JP2012012346A - Bath agent composition - Google Patents

Bath agent composition Download PDF

Info

Publication number
JP2012012346A
JP2012012346A JP2010151270A JP2010151270A JP2012012346A JP 2012012346 A JP2012012346 A JP 2012012346A JP 2010151270 A JP2010151270 A JP 2010151270A JP 2010151270 A JP2010151270 A JP 2010151270A JP 2012012346 A JP2012012346 A JP 2012012346A
Authority
JP
Japan
Prior art keywords
fragrance
mass
component
bath agent
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2010151270A
Other languages
Japanese (ja)
Other versions
JP5670660B2 (en
Inventor
Minako Nakajima
美奈子 中島
Michisane Kudo
道誠 工藤
Takao Murakawa
孝雄 村川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP2010151270A priority Critical patent/JP5670660B2/en
Publication of JP2012012346A publication Critical patent/JP2012012346A/en
Application granted granted Critical
Publication of JP5670660B2 publication Critical patent/JP5670660B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

PROBLEM TO BE SOLVED: To provide a foamable tablet type bath agent, which has moderate fragrance, excellent stability of fragrance, and excellent storage stability even at a high temperature of 50°C.SOLUTION: The bath agent composition is a foamable tablet containing the following ingredients (A)-(C) wherein the total content of ingredients (a1) and (a2) in the bath agent composition is 1-3 mass%: (A) is perfume particles including ingredients (a1)-(a4), and constitutes 10-30 mass% of the bath agent composition, (a1) is a perfume ingredient (however, an ingredient (a2) is excluded therefrom) and constitutes 7-25 mass% of the perfume particles, (a2) is a terpene system hydrocarbon or a sesquiterpene system hydrocarbon and constitutes 0.5-1.9 mass% of the perfume particles, (a3) is a nonionic surfactant and constitutes 0.5-1 mass% of the perfume particles, and (a4) is a water-soluble polymer having weight-average molecular weight of 2000 or more, and constitutes 67-92 mass% of the perfume particles; (B) is sodium acid carbonate and/or sodium carbonate; and (C) is an organic acid.

Description

本発明は、香り立ちが適度であり、高温安定性に優れる発泡性の錠剤型浴用剤組成物に関する。   The present invention relates to an effervescent tablet-type bath composition having a moderate fragrance and excellent high-temperature stability.

炭酸塩と酸とを組み合わせた炭酸ガス発生物を配合した浴用剤が、血行促進効果に優れ、リラックス感や爽快感を高めることが知られている(例えば、特許文献1参照)。   It has been known that a bath preparation containing a carbon dioxide gas generator in which a carbonate and an acid are combined has an excellent blood circulation promoting effect and enhances a feeling of relaxation and refreshment (see, for example, Patent Document 1).

また、浴用剤として期待される重要な効果として、香りによるアロマテラピー効果、リラックス効果等があり、浴用剤中に配合する香料を安定化することが重要になっている。
しかし、香料は揮発性の高い成分を含むため、浴用剤の保存中に香料が揮発して香りが変化したり、異臭が発生することがあった。そこで、香料を水溶高分子で造粒することによって保存中の香りを安定化する技術が報告されている(特許文献2参照)。
In addition, as important effects expected as a bath preparation, there are aromatherapy effects due to aroma, relaxation effects, and the like, and it is important to stabilize the fragrance blended in the bath preparation.
However, since the perfume contains highly volatile components, the perfume volatilizes during storage of the bath preparation, and the scent may change or a strange odor may be generated. Then, the technique which stabilizes the fragrance during preservation | save by granulating a fragrance | flavor with water-soluble polymer is reported (refer patent document 2).

また、炭酸ガス発生物を配合した浴用剤においては、発泡と同時に香料が揮散しやすいため、入浴中に長時間、安定な香りを維持することが困難であるという問題がある。   Moreover, in the bath agent which mix | blended the carbon dioxide generator, since a fragrance | flavor tends to volatilize simultaneously with foaming, there exists a problem that it is difficult to maintain a stable fragrance for a long time during bathing.

特開昭59-70609号公報JP 59-70609 特開2000-229843号公報JP 2000-229843 A

香料を水溶高分子で造粒した香料粒子を、炭酸塩と酸とを組み合せた炭酸ガス発生物とともに圧縮成形した浴用剤は、賦香率(浴用剤中の香料成分の割合)が低い場合には、特に保存安定性上の問題は見られない。しかし、賦香率が1質量%以上になると、浴用剤が50℃程度の高温環境下に置かれた場合、香料粒子の溶解により、溶解した水溶性高分子や染み出した香料により炭酸塩と酸の反応が進んで炭酸ガスが発生し、包装材料の膨れ、錠剤の溶解性低下などの現象が認められる。また、水溶性高分子と香料からなる香料粒子を、賦香率が1質量%以上になるように浴用剤に賦香した場合、香料成分が浴水表面に浮き、過剰な香り立ちになる問題も生じるおそれがある。   A bath agent made by compressing perfume particles granulated with a water-soluble polymer together with a carbon dioxide gas generator that combines carbonate and acid has a low perfume rate (ratio of perfume ingredients in the bath agent). There is no particular problem with storage stability. However, when the aromatization rate is 1% by mass or more, when the bath agent is placed in a high temperature environment of about 50 ° C., the dissolution of the perfume particles causes the dissolved water-soluble polymer or the perfume to dissolve the carbonate. The reaction of the acid proceeds to generate carbon dioxide, and phenomena such as swelling of the packaging material and reduced tablet solubility are observed. In addition, when a fragrance particle composed of a water-soluble polymer and a fragrance is perfumed into a bath agent so that the perfume rate is 1% by mass or more, the perfume component floats on the surface of the bath water, resulting in excessive fragrance. May also occur.

従って、本発明の課題は、適度な香り立ちを有し、香りの安定性に優れ、50℃の高温においても保存安定性が良好な、発泡性の錠剤型浴用剤を提供することにある。   Accordingly, an object of the present invention is to provide an effervescent tablet-type bath agent having an appropriate scent, excellent scent stability, and good storage stability even at a high temperature of 50 ° C.

