JP2005194308A - Sustained release perfume carrier and sustained release perfume - Google Patents
Sustained release perfume carrier and sustained release perfume Download PDFInfo
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本発明は徐放性香料担体及びそれを用いた徐放性香料に関し、更に詳しくは、香粧品香料や食品香料等として使用される成分を貯留するとともに、これらの香料成分を経時的に徐々に放出させるための徐放性香料担体、及び、これに香料成分を担持させた徐放性香料に関する。 The present invention relates to a sustained-release fragrance carrier and a sustained-release fragrance using the same. More specifically, the present invention stores components used as cosmetic fragrances, food fragrances and the like, and gradually adds these fragrance components over time. The present invention relates to a sustained release fragrance carrier for release and a sustained release fragrance on which a fragrance component is supported.
食品、化粧品、防虫剤、繊維、インク等様々な産業分野において、香料を徐放性の担体に担持させ、徐放性香料として使用したいという要求がある。 In various industrial fields such as foods, cosmetics, insect repellents, fibers, and inks, there is a demand to support a fragrance on a sustained-release carrier and use it as a sustained-release fragrance.
かかる目的から、従来、有機高分子やそのゲル状化合物に香料成分等を担持させたり（特許文献１〜４）、シリカ、ゼオライト等の無機高分子に香料成分等を担持させたり（特許文献５〜９）する手法が用いられていた。 For this purpose, conventionally, a perfume component or the like is supported on an organic polymer or a gel compound thereof (Patent Documents 1 to 4), or a perfume component or the like is supported on an inorganic polymer such as silica or zeolite (Patent Document 5). ˜9) was used.
しかし、上記の従来技術にはそれぞれ課題があった。
例えば、有機高分子を使用する場合には、担体の強度が課題となることが多かったし、従来のシリカ等の無機材料を用いた場合には、少量含有される不純物の影響で担持香料が分解するという課題が危惧された他、徐放性能を制御するために厚さや成分等を微妙に調製した被覆層を設ける必要があることも多く、生産工程が複雑になっていた。また、被覆層を形成する必要がある場合の被覆層の材料は高価なものが多い。
However, each of the above conventional techniques has problems.
For example, when an organic polymer is used, the strength of the carrier often becomes a problem. When a conventional inorganic material such as silica is used, the supported flavor is affected by impurities contained in a small amount. In addition to fear of the problem of decomposing, it is often necessary to provide a coating layer in which the thickness, components, etc. are delicately controlled in order to control the sustained release performance, which complicates the production process. Further, the material of the coating layer when it is necessary to form the coating layer is often expensive.
以上の背景から、生産が容易且つ安価であり、担持できる香料成分の種類やその分子の大きさに対する選択の幅が広く、これらを多量に含浸可能であるとともに、純度が高く含浸させる香料成分にダメージを与えず、加えて耐水性や耐熱性，長期における物性安定性等にも優れた徐放性香料担体が望まれていた。 In view of the above background, it is easy and inexpensive to produce, has a wide range of choices for the types of perfume components that can be supported and the size of the molecules, and can be impregnated in large quantities, and can be impregnated with high purity. There has been a demand for a sustained-release fragrance carrier that does not give damage and is excellent in water resistance, heat resistance, and long-term physical stability.
本発明は、上述の課題に鑑みてなされたものである。すなわち、本発明の目的は、生産が容易且つ安価であり、担持できる香料成分の種類やその分子の大きさに対する選択の幅が広く、これらを多量に担持可能であるとともに、純度が高く担持する香料成分への悪影響が少なく、加えて耐水性や耐熱性、長期における物性安定性等にも優れた徐放性香料担体、及びそれを用いた徐放性香料を提供することにある。 The present invention has been made in view of the above-described problems. That is, the object of the present invention is easy and inexpensive to produce, has a wide range of choices for the types of perfume components that can be supported and the size of their molecules, and can support a large amount of these components while supporting them with high purity. Another object of the present invention is to provide a sustained release fragrance carrier that has little adverse effects on the fragrance component and is excellent in water resistance, heat resistance, long-term physical property stability, and the like, and a sustained release fragrance using the same.
そこで、本発明者らは、上記の課題を解決すべく鋭意検討した結果、香料成分を担持させる徐放性香料担体として、シャープな細孔分布を有するとともに、純度が高く、且つ、構造が均質で歪みの少ないシリカゲルを用いることによって、上記課題が効果的に解決されることを見出し、本発明を完成するに至った。 Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have a sharp pore distribution, a high purity, and a homogeneous structure as a sustained-release fragrance carrier for supporting a fragrance component. Thus, the present inventors have found that the above problems can be effectively solved by using silica gel with little distortion, and have completed the present invention.
即ち、本発明の要旨は、シリカゲルを有し、細孔内に担持した香料を徐放し得る徐放性香料担体であって、（ａ）細孔容積が０．０５ｍｌ／ｇ以上、３．０ｍｌ／ｇ以下であり、（ｂ）比表面積が１００ｍ2／ｇ以上、１５００ｍ2／ｇ以下であり、（ｃ）細孔の最頻直径（Ｄmax）が３５ｎｍ未満であり、（ｄ）直径がＤmax±２０％の範囲内にある細孔の総容積が、全細孔の総容積の５０％以上であり、（ｅ）非晶質であり、（ｆ）金属不純物の総含有率が５００ｐｐｍ以下であり、且つ、（ｇ）固体Ｓｉ−ＮＭＲでのＱ4ピークのケミカルシフトをδ（ｐｐｍ）とした場合に、δが下記式（Ｉ）を満足する
−０．０７０５×（Ｄmax）−１１０．３６＞δ ・・・式（Ｉ）
ことを特徴とする、徐放性香料担体に存する。
また、本発明の別の要旨は、上述の徐放性香料担体の細孔内に被徐放香料成分が担持されていることを特徴とする、徐放性香料に存する。
That is, the gist of the present invention is a sustained-release fragrance carrier having silica gel and capable of gradual release of a fragrance carried in pores, wherein (a) the pore volume is 0.05 ml / g or more and 3.0 ml. (B) the specific surface area is 100 m 2 / g or more and 1500 m 2 / g or less, (c) the mode diameter (D max ) of the pores is less than 35 nm, and (d) the diameter is The total volume of pores in the range of D max ± 20% is 50% or more of the total volume of all pores, (e) amorphous, and (f) the total content of metal impurities is 500 ppm. And (g) where the chemical shift of the Q 4 peak in solid Si-NMR is δ (ppm), δ satisfies the following formula (I): −0.0705 × (D max ) −110.36> δ Formula (I)
It exists in the sustained release fragrance | flavor carrier characterized by the above-mentioned.
Another gist of the present invention resides in a sustained-release fragrance characterized in that a sustained-release fragrance component is supported in the pores of the above-mentioned sustained-release fragrance carrier.
本発明の徐放性香料担体は、従来の徐放性香料担体と比較して、生産が容易且つ安価であり、被担持香料成分の種類や被担持成分分子の大きさに対する選択の幅が広く、より多量の被担持香料成分が担持可能である上に、純度が高いので担持する香料成分への悪影響が少ない。加えて、耐水性や耐熱性に優れており、しかも細孔特性等の各種物性が長期間にわたって安定して維持される。 The sustained-release fragrance carrier of the present invention is easier and cheaper to produce than the conventional sustained-release fragrance carrier, and has a wide range of choices for the type of supported fragrance component and the size of the supported component molecule. In addition, a larger amount of the perfume component to be supported can be supported, and since the purity is high, there is little adverse effect on the perfume component to be supported. In addition, it is excellent in water resistance and heat resistance, and various physical properties such as pore characteristics are stably maintained over a long period of time.
また、上記徐放性香料担体に香料成分を担持させて作製した本発明の徐放性香料は、従来の徐放性香料と比較して、徐放性能がより正確に制御可能であるとともに、長期にわたり安定した徐放効果が得られる。 In addition, the sustained release fragrance of the present invention produced by supporting the fragrance component on the sustained release fragrance carrier can be controlled more accurately as compared with the conventional sustained release fragrance, A stable sustained release effect can be obtained over a long period of time.
以下、本発明を詳細に説明する。
本発明の徐放性香料担体は、シリカゲルより構成され、細孔内に担持した香料物質を徐放するものであって、以下に挙げる特徴を有する。
Hereinafter, the present invention will be described in detail.
The sustained-release fragrance carrier of the present invention is composed of silica gel, and gradually releases the fragrance substance carried in the pores, and has the following characteristics.
まず、本発明の徐放性香料担体は、細孔容積及び比表面積が以下の範囲にあることを特徴とする。具体的に、細孔容積の値は、通常０．０５ｍｌ／ｇ以上、好ましくは０．６ｍｌ／ｇ以上、また、通常３．０ｍｌ／ｇ以下、好ましくは２．０ｍｌ／ｇ以下であり、比表面積の値は、通常１００ｍ2／ｇ以上、好ましくは３００ｍ2／ｇ以上、また、通常１５００ｍ2／ｇ以下、好ましくは１０００ｍ2／ｇ以下、更に好ましくは９００ｍ2／ｇ以下の範囲に存在する。これらの細孔容積及び比表面積の値は、窒素ガス吸脱着によるＢＥＴ法で測定される。 First, the sustained-release fragrance carrier of the present invention is characterized in that the pore volume and specific surface area are in the following ranges. Specifically, the value of the pore volume is usually 0.05 ml / g or more, preferably 0.6 ml / g or more, and usually 3.0 ml / g or less, preferably 2.0 ml / g or less. The surface area value is usually in the range of 100 m 2 / g or more, preferably 300 m 2 / g or more, and usually 1500 m 2 / g or less, preferably 1000 m 2 / g or less, more preferably 900 m 2 / g or less. . These pore volume and specific surface area values are measured by the BET method by nitrogen gas adsorption / desorption.
また、本発明の徐放性香料担体は、細孔の最頻直径Ｄmaxが３５ｎｍ未満であることを特徴とする。最頻直径Ｄmaxは、気体や液体の吸着や吸収に関する特性であり、最頻直径Ｄmaxが小さいほど吸着や吸収性能が高い。従って、種々の特性の中で最頻直径Ｄmaxは、特に触媒担体や薬剤担体，吸着剤として使用するシリカゲルにとって重要な物性である。本発明の徐放性香料担体の好ましい最頻直径Ｄmaxは、中でも２０ｎｍ以下、更には１８ｎｍ以下である。また、下限は特に制限されないが、通常は１ｎｍ以上である。 The sustained-release fragrance carrier of the present invention is characterized in that the mode diameter D max of the pores is less than 35 nm. The mode diameter Dmax is a characteristic related to adsorption and absorption of gas and liquid, and the adsorption and absorption performance is higher as the mode diameter Dmax is smaller. Therefore, the mode diameter D max among various characteristics is an important physical property particularly for silica gel used as a catalyst carrier, a drug carrier, and an adsorbent. The preferred mode diameter D max of the sustained release fragrance carrier of the present invention is 20 nm or less, more preferably 18 nm or less. Moreover, although a minimum in particular is not restrict | limited, Usually, it is 1 nm or more.
