JPH07196946A - Pigment or extender pigment treated with organic silicon compound, its production and cosmetic - Google Patents

Pigment or extender pigment treated with organic silicon compound, its production and cosmetic

Info

Publication number
JPH07196946A
JPH07196946A JP35319593A JP35319593A JPH07196946A JP H07196946 A JPH07196946 A JP H07196946A JP 35319593 A JP35319593 A JP 35319593A JP 35319593 A JP35319593 A JP 35319593A JP H07196946 A JPH07196946 A JP H07196946A
Authority
JP
Japan
Prior art keywords
pigment
treated
molecular weight
group
extender
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
JP35319593A
Other languages
Japanese (ja)
Other versions
JP3567335B2 (en
Inventor
Yukio Hasegawa
幸夫 長谷川
Ryota Miyoshi
良太 三好
Isao Imai
功 今井
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.)
Miyoshi Kasei Inc
Original Assignee
Miyoshi Kasei Inc
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Filing date
Publication date
Application filed by Miyoshi Kasei Inc filed Critical Miyoshi Kasei Inc
Priority to JP35319593A priority Critical patent/JP3567335B2/en
Publication of JPH07196946A publication Critical patent/JPH07196946A/en
Application granted granted Critical
Publication of JP3567335B2 publication Critical patent/JP3567335B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

PURPOSE:To obtain a pigment treated with an organic silicon compound, having high silicone oil absorption, free from residual hydrogen, exhibiting extremely high smoothness and good adhesion, giving fine particles of colored pigment having excellent color developability and, accordingly, useful to be compounded to make-up cosmetics such as powder foundation, liquid foundation, rouge and eye shadow to remarkably contribute to the quality improvement and give a cosmetic exhibiting smooth feeling unattainable by conventional cosmetic. CONSTITUTION:This pigment or extender pigment treated with an organic silicon compound is produced by adsorbing a straight-chain reactive alkylpolysiloxane having amino-hydrogen group, halogen atom, hydroxyl group or alkoxy group on one molecular chain terminal and having a degree of polymerization of 25-100 and an Mw/Mn ratio of 1.0-1.3 (Mw is weight-average molecular weight and Mn is number-average molecular weight) to the surface of a pigment or an extender pigment by heat-treatment. This invention also relates to the process for the production of the treated pigment and a cosmetic containing the treated pigment.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は有機ケイ素化合物処理顔
料または体質顔料、その製法および化粧料に関するもの
である。さらに詳しくは、本発明は、滑らかで、付着
性、展色性に優れ、かつ残留水素の全くない、有機ケイ
素化合物で表面処理された顔料または体質顔料、その製
法ならびにそれらの顔料を含む化粧料に関するものであ
り、特に本発明の上記処理顔料または体質顔料は滑らか
さに優れ、化粧料用として好適である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organosilicon compound-treated pigment or an extender pigment, a process for producing the same and a cosmetic. More specifically, the present invention relates to a pigment or an extender pigment surface-treated with an organosilicon compound, which is smooth, has excellent adhesion and color development properties, and has no residual hydrogen, a process for producing the same, and a cosmetic composition containing the pigment. In particular, the treated pigment or extender pigment of the present invention is excellent in smoothness and is suitable for cosmetics.

【０００２】[0002]

【従来の技術】有機ケイ素化合物、特にメチルハイドロ
ジェンポリシロキサンで表面処理された顔料または体質
顔料は撥水性が高く、主に化粧くずれの防止や２ウェイ
タイプの化粧料に近年広く用いられている。通常、よく
行われている表面処理法ではシリコーン分子内の反応基
Ｓｉ−Ｈは１００％反応せず、水素の残留率（反応率）
は３０％〜６０％である。メチルハイドロジェンポリシ
ロキサンの場合、架橋重合反応は立体障害のために完全
には進行せず、水素が残留する。水素の残留する顔料ま
たは体質顔料を化粧料に配合すると、化粧料製造工程に
おいてアルカリ成分または酸性条件下で残留水素がガス
として発生して爆発の危険性があり、また製造後の製品
において経時的に化粧料容器の膨張やコンパクトのミラ
ーの曇り等を引き起こす等の問題があった。また、熱に
弱い顔料、例えば黄色酸化鉄、紺青、赤色２０２号（リ
ゾールルビンＢＣＡ）は触媒を用いて低温で処理するこ
とも提案されているが、この方法は触媒が残留するため
に好ましくない。2. Description of the Related Art Pigments surface-treated with an organosilicon compound, especially methylhydrogenpolysiloxane, or extender pigments have high water repellency and have been widely used in recent years mainly for preventing makeup loss and for 2-way type cosmetics. . Generally, in the surface treatment method that is often performed, the reactive group Si-H in the silicone molecule does not react 100%, and the residual rate of hydrogen (reaction rate)
Is 30% to 60%. In the case of methyl hydrogen polysiloxane, the cross-linking polymerization reaction does not proceed completely due to steric hindrance, and hydrogen remains. When a pigment or extender pigment with residual hydrogen is mixed with cosmetics, there is a risk of explosion due to residual hydrogen being evolved as a gas under alkaline conditions or acidic conditions in the cosmetic production process. However, there are problems such as expansion of the cosmetic container and fogging of the compact mirror. It has also been proposed to treat a heat-sensitive pigment such as iron oxide yellow, navy blue, red No. 202 (Resol Rubin BCA) at a low temperature with a catalyst, but this method is not preferable because the catalyst remains.