そこで本発明者は、発泡性の錠剤型浴用剤における適度な香り立ちと香料粒子の50℃での保存安定性を図るべく種々検討した結果、テルペン系又はセスキテルペン系炭化水素を含む香料成分に水溶性高分子及び非イオン界面活性剤を加えて香料粒子を造粒して、炭酸ガス発生物とともに製剤化することにより、香りの安定性が良く、香料成分が本来持つ香りの質と強さを保持することができ、更に賦香率が1質量%以上であっても、50℃の高温下で安定性に優れる錠剤型浴用剤が得られることを見出した。   Therefore, as a result of various investigations aimed at achieving an appropriate fragrance in the foamable tablet-type bath agent and the storage stability of the fragrance particles at 50 ° C., the present inventors have found that the fragrance component contains a terpene or sesquiterpene hydrocarbon. By adding water-soluble polymer and nonionic surfactant to granulate perfume particles and formulating it with a carbon dioxide gas generator, the stability of the aroma is good, and the quality and strength of the aroma inherent in the perfume ingredients. It was also found that a tablet-type bath preparation having excellent stability at a high temperature of 50 ° C. can be obtained even when the perfume is 1% by mass or more.

すなわち、本発明は、次の成分(A)〜(C)を含有する発泡性錠剤であって、成分(a1)及び(a2)の浴用剤組成物中における合計含有量が1〜3質量%である浴用剤組成物を提供するものである。
(A) 成分(a1)〜(a4)を含む香料粒子 浴用剤組成物中10〜30質量%
(a1) 香料成分(ただし、成分(a2)を除く) 香料粒子中7〜25質量%
(a2) テルペン系炭化水素又はセスキテルペン系炭化水素 香料粒子中0.5〜1.9質量%
(a3) 非イオン界面活性剤 香料粒子中0.5〜1質量%
(a4) 重量平均分子量2000以上の水溶性高分子 香料粒子中67〜92質量%
(B) 炭酸水素ナトリウム及び/又は炭酸ナトリウム
(C) 有機酸
That is, the present invention is an effervescent tablet containing the following components (A) to (C), and the total content of the components (a1) and (a2) in the bath preparation composition is 1 to 3% by mass. A bath agent composition is provided.
(A) Fragrance particles containing components (a1) to (a4) 10 to 30% by mass in bath agent composition
(a1) Fragrance ingredient (excluding ingredient (a2)) 7-25% by mass in the fragrance particles
(a2) Terpene hydrocarbon or sesquiterpene hydrocarbon 0.5 to 1.9% by mass in perfume particles
(a3) Nonionic surfactant 0.5 to 1% by mass in perfume particles
(a4) Water-soluble polymer having a weight average molecular weight of 2000 or more 67 to 92% by mass in perfume particles
(B) Sodium bicarbonate and / or sodium carbonate
(C) Organic acid

本発明の浴用剤組成物は、香料成分が本来持つ香りの質のまま、適度な香り強度の香り立ちが得られ、香りの安定性に優れ、かつ50℃でも保存安定性に優れる。更に本発明の浴用剤組成物は、香料粒子中に非イオン界面活性剤を添加したことにより使用時における浴水表面への香料による油浮きが防止できるため、使用時の見た目も良好である。   The bath agent composition of the present invention provides a fragrance with an appropriate fragrance strength while maintaining the quality of the scent inherent in the fragrance component, is excellent in scent stability, and is excellent in storage stability even at 50 ° C. Furthermore, since the bath agent composition of the present invention can prevent oil from being floated by the fragrance on the surface of the bath water during use by adding a nonionic surfactant to the fragrance particles, the appearance during use is also good.

〔(A):香料粒子〕
本発明の浴用剤組成物は、成分(A)として、前記成分(a1)、(a2)、(a3)及び(a4)を含む香料粒子を含有する。成分(a1)、(a2)、(a3)及び(a4)は、浴用剤中に単に配合するのではなく香料粒子に配合することが、高濃度で香料を賦香する際の香り立ち、香りの安定性及び50℃における高温安定性を担保するうえで重要である。
[(A): Fragrance particles]
The bath agent composition of the present invention contains perfume particles containing the components (a1), (a2), (a3) and (a4) as the component (A). Ingredients (a1), (a2), (a3), and (a4) are not simply blended into the bath preparation, but are blended into the fragrance particles so that the fragrance and fragrance when flavoring the fragrance at a high concentration It is important to ensure the stability of the material and the high temperature stability at 50 ℃.

・成分(a1):成分(a2)以外の香料成分
成分(a1)の香料成分としては、例えば、「合成香料 化学と商品知識」(印藤元一著、化学工業日報社、2005年増補改定版)に記載の香料のうち、成分(a2)に該当するテルペン系炭化水素、セスキテルペン系炭化水素以外のもの、すなわちアルコール系、アルデヒド系、ケトン系、エーテル系、オキサイド系、エステル系、ラクトン系香料等を使用することができる。成分(a1)の香料成分は、シトラス、グリーン、フローラル、ハーブ等の所望の香りに合わせて種々の調合香料としても香料粒子に配合することができる。
Ingredient (a1): Perfume ingredients other than ingredient (a2) As perfume ingredients of ingredient (a1), for example, “Synthetic perfume chemistry and product knowledge” (Motoichi Indo, Kagaku Kogyo Nippo, revised edition 2005) ), Other than terpene hydrocarbons and sesquiterpene hydrocarbons corresponding to component (a2), that is, alcohols, aldehydes, ketones, ethers, oxides, esters, lactones A fragrance | flavor etc. can be used. The fragrance component of component (a1) can be blended into the fragrance particles as various blended fragrances according to the desired fragrance such as citrus, green, floral, herb and the like.

成分(a1)は、成分(A)の香料粒子中に7〜25質量%、好ましくは10〜25質量%含有され、これにより、濃厚で芳醇な香り立ちと、香りの持続性が得られ、トップノートのフレッシュ感をも出すことができ、また入浴後の肌への香りの持続性を高める点で効果的となる。   The component (a1) is contained in the fragrance particles of the component (A) in an amount of 7 to 25% by mass, preferably 10 to 25% by mass, whereby a rich and mellow fragrance and scent persistence are obtained, It can also give a fresh feeling to the top note and is effective in enhancing the sustainability of the scent on the skin after bathing.