なお、上記の最頻直径Ｄmaxは、窒素ガス吸脱着によるＢＥＴ法で測定した等温脱着曲線から、E. P. Barrett, L. G. Joyner, P. H. Haklenda, J. Amer. Chem. Soc., vol. 73, 373 (1951) に記載のＢＪＨ法により算出される細孔分布曲線をプロットして求められる。ここで、細孔分布曲線とは、微分細孔容積、すなわち、細孔直径ｄ（ｎｍ）に対する微分窒素ガス吸着量（ΔＶ／Δ（ｌｏｇｄ））を言う。上記のＶは、窒素ガス吸着容積を表す。 The mode diameter D max is determined from the isothermal desorption curve measured by the BET method by nitrogen gas adsorption / desorption, from EP Barrett, LG Joyner, PH Haklenda, J. Amer. Chem. Soc., Vol. 73, 373 ( 1951) is plotted to obtain a pore distribution curve calculated by the BJH method. Here, the pore distribution curve refers to the differential pore volume, that is, the differential nitrogen gas adsorption amount (ΔV / Δ (logd)) with respect to the pore diameter d (nm). Said V represents nitrogen gas adsorption volume.
更に、本発明の徐放性香料担体は、上記の最頻直径Ｄmaxの値を中心として±２０％の範囲にある細孔の総容積が、全細孔の総容積の通常５０％以上、好ましくは６０％以上であることを特徴とする。このことは、本発明の徐放性香料担体が有する細孔の直径が、最頻直径Ｄmax付近の細孔で揃っていることを意味する。なお、上記の最頻直径Ｄmax±２０％の範囲にある細孔の総容積について、特に上限は無いが、通常は全細孔の総容積の９０％以下である。 Furthermore, the sustained-release fragrance carrier of the present invention has a total volume of pores in the range of ± 20% centering on the value of the mode diameter Dmax , usually 50% or more of the total volume of all pores, Preferably, it is 60% or more. This means that the diameters of the pores of the sustained-release fragrance carrier of the present invention are uniform in the pores near the mode diameter D max . The total volume of the pores in the range of the mode diameter D max ± 20% is not particularly limited, but is usually 90% or less of the total volume of all the pores.
かかる特徴に関連して、本発明の徐放性香料担体は、上記のＢＪＨ法により算出された最頻直径Ｄmaxにおける微分細孔容積ΔＶ／Δ（ｌｏｇｄ）が、通常２ｍｌ／ｇ以上、特に５ｍｌ／ｇ以上、また、通常２０ｍｌ／ｇ以下、特に１２ｍｌ／ｇ以下の範囲であることが好ましい（なお、上式において、ｄは細孔直径（ｎｍ）であり、Ｖは窒素ガス吸着容積である）。微分細孔容積ΔＶ／Δ（ｌｏｇｄ）が前記範囲に含まれるものは、最頻直径Ｄmaxの付近に揃っている細孔の絶対量が極めて多いものと言える。 In relation to such characteristics, the sustained release fragrance carrier of the present invention has a differential pore volume ΔV / Δ (logd) at the mode diameter D max calculated by the BJH method of usually 2 ml / g or more, particularly It is preferably in the range of 5 ml / g or more, usually 20 ml / g or less, particularly 12 ml / g or less (where, d is the pore diameter (nm), and V is the nitrogen gas adsorption volume) is there). When the differential pore volume ΔV / Δ (logd) is included in the above range, it can be said that the absolute amount of pores aligned in the vicinity of the mode diameter D max is extremely large.
加えて、本発明の徐放性香料担体は、その三次元構造を見るに、非晶質であること、即ち、結晶性構造が認められないことを特徴とする。このことは、本発明の徐放性香料担体をＸ線回折で分析した場合に、結晶性ピークが実質的に認められないことを意味する。なお、本明細書において結晶質であるシリカゲルとは、Ｘ線回折パターンで０．６ｎｍ（Units d-spacing）を越えた位置に、少なくとも一つの結晶構造のピークを示すものを指す。結晶性構造を有するシリカゲルの例として、前述のミセルテンプレートシリカが挙げられる。非結晶質のシリカゲルは、結晶性のシリカゲルに較べて、極めて生産性に優れている。 In addition, the sustained-release fragrance carrier of the present invention is characterized in that it is amorphous, that is, no crystalline structure is observed in view of its three-dimensional structure. This means that when the sustained-release fragrance carrier of the present invention is analyzed by X-ray diffraction, substantially no crystalline peak is observed. In the present specification, crystalline silica gel refers to a material having a peak of at least one crystal structure at a position exceeding 0.6 nm (Units d-spacing) in an X-ray diffraction pattern. Examples of the silica gel having a crystalline structure include the aforementioned micelle template silica. Amorphous silica gel is extremely excellent in productivity as compared with crystalline silica gel.
また、本発明の徐放性香料担体は、不純物の含有率が非常に低く、極めて高純度であることを特徴とする。具体的には、シリカゲル中に存在することでその物性に影響を与えることが知られている、アルカリ金属，アルカリ土類金属，周期表の１３族，１４族及び１５族並びに遷移金属からなる群に属する金属元素（金属不純物）の合計の含有率が、通常５００ｐｐｍ以下、好ましくは１００ｐｐｍ以下、更に好ましくは５０ｐｐｍ以下、最も好ましくは３０ｐｐｍ以下の範囲である。このように不純物の影響が少ないことが、本発明の徐放性香料担体が高い耐熱性や耐水性などの優れた性質を発現できる大きな要因の一つである。 In addition, the sustained-release fragrance carrier of the present invention is characterized by having a very low impurity content and extremely high purity. Specifically, the group consisting of alkali metals, alkaline earth metals, groups 13, 14 and 15 of the periodic table, and transition metals, which are known to affect their physical properties by being present in silica gel. The total content of metal elements (metal impurities) belonging to is usually in the range of 500 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 30 ppm or less. Such a small influence of impurities is one of the major factors that allow the sustained release fragrance carrier of the present invention to exhibit excellent properties such as high heat resistance and water resistance.
更に、本発明の徐放性香料担体は、その構造に歪みが少ないことを特徴とする。ここで、シリカゲルの構造的な歪みは、固体Ｓｉ−ＮＭＲ測定におけるＱ4ピークのケミカルシフトの値によって表わすことができる。以下、シリカゲルの構造的な歪みと、前記のＱ4ピークのケミカルシフトの値との関連について、詳しく説明する。 Furthermore, the sustained release fragrance carrier of the present invention is characterized in that its structure is less distorted. Here, the structural strain of silica gel can be expressed by the value of the chemical shift of the Q 4 peak in the solid-state Si-NMR measurement. Hereinafter, the relationship between the structural distortion of silica gel and the chemical shift value of the Q 4 peak will be described in detail.
本発明の徐放性香料担体は非晶質ケイ酸の水和物であり、ＳｉＯ2・ｎＨ2Ｏの示性式で表されるが、構造的には、Ｓｉの四面体の各頂点にＯが結合され、これらのＯに更にＳｉが結合して、ネット状に広がった構造を有する。そして、Ｓｉ−Ｏ−Ｓｉ−Ｏ−の繰り返し単位において、Ｏの一部が他の成員（例えば−Ｈ、−ＣＨ3など）で置換されているものもあり、一つのＳｉに注目した場合、下記式（Ａ）に示す様に４個の−ＯＳｉを有するＳｉ（Ｑ4）や、下記式（Ｂ）に示す様に３個の−ＯＳｉを有するＳｉ（Ｑ3）等が存在する（下記式（Ａ）及び（Ｂ）では、上記の四面体構造を無視し、Ｓｉ−Ｏのネット構造を平面的に表わしている）。そして、固体Ｓｉ−ＮＭＲ測定において、上記の各Ｓｉに基づくピークは、順にＱ4ピーク、Ｑ3ピーク、・・と呼ばれる。 The sustained-release fragrance carrier of the present invention is a hydrate of amorphous silicic acid, and is represented by the SiO 2 · nH 2 O formula, but structurally, at each vertex of the Si tetrahedron. O is bonded, and Si is further bonded to these Os to form a net-like structure. In some repeating units of Si—O—Si—O—, some of O is substituted with other members (for example, —H, —CH 3, etc.). As shown in the following formula (A), there are Si (Q 4 ) having 4 —OSi, Si (Q 3 ) having 3 —OSi as shown in the following formula (B), etc. In the formulas (A) and (B), the tetrahedral structure is ignored and the Si—O net structure is represented in a plane). In the solid Si-NMR measurement, the peaks based on the respective Si are called Q 4 peak, Q 3 peak,.
本発明の徐放性香料担体は、上記のＱ4ピークのケミカルシフトをδ（ｐｐｍ）とした場合に、δが下記式（Ｉ）を満足することを特徴とする。
−０．０７０５×Ｄmax−１１０．３６＞δ ・・・式（Ｉ）
The sustained release fragrance carrier of the present invention is characterized in that δ satisfies the following formula (I) when the chemical shift of the Q 4 peak is δ (ppm).
−0.0705 × D max −110.36> δ Formula (I)
従来のシリカゲルでは、上記のＱ4ピークのケミカルシフトの値δは、上記式（Ｉ）の左辺に基づいて計算した値よりも、一般に大きくなる。よって、本発明の徐放性担体は、従来のシリカゲルに比べて、Ｑ4ピークのケミカルシフトがより小さな値を有することになる。これは、本発明の徐放性担体において、Ｑ4ピークのケミカルシフトがより高磁場に存在するということに他ならず、ひいては、Ｓｉに対して２個の−ＯＳｉで表される結合角がより均質であり、構造的な歪みがより少ないことを意味している。 In the conventional silica gel, the chemical shift value δ of the Q 4 peak is generally larger than the value calculated based on the left side of the formula (I). Therefore, the sustained-release carrier of the present invention has a smaller value of the chemical shift of the Q 4 peak as compared with the conventional silica gel. This is nothing but the fact that the chemical shift of the Q 4 peak exists in a higher magnetic field in the sustained-release carrier of the present invention. As a result, the bond angle represented by two —OSi with respect to Si is It means more homogenous and less structural distortion.
本発明の徐放性香料担体において、Ｑ4ピークのケミカルシフトδは、上記式（Ｉ）の左辺（−０．０７０５×Ｄmax−１１０．３６）に基づき算出される値よりも、好ましくは０．０５％以上小さい値であり、更に好ましくは０．１％、特に好ましくは０．１５％以上小さい値である。通常、シリカゲルのＱ4ピークの最小値は−１１３ｐｐｍである。 In the sustained release fragrance carrier of the present invention, the chemical shift δ of the Q 4 peak is preferably more than the value calculated based on the left side of the formula (I) (−0.0705 × D max −110.36). The value is 0.05% or less, more preferably 0.1%, and particularly preferably 0.15% or more. Usually, the minimum value of the Q 4 peak of silica gel is −113 ppm.
本発明の徐放性香料担体が有する、優れた耐熱性や耐水性と、上記の様な構造的歪みの関係については、必ずしも明らかではないが、次の様に推定される。すなわち、シリカゲルは大きさの異なる球状粒子の集合体で構成されているが、上記の様な構造的に歪みの少ない状態においては、球状粒子全体のミクロ構造的な高度の均質性が維持されるので、その結果、優れた耐熱性や耐水性が発現されるものと考えられる。なお、Ｑ3以下のピークは、Ｓｉ−Ｏのネット構造の広がりに制限があるため、シリカゲルの構造的な歪みが現れにくい。 The relationship between the excellent heat resistance and water resistance of the sustained-release fragrance carrier of the present invention and the structural strain as described above is not necessarily clear, but is estimated as follows. In other words, silica gel is composed of aggregates of spherical particles of different sizes, but in a state where there is little structural distortion as described above, high microstructural homogeneity of the entire spherical particles is maintained. As a result, it is considered that excellent heat resistance and water resistance are exhibited. Note that the peak of Q 3 or less is not easily affected by the structural distortion of silica gel because the expansion of the Si—O net structure is limited.
