JP3367863B2 - Silicone emulsion, method for producing the same, and hair cosmetic - Google Patents
Silicone emulsion, method for producing the same, and hair cosmeticInfo
- Publication number
- JP3367863B2 JP3367863B2 JP11677597A JP11677597A JP3367863B2 JP 3367863 B2 JP3367863 B2 JP 3367863B2 JP 11677597 A JP11677597 A JP 11677597A JP 11677597 A JP11677597 A JP 11677597A JP 3367863 B2 JP3367863 B2 JP 3367863B2
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- Prior art keywords
- emulsion
- particle size
- water
- stirring
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- Cosmetics (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
Description
【０００１】[0001]
【発明の技術分野】本発明は、艶出し、消泡、離型、滑
りおよび感触改良などを目的として各種分野で使用され
るＯ／Ｗ型シリコーンエマルションおよびその製造方法
に関する。特に、感触向上などの目的で化粧品／香粧品
分野で好適に使用されるシリコーンエマルションおよび
その製造方法に関する。TECHNICAL FIELD The present invention relates to an O / W type silicone emulsion used in various fields for the purpose of polishing, defoaming, releasing, slipping and improving the feel, and a method for producing the same. In particular, the present invention relates to a silicone emulsion preferably used in the field of cosmetics / cosmetics for the purpose of improving the feel and the like, and a method for producing the same.
【０００２】[0002]
【発明の技術的背景とその問題点】従来から、毛髪や肌
に滑らかさ、艶などの感触を与える目的で、シリコーン
エマルションが多く使用されている。シリコーンの特徴
を付与させる場合、毛髪や肌に速やかに付着し、使用時
に流れ落ちないものが有利であるため、特性上はエマル
ション粒子径が大きいほど優れた特性が得られると期待
されるが、粒子径を大きくするとエマルションの安定性
が低下し、さらに各種製品に配合する場合、それらとの
配合安定性が著しく低下するという問題があった。エマ
ルションは一般に粒子径が大きいほどその安定性が悪く
なる傾向を有するが、これは粒子径を大きくしようとし
た場合、その粒子径分布が広くなり、さらには複数のピ
ークを持つ粒子径分布になることが多く、このことが極
端な安定性低下を引き起こしていると考えられる。その
ため現在は、シリコーンエマルションの粒子径が１μｍ
未満の比較的小粒子径のものが多く使用されている。こ
れまでにエマルション粒子径を制御するには、いくつか
の方法が知られている。例えば、界面活性剤の種類やＨ
ＬＢを選択する方法がある。この場合、使用するシリコ
ーンに合わせて目的の粒子径のエマルションを得るに
は、現在市販されている界面活性剤の種類の多さから見
ても明らかであるように、検討すべき点数が非常に多
く、検討に長期間を要するという問題がある。また逆に
化粧品／香粧品分野などでは、使用できる界面活性剤が
限られており、それらの組み合わせだけでは十分に満足
できる特性のエマルションを得るのが困難であるという
問題があった。エマルションの粒子径を制御する具体的
な手法としては、ＨＬＢ法（Griffin,W.C.:J.Soc.Cosme
t.Chem.,1:311,1949) 、液晶乳化法（鷲谷ら：油化学,3
0,38,1981) 、転相乳化法（T.J.Lin,J.Soc.Cosmet.Che
m., 30 167,976) およびＤ相乳化法（鷲谷ら：日化, 13
99, 1983) など種々のものが提案されている。しかしこ
れらの乳化法は主に１μｍ未満の小粒子径品を得るため
のものであり、本発明のように大粒子径品の粒子径をコ
ントロールするための有効な手段とはいえない。もちろ
ん、使用する界面活性剤によっては１μｍ以上のものが
得られる場合があるが、上述の安定性等の問題点があっ
た。さらに粒子径を制御する他の方法としては、乳化時
の温度を変える、乳化機の種類を変える、乳化時の攪拌
速度を変えるなどにより、乳化時にかかるシェアを変え
る方法が考えられる。しかしこの方法では、温度や攪拌
速度の正確な制御が困難な他、乳化時にかかるシェアが
決して乳化系内全体に均一ではなく、例えば攪拌羽根周
辺などで部分的に差が生じるため、出来上がるエマルシ
ョンの粒子径の分布が広くなったり、複数のピークがあ
る粒子径分布を持つものとなってしまう。こうなると、
エマルションの安定性および他材料との配合安定性が著
しく低下してしまう。この傾向は特に大粒子径品ほど顕
著となる。これは攪拌時にかかるシェアの小さいほどエ
マルションの粒子径は大きくなるが、小さいシェアを全
体に均一にかけることが困難であるためである。また、
実際の製造に際しては、製造スケールが大きいほど乳化
系内全体に均一なシェアを与えることが困難になるう
え、製造装置が変わったり、スケールが変わったりする
と、温度や回転数などの条件が同一であっても、異なる
粒子径となる場合が多く、その都度最適な温度や回転数
などの製造条件を検討する必要が生じるという問題点が
あった。TECHNICAL BACKGROUND OF THE INVENTION AND ITS PROBLEMS Silicone emulsions have been widely used in the past for the purpose of imparting smoothness and luster to the hair and skin. When imparting the characteristics of silicone, it is advantageous that it quickly adheres to hair and skin and does not run off during use, so it is expected that the larger the emulsion particle size, the better the characteristics obtained. When the diameter is increased, the stability of the emulsion is lowered, and when compounded in various products, there is a problem that the compounding stability with them is significantly lowered. Emulsion generally has a tendency that its stability becomes worse as the particle size becomes larger, but when it is attempted to increase the particle size, the particle size distribution becomes wider, and further the particle size distribution has multiple peaks. Often, this is believed to cause an extreme decrease in stability. Therefore, the particle size of silicone emulsion is currently 1 μm.
Those having a relatively small particle size of less than 10 are often used. Several methods are known so far for controlling the emulsion particle size. For example, the type of surfactant and H
There is a method of selecting LB. In this case, in order to obtain an emulsion having a target particle size according to the silicone used, the number of points to be examined is very high, as is clear from the large number of types of surfactants currently on the market. Many have a problem that it takes a long time to study. On the contrary, in the field of cosmetics / perfumery, etc., usable surfactants are limited, and there is a problem that it is difficult to obtain an emulsion having sufficiently satisfactory characteristics only by combining them. As a specific method for controlling the particle size of the emulsion, the HLB method (Griffin, WC: J.Soc.Cosme
t.Chem., 1: 311,1949), Liquid crystal emulsification method (Washiya et al .: Oil chemistry, 3
0,38,1981), phase inversion emulsification method (TJLin, J.Soc.Cosmet.Che
m., 30 167,976) and D phase emulsification method (Washiya et al .: Nikka, 13
99, 1983) and others have been proposed. However, these emulsification methods are mainly for obtaining a product having a small particle size of less than 1 μm, and cannot be said to be an effective means for controlling the particle size of a product having a large particle size as in the present invention. Of course, depending on the surfactant used, one having a thickness of 1 μm or more may be obtained, but there are problems such as the above-mentioned stability. Further, as another method of controlling the particle size, a method of changing the shear during emulsification by changing the temperature during emulsification, changing the type of emulsifying machine, changing the stirring speed during emulsification, and the like can be considered. However, in this method, it is difficult to accurately control the temperature and the stirring speed, and the share applied during emulsification is not uniform throughout the emulsification system. The particle size distribution becomes wider, or the particle size distribution has a plurality of peaks. This happens when,
The emulsion stability and the compounding stability with other materials will be significantly reduced. This tendency becomes more remarkable as the product having a large particle size is particularly used. This is because the smaller the share that is applied during stirring, the larger the particle size of the emulsion, but it is difficult to apply a small share uniformly throughout the emulsion. Also,
In the actual production, the larger the production scale, the more difficult it is to give a uniform share to the entire emulsion system, and if the production equipment changes or the scale changes, the conditions such as temperature and rotation speed will remain the same. However, there is a problem that the particle diameters are often different, and it is necessary to examine the manufacturing conditions such as the optimum temperature and the number of revolutions each time.
【０００３】[0003]
【発明の目的】本発明の目的は、前記問題点を解決し、
エマルション組成を変えることなく、その粒子径を容易
に制御し、なおかつ、得られる粒子径分布が狭く、大粒
子径を有しながらエマルション安定性および配合安定性
に優れたエマルションを得ることにある。The object of the present invention is to solve the above problems,
An object of the present invention is to easily control the particle size of the emulsion without changing the emulsion composition, to obtain an emulsion having a narrow particle size distribution and a large particle size, and having excellent emulsion stability and formulation stability.