・成分(a2):テルペン系炭化水素、セスキテルペン系炭化水素
成分(a2)のテルペン系炭化水素又はセスキテルペン系炭化水素は、錠剤型浴用剤の高温での保存安定性を高める役割を有する。成分(A)の香料粒子にテルペン系炭化水素又はセスキテルペン系炭化水素を含有させることによって、賦香率が1質量%以上であっても50℃の高温下における保存安定性を担保することができる。
Component (a2): terpene hydrocarbon, sesquiterpene hydrocarbon The terpene hydrocarbon or sesquiterpene hydrocarbon of component (a2) has a role of increasing the storage stability of the tablet bath at high temperatures. By containing the terpene hydrocarbon or sesquiterpene hydrocarbon in the fragrance particles of the component (A), the storage stability at a high temperature of 50 ° C. can be ensured even if the fragrance rate is 1% by mass or more. it can.

成分(a2)のテルペン系炭化水素、セスキテルペン系炭化水素の具体例としては、ミルセン、オシメン、カンフェン、ターピノレン、アルファーターピネン、フェランドレン、アルファフェランドレン、パラサイメン、ファルネセン、セドレン、ロンジフォレン、コパエン、グアイエン、パチョレン、グルジュネンが挙げられる。成分(a1)の香料成分が本来有する香りの質を際だたせる観点から、成分(a1)の香料成分がシトラス系の香りの場合にはミルセン、アルファフェランドレン、ターピノレンが好ましく、成分(a1)の香料成分がグリーン系の香りの場合には、パラサイメン、オシメンが好ましく、成分(a1)の香料成分がフローラル系の香りの場合にはミルセン、オシメン、ファルネセンが好ましく、成分(a1)の香料成分がハーブ系の香りの場合には、カンフェン、ミルセン、アルファーターピネンが好ましい。中でも、ミルセン、オシメン、ファルネセン、パラサイメンは、繁用される香料でもあり、特に好ましい。   Specific examples of the terpene hydrocarbon and sesquiterpene hydrocarbon of the component (a2) include myrcene, ocimene, camphene, tarpinolene, alpha-terpinene, ferrandlene, alphaferrandlene, paracymene, farnesene, cedrene, longiforene, copaene, Examples include Guayen, Patchoulen, and Gurjunen. From the viewpoint of conspicuous fragrance quality inherent in the fragrance component of the component (a1), when the fragrance component of the component (a1) is a citrus fragrance, myrcene, alphaferrandylene, and terpinolene are preferable, and the component (a1) When the fragrance component is a green scent, paracymene or osymene is preferable.When the fragrance component of the component (a1) is a floral scent, myrcene, osimene or farnesene is preferable, and the fragrance component of the component (a1) is In the case of herbal scents, camphene, myrcene and alphaterpinene are preferred. Of these, myrcene, ocimene, farnesene, and paracymene are also frequently used fragrances and are particularly preferable.

これら成分(a2)のテルペン系又はセスキテルペン系炭化水素は、単独で又は2種以上を組み合わせて使用することができる。成分(A)の香料粒子中における成分(a2)の含有量は、成分(a1)が元々有する本来の香質を維持する観点や、高温における入浴剤の安定性の観点から、0.5〜1.9質量%であり、好ましくは0.8〜1.7質量%、更には1.0〜1.5質量%である。   These component (a2) terpene or sesquiterpene hydrocarbons can be used alone or in combination of two or more. The content of the component (a2) in the fragrance particles of the component (A) is 0.5 to 1.9 mass from the viewpoint of maintaining the original fragrance that the component (a1) originally has and the stability of the bathing agent at high temperature. %, Preferably 0.8 to 1.7% by mass, and more preferably 1.0 to 1.5% by mass.

本発明の浴用剤組成物中における、成分(a1)の香料成分と、成分(a2)のテルペン系炭化水素、セスキテルペン系炭化水素の合計含有量は、香り立ち、香りの持続性、肌への香りの持続性の観点から、1〜3質量%であり、好ましくは1.2〜3質量%、更には1.5〜3質量%である。   In the bath preparation composition of the present invention, the total content of the fragrance component of component (a1) and the terpene hydrocarbons and sesquiterpene hydrocarbons of component (a2) is fragrant, long lasting, to the skin From the viewpoint of sustainability of the scent, it is 1 to 3% by mass, preferably 1.2 to 3% by mass, and more preferably 1.5 to 3% by mass.

また、成分(a1)の香料成分と、成分(a2)のテルペン系炭化水素、セスキテルペン系炭化水素の配合比率(質量比)は、浴用剤組成物の保存安定性に加え、香りの質と強さを保持する観点から、(a1):(a2)=30:1〜5:1が好ましく、更には20:1〜5:1が好ましく、特に12:1〜5:1が好ましい。   In addition, the blending ratio (mass ratio) of the fragrance component of component (a1) and the terpene hydrocarbon and sesquiterpene hydrocarbon of component (a2) is determined in addition to the storage stability of the bath agent composition, From the viewpoint of maintaining strength, (a1) :( a2) = 30: 1 to 5: 1 is preferable, 20: 1 to 5: 1 is more preferable, and 12: 1 to 5: 1 is particularly preferable.

・成分(a3):非イオン界面活性剤
成分(a3)の非イオン界面活性剤を配合することにより、浴用剤の使用時に香料成分が浴水表面に浮き、過剰な香り立ちになるのを回避することができ、更に使用時の見た目も心地よいものとなる。また、賦香率が1質量%以上であっても50℃の高温下で保存安定性に優れたものとなる。
・ Ingredient (a3): Nonionic surfactant By blending the nonionic surfactant of ingredient (a3), the use of the bath agent prevents the fragrance ingredient from floating on the surface of the bath water and causing excessive fragrance. Furthermore, the appearance at the time of use becomes comfortable. Moreover, even if the perfume rate is 1% by mass or more, the storage stability is excellent at a high temperature of 50 ° C.

成分(a3)の非イオン界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル、ショ糖脂肪酸エステルが挙げられる。   Examples of the nonionic surfactant of component (a3) include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, and sucrose fatty acid esters.