上記の特徴に関連して、本発明の徐放性香料担体は、固体Ｓｉ−ＮＭＲ測定によるＱ4／Ｑ3の値が、通常１．３以上、中でも１．５以上であることが好ましい。ここで、Ｑ4／Ｑ3の値とは、上述したシリカゲルの繰り返し単位の中で、−ＯＳｉが３個結合したＳｉ（Ｑ3）に対する−ＯＳｉが４個結合したＳｉ（Ｑ4）のモル比を意味する。一般に、この値が高い程、シリカゲルの熱安定性が高いことが知られており、ここから、本発明の徐放性香料担体は、熱安定性に極めて優れていることが判る。これに対して、結晶性である前述のミセルテンプレートシリカは、Ｑ4／Ｑ3の値が１．３を下回ることが多く、耐熱性が低い。 In relation to the above characteristics, the sustained-release fragrance carrier of the present invention preferably has a Q 4 / Q 3 value of 1.3 or more, preferably 1.5 or more, as measured by solid-state Si-NMR. Here, the value of Q 4 / Q 3 is the mole of Si (Q 4 ) in which four —OSi are bonded to Si (Q 3 ) in which three —OSi are bonded in the above-described repeating unit of silica gel. Means ratio. In general, it is known that the higher the value, the higher the thermal stability of the silica gel. From this, it can be seen that the sustained-release fragrance carrier of the present invention is extremely excellent in thermal stability. On the other hand, the above-mentioned micellar template silica which is crystalline often has a Q 4 / Q 3 value of less than 1.3 and has low heat resistance.
なお、Ｑ4ピークのケミカルシフト及びＱ4／Ｑ3の値は、実施例の説明において後述する方法を用いて固体Ｓｉ−ＮＭＲ測定を行ない、その結果に基づいて算出することができる。また、測定データの解析（ピーク位置の決定）は、例えば、ガウス関数を使用した波形分離解析等により、各ピークを分割して抽出する方法で行なう。 The value of chemical shift and Q 4 / Q 3 of Q 4 peak, performs solid Si-NMR measurement using the method described later in the description of embodiments, it can be calculated based on the result. Further, analysis of measurement data (determination of peak position) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function.
本発明の徐放性香料担体は、従来のゾル−ゲル法とは異なり、シリコンアルコキシドを加水分解する加水分解工程と共に得られたシリカヒドロゾルを縮合する工程縮合工程を経てシリカヒドロゲルを形成する加水分解・縮合工程と、当該加水分解・縮合工程に引き続き、シリカヒドロゲルを熟成することなく水熱処理することにより、所望の物性範囲のシリカゲルを得る物性調節工程とを、ともに包含する方法で製造することができる。 Unlike the conventional sol-gel method, the sustained-release fragrance carrier of the present invention is a hydrolyzate that forms a silica hydrogel through a process condensation step of condensing the silica hydrosol obtained together with a hydrolysis step of hydrolyzing silicon alkoxide. Manufacturing by a method that includes both a decomposition / condensation step and a physical property adjustment step for obtaining silica gel in a desired physical property range by hydrothermal treatment without aging the silica hydrogel following the hydrolysis / condensation step. Can do.
本発明の徐放性香料担体の原料として使用されるシリコンアルコキシドとしては、トリメトキシシラン、テトラメトキシシラン、トリエトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等の炭素数１〜４の低級アルキル基を有するトリ又はテトラアルコキシシラン或いはそれらのオリゴマーが挙げられるが、好ましくはテトラメトキシシラン、テトラエトキシシラン及びそれらのオリゴマーである。以上のシリコンアルコキシドは蒸留により容易に精製し得るので、高純度のシリカゲルの原料として好適である。シリコンアルコキシド中の金属不純物の総含有量は、通常１００ｐｐｍ以下、中でも５０ｐｐｍ以下、更には３０ｐｐｍ以下、特に１０ｐｐｍ以下が好ましい。これらの金属不純物の含有率は、一般的なシリカゲル中の不純物含有率の測定法と同じ方法で測定できる。 The silicon alkoxide used as a raw material for the sustained release fragrance carrier of the present invention has 1 to 4 carbon atoms such as trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Examples thereof include tri- or tetraalkoxysilane having a lower alkyl group or oligomers thereof, and tetramethoxysilane, tetraethoxysilane and oligomers thereof are preferable. Since the above silicon alkoxide can be easily purified by distillation, it is suitable as a raw material for high-purity silica gel. The total content of metal impurities in the silicon alkoxide is usually 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, and particularly preferably 10 ppm or less. The content rate of these metal impurities can be measured by the same method as the measurement method of the impurity content rate in general silica gel.
シリコンアルコキシドの加水分解は、シリコンアルコキシド１モルに対して、通常２モル以上、好ましくは３モル以上、特に好ましくは４モル以上、また、通常２０モル以下、好ましくは１０モル以下、特に好ましくは８モル以下の水を用いて行なう。シリコンアルコキシドの加水分解により、シリカのヒドロゲルとアルコールとが生成する。この加水分解反応は、通常、室温から１００℃程度であるが、加圧下で液相を維持することで、より高い温度で行なうことも可能である。また、加水分解時には必要に応じて、水と相溶性のあるアルコール類等の溶媒を添加してもよい。具体的には、炭素数１〜３の低級アルコール類、ジメチルホルムアミド、ジメチルスルホキシド、アセトン、テトラヒドロフラン、メチルセロルブ、エチルセロルブ、メチルエチルケトン、その他の水と任意に混合できる有機溶媒を任意に用いることができるが、中でも強い酸性や塩基性を示さないものが、均一なシリカヒドロゲルを生成できる理由から好ましい。 The hydrolysis of the silicon alkoxide is usually 2 mol or more, preferably 3 mol or more, particularly preferably 4 mol or more, and usually 20 mol or less, preferably 10 mol or less, particularly preferably 8 mol per mol of silicon alkoxide. Performed with less than a mole of water. Hydrolysis of silicon alkoxide produces silica hydrogel and alcohol. This hydrolysis reaction is usually from room temperature to about 100 ° C., but can be performed at a higher temperature by maintaining the liquid phase under pressure. Moreover, you may add solvents, such as alcohol compatible with water, as needed at the time of a hydrolysis. Specifically, lower alcohols having 1 to 3 carbon atoms, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellolbu, ethyl cellolb, methyl ethyl ketone, and other organic solvents that can be arbitrarily mixed with water can be arbitrarily used. Among them, those that do not exhibit strong acidity or basicity are preferable because a uniform silica hydrogel can be produced.
これらの溶媒を使用しない場合、本発明の徐放性香料担体の製造のためには、特に加水分解の際の攪拌速度が重要である。すなわち、シリコンアルコキシドと加水分解用の水は初期には分液しているため、攪拌によりエマルジョン化し、反応を促進させる。この際の攪拌速度は通常３０ｒｐｍ以上、好ましくは５０ｒｐｍ以上である。斯かる条件を満足しない場合には、本発明の徐放性香料担体を得るのが困難になる。なお、加水分解によりアルコールが生成して液が均一液となり、発熱が収まった後には、均一なヒドロゲルを形成させるために攪拌を停止することが好ましい。 When these solvents are not used, the stirring speed at the time of hydrolysis is particularly important for the production of the sustained release fragrance carrier of the present invention. That is, since silicon alkoxide and water for hydrolysis are separated at the initial stage, they are emulsified by stirring to promote the reaction. The stirring speed at this time is usually 30 rpm or more, preferably 50 rpm or more. When such conditions are not satisfied, it becomes difficult to obtain the sustained-release fragrance carrier of the present invention. In addition, after alcohol produces | generates by hydrolysis and a liquid turns into a uniform liquid and heat_generation | fever stops, it is preferable to stop stirring in order to form a uniform hydrogel.
結晶構造を有するシリカゲルは、水中熱安定性に乏しくなる傾向にあり、ゲル中に細孔を形成するのに用いられる界面活性剤等のテンプレートの存在下でシリコンアルコキシドを加水分解すると、ゲルは容易に結晶構造を含むものとなる。従って、本発明においては、界面活性剤等のテンプレートの非存在下で、即ち、これらがテンプレートとしての機能を発揮する程の量は存在しない条件下で、加水分解を行なうことが好ましい。 Silica gel with a crystal structure tends to have poor thermal stability in water, and gels are easy to hydrolyze silicon alkoxide in the presence of a template such as a surfactant used to form pores in the gel. Includes a crystal structure. Therefore, in the present invention, it is preferable to perform the hydrolysis in the absence of a template such as a surfactant, that is, in a condition where there is no such an amount that it functions as a template.
反応時間は、反応液組成（シリコンアルコキシドの種類や、水とのモル比）並びに反応温度に依存し、ゲル化するまでの時間が異なるので、一概には規定されない。なお、反応系に触媒として、酸，アルカリ，塩類などを添加することで加水分解を促進させることができる。しかしながら、斯かる添加物の使用は、後述するように、生成したヒドロゲルの熟成を引き起こすことになるので、本発明の徐放性香料担体の製造においてはあまり好ましくない。 The reaction time depends on the reaction solution composition (type of silicon alkoxide and molar ratio with water) and the reaction temperature, and the time until gelation differs, so it is not unconditionally specified. In addition, hydrolysis can be accelerated | stimulated by adding an acid, an alkali, salts, etc. to a reaction system as a catalyst. However, the use of such an additive causes aging of the produced hydrogel, as will be described later, and therefore is not so preferable in the production of the sustained release fragrance carrier of the present invention.
上記のシリコンアルコキシドの加水分解反応では、シリコンアルコキシドが加水分解してシリケートが生成するが、引き続いて該シリケートの縮合反応が起こり、反応液の粘度が上昇し、最終的にゲル化してシリカヒドロゲルとなる。本発明の徐放性香料担体を製造するためには、上記の加水分解により生成したシリカのヒドロゲルの硬さが上昇しないように、実質的に熟成することなく、直ちに水熱処理を行なうことが重要である。シリコンアルコキシドを加水分解すると、軟弱なシリカのヒドロゲルが生成するが、このヒドロゲルを安定した熟成、あるいは乾燥させ、更にこれに水熱処理を施し、最終的に細孔特性の制御されたシリカゲルとする従来の方法では、本発明で規定する物性範囲の徐放性香料担体を製造することができない。 In the above silicon alkoxide hydrolysis reaction, the silicon alkoxide is hydrolyzed to produce a silicate. Subsequently, a condensation reaction of the silicate occurs, the viscosity of the reaction solution rises, and finally gelates to form a silica hydrogel. Become. In order to produce the sustained release fragrance carrier of the present invention, it is important to immediately perform a hydrothermal treatment without substantial aging so that the hardness of the hydrogel of silica generated by the above hydrolysis does not increase. It is. Hydrolysis of silicon alkoxide produces a soft silica hydrogel. This hydrogel is stably aged or dried, and then hydrothermally treated, finally resulting in silica gel with controlled pore properties. In this method, it is impossible to produce a sustained-release fragrance carrier having a physical property range defined in the present invention.