【０００４】[0004]
【発明の構成】本発明者らは、上記目的を達成するため
鋭意検討を重ねた結果、シリコーンと界面活性剤の混合
物に転相点以上の水を１度に加えて混合攪拌後、残りの
水で希釈することで粒子径分布の狭いエマルションが得
られること、さらに、最初に加える水の量を変えること
で得られる粒子径が制御できることを見出し、本発明を
完成するに至った。即ち、本発明は、ポリオルガノシロ
キサンのＯ／Ｗ型シリコーンエマルションを製造するに
あたり、界面活性剤としてノニオン系界面活性剤を使用
し、且つポリオルガノシロキサンとノニオン系界面活性
剤との混合物中に、転相点以上の水を１度に加えて混合
攪拌後、残りの水を加えて希釈することを特徴とするシ
リコーンエマルションの製造方法、及び該製造方法で得
られた、エマルション平均粒子径が１〜100 μｍである
シリコーンエマルション、並びに該シリコーンエマルシ
ョンを含んでなる毛髪化粧料に関するものである。The present inventors have conducted extensive studies to achieve the above object, and as a result, after adding water having a phase inversion point or more to a mixture of silicone and a surfactant at once, mixing and stirring the remaining water. They have found that an emulsion having a narrow particle size distribution can be obtained by diluting with water, and that the particle size obtained can be controlled by changing the amount of water initially added, and have completed the present invention. That is, the present invention uses a nonionic surfactant as a surfactant in producing an O / W type silicone emulsion of polyorganosiloxane.
In addition, in a mixture of polyorganosiloxane and nonionic surfactant, water having a phase inversion point or higher is added at once and mixed and stirred, and the remaining water is added to dilute the silicone emulsion. The present invention relates to a production method, a silicone emulsion having an emulsion average particle size of 1 to 100 μm obtained by the production method, and a hair cosmetic composition containing the silicone emulsion.
【０００５】[0005]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明に用いられるポリオルガノシロキサンは、
従来公知のものが使用できる。例えば、一般式
ＲａＳｉＯ（４−ａ）／２
（ここでＲ は置換又は非置換の１価炭化水素基、a は
４未満の正の数を示す）で示されるものが例示される。
式中R は置換または非置換の１価炭化水素基であり、同
一であっても、複数の種類のものであっても良く、例え
ば、メチル基、エチル基、ヘキシル基、デシル基などの
アルキル基、フェニル基などのアリール基、２−メチル
フェニルエチル基などのアラルキル基、３−アミノプロ
ピル基、２−アミノエチル−３−アミノプロピル基など
のアミノ含有基、ポリオキシエチレン基、ポリオキシプ
ロピレン基、ポリオキシエチレン−ポリオキシプロピレ
ン基などのポリオキシアルキレン基、3,3,3 −トリフル
オロプロピル基などのフッ素含有基などが例示される。
これらは、使用される目的、用途にあったものを選ぶこ
とができ、例えば毛髪化粧料では、髪へのサラサラ感付
与を目的とする場合はメチル基が好ましく、しっとり感
付与効果や密着性向上の目的ではアミノ基含有基が好ま
しく、艶向上の目的ではアリール基が好ましいといった
様に、種々のR を選ぶことができる。またa は４未満の
正の数であり、乳化のし易さや得られるシロキサンの有
用性などから、 1.0〜2.5 が好ましい。使用するポリオ
ルガノシロキサンは１種であっても複数種であっても良
い。例えば、毛髪に優れた感触を与えることに加え、キ
ューティクル保護効果を持つ粘度が百万cSt を越えるポ
リジメチルシロキサンなどは、そのもの単体では毛髪へ
の広がりが悪く、これを補うために例えば数百cPのポリ
ジメチルシロキサンを併用することが一般に行われてい
る。また、数百cSt のポリジメチルシロキサンの代わり
に、例えばイソパラフィン系溶剤を用いていることもあ
る。もちろん、この場合も本発明の製造方法は適用でき
る。本発明の製造方法においては、粒子径分布が小さ
く、安定性の良好なエマルションが効率よく得られ、ま
た得られるエマルション組成物においては、毛髪化粧料
に使用した場合に毛髪への良好な感触の付与や良好なキ
ューティクル保護効果の付与が行われることから、粘度
が10,000〜100,000,000cSt、特に50,000〜50,000,000cS
t のポリジメチルシロキサンを用いることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polyorganosiloxane used in the present invention is
Conventionally known ones can be used. For example, those represented by the general formula R a SiO (4-a) / 2 (wherein R is a substituted or unsubstituted monovalent hydrocarbon group and a is a positive number less than 4) are exemplified.
In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group, which may be the same or a plurality of types, for example, an alkyl group such as a methyl group, an ethyl group, a hexyl group or a decyl group. Group, aryl group such as phenyl group, aralkyl group such as 2-methylphenylethyl group, amino-containing group such as 3-aminopropyl group, 2-aminoethyl-3-aminopropyl group, polyoxyethylene group, polyoxypropylene Groups, polyoxyalkylene groups such as polyoxyethylene-polyoxypropylene groups, and fluorine-containing groups such as 3,3,3-trifluoropropyl groups.
These can be selected according to the purpose and application to be used.For example, in hair cosmetics, a methyl group is preferable for the purpose of imparting a smooth feeling to the hair, and a moist feeling imparting effect and adhesion improvement Various R 1 can be selected such that an amino group-containing group is preferable for the purpose of (1) and an aryl group is preferable for the purpose of improving gloss. Further, a is a positive number less than 4, and is preferably 1.0 to 2.5 in view of ease of emulsification and usefulness of the obtained siloxane. The polyorganosiloxane used may be one kind or plural kinds. For example, polydimethylsiloxane, which has a cuticle-protecting effect and a viscosity exceeding 1 million cSt in addition to giving a good feel to the hair, does not spread easily to the hair by itself, and for example, several hundred cP It is generally practiced to use the polydimethylsiloxane of. Further, for example, an isoparaffin-based solvent may be used instead of the polydimethylsiloxane of several hundred cSt. Of course, the manufacturing method of the present invention can be applied to this case as well. In the production method of the present invention, an emulsion having a small particle size distribution and good stability can be efficiently obtained, and in the obtained emulsion composition, a good feel to the hair is obtained when used in a hair cosmetic composition. The viscosity is 10,000 to 100,000,000 cSt, especially 50,000 to 50,000,000 cS, because it gives good cuticle protection effect.
It is preferred to use t 3 polydimethylsiloxane.
【０００６】本発明の製造方法においては、粒子径分布
が狭く、安定性の良好なエマルションが得られ、また得
られるエマルション組成物においては、毛髪化粧料に使
用した場合に毛髪への良好な感触の付与が行われること
から、界面活性剤としてはノニオン系界面活性剤が用い
られる。ノニオン系界面活性剤としては、モノラウリン
酸グリセリル、モノミリスチン酸グリセリル、モノステ
アリン酸グリセリル、モノオレイン酸グリセリルのよう
なグリセリン脂肪酸エステル；同様の脂肪酸残基を有す
るポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エ
ステル、ポリオキシエチレングリセリン脂肪酸エステ
ル、ポリオキシエチレンソルビタン脂肪酸エステルおよ
びポリオキシエチレン脂肪酸エステル；ポリオキシエチ
レンラウリルエーテル、ポリオキシエチレンセチルエー
テル、ポリオキシエチレンステアリルエーテル、ポリオ
キシエチレンオレイルエーテルのようなポリオキシエチ
レンアルキルエーテル；ポリオキシエチレンオクチルフ
ェニルエーテル、ポリオキシエチレンノニルフェニルエ
ーテルのようなポリオキシエチレンアルキルフェニルエ
ーテル；オキシエチレン・オキシプロピレン共重合体；
ならびにポリエーテル変性ポリジメチルシロキサンが例
示される。ノニオン系界面活性剤としては、前述したも
のの中でも、ポリオキシエチレンソルビタン脂肪酸エス
テル、ポリオキシエチレン脂肪酸エステル、ポリオキシ
エチレンアルキルエーテルが好ましく使用される。これ
らの界面活性剤は、２種以上のものを併用することもで
きる。界面活性剤は、ポリオルガノシロキサン 100重量
部に対して、１〜30重量部が使用される。これは、１重
量部未満であると乳化が十分にできず、一方、30重量部
を越えると得られるエマルションを使用する場合に、シ
リコーン本来の特性が界面活性剤の量が多いために十分
発揮されないことがあるためである。好ましくはポリオ
ルガノシロキサン 100重量部に対して、２〜20重量部、
特に好ましくは５〜15重量部使用される。In the production method of the present invention, the particle size distribution
A narrow and stable emulsion can be obtained.
