JP6017120B2 - Solid volatilization preparation and composition used therefor - Google Patents
Solid volatilization preparation and composition used therefor Download PDFInfo
- Publication number
- JP6017120B2 JP6017120B2 JP2011128808A JP2011128808A JP6017120B2 JP 6017120 B2 JP6017120 B2 JP 6017120B2 JP 2011128808 A JP2011128808 A JP 2011128808A JP 2011128808 A JP2011128808 A JP 2011128808A JP 6017120 B2 JP6017120 B2 JP 6017120B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- volatile
- volatilization
- surfactant
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000002360 preparation method Methods 0.000 title claims description 47
- 239000000203 mixture Substances 0.000 title claims description 45
- 239000007787 solid Substances 0.000 title claims description 23
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- 239000011347 resin Substances 0.000 claims description 55
- -1 polyoxyethylene Polymers 0.000 claims description 40
- 239000003205 fragrance Substances 0.000 claims description 35
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- 239000004094 surface-active agent Substances 0.000 claims description 25
- 229920005862 polyol Polymers 0.000 claims description 24
- 150000003077 polyols Chemical class 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
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- 239000002250 absorbent Substances 0.000 claims description 19
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- 239000003814 drug Substances 0.000 claims description 15
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- 239000004480 active ingredient Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000005215 alkyl ethers Chemical class 0.000 claims description 10
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Landscapes
- Catching Or Destruction (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、固形揮散製剤に関し、更に詳細には、固形の水性ゲルを用い、香料、殺虫成分、防虫成分等を揮散することができ、かつ揮散に伴うゲルの白濁が抑制された固形揮散製剤およびこれに用いる組成物に関する。 The present invention relates to a solid volatilization preparation, and more specifically, a solid volatilization preparation that can volatilize a fragrance, an insecticidal component, an insecticidal component, and the like using a solid aqueous gel and suppresses the cloudiness of the gel accompanying volatilization. And a composition used therefor.
水性ゲルを用いた製剤(以下、「水性ゲル製剤」ということもある)は、容器から液がこぼれる心配がないことや意匠性に優れるという点から据え置き型の芳香剤などに幅広く取り入れられている。特に、球状にした吸水性樹脂に、香料などの芳香成分を溶解ないし分散させた溶液を吸収させて調製する水性ゲル芳香剤は、ゲルの表面積が大きいため、芳香成分の揮発が促進され、広い空間においても十分に強い香りを充満させることができるとともに、透明なビーズにより意匠性が高いということで広く受け入れられている(特許文献1ないし3等)。 Formulations that use aqueous gels (hereinafter sometimes referred to as “aqueous gel formulations”) are widely used in stationary fragrances because they do not have to worry about liquid spilling from the container and are superior in design. . In particular, an aqueous gel fragrance prepared by absorbing a solution in which a fragrance component such as a fragrance is dissolved or dispersed in a spherical water-absorbent resin has a large surface area of the gel. It can be filled with a sufficiently strong fragrance even in a space, and is widely accepted for its high designability due to transparent beads (Patent Documents 1 to 3, etc.).
上記の水性ゲル製剤の調製に用いられ、香料などの芳香成分を分散した溶液を吸収する吸水性樹脂は、親水性ポリマーを架橋して調製された架橋型吸水性樹脂である。このような水性ゲル製剤に使用される架橋型吸水性樹脂としては、アクリルアミド−アクリル酸ナトリウム共重合体を含む架橋型吸水性樹脂、ノニオン型ポリオキシアルキレンオキシドを含む架橋型吸水性樹脂、イソブチレン−無水マレイン酸共重合体を含む架橋型吸水性樹脂、ポリアクリル酸(塩)を含む架橋型吸水性樹脂などが知られており、これらの架橋型吸水性樹脂は非常に安価で汎用性に優れるため幅広く使用されている。 The water-absorbing resin that is used for the preparation of the aqueous gel preparation and absorbs a solution in which an aromatic component such as a fragrance is dispersed is a cross-linked water-absorbing resin prepared by cross-linking a hydrophilic polymer. Examples of the crosslinked water-absorbing resin used in such an aqueous gel preparation include a crosslinked water-absorbing resin containing an acrylamide-sodium acrylate copolymer, a crosslinked water-absorbing resin containing a nonionic polyoxyalkylene oxide, and isobutylene- Known are cross-linked water-absorbing resins containing maleic anhydride copolymers, cross-linked water-absorbing resins containing polyacrylic acid (salt), and the like. These cross-linked water-absorbing resins are very inexpensive and have excellent versatility. Because it is widely used.
しかしながら、これらの吸水性樹脂を使用して調製したゲル芳香剤は、上面を開口した容器に入れて使用した場合、含有された成分が揮散するに従い、透明であった吸水性樹脂が白濁してしまうという傾向がある。この白濁した吸水性樹脂は、揮散に従いその数が増加するため、意匠性の点で大きくマイナスになるという問題があった。 However, gel fragrances prepared using these water-absorbing resins, when used in a container having an open top, the transparent water-absorbing resin becomes cloudy as the contained components volatilize. There is a tendency to end up. The number of white turbid water-absorbing resins increases with volatilization, and thus has a problem that it is greatly negative in terms of design.
特に香料等の揮散性成分の配合割合を多くしたり、一度揮散させて収縮した吸収性樹脂に再度芳香液等を加えて再生させるようにした場合には、白濁は多く発生してしまうという問題があった。この白濁の問題を避けるためには、香料の配合量を少なく抑える必要があるが、そうすると水性ゲル製剤中に配合する香料が減り、十分な芳香効果が得られなくなってしまうという別の問題も生じる。 In particular, when increasing the blending ratio of volatile components such as fragrances or regenerating by adding aromatic liquid again to the absorbent resin that has been volatilized once and contracted, a lot of cloudiness will occur was there. In order to avoid this problem of white turbidity, it is necessary to keep the blending amount of the fragrance small, but this causes another problem that the fragrance blended in the aqueous gel preparation is reduced and the sufficient fragrance effect cannot be obtained. .