【０００３】メチルハイドロジェンポリシロキサン処理
の改良法として、酸性物質やアルカリ金属の水酸化物を
添加することによって反応率を上げる方法が提案されて
いる。しかし、メチルハイドロジェンポリシロキサンの
反応は架橋重合であり、反応後は網目状の三次元構造を
とるため、樹脂化の方向へ進み単独のシリコーン樹脂粒
子の生成、顔料粒子の造粒、または強い凝集を引き起こ
してしまう。この結果、生成された処理顔料はガサガサ
した感触となり、展色性および皮膚への付着性が著しく
悪い。その他の改良法としてジェットアトマイザー等に
よるメカノケミカル処理が提案されている。しかし、こ
の方法によっても、メチルハイドロジェンポリシロキサ
ンで処理した場合、顔料の種類によって異なるが反応率
はせいぜい２０〜７０％であり、残留水素による上記問
題は依然として解決されない。また、粉砕力を利用する
ため薄片状や針状等の形状を特徴とする顔料または体質
顔料では形状が変化してしまう。さらに、特殊な設備を
必要とするため少量多品種の生産としては作業性の点で
実用的ではない。さらに別の改良法として、シリコン１
分子中の官能基、すなわちＳｉ−Ｈ基数を減らす方法が
あるが、基材（顔料）表面との反応性に乏しく、撥水性
が低下し、望ましいものではなかった。As a method for improving the treatment of methylhydrogenpolysiloxane, a method of increasing the reaction rate by adding an acidic substance or a hydroxide of an alkali metal has been proposed. However, the reaction of methylhydrogenpolysiloxane is a cross-linking polymerization, and after the reaction takes on a network-like three-dimensional structure, it progresses to the direction of resinization, producing independent silicone resin particles, granulation of pigment particles, or strong It causes aggregation. As a result, the resulting treated pigment has a dull feel, and the color developability and adhesion to the skin are extremely poor. As another improvement method, mechanochemical treatment using a jet atomizer or the like has been proposed. However, even with this method, when treated with methylhydrogenpolysiloxane, the reaction rate is at most 20 to 70%, although it varies depending on the type of pigment, and the above problems due to residual hydrogen cannot be solved yet. Further, since the pulverizing force is used, the shape of a pigment or an extender characterized by a flaky shape or a needle shape changes. Furthermore, since special equipment is required, it is not practical in terms of workability as a small-quantity, high-mix production. As another improvement method, silicon 1
Although there is a method of reducing the number of functional groups in the molecule, that is, the number of Si-H groups, it is not desirable because the reactivity with the surface of the base material (pigment) is poor and the water repellency is reduced.

【０００４】また、上記残留水素の問題を解決するため
に、ジメチルポリシロキサンを表面処理剤として使用す
ることが考えられるが、これにより低温で処理した場
合、顔料表面に吸着せず、また高温（２００〜３５０
℃）で処理した場合、メチル基の切断により架橋重合反
応が起こり、本発明の意図する特性が得られない。Further, in order to solve the above-mentioned problem of residual hydrogen, it is possible to use dimethylpolysiloxane as a surface treatment agent. However, when treated at a low temperature, it does not adsorb on the pigment surface and also at a high temperature ( 200-350
When treated at (° C.), a cross-linking polymerization reaction occurs due to the cleavage of the methyl group, and the characteristics intended by the present invention cannot be obtained.