上記にある、加水分解により生成したシリカのヒドロゲルを、実質的に熟成することなく、直ちに水熱処理を行なうということは、シリカのヒドロゲルが生成した直後の軟弱な状態が維持されたままで、次の水熱処理に供するということを意味する。シリコンアルコキシドの加水分解反応系に酸、アルカリ、塩類等を添加すること、又は該加水分解反応の温度を厳しくし過ぎることなどは、ヒドロゲルの熟成を進行させるため好ましくない。また、加水分解後の後処理における水洗，乾燥，放置などにおいて、必要以上に温度や時間をかけるべきではない。 The hydrothermal treatment of the silica hydrogel formed by hydrolysis, as described above, is performed immediately without substantially aging. This means that the soft state immediately after the formation of the silica hydrogel is maintained and the following conditions are maintained. It means to be subjected to hydrothermal treatment. It is not preferable to add acid, alkali, salt, or the like to the silicon alkoxide hydrolysis reaction system, or to make the temperature of the hydrolysis reaction too strict, since the aging of the hydrogel proceeds. In addition, the temperature and time should not be increased more than necessary in washing, drying, and leaving in post-treatment after hydrolysis.
ヒドロゲルの熟成状態を具体的に確認する手段としては、ヒドロゲルの硬度を参考にすることができる。即ち、破壊応力が、通常６ＭＰａ以下、好ましくは３ＭＰａ以下、更に好ましくは２ＭＰａ以下の柔らかい状態のヒドロゲルを水熱処理することで、本発明で規定する物性範囲の徐放性香料担体を得ることができる。 As means for specifically confirming the aging state of the hydrogel, the hardness of the hydrogel can be referred to. That is, a sustained-release fragrance carrier having a physical property range defined in the present invention can be obtained by hydrothermally treating a soft hydrogel having a fracture stress of usually 6 MPa or less, preferably 3 MPa or less, more preferably 2 MPa or less. .
この水熱処理の条件としては、水の状態が液体、気体の何れでもよく、溶媒や他の気体によって希釈されていてもよいが、好ましくは液体の水が使われる。シリカのヒドロゲルに対して、通常０．１重量倍以上、好ましくは０．５重量倍以上、特に好ましくは１重量倍以上、また、通常１０重量倍以下、好ましくは５重量倍以下、特に好ましくは３重量倍以下の範囲の水を加えてスラリー状とし、通常４０℃以上、好ましくは５０℃以上、また、通常２５０℃以下、好ましくは２００℃以下の温度で、通常０．１時間以上、好ましくは１時間以上、また、通常１００時間以下、好ましくは１０時間以下の範囲で実施される。水熱処理に使用される水には、低級アルコール類、メタノール、エタノール、プロパノールや、ジメチルホルムアミド（ＤＭＦ）やジメチルスルホキシド（ＤＭＳＯ）、その他の有機溶媒などが含まれてもよい。また、シリカゲルを膜状あるいは層状に粒子、基板、あるいは管などの基体上に形成させた材料の場合にも、この水熱処理方法は適用される。なお、加水分解反応の反応器を用い、続けて温度条件変更により水熱処理を行なうことも可能であるが、加水分解反応とその後の水熱処理とでは通常、最適条件が異なっているため、この方法で本発明の徐放性香料担体を得ることは一般的に難しい。 As conditions for this hydrothermal treatment, the state of water may be either liquid or gas, and it may be diluted with a solvent or other gas, but preferably liquid water is used. It is usually 0.1 times by weight or more, preferably 0.5 times by weight or more, particularly preferably 1 by weight or more, and usually 10 times by weight or less, preferably 5 times by weight or less, particularly preferably to silica hydrogel. Water in the range of 3 times by weight or less is added to form a slurry, which is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, usually 0.1 hour or longer, preferably Is carried out in the range of 1 hour or longer, usually 100 hours or shorter, preferably 10 hours or shorter. The water used for the hydrothermal treatment may contain lower alcohols, methanol, ethanol, propanol, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and other organic solvents. The hydrothermal treatment method is also applied to a material in which silica gel is formed in a film or layer on a substrate such as particles, a substrate, or a tube. Although it is possible to perform hydrothermal treatment by changing the temperature condition using a hydrolysis reaction reactor, the optimum conditions are usually different between the hydrolysis reaction and the subsequent hydrothermal treatment. Therefore, it is generally difficult to obtain the sustained release fragrance carrier of the present invention.
以上の水熱処理条件において温度を高くすると、得られるシリカゲルの細孔径、細孔容積が大きくなる傾向がある。水熱処理温度としては、通常１００℃以上、通常２００℃以下の範囲であることが好ましい。また、処理時間とともに、得られるシリカゲルの比表面積は、一度極大に達した後、緩やかに減少する傾向がある。以上の傾向を踏まえて、所望の物性値に応じて条件を適宜選択する必要があるが、水熱処理は、シリカゲルの物性を変化させる目的なので、通常、前記の加水分解の反応条件より高温条件とすることが好ましい。 When the temperature is increased under the hydrothermal treatment conditions described above, the pore diameter and pore volume of the resulting silica gel tend to increase. The hydrothermal treatment temperature is preferably in the range of usually 100 ° C. or higher and usually 200 ° C. or lower. Further, with the treatment time, the specific surface area of the silica gel obtained tends to decrease gradually after reaching the maximum once. Based on the above tendency, it is necessary to appropriately select the conditions according to the desired physical property values, but since hydrothermal treatment is intended to change the physical properties of silica gel, it is usually at a higher temperature than the hydrolysis reaction conditions described above. It is preferable to do.
水熱処理の温度、時間を上記範囲外に設定すると、本発明の徐放性香料担体を得ることが困難となる。例えば、水熱処理の温度が高すぎると、シリカゲルの細孔径、細孔容積が大きくなりすぎ、また、細孔分布も広がる。逆に、水熱処理の温度が低過ぎると、生成するシリカゲルは、架橋度が低く、熱安定性に乏しくなり、細孔分布にピークが発現しなくなったり、前述した固体Ｓｉ−ＮＭＲにおけるＱ4／Ｑ3の値が極端に小さくなったりする。 When the temperature and time of hydrothermal treatment are set outside the above ranges, it is difficult to obtain the sustained release fragrance carrier of the present invention. For example, if the hydrothermal treatment temperature is too high, the pore diameter and pore volume of the silica gel become too large, and the pore distribution is also widened. On the other hand, if the hydrothermal treatment temperature is too low, the resulting silica gel has a low degree of crosslinking, poor thermal stability, no peaks in the pore distribution, or Q 4 / the value of Q 3 may become extremely small.
なお、水熱処理をアンモニア水中で行なうと、純水中で行なう場合よりも低温で同様の効果が得られる。また、アンモニア水中で水熱処理すると、純水中で処理する場合と比較して、最終的に得られるシリカゲルは一般に疎水性となるが、通常３０℃以上、好ましくは４０℃以上、通常２５０℃以下、好ましくは２００℃以下という比較的高温で水熱処理すると、特に疎水性が高くなる。ここでのアンモニア水のアンモニア濃度としては、好ましくは０．００１％以上、特に好ましくは０．００５％以上、また、好ましくは１０％以下、特に好ましくは５％以下の範囲である。 When the hydrothermal treatment is performed in ammonia water, the same effect can be obtained at a lower temperature than in pure water. In addition, when hydrothermal treatment is performed in ammonia water, the silica gel finally obtained is generally hydrophobic as compared with the case of treatment in pure water, but usually 30 ° C. or higher, preferably 40 ° C. or higher, usually 250 ° C. or lower. In particular, when the hydrothermal treatment is performed at a relatively high temperature of 200 ° C. or less, the hydrophobicity becomes particularly high. The ammonia concentration here is preferably 0.001% or more, particularly preferably 0.005% or more, and preferably 10% or less, particularly preferably 5% or less.
水熱処理されたシリカヒドロゲルは、通常４０℃以上、好ましくは６０℃以上、通常２００℃以下、好ましくは１２０℃以下で乾燥する。乾燥方法は特に限定されるものではなく、バッチ式でも連続式でもよく、且つ、常圧でも減圧下でも乾燥することができる。必要に応じ、原料のシリコンアルコキシドに由来する炭素分が含まれている場合には、通常４００℃以上、６００℃以下で焼成除去することができる。また、表面状態をコントロールするため、最高９００℃の温度で焼成することもある。 The hydrothermally treated silica hydrogel is usually dried at 40 ° C. or higher, preferably 60 ° C. or higher, usually 200 ° C. or lower, preferably 120 ° C. or lower. The drying method is not particularly limited, and it may be a batch type or a continuous type, and can be dried under normal pressure or reduced pressure. If necessary, when a carbon component derived from the raw material silicon alkoxide is contained, it can be removed usually by baking at 400 ° C. or more and 600 ° C. or less. Moreover, in order to control a surface state, it may bake at the temperature of a maximum of 900 degreeC.
乾燥（又は焼成）後のシリカゲルを、必要に応じて公知の各種手法により粉砕及び／又は分級することで、本発明の徐放性香料担体を得ることができる。なお、必要に応じて、粉砕及び／又は分級後のシリカゲルを公知の各種手法により成形（例えば、球状，錠剤状，押出品，ペレット品等の形状に成形）して、これを本発明の徐放性香料担体として使用するのも好ましい。 The sustained-release fragrance carrier of the present invention can be obtained by pulverizing and / or classifying the dried (or baked) silica gel by various known methods as necessary. If necessary, the silica gel after pulverization and / or classification is shaped by various known methods (for example, shaped into a spherical shape, a tablet shape, an extruded product, a pellet product, etc.), and this is gradually reduced according to the present invention. It is also preferable to use it as a release fragrance carrier.
本発明の徐放性香料担体の形状は特に限定されず、粉末状、粒状、球状、微粉凝集体、微粉を用いた成形体等の各種の形状の中から、用途に応じて適宜選択することができる。上述の粉砕，分級，成形等の有無及び条件については、選択した形状に応じて適宜決定すればよい。 The shape of the sustained-release fragrance carrier of the present invention is not particularly limited, and may be appropriately selected from various shapes such as powder, granule, sphere, fine powder aggregate, and molded product using fine powder according to applications. Can do. The presence / absence and conditions of the above-described pulverization, classification, molding, and the like may be appropriately determined according to the selected shape.
本発明の徐放性香料担体は、従来のシリカゲル等の徐放性香料担体と比較して、よりシャープな細孔分布を有するとともに、その細孔径をより精密に制御することが可能である。従って、徐放性香料に使用する場合に、細孔内に担持させる各種物質（被担持成分）の分子サイズに応じて細孔径を精密に制御することができ、担持できる香料成分の種類やその分子の大きさに対する選択の幅が広い。また、細孔内に担持させる各種香料物質（被担持成分）の分子サイズに応じて細孔径を適切に制御することによって、安定した速度で被担持香料成分を徐放させることが可能であり、徐放速度を制御するために一般に使用されている添加物の使用量を減らすことができると期待される。加えて、細孔特性等の品質再現性が高いので、徐放量や徐放速度の振れ幅が非常に問題となる高機能香料等の分野においても、安全性が高く品質が安定した徐放性香料製品を提供することが可能となる。 The sustained release fragrance carrier of the present invention has a sharper pore distribution and more precise control of the pore diameter than conventional sustained release fragrance carriers such as silica gel. Therefore, when used in sustained-release fragrances, the pore diameter can be precisely controlled according to the molecular size of various substances (supported components) to be supported in the pores. Wide range of choices for molecular size. In addition, by appropriately controlling the pore diameter according to the molecular size of various fragrance substances (supported components) to be supported in the pores, it is possible to release the supported fragrance components at a stable rate, It is expected that the amount of additives commonly used to control the sustained release rate can be reduced. In addition, since the reproducibility of quality such as pore characteristics is high, even in the field of high-performance fragrances where the controlled release amount and the fluctuation range of the controlled release rate are extremely problematic, the controlled release with high safety and stable quality Perfume products can be provided.