したがって、吸水性樹脂で形成される水性ゲルからの成分の揮散に伴うゲルの白濁を抑制することのできる水性ゲル製剤の開発が望まれていた。 Therefore, development of the aqueous gel formulation which can suppress the cloudiness of the gel accompanying the volatilization of the component from the aqueous gel formed with a water absorbing resin was desired.
本発明者らは、上記問題に鑑み、水性ゲル製剤の配合について鋭意研究を行なっていたところ、揮発性溶剤とポリオールを組み合わせ添加することにより、成分の揮散に伴うゲルの白濁を抑制できることを見出し、本発明に至った。 In view of the above problems, the present inventors have been diligently studying the formulation of an aqueous gel preparation, and found that by adding a combination of a volatile solvent and a polyol, the cloudiness of the gel accompanying the volatilization of the components can be suppressed. The present invention has been reached.
すなわち本発明は、揮散性油性有効成分、界面活性剤、揮発性溶剤、ポリオール及び水を含有する揮散製剤組成物を吸水性樹脂粒子に吸液させてなる固形揮散製剤である。 That is, this invention is a solid volatilization formulation formed by making a water absorbing resin particle absorb the volatilization formulation composition containing a volatile oily active ingredient, surfactant, a volatile solvent, a polyol, and water.
また本発明は、揮散性油性有効成分、界面活性剤、揮発性溶剤、ポリオール及び水を含有する揮散製剤組成物である。 Moreover, this invention is a volatilization formulation composition containing a volatile oily active ingredient, surfactant, a volatile solvent, a polyol, and water.
更に本発明は、揮散性油性有効成分、界面活性剤、揮発性溶剤、ポリオール及び水を含有する揮散製剤組成物と、吸水性樹脂粒子とを組みあわせてなる固形揮散製剤用キットである。 Furthermore, this invention is a kit for solid volatilization preparations which combines a volatilization formulation composition containing a volatile oily active ingredient, a surfactant, a volatile solvent, a polyol and water, and water-absorbent resin particles.
本発明の固形揮散製剤は、これに使用する揮散製剤組成物中に、揮発性溶剤とポリオールとを必須成分として配合する結果、揮散性油性有効成分を含む溶液を吸水性樹脂粒子中に吸収させ、ゲルとして使用した場合に揮散に伴うゲルの白濁を抑制することが可能である。従って、特に揮散性油性有効成分の配合割合を多くした場合や、一旦揮散性油性有効成分を揮散してしまい、収縮した水性ゲルに再度揮散製剤組成物を加えて再生させるような場合であっても、揮散に伴うゲルの白濁の発生を抑制できる。 The solid volatilization preparation of the present invention has a solution containing a volatile oily active ingredient absorbed in the water-absorbent resin particles as a result of blending a volatile solvent and a polyol as essential components in the volatilization preparation composition used therein. When used as a gel, it is possible to suppress the cloudiness of the gel accompanying volatilization. Therefore, especially when the blending ratio of the volatile oily active ingredient is increased, or when the volatile oily active ingredient is once volatilized, the volatilized pharmaceutical composition is added again to the contracted aqueous gel and regenerated. Moreover, generation | occurrence | production of the cloudiness of the gel accompanying volatilization can be suppressed.
したがって、本発明によれば、十分な揮散効果を発揮できるとともに意匠性にも優れた、固形揮散製剤を提供することができる。 Therefore, according to this invention, the solid volatilization formulation which can exhibit sufficient volatilization effect and was excellent also in the designability can be provided.
本発明の固形揮散製剤(以下、「揮散製剤」と略称する)は、揮散性油性有効成分、界面活性剤、揮発性溶剤、ポリオール及び水を含有する溶液状の揮散製剤組成物を、吸水性樹脂粒子に吸液させたものである。 The solid volatile formulation of the present invention (hereinafter abbreviated as “volatile formulation”) is a solution-type volatile formulation composition containing a volatile oily active ingredient, a surfactant, a volatile solvent, a polyol and water. The liquid is absorbed by resin particles.
本発明の揮散製剤において使用される揮散性油性有効成分(以下、「油性成分」と略称する)は、水性ゲル中から放出され、環境内でその効果を発揮するものである。具体的な油性成分の例としては、防虫・殺虫成分、害虫忌避成分、誘引成分、香料等を挙げることができるが、これに限られるものではない。なお、本明細書において、揮散性とは、常温(25℃)において、その蒸気圧が1.0×10−6mmHg以上である性質を意味する。 The volatile oily active ingredient (hereinafter abbreviated as “oily ingredient”) used in the volatile preparation of the present invention is released from the aqueous gel and exhibits its effect in the environment. Specific examples of the oil component include, but are not limited to, insect repellent / insecticide component, pest repellent component, attractant component, perfume and the like. In addition, in this specification, volatility means the property that the vapor pressure is 1.0 * 10 < -6 > mmHg or more in normal temperature (25 degreeC).
上記の油性成分のうち、防虫・殺虫成分としては、エンペントリン、トランスフルスリン、アレスリン、フェノトリン、エミネンス、プロフルトリン等のピレスロイド系防虫剤、パラジクロロベンゼン、ナフタリン、樟脳、2−フェノキシエタノール、ヒノキチオール、アリルイソチオシアネート等の揮散性防虫・殺虫剤が例示でき、これらの1種又は2種以上を混合して用いることができる。 Among the oily components described above, insecticides and insecticides include pyrethroid insecticides such as empentrin, transfluthrin, allethrin, phenothrin, eminence, profluthrin, paradichlorobenzene, naphthalene, camphor, 2-phenoxyethanol, hinokitiol, allyl isothiocyanate. Such volatile insecticides and insecticides can be exemplified, and one or more of these can be used in combination.