ポリオキシアルキレンアルキルエーテルとしては、アルキレンの炭素数が2〜3、オキシアルキレンの繰り返し数が7〜14、アルキルの炭素数が14〜20であるものが好ましい。具体例としては、ポリオキシエチレン(EO=7)セチルエーテル、ポリオキシエチレン(EO=10)セチルエーテル、ポリオキシエチレン(EO=12)セチルエーテル、ポリオキシエチレン(EO=13)セチルエーテル、ポリオキシエチレン(EO=8)ステアリルエーテル、ポリオキシエチレン(EO=9)ステアリルエーテル、ポリオキシエチレン(EO=13)ステアリルエーテル等が挙げられる。   As the polyoxyalkylene alkyl ether, those having 2 to 3 carbon atoms of alkylene, 7 to 14 carbon atoms of oxyalkylene, and 14 to 20 carbon atoms of alkyl are preferable. Specific examples include polyoxyethylene (EO = 7) cetyl ether, polyoxyethylene (EO = 10) cetyl ether, polyoxyethylene (EO = 12) cetyl ether, polyoxyethylene (EO = 13) cetyl ether, poly Examples thereof include oxyethylene (EO = 8) stearyl ether, polyoxyethylene (EO = 9) stearyl ether, polyoxyethylene (EO = 13) stearyl ether and the like.

ポリオキシアルキレンアルケニルエーテルとしては、アルキレンの炭素数が2〜3、オキシアルキレンの繰り返し数が7〜14、アルケニルの炭素数が14〜20であるものが好ましい。具体例としては、ポリオキシエチレン(EO=8)オレイルエーテル、ポリオキシエチレン(EO=9)オレイルエーテルが挙げられる。   As the polyoxyalkylene alkenyl ether, those having 2 to 3 carbon atoms of alkylene, 7 to 14 carbon atoms of oxyalkylene, and 14 to 20 carbon atoms of alkenyl are preferable. Specific examples include polyoxyethylene (EO = 8) oleyl ether and polyoxyethylene (EO = 9) oleyl ether.

このうち、成分(a1)の香料成分の浴水への分散と香り立ちの観点から、ポリオキシエチレン(EO=7)セチルエーテル、ポリオキシエチレン(EO=13)セチルエーテル、ポリオキシエチレン(EO=9)オレイルエーテルが特に好ましい。   Of these, polyoxyethylene (EO = 7) cetyl ether, polyoxyethylene (EO = 13) cetyl ether, polyoxyethylene (EO = 9) Oleyl ether is particularly preferred.

またショ糖脂肪酸エステルとしては、成分(a1)の香料成分の浴水への分散と香り立ちの観点から、HLBが16以下のものが好ましく、特に15以下のものがより好ましい。例えば、ショ糖ベヘニン酸エステル、ショ糖ステアリン酸エステル、ショ糖パルミチン酸エステル、ショ糖ミリスチン酸エステル、ショ糖ラウリン酸エステル、ショ糖オレイン酸エステル等が挙げられる。   In addition, the sucrose fatty acid ester is preferably one having an HLB of 16 or less, more preferably 15 or less, from the viewpoint of dispersion of the fragrance component of the component (a1) in the bath water and fragrance. Examples include sucrose behenic acid ester, sucrose stearic acid ester, sucrose palmitic acid ester, sucrose myristic acid ester, sucrose lauric acid ester, sucrose oleic acid ester and the like.

成分(a3)の非イオン界面活性剤は、成分(a1)の香料成分の浴水への分散と香り立ちの観点から、ポリオキシアルキレンアルキル又はポリオキシアルケニルエーテルと、ショ糖脂肪酸エステルとを組合せて使用することが好ましく、香り立ちの点から、ポリオキシアルキレンアルキルエーテル又はポリオキシアルキレンアルケニルエーテルと、ショ糖脂肪酸エステルとの配合比(質量比)は、2:1〜5:1が好ましく、更には3:1〜5:1が特に好ましい。   The nonionic surfactant of component (a3) is a combination of polyoxyalkylene alkyl or polyoxyalkenyl ether and sucrose fatty acid ester from the viewpoint of dispersion and flavoring of the fragrance component of component (a1) in bath water. From the viewpoint of fragrance, the compounding ratio (mass ratio) of polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether and sucrose fatty acid ester is preferably 2: 1 to 5: 1. Further, 3: 1 to 5: 1 is particularly preferable.

成分(A)の香料粒子中における成分(a3)の含有量は、成分(a1)の香料成分の浴水への分散と浴水への溶解時の適度な香り立ちの観点から、特に成分(a1)が本来持つ香りの質と強度を保持する点で0.5〜1.0質量%であり、好ましくは0.6〜1.0質量%である。   The content of the component (a3) in the fragrance particles of the component (A) is particularly preferable from the viewpoint of dispersion of the fragrance component of the component (a1) in the bath water and appropriate scenting at the time of dissolution in the bath water. It is 0.5 to 1.0% by mass, and preferably 0.6 to 1.0% by mass in terms of maintaining the fragrance quality and strength inherent in a1).

また、成分(a1)及び(a2)の合計含有量と成分(a3)の含有量との比は、香料成分への浴水への分散と香り立ちの観点から、10:1〜40:1が好ましく、更には15:1〜25:1が好ましい。   The ratio of the total content of components (a1) and (a2) to the content of component (a3) is 10: 1 to 40: 1 from the viewpoint of dispersion in the fragrance components in the bath water and fragrance. Is more preferable, and 15: 1 to 25: 1 is more preferable.

・成分(a4):重量平均分子量2000以上の水溶性高分子
成分(a4)は、重量平均分子量2000以上の水溶性高分子であり、香料の安定化、香り立ちの点から重要な成分である。
Ingredient (a4): Water-soluble polymer with a weight average molecular weight of 2000 or more Component (a4) is a water-soluble polymer with a weight average molecular weight of 2000 or more, and is an important component from the viewpoint of stabilization of perfume and smell .