また、本発明の徐放性香料担体は、非常に高純度である上に、細孔壁が比較的厚く、シロキサン結合角の歪みが少ない均質で安定な構造を有するので、過酷な使用条件においても細孔特性等の物性変化が少ないという特徴を有する。従って、従来のシリカゲル等の徐放性香料担体と比較して、耐熱性や耐水性等の各種物性に優れているともに、農薬などの長期にわたる使用条件下や、高分子材料への添加時における高温成形加工等の過酷な条件下で使用した場合、或いは、反応性が高く担体を劣化させ易い被担持香料成分等と使用した場合でも、これらの各種物性が安定して維持されるものと考えられる。また、非常に高純度であることから、被担持香料成分に対して不要な活性を示すことが無く、各種香料成分を安定に担持できるものと期待される。 In addition, the sustained-release fragrance carrier of the present invention has a homogeneous and stable structure with very high purity, relatively small pore walls, and little distortion of siloxane bond angle. Is also characterized by little change in physical properties such as pore characteristics. Therefore, compared with conventional sustained-release fragrance carriers such as silica gel, it is excellent in various physical properties such as heat resistance and water resistance, as well as under long-term use conditions such as agricultural chemicals and when added to polymer materials. Even when used under severe conditions such as high-temperature molding, or when used with supported perfume ingredients that are highly reactive and easily deteriorate the carrier, these various physical properties are considered to be stably maintained. It is done. Moreover, since it is very high purity, it does not show unnecessary activity with respect to a to-be-supported fragrance component, and it is expected that various fragrance components can be stably supported.
更に、本発明の徐放性香料担体は、同程度の細孔径を有する従来の徐放性香料担体と比較して、比較的より高比表面積かつ高細孔容積という特徴を有するので、被担持香料成分の担持可能容量がより大きく、これらを多量に担持可能である上に、被担持香料成分の吸着能力がより優れている。これによって、被担持香料成分を長期にわたり安定して、経時的に徐々に放出することができると考えられる。加えて、非結晶性であるので、生産が容易であり価格も安く抑えられる。 Furthermore, the sustained-release fragrance carrier of the present invention has a relatively higher specific surface area and a higher pore volume than the conventional sustained-release fragrance carrier having the same pore diameter, The capacity of the perfume component to be supported is larger, a large amount of these can be supported, and the adsorption ability of the supported perfume component is more excellent. Thereby, it is considered that the supported flavor component can be stably released over time and gradually released over time. In addition, since it is non-crystalline, production is easy and the price can be kept low.
以上列挙した各種の利点を有することから、本発明の徐放性香料担体は、食品、化粧品、防虫剤、繊維、インク等様々な産業分野に供与され得る香料を被担持成分として担持させることにより、これらの香料成分を貯留すると共に経時的に徐々に放出させる徐放性香料として、好適に使用することができる。 Because of the various advantages listed above, the sustained-release fragrance carrier of the present invention supports the fragrances that can be provided in various industrial fields such as foods, cosmetics, insect repellents, fibers and inks as supported components. These fragrance components can be suitably used as sustained-release fragrances that store and gradually release them over time.
本発明の徐放性香料担体に各種香料成分等を担持させ、徐放性香料（本発明の徐放性香料）として使用する場合、その香料成分等は用途に応じて自由に選択することができる。具体例としては、脂肪族炭化水素、テルペン炭化水素、芳香族炭化水素等の炭化水素類；脂肪族アルコール、テルペンアルコール、芳香族アルコール等のアルコール類；脂肪族エーテル、芳香族エーテル等のエーテル類；脂肪族オキサイド、テルペン類のオキサイド等のオキサイド類；脂肪族アルデヒド、チオアルデヒド、芳香族アルデヒド等のアルデヒド類；脂肪族ケトン、テルペンケトン、水素化芳香族ケトン、脂肪族環状ケトン、非ベンゼン系芳香族ケトン、芳香族ケトン等のケトン類；アセタール類、ケタール類、フェノール類、フェノールエーテル類、脂肪酸、テルペン系カルボン酸、水素化芳香族カルボン酸、芳香族カルボン酸等の酸類；酸アマイド類、脂肪族ラクトン、環状ラクトン、テルペン系ラクトン、水素化芳香族ラクトン、芳香族ラクトン等のラクトン類、脂肪族エステル、フラン系のカルボン酸族エステル；脂肪族環状カルボン酸エステル、芳香族カルボン酸エステル等のエステル類；ニトロムスク類、ニトリル、アミン、ピリジン類、キノリン類、ピロール、インドール等の含窒素化合物などの合成香料；動物、植物からの天然香料；天然香料及び／又は合成香料を含む調合香料などを挙げることができる。これらは一種を単独で使用してもよく、二種以上を適宜併用してもよい。 In the case where the sustained-release fragrance carrier of the present invention is loaded with various fragrance components and used as a sustained-release fragrance (sustained-release fragrance of the present invention), the fragrance components and the like can be freely selected according to the application. it can. Specific examples include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons, and aromatic hydrocarbons; alcohols such as aliphatic alcohols, terpene alcohols, and aromatic alcohols; ethers such as aliphatic ethers and aromatic ethers. Oxides such as aliphatic oxides and terpene oxides; Aldehydes such as aliphatic aldehydes, thioaldehydes and aromatic aldehydes; Aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclic ketones, non-benzenes Ketones such as aromatic ketones and aromatic ketones; acids such as acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids; acid amides , Aliphatic lactone, cyclic lactone, terpene lactone, hydrogenated aromatic lacquer Lactones, aromatic lactones, etc., aliphatic esters, furan carboxylic acid esters; aliphatic cyclic carboxylic acid esters, aromatic carboxylic acid esters, etc .; nitromusks, nitriles, amines, pyridines, quinolines , Synthetic fragrances such as nitrogen-containing compounds such as pyrrole and indole; natural fragrances from animals and plants; blended fragrances containing natural fragrances and / or synthetic fragrances. These may be used individually by 1 type and may use 2 or more types together suitably.
香料成分をその官能性（機能）によって分類した場合、具体例としては、ペパーミント、プチグレイン、シトロネラ、スペアミント、ライム、マンダリンなどの気分をリフレッシュさせる香料、安息香酸、ゼラニウム、乳香、白檀、マジョラム、ラベンダー、ラバンディンなどのリラックスさせる香料、スィートオレンジ、ジャーマンカモマイル、ローマンカモマイル、リンデンなどの心地よい眠りを誘う香料、フェンネル、カルダモン、クラリーセージ、ブラックペッパー、ジュニパー、パーチュリー、ヒソップ、メリッサ、没薬、コリアンダー、アンジエリカルート、スターアニス、タラゴン、サッサフラスなどの強壮・活力あふれる気分にさせる香料、イランイラン、ビターオレンジ、ジャスミン、ダマクローズ、チャイナローズ、ブチバー、チュベローズ、バイオレットリーフ、アーモンドビター、バニラ、バルサムなどの気分を高めムードづくりに役立つ香料、バジル、ローズマリー、ローレルなどの集中力向上に役立つ香料、サイプレス、カンファー、ベルガモット、ユーカリ、ローズウッド、ニアウリ、シダーリーフ、シナモンリーフなどのエアーフレッシュ効果を有する香料、更にカラマスルート、オリスルート、グリーンハーブ、フローラルなどの香料が挙げられる。 When the perfume ingredients are classified according to their functionality (function), specific examples include perfume that refreshes the mood, such as peppermint, petit grain, citronella, spearmint, lime, mandarin, benzoic acid, geranium, frankincense, sandalwood, marjoram, Relaxing fragrances such as lavender, lavandin, sweet oranges, German camomile, roman camomile, linden and other fragrances that invite a good night's sleep Root, Star Anise, Tarragon, Sassafras, and other fragrances that make you feel vibrant and energetic, Ylang Ylang, Bitter Orange, Jasmine, Dama Close, China Rose, Blue Bars, tuberose, violet leaf, almond bitter, vanilla, balsam, etc. Examples include fragrances having an air fresh effect such as near cucumber, cedar leaf, cinnamon leaf, and fragrances such as caramas root, oris root, green herb, and floral.
また、これらのほかに、抗菌性等を有する機能性香料、例えばヒバオイル、月桃オイル、ペニーロイヤル、レモングラス、レモン、スパイスクラベンダー、ナツメグ、オレガノ、セージ、ジンジャー、セーボリー、タイム、オールスパイス、シダーウッド、シナモンバーク、クローブバッズ、カユブテ、パイン、ティートゥリー、カプサイシン、スクワレン、スクワラン、ヒアルロン酸化合物等を使用することで、芳香のほかに抗菌性等の機能も付与することができる。 In addition to these, functional fragrances having antibacterial properties such as hiba oil, moon peach oil, penny royal, lemongrass, lemon, spice lavender, nutmeg, oregano, sage, ginger, savory, thyme, allspice, By using cedarwood, cinnamon bark, clovebuds, cayubute, pine, tea tree, capsaicin, squalene, squalane, hyaluronic acid compounds, etc., functions such as antibacterial properties can be imparted in addition to fragrance.
更には、各種吸着剤として機能する成分を上記香料成分と同時に使用することで、芳香性のみならず、消臭性も新たな機能として付与することができる。
但し、上に列挙した香料成分はあくまでも一例であり、本発明の徐放性香料担体に担持させることのできる香料はこれらに限定されるものではない。
Furthermore, by using components that function as various adsorbents together with the above fragrance components, not only fragrance but also deodorizing properties can be imparted as a new function.
However, the fragrance components listed above are merely examples, and the fragrances that can be carried on the sustained-release fragrance carrier of the present invention are not limited to these.
上述の各種香料成分等が本発明の徐放性香料担体の細孔内に担持されている状態としては、固体状でも液体状でも良く、また、水や溶媒・分散媒等に溶解又は分散した溶液状・分散液状などの何れの状態であっても良い。更に、これらの香料成分等は、水溶性であっても油溶性であっても良い。 The state in which the above-mentioned various fragrance components are supported in the pores of the sustained-release fragrance carrier of the present invention may be solid or liquid, and dissolved or dispersed in water, a solvent, a dispersion medium, or the like. It may be in any state such as a solution or a dispersed liquid. Furthermore, these fragrance components may be water-soluble or oil-soluble.
これらの香料成分等の担持方法には特に制限はなく、任意の方法を用いることができる。担持方法の例としては以下のものが挙げられる。これらの方法は単独に用いても良く、適宜に組み合わせて用いても良い。 There is no restriction | limiting in particular in the carrying | supporting method of these fragrance | flavor components etc., Arbitrary methods can be used. Examples of the supporting method include the following. These methods may be used alone or in appropriate combinations.