また、害虫忌避成分としては、ケロシン、クレオソート、クミンアルデヒド、1,8−シネオール等の揮散性忌避剤が例示でき、更に誘引成分としては、バジル、ローズマリー、パセリシードオイル若しくはラベンダーの抽出物若しくは精油又は1−オクテン−3−オール等の揮散性誘引剤が例示でき、これらはいずれもその1種又は2種以上を混合して用いることができる。 Examples of the pest repellent component include volatile repellents such as kerosene, creosote, cuminaldehyde, and 1,8-cineole. Further, as the attracting component, basil, rosemary, parsley seed oil or lavender extract Alternatively, volatile attractants such as essential oil or 1-octen-3-ol can be exemplified, and any of these can be used alone or in combination.
また香料としては、例えば、麝香、霊猫香、竜延香等の動物性香料、アビエス油、アクジョン油、アルモンド油、アンゲリカルート油、ページル油、ベルガモット油、パーチ油、ボアバローズ油、カヤブチ油、ガナンガ油、カプシカム油、キャラウェー油、カルダモン油、カシア油、セロリー油、シナモン油、シトロネラ油、コニャック油、コリアンダー油、クミン油、樟脳油、バジル油、エストゴラン油、ユーカリ油、フェンネル油、ガーリック油、ジンジャー油、グレープフルーツ油、ホップ油、レモン油、レモングラス油、ナツメグ油、マンダリン油、ハッカ油、オレンジ油、セージ油、スターアニス油、テレピン油、ローズマリー油、ユーカリ油、アニス油、ラベンダー油、クミン油、シナモン油、ヒバ油等の植物性香料を挙げることができる。この香料として、合成香料又は抽出香料等の人工香料を用いることもでき、例えば、ピネン、リモネン等の炭化水素系香料、リナロール、ゲラニオール、シトロネロール、メントール、ボルネオール、ベンジルアルコール、アニスアルコール、βフェネチルアルコール等のアルコール系香料、アネトール、オイゲノール等のフェノール系香料、n−ブチルアルデヒド、イソブチルアルデヒド、ヘキシルアルデヒド、シトラール、シトロネラール、ベンズアルデヒド、シンナミックアルデヒド等のアルデヒド系香料、カルボン、メントン、樟脳、アセトフェノン、イオノン等のケトン系香料、γ―ブチルラクトン、クマリン、シネオール等のラクトン系香料、オクチルアセテート、ベンジルアセテート、シンナミルアセテート、プロピオン酸ブチル、安息香酸メチル等のエステル系香料等が挙げられる。さらに、上記香料の2種以上を混合した調合香料も使用することができる。 Further, as the fragrance, for example, animal fragrance such as musk, ghost cat fragrance, Ryunobu fragrance, Abies oil, Akjon oil, Almond oil, Angelica root oil, paging oil, bergamot oil, perch oil, bore bellows oil, kayabuchi oil, Gananga oil, capsicum oil, caraway oil, cardamom oil, cassia oil, celery oil, cinnamon oil, citronella oil, cognac oil, coriander oil, cumin oil, camphor oil, basil oil, estgolan oil, eucalyptus oil, fennel oil, garlic Oil, ginger oil, grapefruit oil, hop oil, lemon oil, lemongrass oil, nutmeg oil, mandarin oil, peppermint oil, orange oil, sage oil, star anise oil, turpentine oil, rosemary oil, eucalyptus oil, anise oil, List plant flavors such as lavender oil, cumin oil, cinnamon oil, and hiba oil Can. As this fragrance, artificial fragrance such as synthetic fragrance or extracted fragrance can also be used. For example, hydrocarbon fragrance such as pinene and limonene, linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anis alcohol, β-phenethyl alcohol Alcohol flavors such as anetol, eugenol, etc., aldehyde flavors such as n-butyraldehyde, isobutyraldehyde, hexylaldehyde, citral, citronellal, benzaldehyde, cinnamaldehyde, carvone, menthone, camphor, acetophenone, ionone Ketone flavors such as γ-butyl lactone, coumarin, cineol and other lactone flavors, octyl acetate, benzyl acetate, cinnamyl acetate, butyrate propionate And ester-based fragrances such as methyl benzoate. Furthermore, the mixing | blending fragrance | flavor which mixed 2 or more types of the said fragrance | flavor can also be used.
上記の油性成分の配合量は、使用される後記界面活性剤の種類や、目的とする効果によって適宜変更できるが、一般には、吸水性樹脂粒子に吸液させる前の溶液状の揮散製剤組成物として、0.1〜10質量%(以下、単に「%」で示す)であり、好ましくは、0.1〜5%である。 The blending amount of the oil component can be appropriately changed depending on the type of surfactant used and the intended effect, but in general, a solution-like volatilized preparation composition before water-absorbing resin particles absorb the liquid. As 0.1 to 10% by mass (hereinafter, simply indicated as “%”), and preferably 0.1 to 5%.
本発明の固形揮散製剤において配合される界面活性剤としては、従来公知の、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤又は両性界面活性剤が挙げられ、これらのいずれをも用いることができ、その1種又は2種以上を混合して用いることもできる。 Examples of the surfactant to be blended in the solid volatilization preparation of the present invention include conventionally known anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. 1 type, or 2 or more types can also be mixed and used.