The emulsion composition used is used for hair cosmetics.
When used, it gives a good feel to the hair.
Therefore, nonionic surfactant is used as the surfactant.
To be Nonionic surfactants include glyceryl fatty acid esters such as glyceryl monolaurate, glyceryl monomyristate, glyceryl monostearate, and glyceryl monooleate; polyglycerin fatty acid esters having similar fatty acid residues, sorbitan fatty acid esters, poly Oxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester and polyoxyethylene fatty acid ester; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether ; Polyoxyethylene such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Alkylphenyl ethers; polyoxyethylene-oxypropylene copolymer;
And polyether-modified polydimethylsiloxane Ru is illustrated. Among the above-mentioned nonionic surfactants, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkyl ether are preferably used. Two or more kinds of these surfactants can be used in combination. The surfactant is used in an amount of 1 to 30 parts by weight based on 100 parts by weight of polyorganosiloxane. This is because when the amount is less than 1 part by weight, the emulsification cannot be sufficiently performed, while when the amount obtained exceeds 30 parts by weight, the inherent characteristics of silicone are sufficiently exerted due to the large amount of the surfactant. This is because it may not be done. Preferably 2 to 20 parts by weight with respect to 100 parts by weight of polyorganosiloxane,
Particularly preferably 5 to 15 parts by weight are used.
【０００７】従来は、通常、Ｏ／Ｗ型エマルションを調
製する場合、油相成分と界面活性剤を必要に応じて加熱
して混合し、ここに水を徐々に加えながら、さらに混合
して得られる。この場合必要に応じてコロイドミル、ホ
モミキサー、加圧ホモジナイザーなどの乳化機を使用す
る。例えば、従来技術として前述した転相乳化法では、
油相成分と界面活性剤の混合物に水を徐々に加えてい
く。まず、Ｗ／Ｏ型を経由したのち、Ｄ相を形成させ
る。Ｄ相は、界面活性剤相とも呼ばれ、油と水が界面活
性剤のラメラ相によってサンドイッチ型に配列した液晶
相であり、ここで、外観上は透明性が出てくる。通常こ
の点を転相点としている。この液晶相では、油滴は無限
に細かく分散した状態となり、ここでさらに水を加え、
Ｏ／Ｄエマルションを形成させる。この時、分散相であ
る油相に影響することなく連続相がＤ相となる。さらに
水を加えてＯ／Ｗ型エマルションを作る。こうすること
で、油滴が微細に分散したＯ／Ｗ型エマルションが得ら
れる。この方法では徐々に水を加えていき、各段階毎に
乳化系内を均一とすることで、均一な小粒子径のＯ／Ｗ
型エマルションを得ようとするものであり、すなわち、
注水回数は３回以上、実際には通常５〜10回となる。こ
の場合、その都度、系内を均一にするため、十分な攪拌
が必要となり、製造に長時間を要する。また、Ｄ相は通
常硬いゲル状物で、均一とさせるには高い攪拌効率と大
きな動力が必要となり、被乳化物が高粘度なほど、系内
を均一にすることが困難となる。この場合、部分的に攪
拌不十分なところが存在し易く、結果的に粒子径がばら
つく。こうしたことがあるため、装置やスケールが変わ
ると得られるエマルションの粒子径分布が変化し易く、
制御が難しいという問題がある。尚、転相点となる水の
量は、予め油相成分と界面活性剤の混合物に、一定温度
に保った状態で水を少量加えて攪拌することを繰り返し
てゆき、内容物の透明性が最も高い点を転相点として評
価する、などの方法で測定することができる。Conventionally, when an O / W type emulsion is usually prepared, an oil phase component and a surfactant are heated and mixed as necessary, and water is gradually added to the mixture to obtain an oil phase component and a surfactant. To be In this case, an emulsifier such as a colloid mill, a homomixer, or a pressure homogenizer is used as needed. For example, in the phase inversion emulsification method described above as the prior art,
Water is gradually added to the mixture of the oil phase component and the surfactant. First, after passing through the W / O type, the D phase is formed. The D phase is also called a surfactant phase, and is a liquid crystal phase in which oil and water are arranged in a sandwich type by a lamella phase of the surfactant, and here, transparency appears in appearance. Normally, this point is used as the phase inversion point. In this liquid crystal phase, the oil droplets are infinitely dispersed in a fine state, where water is further added,
Form an O / D emulsion. At this time, the continuous phase becomes the D phase without affecting the oil phase as the dispersed phase. Further, water is added to make an O / W emulsion. By doing so, an O / W type emulsion in which oil droplets are finely dispersed can be obtained. In this method, water is gradually added to make the inside of the emulsification system uniform at each stage, so that O / W with a uniform small particle size is obtained.
To obtain a type emulsion, that is,
The frequency of water injection is 3 times or more, and actually 5 to 10 times. In this case, in order to make the inside of the system uniform each time, sufficient agitation is required and the production requires a long time. In addition, the D phase is usually a hard gel, and high stirring efficiency and large power are required to make it uniform, and the higher the viscosity of the emulsion, the more difficult it is to make the system uniform. In this case, a portion where the stirring is insufficient tends to exist, and as a result, the particle diameter varies. Because of these things, the particle size distribution of the resulting emulsion tends to change when the device and scale change,
There is a problem that it is difficult to control. The amount of water serving as the phase inversion point is determined by adding a small amount of water to the mixture of the oil phase component and the surfactant in advance while keeping the mixture at a constant temperature and stirring the mixture until the transparency of the contents becomes It can be measured by a method such as evaluating the highest point as a phase inversion point.
【０００８】本発明では、油相成分と界面活性剤の混合
系に転相点以上の水を１度に加えることを特徴とする
が、この注水量は前記のＤ相となる量以上である。使用
する油相成分や界面活性剤によって、Ｄ相が形成される
水の量が変化するので、例えば油相成分に対する注水量
を規定するなどの限定は困難である。本発明では、転相
点の水量を基準として、その量の１〜５倍量の水を初回
注水する。これは、１倍未満であると、希釈水を添加し
ても、油相成分と界面活性剤と水の混合物が均一に分散
出来なかったり、分散するために長時間を要するためで
ある。また、５倍量以上の水を初回に注水すると、やは
り油相成分と界面活性剤の混合物が水に分散出来なかっ
たり、分散するために長時間を要するためである。注水
工程と希釈工程の両方で容易に分散し、かつ均一な粒子
径分布を得るためには、好ましくは1.1 〜３倍量、特に
好ましくは 1.5〜２倍量の水量である。本発明によれ
ば、得られる粒子径は、転相点の水量を注水した後、希
釈水を加えると小さなものとなり、また転相点以上の水
を１度に注水すると、その量が大きくなるに従って、得
られる粒子径は徐々に大きくなる。即ち、初回注水量を
変えることで得られるエマルションの粒子径を制御する
ことが可能となる。本発明においては、基本的には、水
を２回に分けて注水するだけであるので、製造工程を短
縮できる。また、硬いゲル相を形成させないため、系内
を均一に混合し易い。即ち、装置やスケールの影響を受
けにくい。この方法は、製造工程数が少なく、装置やス
ケールの影響を受けにくいことから、バッチ式製造はも
ちろん連続製造する場合にも適した方法である。The present invention is characterized in that water having a phase inversion point or higher is added at once to a mixed system of an oil phase component and a surfactant. . Since the amount of water that forms the D phase changes depending on the oil phase component and the surfactant used, it is difficult to limit the amount of water injected to the oil phase component, for example. In the present invention, the amount of water at the phase inversion point is used as a reference, and 1 to 5 times the amount of water is initially injected. This is because if it is less than 1 time, the mixture of the oil phase component, the surfactant and the water cannot be uniformly dispersed even if the dilution water is added, or it takes a long time for the dispersion. In addition, if water of 5 times or more is poured for the first time, the mixture of the oil phase component and the surfactant cannot be dispersed in water or it takes a long time to disperse. In order to easily disperse in both the water injection step and the dilution step and to obtain a uniform particle size distribution, the amount of water is preferably 1.1 to 3 times, particularly preferably 1.5 to 2 times. According to the present invention, the obtained particle size becomes small by adding dilution water after pouring the amount of water at the phase inversion point, and increasing the amount by pouring water at the phase inversion point or more at once. Accordingly, the obtained particle size gradually increases. That is, it is possible to control the particle size of the emulsion obtained by changing the initial water injection amount. In the present invention, basically, the water is simply injected in two times, so that the manufacturing process can be shortened. Further, since a hard gel phase is not formed, it is easy to uniformly mix the system. That is, it is unlikely to be affected by the device or scale. Since this method has a small number of manufacturing steps and is not easily affected by the apparatus and scale, it is a method suitable not only for batch manufacturing but also for continuous manufacturing.