ｉ）担持させる香料成分等を容器に密封し、加熱して機能性分子をガス化させ、本発明の徐放性香料担体をこのガス中に晒して、その細孔中に機能性分子を吸着させる方法。 i) Sealing the fragrance component to be supported in a container, heating to gasify the functional molecule, exposing the sustained-release fragrance carrier of the present invention to this gas, and adsorbing the functional molecule in the pores How to make.
ii）香料成分等を加熱して溶融させ、その溶融液中に本発明の徐放性香料担体を浸漬して香料等を含浸させる方法。 ii) A method in which a fragrance component or the like is heated and melted, and the sustained-release fragrance carrier of the present invention is immersed in the melt to impregnate the fragrance or the like.
iii）香料成分等を溶媒に溶解し、その溶液に本発明の徐放性香料担体を浸漬して細孔内に香料成分等を含浸させ、その後溶媒を蒸発させる方法。 iii) A method in which a fragrance component or the like is dissolved in a solvent, the sustained-release fragrance carrier of the present invention is immersed in the solution to impregnate the fragrance component or the like in pores, and then the solvent is evaporated.
iv）その他、本発明の徐放性香料担体と香料成分等とを適当な量比で混合した後にその混合物を香料成分等の融点以上に加熱する方法、香料成分等の原料物質を本発明の徐放性香料担体の細孔中に含浸させた後に、加熱等により細孔中で香料成分等を合成する方法等。 iv) In addition, after mixing the sustained-release fragrance carrier of the present invention and the fragrance component in an appropriate quantity ratio, the mixture is heated to the melting point of the fragrance component or the like. A method of synthesizing a fragrance component or the like in the pores by heating or the like after impregnating into the pores of the sustained release fragrance carrier.
以上のような含浸処理の後、更に、本発明の徐放性香料担体の表面を高分子膜やデキストリン等で覆うことにより、香料成分等の放出速度が一層遅くなるように調節することもできる。一方、以上のプロセスにより製造した徐放性香料の濃度が高すぎる場合には、これを粘土やシリカゲル等の安価な粉体やバインダで増量しても良い。 After the impregnation treatment as described above, the surface of the sustained-release perfume carrier of the present invention is further covered with a polymer film, dextrin, etc., so that the release rate of the perfume components and the like can be further adjusted. . On the other hand, when the concentration of the sustained-release fragrance produced by the above process is too high, it may be increased with an inexpensive powder or binder such as clay or silica gel.
更には、従来より徐放性香料の材料として用いられている各種高分子樹脂材料と併用してもよい。具体的に、例えば高分子樹脂材料中に香料を分散させた形態の徐放性香料へ応用する際には、先述の高分子樹脂材料（又はその溶液）に、香料とともに本発明のシリカゲルよりなる香料担体を分散させ、これをスプレードライ等の従来公知の方法によって微粒子化することで、徐放性香料を得ることができる。この際、本発明のシリカゲルよりなる徐放性香料担体は、その細孔特性等によって高分子樹脂材料（又はその溶液）中に均一に分散させることができるので、安定した品質の徐放性香料を得ることが可能となる。 Furthermore, you may use together with the various polymeric resin material conventionally used as a material of sustained release fragrance | flavor. Specifically, for example, when applied to a sustained-release fragrance in a form in which a fragrance is dispersed in a polymer resin material, the above-described polymer resin material (or a solution thereof) is made of the silica gel of the present invention together with the fragrance. A sustained-release fragrance can be obtained by dispersing a fragrance carrier and making it fine particles by a conventionally known method such as spray drying. At this time, the sustained-release fragrance carrier comprising the silica gel of the present invention can be uniformly dispersed in the polymer resin material (or solution thereof) due to its pore characteristics and the like, so that the sustained-release fragrance of stable quality can be obtained. Can be obtained.
こうして作製された本発明の徐放性香料の使用形態は特に限定されず、その目的に応じて、そのままの状態で、又は、他の徐放性香料の使用方法に倣い適宜な形状に成形されたり、通気・通水性の容器に封入されたりして、適宜使用される。 The use form of the sustained-release fragrance of the present invention produced in this way is not particularly limited, and depending on the purpose, it is molded as it is or according to the method of using other sustained-release fragrances. Or sealed in a ventilated / water-permeable container.
本発明の徐放性香料は、先述した利点を有する徐放性香料担体を用い、この細孔内に各種香料成分等の被担持成分を担持させているので、従来のシリカゲル等の徐放性香料担体を用いた従来の徐放性香料と比較して、被担持成分の徐放速度や徐放期間、徐放量の経時的変化等の各種徐放性能をより正確に制御することができる。また、従来の徐放性香料と比較して、より多くの被担持成分を徐放性香料担体に担持させることができるとともに、徐放性香料担体や被担持成分の変性や劣化が少ないので、長期にわたり安定した徐放効果が得られるものと考えられる。 The sustained-release fragrance of the present invention uses the sustained-release fragrance carrier having the advantages described above, and supports supported components such as various fragrance components in the pores. As compared with conventional sustained-release fragrances using a fragrance carrier, various sustained-release performances such as the sustained-release rate, sustained-release period, and time-dependent change of the sustained-release amount of the supported component can be controlled more accurately. In addition, as compared with the conventional sustained release fragrance, more sustained components can be supported on the sustained release fragrance carrier, and since the sustained release fragrance carrier and the supported components are less modified and deteriorated, It is considered that a stable sustained release effect can be obtained over a long period of time.
以下、本発明を実施例により詳細に説明するが、本発明はその要旨を逸脱しない範囲において、以下の実施例に制限されること無く、任意に変形して実施することができる。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention can be arbitrarily changed and implemented in the range which does not deviate from the summary, without being restrict | limited to a following example.
（１）徐放性香料担体の分析方法：
（１−１）細孔容積、比表面積：
カンタクローム社製ＡＳ−１にてＢＥＴ窒素吸着等温線を測定し、細孔容積、比表面積を求めた。具体的には細孔容積は相対圧Ｐ／Ｐ0＝０．９８のときの値を採用し、比表面積はＰ／Ｐ0＝０．１，０．２，０．３の３点の窒素吸着量よりＢＥＴ多点法を用いて算出した。また、ＢＪＨ法で細孔分布曲線及び最頻直径（Ｄmax）における微分細孔容積を求めた。測定する相対圧の各点の間隔は０．０２５とした。
(1) Analytical method of sustained release fragrance carrier:
(1-1) Pore volume, specific surface area:
The BET nitrogen adsorption isotherm was measured with AS-1 manufactured by Cantachrome, and the pore volume and specific surface area were determined. Specifically, the pore volume adopts a value when the relative pressure P / P 0 = 0.98, and the specific surface area is nitrogen at three points of P / P 0 = 0.1, 0.2, 0.3. It calculated using the BET multipoint method from the adsorption amount. Further, the pore distribution curve and the differential pore volume at the mode diameter (D max ) were determined by the BJH method. The interval between each point of the relative pressure to be measured was 0.025.
（１−２）粉末Ｘ線回折：
理学電機社製ＲＡＤ−ＲＢ装置を用い、ＣｕＫαを線源として測定を行なった。発散スリット１／２ｄｅｇ、散乱スリット１／２ｄｅｇ、受光スリット０．１５ｍｍとした。
(1-2) Powder X-ray diffraction:
Using a RAD-RB apparatus manufactured by Rigaku Corporation, measurement was performed using CuKα as a radiation source. The divergence slit was ½ deg, the scattering slit was ½ deg, and the light receiving slit was 0.15 mm.
（１−３）金属不純物の含有量：
試料２．５ｇにフッ酸を加えて加熱し、乾涸させたのち、水を加えて５０ｍｌとした。この水溶液を用いてＩＣＰ発光分析を行なった。なお、ナトリウム及びカリウムはフレーム炎光法で分析した。
(1-3) Content of metal impurities:
Hydrofluoric acid was added to 2.5 g of the sample and heated to dryness, and then water was added to make 50 ml. ICP emission analysis was performed using this aqueous solution. Sodium and potassium were analyzed by flame flame light method.
（１−４）固体Ｓｉ−ＮＭＲ測定：
Ｂｒｕｋｅｒ社製固体ＮＭＲ装置（「ＭＳＬ３００」）を使用するとともに、共鳴周波数５９．２ＭＨｚ（７．０５テスラ）、７ｍｍのサンプルチューブを使用し、ＣＰ／ＭＡＳ（Cross Polarization / Magic Angle Spinning）プローブの条件で測定した。具体的な測定条件を下の表１に示す。
(1-4) Solid Si-NMR measurement:
Conditions of CP / MAS (Cross Polarization / Magic Angle Spinning) probe using a Bruker solid-state NMR device (“MSL300”), a resonance frequency of 59.2 MHz (7.05 Tesla), and a 7 mm sample tube Measured with Specific measurement conditions are shown in Table 1 below.
測定データの解析（Ｑ4ピーク位置の決定）は、ピーク分割によって各ピークを抽出する方法で行なう。具体的には、ガウス関数を使用した波形分離解析を行なう。この解析には、サーモガラテック（Thermogalatic)社製の波形処理ソフト「ＧＲＡＭＳ３８６」を使用することができる。 Analysis of measured data (Q 4 Determination of the peak position) is performed by a method of extracting each peak by the peak division. Specifically, waveform separation analysis using a Gaussian function is performed. For this analysis, waveform processing software “GRAMS386” manufactured by Thermogalatic can be used.
（２）徐放性香料担体の製造及び評価：
・実施例１〜３：
ガラス製で、上部に大気開放の水冷コンデンサが取り付けてある５Ｌセパラブルフラスコ（ジャケット付き）に、純水１０００ｇを仕込んだ。１００ｒｐｍで撹拌しながら、これにテトラメトキシシラン１４００ｇを３分間かけて仕込んだ。水／テトラメトキシシランのモル比は約６である。セパラブルフラスコのジャケットには５０℃の温水を通水した。引き続き撹拌を継続し、内容物が沸点に到達した時点で、撹拌を停止した。引き続き約０．５時間、ジャケットに５０℃の温水を通水して生成したゾルをゲル化させた。その後、速やかにゲルを取り出し、目開き６００ミクロンのナイロン製網を通してゲルを粉砕し、粉体状のウェットゲル（シリカヒドロゲル）を得た。このヒドロゲル４５０ｇと純水４５０ｇを１Ｌのガラス製オートクレーブに仕込み、実施例１については１３０℃×３Ｈｒ、実施例２については１５０℃×３Ｈｒ、実施例３については２００℃×３Ｈｒの条件で、それぞれ水熱処理を実施した。所定時間水熱処理した後、Ｎｏ．５Ａ濾紙で濾過し、得られたシリカゲルを水洗することなく１００℃で恒量となるまで減圧乾燥した。乾燥後、乳鉢にて粉砕し、篩により分級して、いずれも平均粒径１０μｍの粉体のシリカゲルを得た。これらをそれぞれ実施例１〜３の徐放性香料担体とする。
(2) Production and evaluation of sustained release fragrance carrier:
-Examples 1-3:
1000 g of pure water was charged into a 5 L separable flask (with a jacket) made of glass and fitted with a water-cooled condenser open to the atmosphere at the top. While stirring at 100 rpm, 1400 g of tetramethoxysilane was charged into this over 3 minutes. The water / tetramethoxysilane molar ratio is about 6. Warm water at 50 ° C. was passed through the jacket of the separable flask. Stirring was continued, and the stirring was stopped when the contents reached the boiling point. Subsequently, hot water of 50 ° C. was passed through the jacket for about 0.5 hour to gel the sol produced. Thereafter, the gel was quickly taken out and pulverized through a nylon net having an opening of 600 microns to obtain a powdery wet gel (silica hydrogel). 450 g of this hydrogel and 450 g of pure water were charged into a 1 L glass autoclave. The conditions were 130 ° C. × 3 Hr for Example 1, 150 ° C. × 3 Hr for Example 2, and 200 ° C. × 3 Hr for Example 3. Hydrothermal treatment was performed. After hydrothermal treatment for a predetermined time, no. It filtered with 5A filter paper, and it dried under reduced pressure until it became constant weight at 100 degreeC, without washing the obtained silica gel with water. After drying, the mixture was pulverized in a mortar and classified by a sieve to obtain a silica gel powder having an average particle size of 10 μm. These are used as the sustained release fragrance carriers of Examples 1 to 3, respectively.