上記界面活性剤のうち、アニオン系界面活性剤としては、例えば、高級脂肪酸石けん、石けん用素地、金属石けん、N−アシル−L−グルタミン酸トリエタノールアミン、N−アシル−L−グルタミン酸ナトリウム、アルキル硫酸ナトリウム、アルキルスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテルリン酸、ポリオキシエチレンアルキルフェニルエーテルリン酸、ヤシ油脂肪酸メチルタウリンナトリウム(N−ココイル−N−メチルタウリンナトリウム)、ラウリル硫酸トリエタノールアミン、ラウリル硫酸ナトリウム、ラウロイルサルコシンナトリウム、ラウロイルメチルβ−アラニンナトリウム液、ラウロイルメチルタウリンナトリウム等の1種若しくは2種以上を混合して用いることができる。 Among the above surfactants, anionic surfactants include, for example, higher fatty acid soap, soap base, metal soap, N-acyl-L-glutamic acid triethanolamine, N-acyl-L-glutamic acid sodium, alkyl sulfate Sodium, sodium alkyl sulfonate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, coconut oil fatty acid methyl taurine sodium (N-cocoyl-N-methyl taurine sodium), One or more of triethanolamine lauryl sulfate, sodium lauryl sulfate, sodium lauroyl sarcosine, sodium lauroylmethyl β-alanine solution, sodium lauroylmethyl taurine, etc. Combined and can be used.
また、カチオン系界面活性剤としては、エチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム、塩化アルキルトリメチルアンモニウム、塩化ジアルキルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化ステアリルジメチルベンジルアンモニウム、塩化ステアリルトリメチルアンモニウム、塩化ベンザルコニウム、塩化ベンゼトニウム等の1種又は2種以上を混合して用いることができる。 Examples of the cationic surfactant include ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearyltrimethylammonium chloride, benzalkco chloride. One kind or a mixture of two or more kinds such as nium and benzethonium chloride can be used.
更にノニオン系界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレン硬化ひまし油エーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレンアルキルアミンエーテル、脂肪酸アルカノールアミド、第3級アミンオキサイド等が挙げられる。このポリオキシエチレンアルキルエーテルはポリオキシエチレン鎖が3から18好ましくは7から12であり、アルキル鎖は直鎖または分岐のどちらでも良く、アルキル鎖長は8〜22好ましくは12〜14である。また、前記脂肪酸アルカノールアミドは、椰子油脂肪酸、ステアリン酸、ラウリン酸のモノエタノールアミド、ジエタノールアミド等が挙げられ、第3級アミンオキサイドとしては、ラウリルジメチルアミンオキサイド、椰子油脂肪酸ジメチルアミンオキサイド、ラウロイルアミノプロピルジメチルアミンオキサイド、オクチルジメチルアミンオキサイド、ミリスチルジメチルアミンオキサイド等が挙げられる。 Further, nonionic surfactants include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylphenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid. Examples thereof include esters, sucrose fatty acid esters, glycerin fatty acid esters, polyoxyethylene polyoxypropylene block polymers, polyoxyethylene alkylamine ethers, fatty acid alkanolamides, and tertiary amine oxides. In this polyoxyethylene alkyl ether, the polyoxyethylene chain has 3 to 18, preferably 7 to 12, the alkyl chain may be either linear or branched, and the alkyl chain length is 8 to 22, preferably 12 to 14. Examples of the fatty acid alkanolamide include coconut oil fatty acid, stearic acid, monoethanolamide of lauric acid, diethanolamide and the like, and tertiary amine oxides include lauryl dimethylamine oxide, coconut oil fatty acid dimethylamine oxide, lauroyl. Aminopropyl dimethylamine oxide, octyl dimethylamine oxide, myristyl dimethylamine oxide, etc. are mentioned.
更にまた、両性界面活性剤としては、2−アルキル−N−カルボキシメチル−N−ヒドロキシエチルイミダゾリニウムベタイン、塩酸アルキルジアミノエチルグリシン液、ラウリルジメチルアミノ酢酸ベタイン等の1又は2種以上を混合して用いることができる。 Furthermore, as the amphoteric surfactant, one or more kinds of 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyldiaminoethylglycine hydrochloride, lauryldimethylaminoacetic acid betaine, etc. are mixed. Can be used.
上記した界面活性剤のうち、油性成分に対する可溶化力および揮散製剤組成物の吸水性樹脂粒子に対する吸液性の点でノニオン系界面活性剤を用いることが好ましい。更に、ノニオン系界面活性剤のうちでも特にポリオキシエチレンアルキルエーテル、ラウリルジメチルアミンオキサイドを用いることが好ましい。 Among the above-mentioned surfactants, it is preferable to use a nonionic surfactant in terms of solubilizing power with respect to oil components and liquid absorbability with respect to water-absorbent resin particles of the volatilized preparation composition. Furthermore, among nonionic surfactants, it is particularly preferable to use polyoxyethylene alkyl ether and lauryl dimethylamine oxide.
本発明の揮散製剤組成物における上記界面活性剤の配合量は、配合される油性成分の種類、量により適宜選択することができるが、一般的には、揮散製剤組成物中0.1〜30%であり、好ましくは、0.1〜20%、さらに好ましくは、0.1〜10%である。これより少ないと油性成分を安定に分散もしくは可溶化することが困難となる場合があり、揮散製剤組成物が白濁や相分離する場合がある。また、これより多いと揮散残渣が多くなり、揮散速度が低下したり、取替え時期が不明瞭になる虞や、水性ゲルの離水の原因にもなる場合がある。 Although the compounding quantity of the said surfactant in the volatilization pharmaceutical composition of this invention can be suitably selected with the kind and quantity of the oil-based component mix | blended, generally 0.1-30 in a volatilization pharmaceutical composition. %, Preferably 0.1 to 20%, and more preferably 0.1 to 10%. If the amount is less than this, it may be difficult to stably disperse or solubilize the oil component, and the volatilized preparation composition may become cloudy or phase separated. Moreover, when more than this, volatilization residue will increase, volatilization speed | velocity | rate may fall, it may become the cause of water separation of an aqueous gel, the possibility that the replacement time may become unclear.
