成物のみがやや香
りが変化し、９０日後には香料の快い香りが減少し不快
臭がまざった香りとなった。When the aroma compositions of Example 1 and this example were stored in a sealed container and the change in scent over time was checked, no difference was observed for 30 days, but after 60 days, only the aroma composition of this example had a slight scent. After 90 days, the pleasant scent of the fragrance decreased and became a scent mixed with unpleasant odors.

実施例２． 市販合成珪酸カルシウム（鉄含有量、Ｆｅ２Ｏ３として
０．０９％、和光純薬製）に水を加えて約２０％のウエ
ットケーキ状にした後、球状に成形して乾燥させた。こ
うしてえられた３〜５ｍ／ｍ中の球状成形物１００部に
２部の水、次いで４８部のばら様の香料（商品名ローズ
ドメイ、牛田香料株式会社製）を吸着させた。Example 2. Water was added to commercially available synthetic calcium silicate (iron content: 0.09% as Fe2O3, manufactured by Wako Pure Chemical Industries, Ltd.) to form a wet cake of approximately 20%, which was shaped into a sphere and dried. 2 parts of water and then 48 parts of a rose-like fragrance (trade name: Rose Domei, manufactured by Ushida Perfume Co., Ltd.) were adsorbed onto 100 parts of the thus obtained spherical molded product having a diameter of 3 to 5 m/m.

一方、球状活性アルミナゲル１００部（商品名ＤＢＳ―
１３、水沢化学工業株式会社製）に同様にばら様の香料
５０部を吸着させて従来品固形芳香剤をうる。両者を比
較すると本発明芳香組成成物が明らかに香りが強く、し
かもばら様の香料としての香りが液状香料に近かった。On the other hand, 100 parts of spherical activated alumina gel (product name: DBS-
13, manufactured by Mizusawa Chemical Industry Co., Ltd.) to similarly adsorb 50 parts of a loose fragrance to obtain a conventional solid fragrance. Comparing the two, the aroma composition of the present invention clearly had a stronger aroma, and moreover, the aroma as a rose-like perfume was close to that of a liquid perfume.

実施例３． 鉄分含物がＦｅ２Ｏ３として０．０６％の合成珪酸カル
シウム粉末（ＰＨ８．３〜８．６、表面積９０ｍ２／ｇ
、ジョンズ、マンビレ、コーポレーション社製、商品名
マイクロセルＥ）に１５％の粉末状ヒドロキシプロピル
メチルセルロース（信越化学工業株式会社製）を添加し
て実施１同様の方法で成形物をうる。Example 3. Synthetic calcium silicate powder with iron content of 0.06% as Fe2O3 (PH8.3-8.6, surface area 90m2/g
A molded product was obtained in the same manner as in Example 1 by adding 15% powdered hydroxypropyl methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) to Microcell E (trade name, manufactured by John's Manbire Corporation).

実施例１と本例とでえられた合成珪酸カルシウムの成形
物をそれぞれ、７０ｍ／ｍ×５０ｍ／ｍ×５ｍ／ｍの形
状にととのえたものの重量は５．５ｇであった。The weight of each of the synthetic calcium silicate molded products obtained in Example 1 and this example, each shaped into a shape of 70 m/m x 50 m/m x 5 m/m, was 5.5 g.

これらの両成形物に水（脱イオン水）２ｇ次いで実施例
１で使用したシャネル＃５調香料７ｇを吸着させる。こ
うしてえられた本発明芳香組成物の各２０ヶを１．５ｍ
の高さからコンクリート床に落下させてその耐衝撃強度
（成形物としてのもろさ）をテストしたところ、実施例
１でえた成形物は３ヶに割れを生じたのに対し、本例で
えた成形物は１ヶにひびを生じたにとどまった。2 g of water (deionized water) and then 7 g of the Chanel #5 perfume used in Example 1 are adsorbed onto both moldings. Each 20 pieces of the aromatic composition of the present invention obtained in this way was placed in a 1.5 m
When testing the impact strength (brittleness of the molded product) by dropping it from a height of Only one item had a crack.

さらに、これらの各２ヶを室内で開放下に放置した場合
の時間経過による重量減は下表の通りであった。数値は
２ヶの算述平均によった。Furthermore, the weight loss over time when two of these were left open indoors was as shown in the table below. The numerical value is based on the average of two calculations.

以上の実験結果より、粉末状セルロース誘導体の成形物
中への添加が成形物のもろさの改善に効果的であること
、および成形物中に吸着された揮発成分がとくに初期に
おいて一度に発散されることを抑制して保香寿命を延ば
す効果があることが確認された。The above experimental results show that the addition of a powdered cellulose derivative into a molded product is effective in improving the brittleness of the molded product, and that the volatile components adsorbed in the molded product are released all at once, especially in the initial stage. It was confirmed that this product has the effect of suppressing this and extending the life of fragrance retention.

実施例４． 実施例１で用いた合成珪酸カルシウム粉末に、３０％の
硫酸ばん土を混合して水を加えウエットケーキ状にした
。そのＰＨ（５％スラリー液で測定）は、７．６〜８．
０であった。実施例２同様の方法で３〜５ｍ／ｍ中の粒
状成形物とする。一方、実施例１で用いた合成珪酸カル
シウム粉末のみを用いて同様に３〜５ｍ／ｍ中の粒状成
形物を用意する。Example 4. The synthetic calcium silicate powder used in Example 1 was mixed with 30% sodium sulfate, and water was added to form a wet cake. Its pH (measured with 5% slurry liquid) is 7.6-8.
It was 0. A granular molded product with a size of 3 to 5 m/m is prepared in the same manner as in Example 2. On the other hand, using only the synthetic calcium silicate powder used in Example 1, a granular molded product with a size of 3 to 5 m/m is similarly prepared.