得られた実施例１〜３の徐放性香料担体の諸物性を表２に示す。何れのシリカゲルにおいても、周期的構造による低角度側（２θ≦５ｄｅｇ）のピークは認められない。なお、実施例１〜３の徐放性香料担体の不純物金属含有率は、何れについても、ナトリウム０．２ｐｐｍ、カリウム０．１ｐｐｍ、カルシウム０．２ｐｐｍであり、その他の金属は検出されなかった。また、固体Ｓｉ−ＮＭＲのＱ4ピークのケミカルシフトの値δは、いずれも前述した式（Ｉ）の左辺｛−０．０７０５×（Ｄmax）−１１０．３６｝で計算される値より小さな値（よりマイナス側に存在する値）となった。 Table 2 shows various physical properties of the obtained sustained release fragrance carriers of Examples 1 to 3. In any silica gel, no peak on the low angle side (2θ ≦ 5 deg) due to the periodic structure is observed. In addition, the impurity metal content rate of the sustained release fragrance | flavor carrier of Examples 1-3 is 0.2 ppm of sodium, 0.1 ppm of potassium, and 0.2 ppm of calcium in any case, and other metals were not detected. In addition, the chemical shift value δ of the Q 4 peak of solid-state Si-NMR is smaller than the value calculated by the left side {−0.0705 × (D max ) −11.36} of the above-described formula (I). It became a value (a value existing on the more negative side).
・参考例１，２：
富士シリシア化学（株）製のシリカゲルＣＡＲＩＡＣＴ Ｇ−６を参考例１の徐放性香料担体として、同ＣＡＲＩＡＣＴ Ｇ−１０を参考例２の徐放性香料担体として用いた。それらの諸物性を下の表２に示す。粉末Ｘ線回折図によれば、参考例１及び２の何れの徐放性香料担体についても、周期的構造による低角度側のピークは認められない。また、固体Ｓｉ−ＮＭＲのＱ4ピークのケミカルシフトの値δは、参考例１及び２の何れの徐放性香料担体も、実施例１〜３のいずれの徐放性香料担体より大きく、且つ前述した式（Ｉ）の左辺｛−０．０７０５×（Ｄmax）−１１０．３６｝より計算される値より大きな値（よりプラス側に存在する値）となった。すなわち、参考例１及び２の徐放性香料担体は、実施例１〜３の徐放性香料担体と比べて、その構造に歪みが多く、物性変化を受け易いものと判断される。
Reference examples 1 and 2:
Silica gel CARIACT G-6 manufactured by Fuji Silysia Chemical Co., Ltd. was used as the sustained release fragrance carrier of Reference Example 1, and the same CARIACT G-10 was used as the sustained release fragrance carrier of Reference Example 2. Their physical properties are shown in Table 2 below. According to the powder X-ray diffraction diagram, no peak on the low angle side due to the periodic structure is observed in any of the sustained release fragrance carriers of Reference Examples 1 and 2. Further, the chemical shift value δ of the Q 4 peak of solid Si-NMR is larger than any of the sustained-release fragrance carriers of Examples 1 to 2 in any of Reference Examples 1 and 2, and The value was larger than the value calculated from {−0.0705 × (D max ) −11.36} on the left side of the formula (I) described above (a value existing on the plus side). That is, it is judged that the sustained-release fragrance carriers of Reference Examples 1 and 2 are more distorted in structure than the sustained-release fragrance carriers of Examples 1 to 3, and are susceptible to changes in physical properties.
・徐放性香料担体の水中熱安定性試験：
実施例１〜３並びに参考例１及び２の徐放性香料担体に、各々純水を加えて４０重量％のスラリーを調製した。容積６０ｍｌのステンレススチール製のミクロボンベに、上記で調製したスラリー約４０ｍｌを入れて密封し、２８０±１℃のオイルバス中に３日間浸漬した。ミクロボンベからスラリーの一部を抜出し、５Ａ濾紙で濾過した。濾滓は１００℃で５時間真空乾燥した。この試料について比表面積を測定した結果を表２及び表３に示す。実施例１〜３の徐放性香料担体は、参考例１及び２の徐放性香料担体に比べて、比表面積の減少が少なく、水熱安定性に優れていた。
・ Underwater thermal stability test of sustained release fragrance carrier:
Pure water was added to each of the sustained-release fragrance carriers of Examples 1 to 3 and Reference Examples 1 and 2 to prepare a 40 wt% slurry. About 40 ml of the slurry prepared above was sealed in a stainless steel microbomb having a volume of 60 ml, and immersed in an oil bath at 280 ± 1 ° C. for 3 days. A part of the slurry was extracted from the microbomb and filtered through 5A filter paper. The filter cake was vacuum dried at 100 ° C. for 5 hours. The results of measuring the specific surface area of this sample are shown in Tables 2 and 3. The sustained release fragrance carriers of Examples 1 to 3 had less reduction in specific surface area and excellent hydrothermal stability than the sustained release fragrance carriers of Reference Examples 1 and 2.
表２の結果から、実施例１〜３の徐放性香料担体は、参考例１及び２に代表される従来の徐放性香料担体と比較して、よりシャープで制御された細孔分布を有していることが分かる。従って、徐放剤に使用した場合に、細孔内に担持させる各種物質（被担持香料成分）の分子サイズに応じて細孔径を適切に制御することによって、被担持香料成分を安定した任意の速度で徐放させることが可能であると考えられる。 From the results in Table 2, the sustained-release fragrance carriers of Examples 1 to 3 have a sharper and more controlled pore distribution than the conventional sustained-release fragrance carriers represented by Reference Examples 1 and 2. You can see that Therefore, when used as a sustained-release agent, by appropriately controlling the pore diameter according to the molecular size of various substances (supported fragrance components) to be supported in the pores, the supported fragrance components can be stabilized arbitrarily. It is thought that it can be released slowly at a speed.
また、実施例１〜３の徐放性香料担体は、参考例１及び２に代表される従来の徐放性香料担体と比較して、金属不純物が少なく遥かに高純度であるとともに、シロキサン結合角の歪みが少ない均質で安定な構造を有していることから、反応性が低く、耐熱性や耐水性等に優れており、且つ、過酷な使用条件においても細孔特性等の物性変化が少ないことが分かる。従って、徐放剤に使用した場合に、被担持香料成分に対して不要な活性を示すことが無く、各種薬剤等を安定に担持できるとともに、活性の高い被担持香料成分と共に用いても、変性や劣化が生じ難いものと考えられる。 In addition, the sustained-release fragrance carriers of Examples 1 to 3 are much more pure and contain less metal impurities than the conventional sustained-release fragrance carriers represented by Reference Examples 1 and 2, and have a siloxane bond. Because it has a homogeneous and stable structure with little angular distortion, it has low reactivity, excellent heat resistance, water resistance, etc., and changes in physical properties such as pore characteristics even under severe use conditions I understand that there are few. Therefore, when used as a sustained release agent, it does not exhibit unnecessary activity with respect to the supported fragrance component, and can stably carry various drugs, etc. It is considered that deterioration is difficult to occur.
従って、実施例１〜３の徐放性香料担体は、各種香料等を被担持成分として担持させ徐放性香料として使用した場合に、参考例１及び２に代表される従来の徐放性香料担体を用いた徐放性香料と比較して、より優れた徐放性能を得ることができるものと推測される。 Accordingly, the sustained-release fragrance carriers of Examples 1 to 3 are conventional sustained-release fragrances represented by Reference Examples 1 and 2 when various fragrances are supported as supported components and used as sustained-release fragrances. It is presumed that superior sustained release performance can be obtained as compared with sustained release fragrances using a carrier.
なお、実施例１〜３の徐放性香料担体は粉砕された破砕状の粒子として得られたが、公知の成形技術により他の形状（例えば球状，錠剤状，押出品，ペレット品等）に成形しても良い。 In addition, although the sustained release fragrance carriers of Examples 1 to 3 were obtained as pulverized crushed particles, they were formed into other shapes (for example, spherical, tablet-like, extruded products, pellet products, etc.) by a known molding technique. It may be molded.
（３）徐放性香料の製造：
実施例１〜３の徐放性香料担体は、種々の機能や作用を持つ化学物質（香料）を担持させることにより、これらの香料を貯留すると共に経時的に徐々に放出させる徐放性香料（実施例１〜３の徐放性香料）として使用することができる。担持させる香料成分の種類、被担持時の状態、香料を担持させる手法については、上に詳述した通りである。
(3) Production of sustained release fragrance:
The sustained-release fragrance carriers of Examples 1 to 3 have sustained release fragrances that store chemicals (fragrances) having various functions and actions and store these fragrances and gradually release them over time. It can be used as a sustained release fragrance of Examples 1 to 3. The kind of the fragrance component to be supported, the state when being supported, and the method for supporting the fragrance are as described in detail above.
具体例として、実施例１の徐放性香料担体に、シナモン様香料の一種である桂皮酸を含浸させて、徐放性香料を作製した。まず、上記桂皮酸をアセトンに約１０重量％の濃度となるよう溶解し、この溶液５０ｍｌに実施例１の徐放性香料担体１０ｇを添加して攪拌した後、濾過してアセトンを乾燥除去し、桂皮酸担持シリカゲル（実施例１の徐放性香料）を得た。桂皮酸の担持前に対する担持後のシリカゲルの重量増分を測定し、これを基に実施例１の徐放性香料の桂皮酸含浸量を求めたところ、８重量％であった。 As a specific example, a sustained release fragrance was prepared by impregnating the sustained release fragrance carrier of Example 1 with cinnamic acid, which is a kind of cinnamon-like fragrance. First, the cinnamic acid was dissolved in acetone to a concentration of about 10% by weight, and 10 g of the sustained-release fragrance carrier of Example 1 was added to 50 ml of this solution and stirred, followed by filtration to remove the acetone by drying. Then, cinnamic acid-supporting silica gel (sustained release fragrance of Example 1) was obtained. When the weight increment of the silica gel after loading with respect to the cinnamic acid before loading was measured and the amount of the cinnamic acid impregnation of the sustained release fragrance of Example 1 was determined based on this, it was 8% by weight.
（４）徐放性香料の性能評価：
実施例１〜３の徐放性香料の各種性能は、例えば以下の手法により評価することができる。
(4) Performance evaluation of sustained release fragrance:
Various performances of the sustained release fragrances of Examples 1 to 3 can be evaluated by, for example, the following methods.
＜香料成分担持量評価＞
担持される香料成分が有機物である場合には、担持前後の重量増分が目安となる他、熱重量分析法による重量減分を担持量の目安とする方法、担持された香料成分を溶媒等で抽出し、滴定法、吸光光度法、ガスクロマトグラフィー、液体クロマトグラフィー、赤外吸収分光法、ＮＭＲ等の手段で定量する方法、担持された香料成分を担持状態のまま滴定法、全炭素量分析法、各種分光分析法等により定量する方法などがある。
<Evaluation of amount of perfume ingredients>
When the supported fragrance component is an organic substance, in addition to the weight increment before and after loading, the weight loss by thermogravimetric analysis is used as a measure of loading, and the loaded fragrance component is removed with a solvent or the like. Extraction, titration method, absorptiometry, gas chromatography, liquid chromatography, infrared absorption spectroscopy, methods such as NMR spectroscopy, titration method, total carbon content analysis And methods for quantification by various spectroscopic methods.