【０００９】本発明のエマルションの製造方法において
は、前述したようにポリオルガノシロキサンをイソパラ
フィン系溶剤を併用して乳化を行ってもよく、このよう
に併用して配合してもよい材料としては、得られるエマ
ルションを例えば毛髪化粧料に使用した場合に、ポリオ
ルガノシロキサンを希釈して濡れ広がり性を与えるなど
の目的で、ヘキサン、ヘプタンなどのパラフィン系溶
剤、トルエン、キシレンなどの芳香族系溶剤、イソヘプ
タン、イソオクタンなどのイソパラフィン系溶剤、クロ
ロホルムなどの塩素系溶剤、エステル系溶剤、グリコー
ル系溶剤など種々の溶剤類が例示される。また得られる
エマルションの消泡目的でシリカ粉末を、またチクソ性
付与目的でゼオライトなどの固体粉末を、艶向上目的で
カルナバワックスなどのワックス類など、さらにｐ−ヒ
ドロキシ安息香酸プロピル、安息香酸ナトリウム、クエ
ン酸、サリチル酸などの防腐剤、アルギン酸、アラビア
ゴム、カゼイン、メチルセルロース、ヒドロキシエチル
セルロース、陽イオン変性エーテル化セルロース、ヒド
ロキシプロピルデン粉、ポリビニルアルコール、ポリビ
ニルピロリドン、ベントナイトなどの増粘剤なども併用
できる。これらをポリオルガノシロキサンと併用した場
合も本発明の製造方法は適用できる。In the method for producing the emulsion of the present invention, the polyorganosiloxane may be emulsified by using an isoparaffinic solvent together as described above, and the materials which may be blended together in this manner include: When the obtained emulsion is used for hair cosmetics, for example, for the purpose of diluting the polyorganosiloxane to give wet spreading properties, hexane, paraffin solvents such as heptane, aromatic solvents such as toluene and xylene, Examples include various solvents such as isoparaffin solvents such as isoheptane and isooctane, chlorine solvents such as chloroform, ester solvents, glycol solvents and the like. Further, silica powder is used for defoaming the obtained emulsion, solid powder such as zeolite for the purpose of imparting thixotropy, waxes such as carnauba wax for improving luster, propyl p-hydroxybenzoate, sodium benzoate, Preservatives such as citric acid and salicylic acid, alginic acid, acacia, casein, methyl cellulose, hydroxyethyl cellulose, cation-modified etherified cellulose, hydroxypropylden powder, polyvinyl alcohol, polyvinylpyrrolidone, thickeners such as bentonite, and the like can be used in combination. The production method of the present invention can also be applied when these are used in combination with polyorganosiloxane.
【００１０】本発明の製造方法により得られるエマルシ
ョンは、粒子径分布が単分散で狭いという特徴があり、
またエマルションの安定性に優れるという特徴がある。
そのため化粧品などの材料として使用した場合に、得ら
れる化粧品の保存性に優れるという有用性がある。本発
明の製造方法では、一般に平均粒子径が 0.1〜200 μｍ
のエマルションが効率よく得られるが、これまで安定性
の良好なものを得るのが困難であった比較的粒子径の大
きいもの、例えば１〜100 μｍ、特に３〜80μｍのもの
が効率良く得られるという特徴がある。本発明の製造方
法により得られるこのような粒子径の大きいエマルショ
ンは、その安定性に優れるだけでなく、化粧料などに配
合した場合にシリコーン本来の優れた特性が発揮される
という特徴がある。The emulsion obtained by the production method of the present invention is characterized in that the particle size distribution is monodisperse and narrow,
Further, it has a feature that the stability of the emulsion is excellent.
Therefore, when used as a material for cosmetics and the like, it has the usefulness that the resulting cosmetics have excellent storage stability. In the production method of the present invention, the average particle size is generally 0.1 to 200 μm.
The emulsion of 1) can be efficiently obtained, but it is possible to efficiently obtain an emulsion having a relatively large particle size, for example, 1 to 100 μm, particularly 3 to 80 μm, which has been difficult to obtain a highly stable emulsion. There is a feature called. The emulsion having such a large particle size obtained by the production method of the present invention is not only excellent in its stability, but also has the characteristic that when it is compounded in a cosmetic or the like, the original excellent characteristics of silicone are exhibited.
【００１１】[0011]
【発明の効果】本発明の製造方法によれば、粒子径分布
の狭い、安定性の良好なシリコーンエマルションが得ら
れ、特にこれまで製造が困難であった粒子径の大きい安
定性の良好なシリコーンエマルションが得られるという
特徴がある。さらにエマルションの粒子径を制御するの
が容易であり、また装置の種類やスケールによる影響を
受けにくく、従来の製造方法よりも短縮された製造工程
で実施できるという特徴がある。According to the production method of the present invention, a silicone emulsion having a narrow particle size distribution and good stability can be obtained, and particularly, a silicone emulsion having a large particle size and good stability, which has been difficult to produce until now, can be obtained. The feature is that an emulsion is obtained. Furthermore, it is easy to control the particle size of the emulsion, is less affected by the type and scale of the apparatus, and can be carried out in a manufacturing process shorter than the conventional manufacturing method.
【００１２】[0012]
【実施例】以下に実施例を挙げて、本発明をさらに詳し
く説明する。なお実施例中において「％」は「重量％」
を表す。また粘度は25℃における値を示す。表１に実施
例で使用したエマルションの組成を示す。またエマルシ
ョンの粒子径は以下に示す方法により測定した。また各
エマルション組成において、70℃での転相点を以下に示
す方法により測定した。ここで得られた転相点水量を表
１に示す。EXAMPLES The present invention will be described in more detail with reference to the following examples. In the examples, "%" means "% by weight"
Represents The viscosity is the value at 25 ° C. Table 1 shows the composition of the emulsion used in the examples. The particle size of the emulsion was measured by the method described below. Further, in each emulsion composition, the phase inversion point at 70 ° C. was measured by the method shown below. Table 1 shows the amount of water at the phase inversion point obtained here.
【００１３】[0013]
【表１】 [Table 1]
【００１４】注）
ポリジメチルシロキサン１：200cStポリジメチルシロキ
サン
ポリジメチルシロキサン２：10万cSt ポリジメチルシロ
キサン
ポリジメチルシロキサン３：2000万cSt ポリジメチルシ
ロキサン
アミノ基含有シロキサン ：1000cSt 、窒素原子含有量
0.9％の２−アミノエチル−３−アミノプロピル基含有
ポリジメチルシロキサン
ノニオン系界面活性剤１ ：ポリオキシエチレン（23）
ラウリルエーテル
ノニオン系界面活性剤２ ：ポリオキシエチレン（６）
ラウリルエーテル
ノニオン系界面活性剤３ ：ポリオキシエチレン（55）
モノステアレート
ノニオン系界面活性剤４ ：ポリオキシエチレン（20）
ソルビタンモノステアレート
・エマルション粒子径測定
コールター社製、ＬＳ型（測定原理：レーザー回折／散
乱テクノロジー）を使用した。得られた結果から、平均
粒子径、最頻粒子径および平均粒子径／最頻粒子径を確
認した。なお粒子径分布の広がりは平均粒子径／最頻粒
子径の比率で判定した。即ち、この比率が１に近いほど
分布が単分散で狭いと判断した。
・転相点水量の測定
シロキサン成分と活性剤成分を70℃で加熱下攪拌後、水
を１％量づつ加え攪拌を繰り返した。この時、内容物の
透明性が最も高い点を目視判定し、その時の注水量を転
相点水量とした。Note) Polydimethylsiloxane 1: 200 cSt polydimethylsiloxane polydimethylsiloxane 2: 100,000 cSt polydimethylsiloxane polydimethylsiloxane 3: 20 million cSt polydimethylsiloxane amino group-containing siloxane: 1000 cSt, nitrogen atom content
Polydimethylsiloxane nonionic surfactant 1 containing 0.9% of 2-aminoethyl-3-aminopropyl group: polyoxyethylene (23)
Lauryl ether nonionic surfactant 2: polyoxyethylene (6)
Lauryl ether nonionic surfactant 3: Polyoxyethylene (55)
Monostearate Nonionic Surfactant 4: Polyoxyethylene (20)
Sorbitan monostearate rate-emulsion particle size measurement Coulter, LS type were used: (measurement principle laser diffraction / scattering technology). From the obtained results, the average particle size, the mode particle size and the average particle size / mode particle size were confirmed. The spread of the particle size distribution was determined by the ratio of average particle size / modal particle size. That is, it was judged that the distribution was monodisperse and narrower as the ratio was closer to 1. -Measurement of water amount of phase inversion point After stirring the siloxane component and the activator component under heating at 70 ° C, water was added in an amount of 1% and the stirring was repeated. At this time, the point where the content had the highest transparency was visually determined, and the amount of water injected at that time was taken as the water amount at the phase inversion point.