【０００５】[0005]

【発明が解決しようとする課題】本発明は上記の問題点
を解消するためになされたものであり、皮膚への付着性
に優れ、凝集がなく、特に滑らかで感触がよく、着色顔
料混合時に非常に彩度の高い色調を有し、残留水素がな
い、有機ケイ素化合物処理顔料または体質顔料を提供す
ることを課題とする。本発明の課題はまた、熱に弱い顔
料でも触媒を使用せずに低温で処理でき、しかも従来の
設備を変更することなく簡単に処理できる処理顔料の提
供にある。さらに、上記処理顔料の製法および該処理顔
料を含む化粧料の提供も本発明の課題である。The present invention has been made in order to solve the above-mentioned problems, and it has excellent adhesion to the skin, no aggregation, and is particularly smooth and has a good feel. An object of the present invention is to provide an organosilicon compound-treated pigment or an extender pigment having a very saturated color tone and no residual hydrogen. Another object of the present invention is to provide a treated pigment which can be treated at a low temperature without using a catalyst even with a pigment which is susceptible to heat, and can be easily treated without changing the conventional equipment. Further, it is an object of the present invention to provide a method for producing the above treated pigment and to provide a cosmetic containing the treated pigment.

【０００６】[0006]

【課題を解決するための手段】すなわち、本発明は、重
合度が２５〜１００、重量平均分子量（Ｍｗ）と数平均
分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が１．０〜１．３
である、一方の分子鎖末端にアミノ水素基、ハロゲン原
子、水酸基またはアルコキシ基を有する直鎖状の反応性
アルキルポリシロキサンを加熱処理により顔料または体
質顔料の表面に配向吸着させたことを特徴とする有機ケ
イ素化合物処理顔料または体質顔料に関する。That is, according to the present invention, the degree of polymerization is 25 to 100, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 1. Three
Which is characterized in that a linear reactive alkylpolysiloxane having an amino hydrogen group, a halogen atom, a hydroxyl group or an alkoxy group at one of the molecular chain ends is oriented and adsorbed on the surface of a pigment or an extender pigment by heat treatment. And an extender pigment treated with an organosilicon compound.

【０００７】本発明において使用される直鎖状の反応性
アルキルポリシロキサンは、一方のみの分子鎖末端にア
ミノ水素基（ＮＨ，ＮＨ2 ）、ハロゲン原子（例えばＣ
ｌ，Ｂｒ，Ｉ）、水酸基（ＯＨ）またはアルコキシ基
（ＯＲ，ただしＲはアルキル基を表す）の反応性基を有
し、かつ、重合度２５〜１００、好ましくは３０〜６
０、特に３０ないし５０で、重量平均分子量（Ｍｗ）と
数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が１．０〜
１．３である反応性アルキルポリシロキサンである。The linear reactive alkyl polysiloxane used in the present invention has an amino hydrogen group (NH, NH 2 ) and a halogen atom (for example, C
1, Br, I), a hydroxyl group (OH) or an alkoxy group (OR, where R represents an alkyl group) as a reactive group and has a degree of polymerization of 25 to 100, preferably 30 to 6
0, particularly 30 to 50, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to
It is a reactive alkyl polysiloxane which is 1.3.