＜徐放性能評価＞
香料成分が液体への溶出により徐放される系の簡易な評価法としては、香料成分を担持した徐放性香料をガラスカラム等に充填し、一定速度で水等の溶媒（実際の使用条件に類似した溶媒の種類、温度、ｐＨ等の条件を道宜選択する）を流通させ、溶出してくる香料成分の濃度を全炭素量分析法、滴定法、吸光光度法、ガスクロマトグラフィー、液体クロマトグラフィー、赤外吸収分光法、ＮＭＲ等の方法で経時的に追跡する方法や、香料成分を担持した徐放性香料をガラスビーカーやフラスコ中にて実際の使用条件に類似した環境の溶媒中に浸漬し、一定温度に保持して、溶媒中に溶出してくる香料成分の濃度を上記分析法にて経時的に追跡する方法などがある。
<Slow release performance evaluation>
As a simple evaluation method for a system in which a fragrance component is gradually released by elution into a liquid, a sustained-release fragrance carrying the fragrance component is filled in a glass column or the like, and a solvent such as water (actual use conditions) at a constant rate. (The type of solvent, temperature, pH, etc., which are similar to the above) are distributed appropriately, and the concentration of the fragrance components eluted is determined by total carbon analysis, titration method, absorptiometry, gas chromatography, liquid Chromatography, infrared absorption spectroscopy, NMR, and other methods for tracking over time, and sustained-release fragrances carrying fragrance components in a solvent in an environment similar to the actual use conditions in a glass beaker or flask There is a method in which the concentration of the fragrance component eluted in the solvent is traced over time by the above analysis method.
香料成分が揮発により徐放される系においては、徐放性香料の経時的な重量減を追跡する方法が最も簡便である他、上記の方法に準じる方法として、徐放性香料を液体の代わりに空気などの気体と接触させ、揮発した香料成分を含む気体を経時的にサンプリングして、その気体における香料成分の含有量をガスクロマトグラフィー等により分析する方法などがある。 In a system in which the fragrance component is gradually released by volatilization, the method of tracking the weight loss with time of the sustained-release fragrance is the simplest, and as a method according to the above method, the sustained-release fragrance is replaced with a liquid. There is a method of contacting a gas such as air with a gas, sampling a gas containing a volatilized fragrance component over time, and analyzing the content of the fragrance component in the gas by gas chromatography or the like.
これら徐放性香料に担持される香料成分の種類や使用形態は様々であるので、簡易評価が難しい場合には、徐放性香料を実際の使用条件に供し、その徐放性能の評価を各用途における実使用効果として直接観察する方法（人の鼻や口による官能評価、人の脳波の測定等によるリラクゼーション効果等の確認・評価、殺菌・抗菌性能の持続性、消臭効果の持続性）等を行なっても良い。これらの各種評価方法は、評価の目的や評価対象の徐放性香料の種類に応じて適宜選択される。 Since there are various kinds and usage forms of the fragrance components supported by these sustained-release fragrances, when simple evaluation is difficult, the sustained-release fragrance is subjected to actual use conditions, and the evaluation of the sustained-release performance is performed for each. Method of direct observation as actual use effect in application (sensory evaluation by human nose and mouth, confirmation / evaluation of relaxation effect by measuring human brain wave, etc., sustainability of bactericidal and antibacterial performance, sustainability of deodorizing effect) Etc. may be performed. These various evaluation methods are appropriately selected according to the purpose of the evaluation and the type of sustained-release fragrance to be evaluated.
実施例１〜３の徐放性香料は、先述した利点を有する実施例１〜３の徐放性香料担体を用い、この細孔内に各種の被担持香料成分を担持させているので、徐放速度や徐放期間、徐放量の経時的変化等の各種徐放性能について評価を行なった場合に、従来の徐放性香料、例えば参考例１及び２の徐放性香料担体を用いた徐放性香料と比較して、より制御された正確な徐放性能が得られると共に、その徐放性能が長期にわたって安定して得られると考えられる。 The sustained-release fragrances of Examples 1 to 3 use the sustained-release fragrance carrier of Examples 1 to 3 having the advantages described above, and various supported fragrance components are supported in the pores. When various sustained release performances such as release rate, sustained release period, time-dependent change in sustained release, etc. were evaluated, a sustained release fragrance such as the sustained release fragrance carriers of Reference Examples 1 and 2 was used. Compared with a release fragrance | flavor, while being able to obtain the exact controlled release performance more controlled, it is thought that the sustained release performance is obtained stably over a long period of time.
本発明の徐放性香料担体は、従来の徐放性香料担体と比較して、生産が容易且つ安価であり、被担持香料成分の種類や被担持成分分子の大きさに対する選択の幅が広く、より多量の被担持香料成分が担持可能である上に、純度が高いので担持する香料成分への悪影響が少ない。加えて、耐水性や耐熱性に優れており、しかも細孔特性等の各種物性が長期間にわたって安定して維持される。また、上記徐放性香料担体に香料成分を担持させて作製した本発明の徐放性香料は、従来の徐放性香料と比較して、徐放性能がより正確に制御可能であるとともに、長期にわたり安定した徐放効果が得られる。従って、本発明は従来の各種香料分野に好適に用いることができ、産業上の利用可能性は極めて高い。 The sustained-release fragrance carrier of the present invention is easier and cheaper to produce than the conventional sustained-release fragrance carrier, and has a wide range of choices for the type of supported fragrance component and the size of the supported component molecule. In addition, a larger amount of the perfume component to be supported can be supported, and since the purity is high, there is little adverse effect on the perfume component to be supported. In addition, it is excellent in water resistance and heat resistance, and various physical properties such as pore characteristics are stably maintained over a long period of time. In addition, the sustained release fragrance of the present invention produced by supporting the fragrance component on the sustained release fragrance carrier can be controlled more accurately as compared with the conventional sustained release fragrance, A stable sustained release effect can be obtained over a long period of time. Therefore, the present invention can be suitably used in various conventional fragrance fields, and the industrial applicability is extremely high.
Claims (5)
（ａ）細孔容積が０．０５ｍｌ／ｇ以上、３．０ｍｌ／ｇ以下であり、
（ｂ）比表面積が１００ｍ2／ｇ以上、１５００ｍ2／ｇ以下であり、
（ｃ）細孔の最頻直径（Ｄmax）が３５ｎｍ未満であり、
（ｄ）直径がＤmax±２０％の範囲内にある細孔の総容積が、全細孔の総容積の５０％以上であり、
（ｅ）非晶質であり、
（ｆ）金属不純物の総含有率が５００ｐｐｍ以下であり、且つ、
（ｇ）固体Ｓｉ−ＮＭＲでのＱ4ピークのケミカルシフトをδ（ｐｐｍ）とした場合に、δが下記式（Ｉ）を満足する
−０．０７０５×（Ｄmax）−１１０．３６＞δ ・・・式（Ｉ）
ことを特徴とする、徐放性香料担体。 A sustained-release fragrance carrier having silica gel and capable of gradual release of a fragrance carried in pores,
(A) The pore volume is 0.05 ml / g or more and 3.0 ml / g or less,
(B) The specific surface area is 100 m 2 / g or more and 1500 m 2 / g or less,
(C) the mode diameter (D max ) of the pores is less than 35 nm,
(D) the total volume of pores having a diameter in the range of D max ± 20% is 50% or more of the total volume of all pores;
(E) is amorphous,
(F) the total content of metal impurities is 500 ppm or less, and
(G) When the chemical shift of the Q 4 peak in solid Si-NMR is δ (ppm), δ satisfies the following formula (I): −0.0705 × (D max ) −11.36> δ ... Formula (I)
A sustained release fragrance carrier characterized by the above.
ことを特徴とする、請求項１記載の徐放性香料担体。 The sustained-release fragrance carrier according to claim 1, wherein the differential pore volume at the mode diameter ( Dmax ) of the pore is 2 ml / g or more and 20 ml / g or less.
ことを特徴とする、請求項１又は請求項２に記載の徐放性香料担体。 The sustained-release fragrance carrier according to claim 1 or 2, wherein a Q 4 / Q 3 peak value in solid-state Si-NMR measurement is 1.3 or more.
ことを特徴とする、請求項１〜３の何れか一項に記載の徐放性香料担体。 The sustained-release fragrance carrier according to any one of claims 1 to 3, which is produced through a step of hydrolyzing silicon alkoxide.
ことを特徴とする、徐放性香料。 A sustained-release fragrance, wherein a sustained-release fragrance component is supported in the pores of the sustained-release fragrance carrier according to any one of claims 1 to 4.
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| US8927026B2 (en) | 2011-04-07 | 2015-01-06 | The Procter & Gamble Company | Shampoo compositions with increased deposition of polyacrylate microcapsules |
| US8980292B2 (en) | 2011-04-07 | 2015-03-17 | The Procter & Gamble Company | Conditioner compositions with increased deposition of polyacrylate microcapsules |
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| US9162085B2 (en) | 2011-04-07 | 2015-10-20 | The Procter & Gamble Company | Personal cleansing compositions with increased deposition of polyacrylate microcapsules |
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| US11096875B2 (en) | 2010-04-28 | 2021-08-24 | The Procter & Gamble Company | Delivery particle |
| US9186642B2 (en) | 2010-04-28 | 2015-11-17 | The Procter & Gamble Company | Delivery particle |
| US10507257B2 (en) | 2010-12-27 | 2019-12-17 | The Hong Kong University Of Science And Technology | Inorganic gel for controlled releasing of fragrance and disinfectant |
| US10155060B2 (en) | 2010-12-27 | 2018-12-18 | The Hong Kong University Of Science And Technology | Inorganic gel for controlled releasing of fragrance and disinfectant |
| KR101457648B1 (en) | 2010-12-27 | 2014-10-31 | 더 홍콩 유니버시티 오브 사이언스 앤드 테크놀러지 | Inorganic gel for controlled releasing of fragrance and disinfectant |
| US10143632B2 (en) | 2011-04-07 | 2018-12-04 | The Procter And Gamble Company | Shampoo compositions with increased deposition of polyacrylate microcapsules |
| US9561169B2 (en) | 2011-04-07 | 2017-02-07 | The Procter & Gamble Company | Conditioner compositions with increased deposition of polyacrylate microcapsules |
| US9162085B2 (en) | 2011-04-07 | 2015-10-20 | The Procter & Gamble Company | Personal cleansing compositions with increased deposition of polyacrylate microcapsules |
| US8980292B2 (en) | 2011-04-07 | 2015-03-17 | The Procter & Gamble Company | Conditioner compositions with increased deposition of polyacrylate microcapsules |
| US8927026B2 (en) | 2011-04-07 | 2015-01-06 | The Procter & Gamble Company | Shampoo compositions with increased deposition of polyacrylate microcapsules |
| JP2015116334A (en) * | 2013-12-18 | 2015-06-25 | 花王株式会社 | Perfume application agent |
| WO2018184362A1 (en) * | 2017-04-07 | 2018-10-11 | 济南舜景医药科技有限公司 | Special sustained release salt for stuffing and preparation method therefor |
| FR3073147A1 (en) * | 2017-11-07 | 2019-05-10 | Carole Des Mazis | AROMATHERAPY COMPOSITION |
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