この２種類の球状成形物にアルデヒド基、アルコール性
水酸基、フェノール性水酸基とそのアルキル誘導体、ケ
ント基、およびカルボキシル基をそれぞれ分子構造内に
もった単体液状香料を別個に吸着させて密閉保存して約
６ヶ月間の経時変化をみた。Single liquid fragrances each having an aldehyde group, an alcoholic hydroxyl group, a phenolic hydroxyl group and its alkyl derivative, a Kent group, and a carboxyl group in its molecular structure are adsorbed onto these two types of spherical moldings, and the mixture is sealed and stored. Changes over time were observed over a period of approximately 6 months.

その結果、硫酸ばん土を用いた成形物（ＰＨが７．６〜
８．０）への吸着物は前述の官能基をもつ各単体香料と
も香りがほとんど変化しなかったのに対し、合成珪酸カ
ルシウムのみを用いた成形物（ＰＨ９．２〜９．４）は
アルデヒド基、カルボキシル基を分子内にもつ単体香料
を吸着させた場合経時的に香りが変化することが判明し
た。As a result, molded products using sulfate clay (with a pH of 7.6 to
8.0) had almost no change in aroma with each of the individual fragrances with the aforementioned functional groups, whereas the molded products (PH9.2-9.4) using only synthetic calcium silicate had aldehyde It has been found that when a single fragrance having a carboxyl group or a carboxyl group in its molecule is adsorbed, the fragrance changes over time.

従って、調合香料中にこれらの基を含む香料が主成分と
して配合される場合は、香りの経時変化をさけるために
吸着担体としては硫酸ばん土を混合して作った成形物を
用いる方が好ましい。Therefore, when a fragrance containing these groups is used as a main component in a prepared fragrance, it is preferable to use a molded product made by mixing sulfuric acid as an adsorption carrier in order to avoid changes in fragrance over time. .

実施例５． フルーツ系香料３種（ストロベリー、アップル、レモン
）、フローラル系香料３種（ばら、きんもくせい、ゆり
）および香水系香料３種（シャネル１９調、ミスディオ
ール調、ジョイ調）を用意する。実施例２でえられる球
状成形物５０部に上記香料５０部をそれぞれ吸着させる
。一方、上記香料の６０％を水と代替えした配合、すな
わち水３０部と香料２０部とを同様に吸着させた。Example 5. Three types of fruit fragrances (strawberry, apple, lemon), three types of floral fragrances (rose, osmanthus, lily), and three types of perfume fragrances (Chanel 19 style, Miss Dior style, Joy style) are prepared. 50 parts of the above perfume were adsorbed onto 50 parts of the spherical molded product obtained in Example 2, respectively. On the other hand, a formulation in which 60% of the perfume was replaced with water, ie, 30 parts of water and 20 parts of perfume, was similarly adsorbed.

各香料ごとに、香料のみの吸着物と水および香料を吸着
させた吸着物とを５名のパネラーに香りをかぎ分けさせ
た。For each fragrance, five panelists were asked to smell the scent of an adsorbent containing only the fragrance and an adsorbent adsorbing water and fragrance.

この官能検査の結果、パネラーでは８０％、香料種類で
は７５％の割合で、水および香料を吸着させた吸着物の
方が香りがおだやかでソフトという結果をえた。As a result of this sensory test, 80% of the panelists and 75% of the fragrance types found that the adsorbent that adsorbed water and fragrance had a milder and softer fragrance.

実施例６． 実施例１で用いた珪酸カルシウム粉末１００部にカルボ
キシメチルセルロース粉末５部、メチルセルロース粉末
２５部を均一に混合した後、脱イオン水を加えて油粘土
程度の固さに調製する。Example 6. After uniformly mixing 100 parts of the calcium silicate powder used in Example 1 with 5 parts of carboxymethyl cellulose powder and 25 parts of methyl cellulose powder, deionized water was added to adjust the mixture to a consistency similar to that of oil clay.

この材料を用い粘土細工の要領で犬および造花用花弁を
造形した。８０℃で約２時間乾燥し、次いで室温で２４
時間放置して本発明成形物をうる。Using this material, we modeled a dog and petals for artificial flowers in the same way as clay work. Dry at 80°C for about 2 hours, then at room temperature for 24 hours.
The molded article of the present invention is obtained by standing for a period of time.

ばら色の油溶性染料を２％溶解したばら様香料を上述の
造形物重量の１００％吸着させたものは、発香性置物お
よび造花の部品として開放下で約２ヶ月の保香性があっ
た。A rose-like fragrance containing 2% rose-colored oil-soluble dye dissolved in 100% of the weight of the above-mentioned object had a fragrance retention property of about 2 months in the open as a component for fragrant ornaments and artificial flowers. .

（以上）(that's all)

Claims (2)

【特許請求の範囲】[Claims] （１）、鉄の含有量が、Ｆｅ２Ｏ３として０．０９重量
％以下の合成珪酸カルシウムの成形物１００重量部に、
５０〜２５０重量部の香料含有液体を吸着させたことを
特徴とする実質的に乾燥状態の成形された芳香組成物。(1) 100 parts by weight of a synthetic calcium silicate molded product with an iron content of 0.09% by weight or less as Fe2O3,
A substantially dry shaped fragrance composition, characterized in that it has adsorbed 50 to 250 parts by weight of a perfume-containing liquid. （２）、香料含有液体の４〜６０重量％を水と代替し、
これら両液を混合することなく順次吸着させた特許請求
の範囲第１項記載の芳香組成物。(2) replacing 4 to 60% by weight of the fragrance-containing liquid with water;
The aromatic composition according to claim 1, wherein these two liquids are sequentially adsorbed without mixing.