【００１５】実施例１
エマルション組成−１を合計 100ｇとなる様に各成分を
用いた。200cc フラスコ中に、ポリジメチルシロキサン
１の36ｇとポリジメチルシロキサン３の24ｇの混合物を
入れて70℃に加熱した。この後も70℃の加熱は全量の水
を加えるまで継続した。ここに、ノニオン系界面活性剤
１の 1.2ｇとノニオン系界面活性剤３の3.8ｇを加え、
金属ヘラを用いて手攪拌した。70℃の加熱を維持したま
ま、約５分間攪拌を続けたところ、ノニオン系界面活性
剤が溶融し、ポリジメチルシロキサンと混合された。こ
こに初回注水として水を８ｇ加え、さらに攪拌を続け
た。約10分間攪拌を続け、透明性のあるゲル状物を得
た。次に、希釈水として残りの水27ｇを加え、70℃の加
熱を止めて放冷しながら、約10分間攪拌して乳白色のエ
マルションを得た。このエマルションの平均粒子径、最
頻粒子径および平均粒子径／最頻粒子径を表２に示す。
実施例２
初回注水量を10ｇ、希釈水量を25ｇとした以外は実施例
１と同様に操作した。初回注水、攪拌後に粘稠な若干透
明性のある乳白色液体が得られ、最終的には乳白色のエ
マルションが得られた。粒子径等の評価結果を表２に示
す。
実施例３
初回注水量を12ｇ、希釈水量を23ｇとした以外は実施例
１と同様に操作した。初回注水、攪拌後に粘稠な若干透
明性のある乳白色液体が得られ、最終的には乳白色のエ
マルションが得られた。粒子径等の評価結果を表２に示
す。
実施例４
初回注水量を15ｇ、希釈水量を20ｇとした以外は実施例
１と同様に操作した。初回注水、攪拌後に粘稠な乳白色
液体が得られ、最終的には乳白色のエマルションが得ら
れた。粒子径等の評価結果を表２に示す。
実施例５
初回注水量を18ｇ、希釈水量を17ｇとした以外は実施例
１と同様に操作した。初回注水、攪拌後に粘稠な乳白色
液体が得られ、最終的には乳白色のエマルションが得ら
れた。粒子径等の評価結果を表２に示す。
実施例６
初回注水量を22ｇ、希釈水量を13ｇとした以外は実施例
１と同様に操作した。初回注水、攪拌後に粘稠な乳白色
液体が得られ、最終的には乳白色のエマルションが得ら
れた。粒子径等の評価結果を表２に示す。
実施例７
エマルション組成−１を合計1500ｇとなる様に各成分を
用いた。２リットル容器を備えたアジホモミキサー（特
殊機化（株）製）に、ポリジメチルシロキサン１の 540
ｇとポリジメチルシロキサン３の 360ｇの混合物を入れ
て70℃に加熱した。この加熱は希釈水添加まで続けた。
またパドルミキサーの回転数を 60rpmとして攪拌を続け
た。この攪拌条件は最終エマルション抜き出しまで続け
た。ここにノニオン系界面活性剤１の18ｇとノニオン系
界面活性剤３の48ｇを加え、約20分間攪拌を続け、ノニ
オン系界面活性剤を溶融し、ポリジメチルシロキサンと
混合した。ここに初回注水として水を 225ｇ加え、さら
に攪拌を続けた。約20分間攪拌を続け、透明性のあるゲ
ル状物を得た。次に希釈水として残りの水 300ｇを加
え、約20分間攪拌して乳白色のエマルションを調製し、
実施例１と同様に評価した。なお、この実施例７は、実
施例４の装置変更およびスケールアップしたものとな
る。
実施例８
パドルミキサーの回転数を 15rpmにした以外は、実施例
７と同様に操作して乳白色のエマルションを調製し、同
様に評価した。Example 1 Each component was used so that the total amount of emulsion composition-1 was 100 g. A mixture of 36 g of polydimethylsiloxane 1 and 24 g of polydimethylsiloxane 3 was placed in a 200 cc flask and heated to 70 ° C. After that, heating at 70 ° C. was continued until the entire amount of water was added. To this, 1.2 g of the nonionic surfactant 1 and 3.8 g of the nonionic surfactant 3 were added,
Hand stirring was performed using a metal spatula. When stirring was continued for about 5 minutes while maintaining heating at 70 ° C., the nonionic surfactant was melted and mixed with polydimethylsiloxane. 8 g of water was added here as the first water injection, and stirring was continued. Stirring was continued for about 10 minutes to obtain a transparent gel-like material. Next, the remaining 27 g of water was added as dilution water, and the mixture was stirred for about 10 minutes while stopping heating at 70 ° C. and allowing it to cool to obtain a milky white emulsion. Table 2 shows the average particle size, mode particle size, and average particle size / mode particle size of this emulsion. Example 2 The same operation as in Example 1 was performed except that the initial water injection amount was 10 g and the dilution water amount was 25 g. After the first water injection and stirring, a viscous, slightly transparent milky white liquid was obtained, and finally a milky white emulsion was obtained. Table 2 shows the evaluation results of the particle size and the like. Example 3 The same operation as in Example 1 was carried out except that the initial water injection amount was 12 g and the dilution water amount was 23 g. After the first water injection and stirring, a viscous, slightly transparent milky white liquid was obtained, and finally a milky white emulsion was obtained. Table 2 shows the evaluation results of the particle size and the like. Example 4 The same operation as in Example 1 was carried out except that the initial water injection amount was 15 g and the dilution water amount was 20 g. A viscous milky white liquid was obtained after the initial water injection and stirring, and finally a milky white emulsion was obtained. Table 2 shows the evaluation results of the particle size and the like. Example 5 The same operation as in Example 1 was performed except that the initial water injection amount was 18 g and the dilution water amount was 17 g. A viscous milky white liquid was obtained after the initial water injection and stirring, and finally a milky white emulsion was obtained. Table 2 shows the evaluation results of the particle size and the like. Example 6 The same operation as in Example 1 was carried out except that the initial water injection amount was 22 g and the dilution water amount was 13 g. A viscous milky white liquid was obtained after the initial water injection and stirring, and finally a milky white emulsion was obtained. Table 2 shows the evaluation results of the particle size and the like. Example 7 Each component was used so that the total amount of emulsion composition-1 was 1500 g. Add 540 of polydimethylsiloxane 1 to an Ajihomoki mixer (made by Tokushu Kika Co., Ltd.) equipped with a 2-liter container.
g and 360 g of polydimethylsiloxane 3 were added and heated to 70 ° C. This heating was continued until the dilution water was added.