本発明で用いる水溶性高分子としては、常温(25℃)で固体又はペースト状のものが好ましい。ここでペースト状とは、半固形状の物質である。具体的には、例えば、にかわ、ゼラチン、コラーゲンタンパク、カゼイン、アルギン酸ナトリウム、カラギーナン、ファーセレラン、タマリンドガム、ペクチン、アラビアガム、グアーガム、キサンタンガム、トラガントガム、ローカストビーンガム、デキストリン、デキストラン、寒天、澱粉等の天然水溶性高分子;カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、酢酸フタル酸セルロース、アルギン酸プロピレングリコールエステル、酸化澱粉、エステル化澱粉、エーテル化澱粉、カチオン澱粉等の半合成水溶性高分子;ポリアクリル酸ソーダ、ポリエチレンイミン、ポリビニルアルコール、ポリエチレングリコール、ポリビニルピロリドン等の合成水溶性高分子などが挙げられ、1種以上を用いることができる。これらのうち、ポリエチレングリコール、特に重量平均分子量2000〜20000のポリエチレングリコールが好ましい。   The water-soluble polymer used in the present invention is preferably a solid or paste at room temperature (25 ° C.). Here, the paste form is a semi-solid substance. Specifically, for example, glue, gelatin, collagen protein, casein, sodium alginate, carrageenan, fur celerin, tamarind gum, pectin, gum arabic, guar gum, xanthan gum, tragacanth gum, locust bean gum, dextrin, dextran, agar, starch, etc. Natural water-soluble polymers; semi-synthetic water-soluble polymers such as carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose acetate phthalate, propylene glycol alginate, oxidized starch, esterified starch, etherified starch, and cationic starch; Synthetic water-soluble polymers such as polyacrylic acid soda, polyethyleneimine, polyvinyl alcohol, polyethylene glycol, and polyvinylpyrrolidone Gerare can use one or more. Among these, polyethylene glycol, particularly polyethylene glycol having a weight average molecular weight of 2000 to 20000 is preferable.

これら成分(a4)の水溶性高分子は、単独で又は2種以上を組み合せて使用することができ、成分(A)の香料粒子中における成分(a4)の含有量は、香り立ち、香りの持続性及び浴用剤組成物の高温時の保存安定性の点から、67〜92質量%であり、好ましくは70〜90質量%、更には73〜90質量%である。   These water-soluble polymers of component (a4) can be used alone or in combination of two or more, and the content of component (a4) in the fragrance particles of component (A) From the standpoint of sustainability and storage stability of the bath agent composition at high temperatures, it is 67 to 92% by mass, preferably 70 to 90% by mass, and more preferably 73 to 90% by mass.

成分(A)の香料粒子は、例えば転動式造粒法、噴霧乾燥造粒法、遠心式造粒法、攪拌造粒法、板上滴下造粒法等により製造することができる。特に、塊状や液体から粒径の小さい粒子を製造できる方法が好ましい。例えば、本発明の香料粒子は、成分(a1)〜(a4)を加熱溶融して均一に混合した後、一定量を平らな板状物の上に滴下して、固化、造粒し、顆粒状の粒子を得るのが好ましい(板上滴下造粒法)。加熱溶融の温度は、使用する成分(a4)の水溶性高分子が溶融する温度であることが好ましい。   The perfume particles of the component (A) can be produced, for example, by a rolling granulation method, a spray drying granulation method, a centrifugal granulation method, a stirring granulation method, a drop-on-plate granulation method or the like. In particular, a method capable of producing particles having a small particle diameter from a lump or liquid is preferable. For example, the fragrance particles of the present invention are obtained by heating and melting the components (a1) to (a4) and mixing them uniformly, then dropping a certain amount onto a flat plate, solidifying, granulating, and granulating It is preferable to obtain a shaped particle (drop-on-plate granulation method). The heating and melting temperature is preferably a temperature at which the water-soluble polymer of the component (a4) to be used melts.

成分(A)の香料粒子は、香り立ち、香りのフレッシュ感、香りの持続性の点から、粒子径が100〜2000μm、特に500〜1500μmであることが好ましい。粒径は、ふるい分け法によって、JIS Z 8801で規定された目開きのふるいを用いて選別、測定する。   The perfume particles of component (A) preferably have a particle size of 100 to 2000 μm, particularly 500 to 1500 μm, from the standpoint of fragrance, scent freshness, and scent persistence. The particle size is selected and measured by a sieve method using a sieve with openings defined in JIS Z 8801.

成分(A)の香料粒子は、本発明の浴用剤組成物中に10〜30質量%含有するが、10〜25質量%、更には12〜25質量%含有するのが、浴湯に溶解したときの香り立ち、香りの持続性の点で好ましい。   Although the fragrance | flavor particle | grains of a component (A) contain 10-30 mass% in the bath agent composition of this invention, it contains 10-25 mass%, Furthermore, 12-25 mass% contained in the bath water. It is preferable from the standpoint of fragrance and sustainability.

〔(B)+(C):炭酸ガス発生物〕
本発明の浴用剤組成物には、炭酸ガス発生物としての炭酸水素ナトリウム及び/又は炭酸ナトリウムと、有機酸とを含有する。有機酸としては、例えばコハク酸、フマル酸、リンゴ酸、アジピン酸、酒石酸、クエン酸、マロン酸、マレイン酸等が挙げられる。このうち、コハク酸、フマル酸が特に好ましい。
[(B) + (C): Carbon dioxide generator]
The bath agent composition of the present invention contains sodium hydrogen carbonate and / or sodium carbonate as a carbon dioxide gas generator and an organic acid. Examples of the organic acid include succinic acid, fumaric acid, malic acid, adipic acid, tartaric acid, citric acid, malonic acid, maleic acid and the like. Of these, succinic acid and fumaric acid are particularly preferable.

炭酸水素ナトリウム及び/又は炭酸ナトリウムは、本発明の浴用剤組成物中に合計量で10〜60質量%、特に10〜50質量%含有するのが、浴湯中に十分な炭酸ガスを溶解できるので好ましい。また、有機酸は、本発明の浴用剤組成物中に有機酸の合計量で20〜60質量%、特に30〜60質量%含有するのが、浴湯中に十分な炭酸ガスを溶解できるので好ましい。更に、炭酸水素ナトリウム及び/又は炭酸ナトリウムと、有機酸との総含有量は40〜85質量%、特に50〜85質量%が好ましい。   Sodium bicarbonate and / or sodium carbonate is contained in a total amount of 10 to 60% by mass, particularly 10 to 50% by mass, in the bath agent composition of the present invention, so that sufficient carbon dioxide gas can be dissolved in the bath water. Therefore, it is preferable. In addition, since the organic acid is contained in the total amount of the organic acid in the bath agent composition of the present invention in an amount of 20 to 60% by mass, particularly 30 to 60% by mass, sufficient carbon dioxide gas can be dissolved in the bath water. preferable. Furthermore, the total content of sodium bicarbonate and / or sodium carbonate and the organic acid is preferably 40 to 85% by mass, particularly preferably 50 to 85% by mass.