【０００８】上記反応性アルキルポリシロキサンは重合
度が２５〜１００であるが、これは２５未満であると、
撥水効果、滑らかさ等に劣りシリコーンの特性が発揮さ
れず、１００を越えると顔料または体質顔料表面との反
応性に乏しく、好ましくないことによる。また、重量平
均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ
／Ｍｎ）は一般に分子量分散度と呼ばれるが、本発明に
おいては１．０〜１．３の範囲内であることが必要であ
るが、これは１．０未満のものは理論上存在し得ず、そ
して１．３を越えると、分子量分布が広範になり、顔料
に配向吸着した場合に、本発明の意図する特性、特に感
触の滑らかさが得られないことによる。この分子量分散
度はゲル浸透クロマトグラフィー（ＧＰＣ）により慣用
の方法で決定され得るものである。なお、一般に入手可
能なシリコーンの分子量分散度は通常１．４〜２．０の
範囲であるが、本発明においては単分散シリコーンオイ
ルと呼ばれる１．０〜１．３の範囲でなければならな
い。本発明において使用される単分散シリコーンオイル
および従来のシリコーンオイルのＧＰＣにより得られる
クロマトグラム（ＧＰＣチャート）を図１に示した（ａ
が本発明の分子量分散度１．１７のものであり、ｂが従
来の分子量分散度１．９のものである）。なお、図１に
示すＧＰＣチャートは横軸が溶出量（溶出開始からの時
間で表す）を示し、縦軸が溶質の濃度を示す。本発明の
ものが鋭いピークを示すことが明瞭である。本発明にお
いて使用され得るこのような単分散シリコーンオイルは
下で記載する方法により製造され得る。The above-mentioned reactive alkyl polysiloxane has a degree of polymerization of 25 to 100, and when it is less than 25,
This is because the water-repellent effect and smoothness are inferior and the characteristics of silicone are not exhibited. When it exceeds 100, the reactivity with the surface of the pigment or the extender pigment is poor, which is not preferable. In addition, the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn).
/ Mn) is generally called a molecular weight dispersity, but in the present invention, it is necessary that it is in the range of 1.0 to 1.3, but if it is less than 1.0, it cannot theoretically exist. And, when it exceeds 1.3, the molecular weight distribution becomes wide, and when the pigment is oriented and adsorbed, the characteristics intended by the present invention, particularly the smoothness of feeling, cannot be obtained. This molecular weight dispersity can be determined by conventional methods by gel permeation chromatography (GPC). The molecular weight dispersity of commonly available silicones is usually in the range of 1.4 to 2.0, but in the present invention, it must be in the range of 1.0 to 1.3 called monodisperse silicone oil. The chromatogram (GPC chart) obtained by GPC of the monodisperse silicone oil used in the present invention and the conventional silicone oil is shown in FIG.
Of the present invention has a molecular weight dispersity of 1.17, and b has a conventional molecular weight dispersity of 1.9). In the GPC chart shown in FIG. 1, the horizontal axis represents the elution amount (represented by the time from the start of elution) and the vertical axis represents the solute concentration. It is clear that the present invention exhibits a sharp peak. Such monodisperse silicone oils that can be used in the present invention can be prepared by the methods described below.

【０００９】本発明において使用し得る反応性アルキル
ポリシロキサンは例えば次式Ｉ： Ｒ（Ｒ2 ＳｉＯ）n ＳｉＲ3-m （ＹＸ）m （Ｉ） （式中、Ｒは互いに独立してアルキル基、例えばメチル
基、エチル基、プロピル基等を表し、Ｘはアミノ水素
基、ハロゲン原子、水酸基またはアルコキシ基を表し、
Ｙは直接結合、または二価の炭化水素基、例えばメチレ
ン基、エチレン基、ブチレン基等を表し、それらの水素
原子はその他の置換基により置換されていてもよく、ｍ
は１〜３の整数を表し、そしてｎは２５ないし１００、
好ましくは３０〜６０、特に３０ないし５０の整数を表
す）で表されるか、または次式ＩＩ： 〔Ｒ（Ｒ2 ＳｉＯ）n ＳｉＲ2 〕2 ＮＨ （ＩＩ） （式中、Ｒおよびｎは上記式Ｉに対して定義されたもの
と同じ意味を表す）で表されるものである。Reactive alkyl polysiloxanes which can be used in the present invention include, for example, the following formula I: R (R 2 SiO) n SiR 3-m (YX) m (I) (wherein R is independently of each other an alkyl group). , For example, a methyl group, an ethyl group, a propyl group and the like, X represents an amino hydrogen group, a halogen atom, a hydroxyl group or an alkoxy group,
Y represents a direct bond or a divalent hydrocarbon group such as a methylene group, an ethylene group, a butylene group, etc., and those hydrogen atoms may be substituted with other substituents, m
Represents an integer of 1 to 3, and n is 25 to 100,
Preferably represented by an integer of 30 to 60, particularly 30 to 50) or represented by the following formula II: [R (R 2 SiO) n SiR 2 ] 2 NH (II) (wherein R and n are Has the same meaning as defined for formula I above).