The rotation speed of the paddle mixer was set to 60 rpm and stirring was continued. This stirring condition was continued until the final emulsion was withdrawn. 18 g of the nonionic surfactant 1 and 48 g of the nonionic surfactant 3 were added thereto, and stirring was continued for about 20 minutes to melt the nonionic surfactant and mix it with polydimethylsiloxane. 225 g of water was added here as the first water injection, and stirring was continued. Stirring was continued for about 20 minutes to obtain a transparent gel-like material. Next, add the remaining 300 g of water as dilution water and stir for about 20 minutes to prepare a milky white emulsion,
Evaluation was performed in the same manner as in Example 1. The seventh embodiment is the same as the fourth embodiment except that the apparatus is changed and scaled up. Example 8 A milky white emulsion was prepared in the same manner as in Example 7 except that the rotation speed of the paddle mixer was changed to 15 rpm, and evaluated in the same manner.
【００１６】比較例１
エマルション組成−１を合計 100ｇとなる様に各成分を
用いた。 200ccフラスコ中に、ポリジメチルシロキサン
１の36ｇとポリジメチルシロキサン３の24ｇの混合物を
入れて70℃に加熱した。この後も70℃の加熱は全量の水
を加えるまで継続した。ここにノニオン系界面活性剤１
の1.2gとノニオン系界面活性剤３の3.8gを加え、金属ヘ
ラを用いて手攪拌した。70℃の加熱を保持したまま、約
５分間攪拌を続け、ノニオン系界面活性剤を溶融し、ポ
リジメチルシロキサンと混合した。ここに初回注水とし
て水を２ｇ加えて約10分間攪拌を続けた。さらに水２ｇ
を加えて10分間攪拌する操作を２回繰り返した。ここ
で、これまで粘稠な乳白色オイル状であったものが、透
明なゲル状物となった。さらに水２ｇを加えて10分間攪
拌する操作を８回繰り返し、次に希釈水として水の13ｇ
を加え、70℃の加熱を止めて放冷しながら攪拌を続けて
乳白色のエマルションを調製し、実施例１と同様に評価
した。
比較例２
初回注水した後の攪拌終了後、70℃の加熱を止めた以外
は、比較例１と同様に操作してエマルションを調製し、
同様に評価した。
比較例３
エマルション組成−１を合計1500ｇとなる様に各成分を
用いた。２リットル容器を備えたアジホモミキサー（特
殊機化（株）製）に、ポリジメチルシロキサン１の 540
ｇとポリジメチルシロキサン３の 360ｇの混合物を入れ
て70℃に加熱した。この加熱は希釈水添加まで続けた。
またパドルミキサーの回転数を 60rpmとして攪拌を続け
た。この攪拌条件は最終エマルション抜き出しまで続け
た。ここにノニオン系界面活性剤１の18ｇとノニオン系
界面活性剤３の48ｇを加え、約20分間攪拌を続け、ノニ
オン系界面活性剤を溶融させ、ポリジメチルシロキサン
と混合した。ここに初回注水として水の30ｇを加えて約
20分間攪拌を続けた。さらに水30ｇを加えて20分間攪拌
する操作を２回繰り返した。ここで、これまで粘稠な乳
白色オイル状であったものが、透明なゲル状物となっ
た。ここに水30ｇを加えて20分攪拌する操作を８回繰り
返し、次に希釈水としての水の 195ｇを加え、70℃の加
熱を止めて放冷しながら攪拌を続けて乳白色のエマルシ
ョンを調製し、実施例１と同様に評価した。なお、この
比較例３は、比較例１の装置変更およびスケールアップ
したものとなる。
比較例４
パドルミキサーの回転数を 15rpmとした以外は、比較例
３と同様に操作してエマルションを調製し、同様に評価
した。
比較例５
初回注水量を４ｇ、希釈水量を31ｇとした以外は実施例
１と同様に操作した。初回注水、攪拌後に粘稠な若干透
明性のある乳白色液体が得られたが、希釈水添加後攪拌
では希釈水がなじまず、乳白色のエマルションを得るこ
とができなかった。Comparative Example 1 Each component was used so that the total amount of emulsion composition-1 was 100 g. A 200 cc flask was charged with a mixture of 36 g of polydimethylsiloxane 1 and 24 g of polydimethylsiloxane 3 and heated to 70 ° C. After that, heating at 70 ° C. was continued until the entire amount of water was added. Nonionic surfactant 1 here
1.2 g and 3.8 g of the nonionic surfactant 3 were added, and the mixture was manually stirred using a metal spatula. While maintaining the heating at 70 ° C., the stirring was continued for about 5 minutes to melt the nonionic surfactant and mix it with polydimethylsiloxane. 2 g of water was added here as the first water injection, and stirring was continued for about 10 minutes. 2 g of water
The procedure of adding and stirring for 10 minutes was repeated twice. Here, what was previously a viscous milky white oil became a transparent gel. The procedure of adding 2 g of water and stirring for 10 minutes is repeated 8 times, and then 13 g of water is used as dilution water.
Was added, and the mixture was heated at 70 ° C. and allowed to cool, and stirring was continued to prepare a milky white emulsion, which was evaluated in the same manner as in Example 1. Comparative Example 2 An emulsion was prepared in the same manner as in Comparative Example 1, except that the heating at 70 ° C. was stopped after the completion of stirring after the initial water injection.
It evaluated similarly. Comparative Example 3 Each component was used so that the total amount of emulsion composition-1 was 1500 g. Add 540 of polydimethylsiloxane 1 to an Ajihomoki mixer (made by Tokushu Kika Co., Ltd.) equipped with a 2-liter container.
g and 360 g of polydimethylsiloxane 3 were added and heated to 70 ° C. This heating was continued until the dilution water was added.
The rotation speed of the paddle mixer was set to 60 rpm and stirring was continued. This stirring condition was continued until the final emulsion was withdrawn. 18 g of the nonionic surfactant 1 and 48 g of the nonionic surfactant 3 were added thereto, and stirring was continued for about 20 minutes to melt the nonionic surfactant and mix it with polydimethylsiloxane. About 30g of water is added as the first water injection here.
Stirring was continued for 20 minutes. The operation of adding 30 g of water and stirring for 20 minutes was repeated twice. Here, what was previously a viscous milky white oil became a transparent gel. Repeat the operation of adding 30 g of water and stirring for 20 minutes 8 times, then add 195 g of water as dilution water, stop heating at 70 ° C and continue stirring while cooling to prepare a milky white emulsion. The evaluation was performed in the same manner as in Example 1. It should be noted that this comparative example 3 is the same as the comparative example 1 except that the apparatus is changed and scaled up. Comparative Example 4 An emulsion was prepared in the same manner as in Comparative Example 3 except that the rotation speed of the paddle mixer was changed to 15 rpm, and the emulsion was evaluated in the same manner. Comparative Example 5 The same operation as in Example 1 was performed except that the initial water injection amount was 4 g and the dilution water amount was 31 g. A viscous, slightly transparent milky white liquid was obtained after the initial water injection and stirring, but the dilution water was not compatible with stirring after addition of the dilution water, and a milky white emulsion could not be obtained.