本発明の揮散製剤組成物には、揮発性溶剤とポリオールが必須成分として配合される。このうち、揮発性溶剤としては、揮発性アルコールまたは揮発性グリコールエーテルが挙げられる。このうち、揮発性アルコールとしてはメタノール、エタノール、1−プロパノール、2−プロパノール等の低級アルコールが挙げられる、また、揮発性グリコールエーテルとしては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテルブチレングリコールモノメチルエーテル、3−メトキシ−1−ブタノール、3−メトキシ−3−メチル−1−ブタノール等を挙げることができる。これらの揮発性溶剤は単独で使用しても2種以上を混合して使用しても良い。 A volatile solvent and a polyol are blended as essential components in the volatilized preparation composition of the present invention. Among these, as a volatile solvent, volatile alcohol or volatile glycol ether is mentioned. Among these, volatile alcohols include lower alcohols such as methanol, ethanol, 1-propanol, and 2-propanol, and volatile glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether. , Propylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether butylene glycol monomethyl ether, 3-methoxy-1- Butanol, 3-methoxy-3-methyl-1-but Mention may be made of the Nord and the like. These volatile solvents may be used alone or in combination of two or more.
一方、ポリオールとしては、その分子構造の末端に少なくとも2個以上の水酸基を持つ化合物を挙げることができ好ましくは二価または三価のアルコールを挙げることができる。具体的なポリオールの例としては、エチレングリコール、プロピレングリコール、グリセリン、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、イソプレングリコール、へキシレングリコール、1,3−ブチレングリコール等を挙げることができ、概ね下記式で表されるものを含む。これらの揮発性溶剤は単独で使用しても2種以上を混合して使用しても良い。 On the other hand, examples of the polyol include compounds having at least two hydroxyl groups at the end of the molecular structure, and preferably include divalent or trivalent alcohols. Specific examples of polyols include ethylene glycol, propylene glycol, glycerin, diethylene glycol, dipropylene glycol, polyethylene glycol, isoprene glycol, hexylene glycol, 1,3-butylene glycol, and the like. Includes what is represented. These volatile solvents may be used alone or in combination of two or more.
上記揮散製剤組成物中における揮発性溶剤の配合量は、油性成分の種類、配合量や、界面活性剤の種類、配合量によって相違するが、一般的には、全組成物中0.1〜20%であり、好ましくは、0.1〜10%である。また、ポリオールの配合量は、一般的には0.1〜20%であり、好ましくは、1〜10%である。 The blending amount of the volatile solvent in the volatilized preparation composition is different depending on the type and blending amount of the oil component, the kind of the surfactant, and the blending amount, but is generally 0.1 to 0.1 in the total composition. 20%, preferably 0.1 to 10%. Moreover, generally the compounding quantity of a polyol is 0.1-20%, Preferably, it is 1-10%.
更に、本発明の揮散製剤組成物中での、上記揮発性溶剤とポリオールの配合割合は、特に制約されるものではないが、一般には、それらの重量比で、1:10ないし10:1であり、好ましくは、1:5ないし5:1、より好ましくは1:2ないし2:1である。ポリオールの比が、上記範囲より少ない場合は、 白濁抑制効果が充分発揮できなくなる虞や、揮散性油性有効成分の可溶化が不十分となる虞があるという問題が生じ、また、ポリオールの比が上記範囲より多い場合は、揮散残渣が多くなり、揮散速度が低下したり、取替え時期が不明瞭になる虞や、水性ゲルの離水の原因にもなるという問題が生じる。 Furthermore, the blending ratio of the volatile solvent and the polyol in the volatilized preparation composition of the present invention is not particularly limited, but is generally 1:10 to 10: 1 by weight ratio thereof. Yes, preferably 1: 5 to 5: 1, more preferably 1: 2 to 2: 1. When the ratio of the polyol is less than the above range, there is a problem that the white turbidity suppressing effect may not be sufficiently exhibited, there is a possibility that the solubilization of the volatile oily active ingredient may be insufficient, and the ratio of the polyol is When the amount is more than the above range, there are problems that volatilization residue increases, the volatilization rate is reduced, the replacement time may be unclear, and the water gel of the aqueous gel may be removed.
更にまた、本発明の揮散製剤組成物中には、水が配合される。この水は、後記する吸水性樹脂粒子を膨潤させ、その形状を維持する役割を有するものである。この水としては、脱イオン水や、水道水を利用することができる。 Furthermore, water is mix | blended in the volatilization formulation composition of this invention. This water has a role of swelling the water-absorbent resin particles described later and maintaining the shape thereof. As this water, deionized water or tap water can be used.
以上の成分と、必要により後記する任意成分とを混合することにより本発明の揮散製剤組成物が調製されるが、この揮散製剤組成物は、次いで吸水性樹脂粒子に吸収させることにより、本発明の揮散製剤を調製することができる。 The volatilized preparation composition of the present invention is prepared by mixing the above components and optional components described later as necessary. The volatilized preparation composition is then absorbed into the water-absorbent resin particles, thereby making the present invention. Can be prepared.
本発明の揮散製剤の調製に使用される吸水性樹脂粒子としては、アクリルアミド−アクリル酸ナトリウム共重合体を含む架橋型吸水性樹脂、ノニオン型ポリオキシアルキレンオキシドを含む架橋型吸水性樹脂、イソブチレン−無水マレイン酸共重合体を含む架橋型吸水性樹脂、ポリアクリル酸(塩)を含む架橋型吸水性樹脂等の粒子を挙げることができる。 Examples of the water-absorbent resin particles used in the preparation of the volatilization preparation of the present invention include a crosslinked water-absorbing resin containing an acrylamide-sodium acrylate copolymer, a crosslinked water-absorbing resin containing a nonionic polyoxyalkylene oxide, and isobutylene- Examples of the particles include a crosslinked water-absorbing resin containing a maleic anhydride copolymer and a crosslinked water-absorbing resin containing a polyacrylic acid (salt).