本発明の浴用剤組成物には、更に通常浴用剤に用いられる成分、例えば無機塩類、無機酸類、生薬類、油脂類、アルコール類、薬効剤、色素類、ビタミン類等を配合できる。
本発明の浴用剤組成物は、圧縮成形法、例えば打錠により、圧縮成形製剤、例えば錠剤の形態とすることができる。
The bath agent composition of the present invention may further contain components usually used in bath agents, such as inorganic salts, inorganic acids, crude drugs, fats and oils, alcohols, medicinal agents, pigments, vitamins and the like.
The bath agent composition of the present invention can be formed into a compression-molded preparation such as a tablet by a compression molding method such as tableting.

本発明の浴用剤組成物は、浴槽溶解時に発泡して炭酸ガスを発生する。当該炭酸ガスは浴湯中に高濃度に溶解し、血行促進効果を発揮する。一方、本発明の浴用剤中に配合された香料粒子は、発泡と同時に浴湯中に放出され、入浴中良好な香りが持続するため、良好なアロマテラピー効果が得られる。   The bath agent composition of the present invention foams and generates carbon dioxide when dissolved in a bathtub. The carbon dioxide gas dissolves in bath water at a high concentration and exhibits a blood circulation promoting effect. On the other hand, the fragrance particles blended in the bath preparation of the present invention are released into the bath water simultaneously with foaming, and a good aroma persists during bathing, so that a good aromatherapy effect is obtained.

製造例1(香料粒子の製造)
ポリエチレングリコール6000(重量平均分子量7500)の87.4質量部を約60℃で溶融し、成分(a1)の香料成分11質量部、成分(a2)のミルセン0.5質量部、オシメン0.5質量部、成分(a3)のポリオキシエチレンセチルエーテル0.5質量部、ショ糖脂肪酸エステル0.1質量部を加えて溶解した。これを均一に混合した後、20℃の平らな板に滴下し、直径100〜2000μm(ふるいにて測定:長径)の範囲の粒状に造粒して香料粒子1を得た。
表1及び2に示す香料粒子2〜15についても同様に製造した。
Production Example 1 (Production of perfume particles)
87.4 parts by mass of polyethylene glycol 6000 (weight average molecular weight 7500) was melted at about 60 ° C., and 11 parts by mass of the fragrance component of component (a1), 0.5 parts by mass of myrcene, 0.5 parts by mass of osimene, and component (a3) of component (a2) And 0.5 part by mass of polyoxyethylene cetyl ether and 0.1 part by mass of sucrose fatty acid ester were added and dissolved. After this was uniformly mixed, it was dropped on a flat plate at 20 ° C. and granulated into particles having a diameter of 100 to 2000 μm (measured with a sieve: major axis) to obtain perfume particles 1.
Fragrance particles 2 to 15 shown in Tables 1 and 2 were produced in the same manner.

Figure 2012012346
Figure 2012012346

Figure 2012012346
Figure 2012012346

実施例1〜8、比較例1〜8
製造例1で得られた表1及び2に示す香料粒子を用い、表3及び4に示す組成で均一に配合し、1錠100gを油圧打錠機にて打錠成形し、浴用剤組成物を得、以下の〔安定性の評価〕、〔水面上の油浮きの評価〕、〔香り立ちと持続性の評価〕を行った。また、香料粒子自体を用い、〔香りの質の評価〕を行った。
Examples 1-8, Comparative Examples 1-8
Using the perfume particles shown in Tables 1 and 2 obtained in Production Example 1, uniformly blended with the compositions shown in Tables 3 and 4, and tableting 100 g with a hydraulic tableting machine, bath composition The following [Evaluation of stability], [Evaluation of oil floating on the water surface] and [Evaluation of fragrance and sustainability] were performed. Moreover, [Evaluation of fragrance quality] was performed using the fragrance particles themselves.

〔50℃での安定性評価〕
打錠成形した、浴用剤組成物1錠100gをアルミピローで包装した後、50℃の恒温槽に入れ、30日後のアルミピローの状態について、5名の専門パネラーが、下記の評価基準に従い目視にて評価した。評価は協議により決定した。結果を表3及び4に示す。
[Stability evaluation at 50 ℃]
After packing 100 g of a bath preparation composition tableted and molded with an aluminum pillow, place it in a thermostatic bath at 50 ° C., and the state of the aluminum pillow after 30 days will be visually checked by five professional panelists according to the following evaluation criteria. Evaluated. Evaluation was determined by consultation. The results are shown in Tables 3 and 4.

(安定性の評価基準)
1:アルミピローの外観にまったく変化を認めない
2:アルミピローの外観にごくわずかに膨れを認める
3:アルミピローにやや膨れを認める
4:アルミピローに膨れを認める
(Stability evaluation criteria)
1: No change in the appearance of the aluminum pillow is observed 2: Slight swelling is observed in the appearance of the aluminum pillow 3: Slight swelling is observed in the aluminum pillow 4: Swelling is recognized in the aluminum pillow

〔溶解後の水面上の油浮き評価〕
250リットルの浴槽に40℃、150リットルの湯を入れ、ここに打錠成形した錠剤1錠100gを溶かし、溶解後の水面上の油浮きの状態について、5名の専門パネラーが、以下の評価基準に従い目視評価を行った。評価は協議により決定した。結果を表3及び4に示す。
[Evaluation of oil floating on the water surface after dissolution]
In a 250 liter bath, put 40 ℃, 150 liter of hot water, dissolve 100 g of the tablet that was molded into a tablet, and five expert panelists evaluated the following conditions of oil floating on the water surface after dissolution. Visual evaluation was performed according to the standard. Evaluation was determined by consultation. The results are shown in Tables 3 and 4.