【００１７】実施例９
エマルション組成−２を合計 100ｇとなる様に各成分を
用いた。 200ccフラスコ中に、ポリジメチルシロキサン
１の36ｇとポリジメチルシロキサン３の24ｇおよびアミ
ノ基含有シロキサンの６ｇの混合物を入れて70℃に加熱
した。ここにノニオン系界面活性剤１の 1.8ｇとノニオ
ン系界面活性剤２の 1.1ｇおよびノニオン系界面活性剤
３の 3.1ｇを加え、金属ヘラを用いて手攪拌した。約５
分間攪拌を続け、ノニオン系界面活性剤を溶融させ、ポ
リジメチルシロキサンと混合した。ここに初回注水とし
て水８ｇを加え、さらに攪拌を続けた。約10分間攪拌を
続けたところ、透明性のあるゲル状物となった。次に、
希釈水として残りの水20ｇを加えて約10分間攪拌し、乳
白色のエマルションを調製し、実施例１と同様に評価し
た。
実施例10
初回注水量を20ｇ、希釈水量を８ｇとした以外は実施例
９と同様に操作した。初回注水、攪拌後に粘稠な乳白色
液体が得られ、最終的には乳白色のエマルションが得ら
れた。粒子径等の評価結果を表２に示す。
実施例11
エマルション組成−３を合計 100ｇとなる様に各成分を
用いた。 200ccフラスコ中に、ポリジメチルシロキサン
２の60ｇを入れて70℃に加熱した。ここにノニオン系界
面活性剤１の 1.5ｇとノニオン系界面活性剤３の２ｇ、
およびノニオン系界面活性剤４の 2.5ｇを加え、金属ヘ
ラを用いて手攪拌した。約５分間攪拌を続けて混合を行
った。ここに初回注水として水を10ｇ加え、さらに攪拌
を続けた。約10分間攪拌を続けたところ、透明性のある
ゲル状物となった。次に希釈水として残りの水24ｇを加
え約10分間攪拌し、乳白色のエマルションを調製して、
実施例１と同様に評価した。
実施例12
初回注水量を15ｇ、希釈水量を19ｇとした以外は実施例
11と同様に操作した。初回注水、攪拌後に粘稠な乳白色
液体が得られ、最終的には乳白色のエマルションが得ら
れた。粒子径等の評価結果を表２に示す。Example 9 Each component was used so that the total amount of emulsion composition-2 was 100 g. A mixture of 36 g of polydimethylsiloxane 1, 24 g of polydimethylsiloxane 3 and 6 g of amino group-containing siloxane was placed in a 200 cc flask and heated to 70 ° C. 1.8 g of the nonionic surfactant 1, 1.1 g of the nonionic surfactant 2 and 3.1 g of the nonionic surfactant 3 were added thereto, and the mixture was manually stirred using a metal spatula. About 5
The stirring was continued for a minute, the nonionic surfactant was melted and mixed with polydimethylsiloxane. 8 g of water was added here as initial water injection, and stirring was further continued. When stirring was continued for about 10 minutes, a transparent gel-like substance was formed. next,
The remaining 20 g of water was added as dilution water and stirred for about 10 minutes to prepare a milky white emulsion, which was evaluated in the same manner as in Example 1. Example 10 The same operation as in Example 9 was carried out except that the initial water injection amount was 20 g and the dilution water amount was 8 g. A viscous milky white liquid was obtained after the initial water injection and stirring, and finally a milky white emulsion was obtained. Shows the evaluation results of the particle diameter and the like in Table 2. Example 11 Emulsion composition- 3 was used with each component so that the total amount was 100 g. 60 g of polydimethylsiloxane 2 was placed in a 200 cc flask and heated to 70 ° C. 1.5 g of the nonionic surfactant 1 and 2 g of the nonionic surfactant 3 are added here.
And 2.5 g of the nonionic surfactant 4 were added, and the mixture was manually stirred using a metal spatula. Mixing was performed by continuing stirring for about 5 minutes. 10 g of water was added here as the first water injection, and stirring was continued. When stirring was continued for about 10 minutes, a transparent gel-like substance was formed. Next, add the remaining 24 g of water as dilution water and stir for about 10 minutes to prepare a milky white emulsion,
Evaluation was performed in the same manner as in Example 1. Example 12 Example except that the initial water injection amount was 15 g and the dilution water amount was 19 g
It operated like 11th . A viscous milky white liquid was obtained after the initial water injection and stirring, and finally a milky white emulsion was obtained. Table 2 shows the evaluation results of the particle size and the like.
【００１８】[0018]
【表２】 [Table 2]
【００１９】実施例１〜６は初回の注水量を変えたもの
であるが、得られる粒子径は変化し、またその分布は小
さいものであった。また、実施例７は実施例４と同一配
合で、装置およびスケールを変更したが、得られる粒子
径分布は同様であった。さらに、実施例８は、実施例７
と同装置、スケールながら攪拌の回転数を変えたが、や
はり得られる粒子径分布は同様であった。これに対し
て、比較例１と２では、乳化温度で得られる粒子径は変
化するものの、温度の高い比較例１では、分布は広くな
った。また、比較例３は比較例１と同一配合、同一温度
で、装置およびスケールを変更したが、得られた粒子径
は小さくなった。さらに、比較例４は、比較例３と同装
置、スケールながら攪拌の回転数を変えたが、得られた
粒子径は大きく、その分布は極端に広くなった。また実
施例９〜12では、界面活性剤やポリオルガノシロキサン
が異なる系でも、初回注水量を変えることで、粒子径を
変えることができ、その粒子径分布は比較的狭いもので
あった。In Examples 1 to 6, the initial water injection amount was changed, but the obtained particle size was changed and the distribution was small. Further, in Example 7, the same composition as in Example 4 was used, and the apparatus and scale were changed, but the obtained particle size distribution was the same. Furthermore, the eighth embodiment is the seventh embodiment.
Although the number of rotations of stirring was changed while using the same apparatus and scale, the particle size distribution obtained was the same. On the other hand, in Comparative Examples 1 and 2, although the particle size obtained at the emulsification temperature changed, in Comparative Example 1 where the temperature was high, the distribution was wide. Further, in Comparative Example 3, the same composition and the same temperature as in Comparative Example 1 were used, but the apparatus and scale were changed, but the obtained particle size became smaller. Further, in Comparative Example 4, although the number of revolutions of stirring was changed while using the same apparatus and scale as Comparative Example 3, the obtained particle size was large and the distribution thereof was extremely wide. Further, in Examples 9 to 12 , even in the system in which the surfactant and the polyorganosiloxane were different, the particle size could be changed by changing the initial water injection amount, and the particle size distribution was relatively narrow.
【００２０】以下に本発明のエマルションを化粧料に使
用した場合の実施例を示す。
実施例13（ヘアセット組成物）
実施例１で調製したエマルションを使用して、以下の組
成のヘアセット組成物を調製し、評価した。 結果を表
３に示す。
・組成
シリコーンエマルション（実施例１） 5.0 ％
ヒドロキシエチルセルロース 0.2 ％
エチルアルコール 10.0 ％
香料 0.2 ％
イオン交換水 84.6 ％
・評価方法
＜しなやかさ＞
長さ25cmの毛髪２ｇにヘアセット組成物４ｇを20cmの距
離から均一に塗布したのち、乾燥前に市販のくしで毛並
みを揃え、この毛髪を40℃の温風で60分間かけて乾燥
し、以下に示す評価基準に従って評価した。
○ … 手で触れるとごわつきがなく、自然な感触であ
る。
△ … 手で触れると少しごわつきがある。
× … 手で触れるとごわつきがひどく、かたい感触が
ある。
＜なめらかさ＞
長さ25cmの毛髪２ｇにヘアセット組成物４ｇを20cmの距
離から均一に塗布したのち、この毛髪を40℃の温風で60
分間かけて乾燥し、市販のくしを用いてそのくし通りの
状態を以下に示す評価基準に従って評価した。
○ … ひっかかりがなく、くしがなめらかに通る。
△ … ひっかかりはあるが、くしを通すことができ
る。
× … くしが通らない。
＜セット保持力＞
長さ25cmの毛髪２ｇにヘアセット組成物４ｇを20cmの距
離から均一に塗布したのち、この毛髪を外径1.2cm のカ
ーラーに巻き、40℃の温風で60分間かけて乾燥した。そ
の後、カーラーから毛髪をはずし、温度30℃、相対湿度
80％の雰囲気中に垂直に吊した直後の長さ（Ｌ１）と１
時間放置後の長さ（Ｌ２）を測定し、カールリテンショ
ンを次式から算出した。
カールリテンション（％）＝（２５−Ｌ２）／（２５−Ｌ１）×１００
尚、カールリテンションが60％以上のものを合格（表
中、「○」印）、また60％未満のものを不合格（表中、
「×」印）とした。The following are examples of using the emulsion of the present invention in cosmetics. Example 13 (Hair setting composition) Using the emulsion prepared in Example 1, a hair setting composition having the following composition was prepared and evaluated. The results are shown in Table 3. -Composition Silicone emulsion (Example 1) 5.0% Hydroxyethylcellulose 0.2% Ethyl alcohol 10.0% Perfume 0.2% Ion-exchanged water 84.6% -Evaluation method <suppleness> 2g hair with a length of 25cm and 4g of hair setting composition at a distance of 20cm Was evenly applied, the hair was lined up with a commercially available comb before drying, the hair was dried with warm air at 40 ° C. for 60 minutes, and evaluated according to the following evaluation criteria. ○… It does not feel stiff to the touch, and it feels natural. △… Slightly stiff when touched by hand. ×… It feels stiff when touched by hand and has a hard feeling. <Smoothness> 2 g of hair having a length of 25 cm is uniformly coated with 4 g of the hair-setting composition from a distance of 20 cm, and the hair is heated at 40 ° C. for 60 hours.