上記の吸水性樹脂は、既に市販されているものであり、その具体例としては、アクアリックCA K4、アクアリックCA H2、アクアリックCA H3(以上、(株)日本触媒製)、サンフレッシュST−250、サンフレッシュST−250MPS、サンフレッシュST−500D、サンフレッシュST−MPSA、サンフレッシュST−573、アクアパールDSC30、アクアパールE−200(以上、サンダイヤポリマー(株)製)、アクアキープ、アクアコークTW、アクアコークTWB(住友精化株式会社製)、KIゲル−201K、KIゲル201K−F2、KIゲル201K−G1(以上、クラレトレーディング(株)製)などが挙げられる。 The above water-absorbing resin is already commercially available, and specific examples thereof include Aquaric CA K4, Aquaric CA H2, Aquaric CA H3 (manufactured by Nippon Shokubai Co., Ltd.), Sun Fresh ST. -250, Sun Fresh ST-250MPS, Sun Fresh ST-500D, Sun Fresh ST-MPSA, Sun Fresh ST-573, Aqua Pearl DSC30, Aqua Pearl E-200 (above, Sundia Polymer Co., Ltd.), Aqua Keep, Aqua Coke TW, Aqua Coke TWB (manufactured by Sumitomo Seika Co., Ltd.), KI Gel-201K, KI Gel 201K-F2, KI Gel 201K-G1 (above, manufactured by Kuraray Trading Co., Ltd.) and the like.
上記の吸水性樹脂粒子は、その形状には特に制約はなく、球状、楕円状、俵状、サイコロ状、直方体状、多面体状等、種々の粒状形状とすること、また、吸収させた後破砕させて使用することも可能であるが、透明あるいは半透明の容器に充填する形態の場合は、その美観の観点から球状であることが好ましい。また、使用する吸水性樹脂の大きさも、適宜決めることができるが、前記した球状の吸水性樹脂粒子を利用する場合は、その美観の点から、揮散薬剤組成物を吸液した後の直径が1〜30mm程度となる粒径のものを使用することが好ましい。なお、揮散薬剤組成物を吸液した後の直径が1〜30mmとするためには、吸液前の直径が0.1〜10mm程度の吸水性樹脂粒子を利用する必要がある。 The shape of the water-absorbent resin particles is not particularly limited, and may be various granular shapes such as a spherical shape, an elliptical shape, a bowl shape, a dice shape, a rectangular parallelepiped shape, and a polyhedral shape, and may be crushed after being absorbed. However, in the case of a form filled in a transparent or translucent container, it is preferably spherical from the viewpoint of aesthetics. In addition, the size of the water-absorbing resin to be used can be appropriately determined, but when using the above-described spherical water-absorbing resin particles, from the point of view of the beauty, the diameter after absorbing the volatilizing drug composition is It is preferable to use one having a particle size of about 1 to 30 mm. In addition, in order to set the diameter after absorbing the volatilizing drug composition to 1 to 30 mm, it is necessary to use water-absorbent resin particles having a diameter before liquid absorption of about 0.1 to 10 mm.
吸水性樹脂粒子に揮散薬剤組成物を吸液させて揮散薬剤を調製するには、常法に従って、前記各成分を混合、攪拌し、均一として得た液状の揮散薬剤組成物を、上記した吸水性樹脂粒子に吸液させれば良い。この吸液は、吸水性樹脂粒子の揮散薬剤組成物の吸液能を勘案し、全ての揮散薬剤組成物を吸液するのに十分な量の吸水性樹脂粒子と揮散薬剤組成物を常温下(25℃程度)で混合し、10分ないし10時間程度放置することにより行われる。また、最終的な揮散製剤における吸水性樹脂粒子の量は、全質量中、0.1ないし10%程度となることが好ましい。 In order to prepare a volatilizing drug by allowing the water-absorbent resin particles to absorb the volatilizing drug composition, according to a conventional method, the liquid volatile drug composition obtained by mixing and stirring the respective components as a uniform is used for the above-described water absorption. What is necessary is just to make liquid crystalline resin absorb liquid. In consideration of the liquid-absorbing ability of the volatile drug composition of the water-absorbent resin particles, this liquid-absorbing agent is charged with a sufficient amount of the water-absorbent resin particles and the volatile drug composition to absorb all the volatile drug composition at room temperature. (About 25 ° C.) and the mixture is allowed to stand for about 10 minutes to 10 hours. Further, the amount of the water-absorbing resin particles in the final volatilized preparation is preferably about 0.1 to 10% in the total mass.
なお、本発明の揮散製剤において使用可能な任意成分としては、消臭剤、防カビ剤、防菌剤、紫外線吸収剤、酸化防止剤、色素、効力増強剤、脱臭剤等を挙げることができ、これらは本発明の効果を損なわない範囲内において、配合することが可能である。 Examples of optional components that can be used in the volatilization preparation of the present invention include deodorants, fungicides, antibacterial agents, ultraviolet absorbers, antioxidants, dyes, efficacy enhancers, and deodorizers. These can be blended within a range not impairing the effects of the present invention.
以上説明した揮散製剤の実施態様の一つとして、揮散薬剤組成物と吸水性樹脂粒子を組みあわせた揮散製剤キットを挙げることができる。この揮散薬剤キットは、例えば、透明ないし半透明容器中に充填された吸水性樹脂粒子と、別の容器に充填された揮散薬剤組成物から構成され、消費者が容器中に充填された吸水性樹脂粒子中に揮散性薬剤組成物を注入することにより、吸水性樹脂粒子が徐々に膨潤し、例えば透明球形の揮散製剤となるものであり、商品として意匠的なおもしろさがある。 As one embodiment of the volatilization preparation described above, a volatilization preparation kit in which a volatilization drug composition and water-absorbing resin particles are combined can be exemplified. This volatilizing drug kit is composed of, for example, a water-absorbing resin particle filled in a transparent or translucent container and a volatilizing drug composition filled in another container, and the water-absorbing drug filled by the consumer in the container. By injecting the volatile drug composition into the resin particles, the water-absorbent resin particles are gradually swollen to become, for example, a transparent spherical volatilized preparation, which is interesting as a product.