(水面上の油浮きの評価基準)
1:油浮きを認めない
2:ごくわずかに油浮きを認める
3:油浮きを認める
(Evaluation criteria for oil float on the water surface)
1: Does not allow oil float 2: Accepts oil float slightly 3: Accepts oil float

〔香り立ちと持続性の評価〕
250リットルの浴槽に40℃、150リットルの湯を入れ、ここに打錠成形した錠剤1錠100gを溶かし、全量溶解直後の香り立ちと、溶解1時間後の香り立ちについて、5名の専門パネラーが以下の評価基準に従い評価を行った。評価は協議により決定した。結果を表3及び4に示す。
更に「溶解直後の香り立ち」と「溶解1時間後の香り立ち」との差を計算し、〔持続性の評価〕とした。(溶解直後の香り立ち)と(溶解1時間後の香り立ち)との差は1以内が好ましい。結果を表3及び4に示す。
[Evaluation of fragrance and sustainability]
Into a 250 liter bath, put 150 liters of hot water at 40 ° C. Dissolve 100 g of a tablet that was molded into a tablet. Five professional panelists will give you a fragrance immediately after dissolution and 1 hour after dissolution. Evaluated according to the following evaluation criteria. Evaluation was determined by consultation. The results are shown in Tables 3 and 4.
Furthermore, the difference between “scenting immediately after dissolution” and “scenting 1 hour after dissolution” was calculated and used as [evaluation of sustainability]. The difference between (fragrance immediately after dissolution) and (fragrance after 1 hour after dissolution) is preferably within one. The results are shown in Tables 3 and 4.

(香り立ちの評価基準)
1:無臭
2:ごくわずかに香る
3:弱く香る
4:ちょうど良く香る(設定範囲)
5:はっきり香る(設定範囲)
6:強く香る
7:かなり強く香る
(Evaluation criteria for fragrance)
1: Odorless 2: Slightly scented 3: Slightly scented 4: Scented well (setting range)
5: Scented clearly (setting range)
6: Strongly scented 7: Slightly scented

〔香りの質の評価〕
成分(a2)のテルペン系又はセスキテルペン系炭化水素は香りを有するため、成分(a1)の香料成分に成分(a2)を加えることにより、成分(a1)が本来有する香りが変わる可能性がある。そこで、成分(a1)の本来有する香りであるか否かを確認するための評価を行った。
すなわち、表1及び2に示す香料粒子の処方において、成分(a2)を含有しない香料粒子を調製し、表1及び2に示す香料粒子の香りの質と、上記成分(a2)を含有しない香料粒子の香りの質と比較評価した。
各香料粒子20gを各々40℃、150リットルの湯に溶かし、全量溶解直後の香調を5名の専門パネラーで官能評価を行った。評価は協議により決定した。結果を表3及び4に併せて示す。
[Evaluation of fragrance quality]
Since the terpene or sesquiterpene hydrocarbon of component (a2) has a fragrance, adding component (a2) to the fragrance component of component (a1) may change the inherent fragrance of component (a1) . Therefore, evaluation was performed to confirm whether or not the fragrance was originally possessed by the component (a1).
That is, in the formulation of fragrance particles shown in Tables 1 and 2, fragrance particles not containing the component (a2) were prepared, and the fragrance quality of the fragrance particles shown in Tables 1 and 2 and the fragrance not containing the above component (a2) The quality of the scent of the particles was compared and evaluated.
20 g of each fragrance particle was dissolved in 150 liters of hot water at 40 ° C., and the fragrance immediately after dissolution of the whole amount was subjected to sensory evaluation by five panelists. Evaluation was determined by consultation. The results are shown in Tables 3 and 4 together.

(香りの質の評価基準)
1:成分(a1)の香料成分本来の香りを有する
2:成分(a1)の香料成分本来の香りとほぼ同等である
3:成分(a1)の香料成分本来の香りとはやや異なる
4:成分(a1)の香料成分本来の香りと異なる
(Evaluation criteria for fragrance quality)
1: It has the original fragrance of the fragrance component of component (a1) 2: It is almost the same as the original fragrance of the fragrance component of component (a1) 3: Slightly different from the original fragrance of the fragrance component of component (a1) 4: Component Different from the original fragrance of the fragrance component of (a1)

〔総合評価〕
総合評価は、〔安定性の評価〕、〔水面上の油浮きの評価〕、〔香りの質の評価〕と、〔香り立ちと持続性の評価〕を考慮して、以下の基準にて総合的に判断した。
(評価基準)
1:各評価を総合的に判断した結果、効果は極めて優れている
2:各評価を総合的に判断した結果、効果は優れている
3:各評価を総合的に判断した結果、効果は十分である
4:各評価を総合的に判断した結果、効果がやや不十分である
5:各評価を総合的に判断した結果、効果が不十分である
〔Comprehensive evaluation〕
The overall evaluation is based on the following criteria in consideration of [stability evaluation], [evaluation of oil floating on the water surface], [evaluation of fragrance quality], and [evaluation of fragrance standing and sustainability]. Judgment.
(Evaluation criteria)
1: As a result of comprehensive evaluation of each evaluation, the effect is extremely excellent 2: As a result of comprehensive evaluation of each evaluation, the effect is excellent 3: As a result of comprehensive evaluation of each evaluation, the effect is sufficient 4: As a result of comprehensive evaluation of each evaluation, the effect is slightly insufficient 5: As a result of comprehensive evaluation of each evaluation, the effect is insufficient

Figure 2012012346
Figure 2012012346

Figure 2012012346
Figure 2012012346

Claims (4)