It was dried over a period of time, and the state of combing was evaluated using a commercially available comb according to the following evaluation criteria. ○… The comb passes smoothly without getting caught. △… Although there is a catch, it can pass through the comb. ×… The comb cannot pass. <Holding power> After uniformly applying 4g of hair setting composition to 2g of hair having a length of 25cm from a distance of 20cm, the hair is wound on a curler having an outer diameter of 1.2cm and heated with hot air at 40 ° C for 60 minutes. Dried. After that, remove the hair from the curlers, temperature 30 ℃, relative humidity
Length (L1) and 1 immediately after hanging vertically in 80% atmosphere
The length (L2) after standing for a time was measured, and the curl retention was calculated from the following equation. Curl retention (%) = (25-L2) / (25-L1) × 100 If the curl retention is 60% or more, it passes (“○” in the table), and if it is less than 60%, it fails. (In the table,
"X").
【００２１】実施例14
実施例４で調製したエマルションを使用した他は、実施
例13と同様にヘアセット組成物を調製し、評価した。
結果を表３に示す。
実施例15
実施例７で調製したエマルションを使用した他は、実施
例13と同様にヘアセット組成物を調製し、評価した。
結果を表３に示す。
実施例16
実施例９で調製したエマルションを使用した他は、実施
例13と同様にヘアセット組成物を調製し、評価した。
結果を表３に示す。
比較例６
比較例１で調製したエマルションを使用した他は、実施
例13と同様にヘアセット組成物を調製し、評価した。
結果を表３に示す。
比較例７
比較例４で調製したエマルションを使用した他は、実施
例13と同様にヘアセット組成物を調製し、評価した。
結果を表３に示す。Example 14 A hair setting composition was prepared and evaluated in the same manner as in Example 13 except that the emulsion prepared in Example 4 was used.
The results are shown in Table 3. Example 15 A hair setting composition was prepared and evaluated in the same manner as in Example 13 except that the emulsion prepared in Example 7 was used.
The results are shown in Table 3. Example 16 A hair setting composition was prepared and evaluated in the same manner as in Example 13 except that the emulsion prepared in Example 9 was used.
The results are shown in Table 3. Comparative Example 6 A hair setting composition was prepared and evaluated in the same manner as in Example 13 except that the emulsion prepared in Comparative Example 1 was used.
The results are shown in Table 3. Comparative Example 7 A hair setting composition was prepared and evaluated in the same manner as in Example 13 except that the emulsion prepared in Comparative Example 4 was used.
The results are shown in Table 3.
【００２２】[0022]
【表３】 [Table 3]
【００２３】実施例17、比較例８（シャンプー組成物）
実施例１または比較例１で調製したエマルションを使用
して、以下の組成のシャンプー組成物を２種類調製し、
評価した。
・組成
シリコーンエマルション（実施例１または比較例１） 3.0 ％
ポリオキシエチレンラウリルエーテル 15.0 ％
ラウリン酸ジエタノールアミド 5.0 ％
香料 0.2 ％
イオン交換水 76.8 ％
実施例１のエマルションを使用したシャンプー組成物
（実施例17）は、髪へ良好なつやを与え、さっぱりとし
た感触を付与することができ、かつ安定性も良好であっ
た。これに対して、比較例１のエマルションを使用した
シャンプー組成物（比較例８）は、やや良好程度の感触
を付与することができるものの、髪へのつやの付与や安
定性が不充分であった。Example 17 , Comparative Example 8 (Shampoo Composition) Using the emulsion prepared in Example 1 or Comparative Example 1, two kinds of shampoo compositions having the following compositions were prepared,
evaluated. Composition Silicone emulsion (Example 1 or Comparative Example 1) 3.0% polyoxyethylene lauryl ether 15.0% Lauric acid diethanolamide 5.0% Fragrance 0.2% Ion-exchanged water 76.8% Shampoo composition using the emulsion of Example 1 (Example 17 ) was able to give good gloss to the hair, give a refreshing feel, and had good stability. On the other hand, the shampoo composition using the emulsion of Comparative Example 1 (Comparative Example 8) was able to impart a somewhat good feel, but was insufficient in imparting gloss to hair and stability. .
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) A61K 7/00 - 7/50 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) A61K 7/ 00-7/50
Claims (3)
コーンエマルションを製造するにあたり、界面活性剤と
してノニオン系界面活性剤を使用し、且つポリオルガノ
シロキサンとノニオン系界面活性剤との混合物中に、転
相点以上の水を１度に加えて混合攪拌後、残りの水を加
えて希釈することを特徴とするシリコーンエマルション
の製造方法。1. When a polyorganosiloxane O / W type silicone emulsion is produced, a surfactant is used.
Then, nonionic surfactant is used, and in the mixture of polyorganosiloxane and nonionic surfactant, water having a phase inversion point or higher is added at once and mixed and stirred, and the remaining water is added to dilute. A method for producing a silicone emulsion, comprising:
マルション平均粒子径が１〜100 μｍであるシリコーン
エマルション。2. A silicone emulsion having an emulsion average particle size of 1 to 100 μm, which is obtained by the production method according to claim 1.
を含んでなることを特徴とする毛髪化粧料。3. A hair cosmetic comprising the silicone emulsion according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11677597A JP3367863B2 (en) | 1997-05-07 | 1997-05-07 | Silicone emulsion, method for producing the same, and hair cosmetic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11677597A JP3367863B2 (en) | 1997-05-07 | 1997-05-07 | Silicone emulsion, method for producing the same, and hair cosmetic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10306013A JPH10306013A (en) | 1998-11-17 |
| JP3367863B2 true JP3367863B2 (en) | 2003-01-20 |
Family
ID=14695421
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11677597A Expired - Lifetime JP3367863B2 (en) | 1997-05-07 | 1997-05-07 | Silicone emulsion, method for producing the same, and hair cosmetic |
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|---|---|---|---|---|
| KR100425259B1 (en) * | 2001-02-15 | 2004-03-30 | 한국콜마 주식회사 | Water in silicone(W/S) emulsion and its manufacturing method using line typed ultra mill |
| GB0209136D0 (en) * | 2002-04-22 | 2002-05-29 | Procter & Gamble | Durable hair treatment composition |
| ATE404570T1 (en) * | 2003-05-16 | 2008-08-15 | Dow Corning | METHOD FOR PRODUCING EMULSIONS CONTAINING ELASTOMERIC SILANES AND SILOXANES WITH QUATERNARY AMMONIUM GROUPS |
| DE602004027047D1 (en) * | 2003-07-23 | 2010-06-17 | Dow Corning | MECHANICAL INVERSION PROCESS FOR THE PRODUCTION OF SILICONE OIL IN WATER EMULSIONS |
| JP4681234B2 (en) * | 2004-01-06 | 2011-05-11 | 株式会社資生堂 | One-phase microemulsion composition and method for producing the same |
| EP1702607B1 (en) | 2004-01-06 | 2017-04-05 | Shiseido Company, Ltd. | Monophase microemulsion composition, o/w ultrafine emulsion external formulation and process for producing the same |
| JP4762495B2 (en) * | 2004-01-06 | 2011-08-31 | 株式会社 資生堂 | Method for producing O / W ultra fine emulsion external preparation |
| JP4246091B2 (en) * | 2004-03-22 | 2009-04-02 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Hair cosmetic composition |
| EP1591102A1 (en) | 2004-04-30 | 2005-11-02 | The Procter & Gamble Company | Process and kit-of-parts for improved hair conditioning after coloring, bleaching or perming |
| JP4728283B2 (en) * | 2006-05-22 | 2011-07-20 | 花王株式会社 | Aqueous hair cleanser |
| JP5551341B2 (en) * | 2008-03-19 | 2014-07-16 | 東レ・ダウコーニング株式会社 | Oil-in-water organopolysiloxane emulsion composition, cosmetic raw material comprising the same, and method for producing hair cosmetics using the same |
| JP2014077150A (en) * | 2014-02-05 | 2014-05-01 | Dow Corning Toray Co Ltd | Oil-in-water type organopolysiloxane emulsion composition, cosmetic raw material containing same and method for producing hair cosmetic using same |
| WO2017061099A1 (en) * | 2015-10-05 | 2017-04-13 | 東レ・ダウコーニング株式会社 | Oil-in-water type organopolysiloxane emulsion and method for producing same, cosmetic raw material, and cosmetic product |
-
1997
- 1997-05-07 JP JP11677597A patent/JP3367863B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10306013A (en) | 1998-11-17 |
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