また、本発明の揮散製剤は、これに吸液させた揮散薬剤組成物が揮散してしまった後に、再度揮散薬剤組成物を加えることで、揮散製剤を再生させて使用することができる。この場合は、揮散薬剤組成物を、別に追加用のものとして販売する。 Moreover, after the volatile chemical | medical agent composition made to absorb this has volatilized, the volatile pharmaceutical of this invention can reproduce | regenerate and use a volatile pharmaceutical by adding a volatile chemical | medical agent again. In this case, the volatilizing drug composition is sold separately for additional use.
以上説明した揮散製剤は、種々の油性成分、例えば、防虫・殺虫成分、害虫忌避成分、誘引成分、香料等を徐々に放出可能なものであり、防虫・殺虫剤や、害虫忌避剤、誘引剤、芳香剤として利用可能なものである。しかもこのものは、油性成分の揮散に伴うゲルの白濁を抑制することが可能であり、外観的にも優れた意匠性の製品となるものである。 The volatilized preparation described above is capable of gradually releasing various oily components such as insect repellent / insecticidal component, pest repellent component, attractant component, perfume, etc., and insect repellent / insecticide, pest repellent, attractant It can be used as a fragrance. And this thing can suppress the cloudiness of the gel accompanying volatilization of an oil-based component, and becomes the product of the design property excellent also in the external appearance.
次に実施例を挙げて、本発明を更に詳しく説明するが、本発明はこれら実施例に何ら制約されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.
実 施 例 1:
球状ゲル芳香消臭剤(1):
下記表1に示す割合で各成分を配合、混合して本発明芳香液1ないし5及び比較芳香液1を作製した。次いでこの各芳香液160gを、上面開口の筒状透明容器(直径5.5mm、高さ9.5cm)に入れたイソブチレン−無水マレイン酸ナトリウム共重合体粒子(球状吸水性樹脂:吸液前の平均直径3.5mm)4.2g(約150粒)中に注ぎ、3時間静置して球状ゲル芳香消臭剤(本発明品1ないし5及び比較品1)をた。吸液した後のゲルの直径は5〜15mmであった。
Example 1:
Spherical gel aroma deodorant (1):
Inventive aromatic liquids 1 to 5 and comparative aromatic liquid 1 were prepared by blending and mixing each component at the ratio shown in Table 1 below. Next, 160 g of each fragrance liquid was placed in a cylindrical transparent container (diameter: 5.5 mm, height: 9.5 cm) having an upper surface opening. Isobutylene-sodium maleate anhydride copolymer particles (spherical water-absorbing resin: before liquid absorption) It was poured into 4.2 g (about 150 grains) having an average diameter of 3.5 mm and allowed to stand for 3 hours to obtain spherical gel aroma deodorants (Products 1 to 5 of the present invention and Comparative product 1). The gel diameter after absorbing the liquid was 5 to 15 mm.
界面活性剤2:ラウリルジメチルアミンオキサイド
化合物1:プロピレングリコール
化合物2:エチレングリコール
化合物3:グリセリン
化合物4:ジエチレングリコール
化合物5:ジプロピレングリコール
香 料*:フローラル香料(高砂香料工業製)
消臭剤**:フレッシュシライマツFS500S(白井松新薬製)
Deodorant **: Fresh Shiramatsu FS500S (Shiraimatsu Shinyaku)
次に、上記で得た球状ゲル芳香消臭剤について、温度25℃、湿度60%の環境中で揮散させ、揮散経過日数における白濁(半透明を含む)したビーズの数を確認した。この結果を下記表2に示す。 Next, the spherical gel aroma deodorant obtained above was volatilized in an environment at a temperature of 25 ° C. and a humidity of 60%, and the number of beads that had become cloudy (including translucent) in the volatilization elapsed days was confirmed. The results are shown in Table 2 below.
表2の結果、比較品では揮散開始から10日目で白濁したビーズが生じ、34日目までに約半数の74個の白濁ビーズが生じてしまい、美観を損ねるものであった。一方、本発明品の白濁したビーズの発生量は、34日経過後も比較品の半分以下の数個〜36個に過ぎなかった。また比較品は変色したビーズのほとんどが白濁しているが、特に本発明品1から4はほとんどが半透明であり、全体の意匠性をあまり低下させるものではなかった。 As a result of Table 2, in the comparative product, beads that became cloudy were produced on the 10th day from the start of volatilization, and about half of the 74 cloudy beads were produced by the 34th day, which impaired the aesthetic appearance. On the other hand, the amount of white turbid beads generated in the product of the present invention was only a few to 36, less than half of the comparative product even after 34 days. Further, in the comparative product, most of the discolored beads are clouded, but in particular, the products 1 to 4 of the present invention are almost translucent, and the overall design is not deteriorated so much.
実 施 例 2
球状ゲル芳香消臭剤(2):
実施例1の本発明芳香液1を用い、これを実施例1と同様に、下記表3に示す球状吸水性樹脂に吸液させて球状ゲル芳香消臭剤を調製した。これを用い、実施例1と同様にして揮散に伴うゲルの白濁を調べた。この結果を表4に示す。
Example 2
Spherical gel aroma deodorant (2):
Using the fragrance liquid 1 of the present invention of Example 1, as in Example 1, the spherical water-absorbing resin shown in Table 3 below was absorbed to prepare a spherical gel fragrance deodorant. Using this, the cloudiness of the gel accompanying volatilization was examined in the same manner as in Example 1. The results are shown in Table 4.
表4の結果から、本発明品の芳香液は吸水性樹脂の種類に関わらず、白濁の発生を抑制できることが明らかになった。 From the results shown in Table 4, it became clear that the aromatic liquid of the present invention can suppress the occurrence of white turbidity regardless of the type of water absorbent resin.