次の成分(A)〜(C)を含有する発泡性錠剤であって、成分(a1)及び(a2)の浴用剤組成物中における合計含有量が1〜3質量%である浴用剤組成物。
(A) 成分(a1)〜(a4)を含む香料粒子 浴用剤組成物中10〜30質量%
(a1) 香料成分(ただし、成分(a2)を除く) 香料粒子中7〜25質量%
(a2) テルペン系炭化水素又はセスキテルペン系炭化水素 香料粒子中0.5〜1.9質量%
(a3) 非イオン界面活性剤 香料粒子中0.5〜1質量%
(a4) 重量平均分子量2000以上の水溶性高分子 香料粒子中67〜92質量%
(B) 炭酸水素ナトリウム及び/又は炭酸ナトリウム
(C) 有機酸
An effervescent tablet containing the following components (A) to (C), wherein the total content of the components (a1) and (a2) in the bath agent composition is 1 to 3% by mass: .
(A) Fragrance particles containing components (a1) to (a4) 10 to 30% by mass in bath agent composition
(a1) Fragrance ingredient (excluding ingredient (a2)) 7-25% by mass in the fragrance particles
(a2) Terpene hydrocarbon or sesquiterpene hydrocarbon 0.5 to 1.9% by mass in perfume particles
(a3) Nonionic surfactant 0.5 to 1% by mass in perfume particles
(a4) Water-soluble polymer having a weight average molecular weight of 2000 or more 67 to 92% by mass in perfume particles
(B) Sodium bicarbonate and / or sodium carbonate
(C) Organic acid
(a3)非イオン界面活性剤が、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル及びショ糖脂肪酸エステルから選ばれる1種以上である請求項1記載の浴用剤組成物。   The bath agent composition according to claim 1, wherein (a3) the nonionic surfactant is at least one selected from polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers and sucrose fatty acid esters. (a4)水溶性高分子が、ポリエチレングリコールである請求項1又は2記載の浴用剤組成物。   (a4) The bath composition according to claim 1 or 2, wherein the water-soluble polymer is polyethylene glycol. 成分(A)の香料粒子の粒子径が、100〜2000μmである請求項1〜4のいずれか1項記載の浴用剤組成物。   The bath agent composition according to any one of claims 1 to 4, wherein the particle diameter of the perfume particles of the component (A) is 100 to 2000 µm.
JP2010151270A 2010-07-01 2010-07-01 Bath agent composition Active JP5670660B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010151270A JP5670660B2 (en) 2010-07-01 2010-07-01 Bath agent composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010151270A JP5670660B2 (en) 2010-07-01 2010-07-01 Bath agent composition

Publications (2)

Publication Number Publication Date
JP2012012346A true JP2012012346A (en) 2012-01-19
JP5670660B2 JP5670660B2 (en) 2015-02-18

Family

ID=45599210

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2010151270A Active JP5670660B2 (en) 2010-07-01 2010-07-01 Bath agent composition

Country Status (1)

Country Link
JP (1) JP5670660B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014094915A (en) * 2012-11-09 2014-05-22 Kao Corp Fragrant granules
KR20150068753A (en) * 2013-12-12 2015-06-22 주식회사 엘지생활건강 A Lipid emulsified fragrance composition for increasing the remaining fragrance
KR20160010638A (en) * 2012-10-23 2016-01-27 주식회사 엘지생활건강 A Emulsified fragrance composition for increasing the remaining fragrance

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000229843A (en) * 1999-02-12 2000-08-22 Kao Corp Bath preparation composition
JP2008303194A (en) * 2007-06-11 2008-12-18 Kao Corp Fragrant granules
JP2009062319A (en) * 2007-09-06 2009-03-26 Tsumura Lifescience Co Ltd Foamable granule

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000229843A (en) * 1999-02-12 2000-08-22 Kao Corp Bath preparation composition
JP2008303194A (en) * 2007-06-11 2008-12-18 Kao Corp Fragrant granules
JP2009062319A (en) * 2007-09-06 2009-03-26 Tsumura Lifescience Co Ltd Foamable granule

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160010638A (en) * 2012-10-23 2016-01-27 주식회사 엘지생활건강 A Emulsified fragrance composition for increasing the remaining fragrance
KR101668358B1 (en) * 2012-10-23 2016-10-21 주식회사 엘지생활건강 A Emulsified fragrance composition for increasing the remaining fragrance
JP2014094915A (en) * 2012-11-09 2014-05-22 Kao Corp Fragrant granules
KR20150068753A (en) * 2013-12-12 2015-06-22 주식회사 엘지생활건강 A Lipid emulsified fragrance composition for increasing the remaining fragrance
KR102048373B1 (en) 2013-12-12 2019-11-25 주식회사 엘지생활건강 A Lipid emulsified fragrance composition for increasing the remaining fragrance

Also Published As

Publication number Publication date
JP5670660B2 (en) 2015-02-18

Similar Documents

Publication Publication Date Title
JP5183984B2 (en) Bath preparation
CN1261785A (en) Method for controlling environmental odors on the body using compositions comprising uncomplexed cyclodextrins and perfume
NZ224303A (en) Aqueous-based gel air-freshener compositions
JP2007223936A (en) Bathing agent
JP5670660B2 (en) Bath agent composition
JP5149614B2 (en) Bath preparation
JP3967028B2 (en) Bath agent composition
JP7335758B2 (en) Effervescent solid bath agent
JP6283342B2 (en) Oil-in-water gel composition and method for improving malodor removal of oil-in-water gel composition
JP2005194419A (en) Perfume capsule and bathing agent containing the same
KR102199533B1 (en) Water-soluble effervescent solid fragrances
JPH1094591A (en) Gel-like fragrant and deodorizing composition
JPS60135058A (en) Transparent aromatic gel composition
JP4295778B2 (en) Bath agent composition
JP7382766B2 (en) Foaming solid bath additive
JP4348208B2 (en) Compression mold bath agent
JP6733066B1 (en) Composition for deodorizing rubber odor and method for deodorizing rubber odor
JP6733067B1 (en) Composition for deodorizing rubber odor and method for deodorizing rubber odor
JP3786862B2 (en) Aqueous gel composition
JPH11192296A (en) Gel aromatic composition
JP6209323B2 (en) Effervescent compression formulation
JP6741489B2 (en) Method for producing smoke agent composition
JP2006182817A (en) Resin composition for slow dissolution of chemical and liquid composition containing the resin composition
JP6991558B2 (en) Gel-like fragrance composition
KR20180074271A (en) foaming type perfume

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20130614

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20140226

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20140513

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20140714

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20141209

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20141218

R151 Written notification of patent or utility model registration

Ref document number: 5670660

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R151

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250