実 施 例 3
球状ゲル芳香剤:
下記表5に示す組成で、揮発性溶剤とポリオールを異なる比率で含有する芳香液を調製し、これを実施例1で用いた球状吸水性樹脂に吸液させ、ゲル芳香剤を調製した。このゲル芳香剤について、実施例1と同様に白濁するまでの時間を調べたところ、下記表6のような結果であった。なお、比較芳香液としては、揮発性溶剤のみを配合したものを使用した。
Example 3
Spherical gel air freshener:
An aromatic liquid containing volatile solvent and polyol in different ratios was prepared with the composition shown in Table 5 below, and this was absorbed into the spherical water-absorbent resin used in Example 1 to prepare a gel fragrance. About this gel fragrance | flavor, when time until it became cloudy was investigated like Example 1, it was a result as shown in following Table 6. In addition, as a comparative aromatic liquid, what mix | blended only the volatile solvent was used.
界面活性剤2:ラウリルジメチルアミンオキサイド
化合物1:プロピレングリコール
香 料*:フローラル香料(高砂香料工業製)
表6の結果から、本発明品のゲル芳香剤は、揮発性溶剤とポリオールが必須であり、揮発性溶剤のみでは白濁の発生を十分に抑制できないことが明らかになった。 From the results of Table 6, it was revealed that the gel air freshener of the present invention requires a volatile solvent and a polyol, and the occurrence of white turbidity cannot be sufficiently suppressed only by the volatile solvent.
実 施 例 4
揮散性防虫剤:
3−メトキシ−3−メチル−1−ブタノール3.2g、界面活性剤としてポリオキシエチレンアルキルエーテル3.2g、ラウリルジメチルアミンオキサイド0.32g、防虫剤として2−フェノキシエタノール1.6g、及び化合物1(プロピレングリコール)8gに水143.68gを入れ揮散性防虫液を作成した。この揮散性防虫液を、上面開口の透明筒状容器(直径5.5mm、高さ9.5mm)に入れたイソブチレン―無水マレイン酸共重合体粒子(球状吸水性樹脂:吸液前の平均直径3.5mm)34.2g(約150粒)中に注ぎ、3時間静置して球状ゲル防虫剤を得た。吸液した後のゲルの直径は5〜15mmであった。
Example 4
Volatile insect repellent:
3.2 g of 3-methoxy-3-methyl-1-butanol, 3.2 g of polyoxyethylene alkyl ether as a surfactant, 0.32 g of lauryldimethylamine oxide, 1.6 g of 2-phenoxyethanol as an insect repellent, and compound 1 ( 143.68 g of water was added to 8 g of propylene glycol to prepare a volatile insect repellent solution. Isobutylene-maleic anhydride copolymer particles (spherical water-absorbent resin: average diameter before liquid absorption) put this volatile insect-repellent liquid in a transparent cylindrical container (diameter: 5.5 mm, height: 9.5 mm). 3.5 mm) was poured into 34.2 g (about 150 grains) and allowed to stand for 3 hours to obtain a spherical gel insect repellent. The gel diameter after absorbing the liquid was 5 to 15 mm.
上記揮散性防虫剤は、20日間揮散させた後であってもゲルの白濁が認められなかった。 Even after the volatile insecticide was volatilized for 20 days, no gel turbidity was observed.
実 施 例 5
揮散性忌避剤:
エタノール16g、界面活性剤としてポリオキシエチレンアルキルエーテル3.2g、ラウリルジメチルアミンオキサイド0.32g、忌避剤としてクミンアルデヒド0.8g、及び化合物1(プロピレングリコール)8gに水131.68gを入れ揮散性害虫忌避剤液を作成した。この忌避剤液を、上面開口の透明筒状容器(直径5.5mm、高さ9.5cm)に入れたイソブチレン―無水マレイン酸共重合体粒子(球状吸水性樹脂:吸液前の平均直径2.3mm)4.2g(約400粒)中に注ぎ、3時間静置して球状ゲル害虫忌避剤を得た。吸液した後のゲルの直径は2〜12mmであった。
Example 5
Volatile repellent:
16g of ethanol, 3.2g of polyoxyethylene alkyl ether as a surfactant, 0.32g of lauryldimethylamine oxide, 0.8g of cuminaldehyde as a repellent, and 131.68g of water in 8g of compound 1 (propylene glycol) A pest repellent solution was prepared. Isobutylene-maleic anhydride copolymer particles (spherical water-absorbing resin: average diameter 2 before liquid absorption) put this repellent liquid in a transparent cylindrical container (diameter 5.5 mm, height 9.5 cm) having an upper surface opening. .3 mm) was poured into 4.2 g (about 400 grains) and allowed to stand for 3 hours to obtain a spherical gel pest repellent. The gel diameter after absorbing the liquid was 2 to 12 mm.
上記揮散性害虫忌避剤は、20日間揮散させた後であってもゲルの白濁が認められなかった。 The volatile pest repellent did not show gel turbidity even after being volatilized for 20 days.
本発明の固形揮散製剤は、吸水性樹脂で形成された水性ゲルから油性成分が揮散していく過程においてゲルの白濁を抑制することができるものである。 The solid volatilization formulation of this invention can suppress the cloudiness of a gel in the process in which an oil-based component volatilizes from the aqueous gel formed with the water absorbing resin.
したがって、本発明の揮散製剤は、油性成分の十分な揮散効果を発揮できるとともに白濁が生じにくい意匠性にも優れた固形揮散製剤として、芳香剤、防虫・殺虫剤、害虫忌避剤、誘引剤等の商品に広く利用しうるものである。
Therefore, the volatilization preparation of the present invention is a solid volatilization preparation that can exhibit a sufficient volatilization effect of the oil component and is also excellent in design properties that are less likely to cause white turbidity. It can be widely used for products.
Claims (13)
で表されるものである請求項1ないし6の何れかの項記載の固形揮散製剤。 The polyol has the formula
The solid volatilization preparation according to any one of claims 1 to 6 , which is represented by:
透明ないし半透明容器に収納された吸水性樹脂粒子とを Water absorbent resin particles stored in a transparent or translucent container
組みあわせてなる揮散薬剤キット。Volatile drug kits combined.
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