【００１０】このようなアルキルポリシロキサンとして
は、例えばジメチルポリシロキシシラザン、α−モノヒ
ドロキシシロキサン、α，ω−ジヒドロキシポリジメチ
ルシロキサン、α−モノアルコキシポリジメチルシロキ
サン、α−ジアルコキシポリジメチルシロキサン、α−
トリアルコキシポリジメチルシロキサン、α，ω−ジア
ルコキシポリジメチルシロキサン、α，ω−ヘキサアル
コキシポリジメチルシロキサン、ジメチルポリシロキシ
クロリド、ジメチルポリシロキシブロミドおよびジメチ
ルポリシロキシイオジン等を挙げることができる。中で
もα−モノアルコキシポリジメチルシロキサン、α−ジ
アルコキシポリジメチルシロキサンおよびα−トリアル
コキシポリジメチルシロキサン（例としてα−トリエト
キシポリジメチルシロキサン等）が顔料表面との反応性
が非常に良好であり、特に滑らかな感触の処理顔料を与
えるため、好ましい。Examples of such alkyl polysiloxanes include dimethylpolysiloxysilazane, α-monohydroxysiloxane, α, ω-dihydroxypolydimethylsiloxane, α-monoalkoxypolydimethylsiloxane, α-dialkoxypolydimethylsiloxane and α. −
Examples thereof include trialkoxypolydimethylsiloxane, α, ω-dialkoxypolydimethylsiloxane, α, ω-hexaalkoxypolydimethylsiloxane, dimethylpolysiloxycyclolide, dimethylpolysiloxybromide and dimethylpolysiloxyiodine. Among them, α-monoalkoxypolydimethylsiloxane, α-dialkoxypolydimethylsiloxane and α-trialkoxypolydimethylsiloxane (eg, α-triethoxypolydimethylsiloxane) have very good reactivity with the pigment surface, It is preferable because it gives a treated pigment having a particularly smooth feel.

【００１１】上記本発明の反応性アルキルポリシロキサ
ンは、例えば以下の方法により製造され得る。 反応性末端基がＯＨ基である化合物（片末端シラノ
ール化合物） 相当する環状トリシロキサン（例えばヘキサメチルシク
ロトリシロキサン）を相当するトリアルキルシラノール
（例えばトリメチルシラノール）の存在下に次式：The above-mentioned reactive alkyl polysiloxane of the present invention can be produced, for example, by the following method. Compounds in which the reactive end group is an OH group (one-end silanol compound) The corresponding cyclic trisiloxane (eg hexamethylcyclotrisiloxane) in the presence of the corresponding trialkylsilanol (eg trimethylsilanol) has the formula:

【化１】 で表される５価のケイ素錯体触媒を使用して開環重合さ
せる。なお、上記片末端シラノール化合物は、例えばア
ニオン重合触媒によるリビング重合、硝酸、トリフロロ
メタンスルホン酸、スルホン酸基含有イオン交換樹脂、
塩酸、活性白土等を用いる酸触媒重合、水酸化カリウ
ム、水酸化リチウム、テトラメチルアンモニウムヒドロ
キシド、トリメチルベンジルアンモニウムヒドロキシ
ド、テトラブチルフォスフォニウムヒドロキシド等を用
いるアルカリ触媒重合などが知られており、これらの方
法を用いて製造し得るが、片末端シラノール化合物中に
不純物として両末端シラノール化合物が少量でも存在す
ると、最終生成物のメタクリル官能性ジアルキルポリシ
ロキサン中に２官能性メタクリレート置換シロキサンが
含有される場合があり、このような２官能性メタクリレ
ート置換シロキサン含有のメタクリル官能性ジアルキル
ポリシロキサンをビニル系モノマーと共重合させると、
ゲル化を起こしやすくなる傾向がある。それ故に、本発
明においては、上記５価のケイ素錯体触媒を使用する開
環重合が、片末端シラノール化合物の製造方法として好
ましいものである。すなわち、この５価のケイ素錯体触
媒を使用する方法により、特定の重合度および分子量分
散度を有し、分子鎖末端に水酸基を持つ、本発明におけ
る使用に適する反応性アルキルポリシロキサンが得られ
る。 その他の反応性末端基の誘導 前項で得られた片末端シラノール化合物を、所望の反
応性末端基を形成し得るオルガノシラン、例えばオルガ
ノシラザン、オルガノハロゲンシラン、またはオルガノ
アルコキシシラン（例：トリエトキシシラン等）と慣用
の方法に従って反応させることにより、水酸基以外の反
応性末端基を有する反応性アルキルポリシロキサンが製
造される。 その他の方法 まず、相当する環状トリシロキサンまたは環状テトラシ
ロキサンを、アルカリ金属シラノレートおよびシロキサ
ノレート、第四アンモニウムおよび第四フォスフォニウ
ムシラノレートおよびシロキサノレート、およびリチウ
ムのアルキル、アルケニルまたはアリル化合物からなる
群から選択される塩基性触媒の存在下、有機溶剤、例え
ばトルエンまたはキシレン中、開環重合を進め、出発物
質の５０重量％またはそれ以下が重合体に変化した段階
で重合を停止させることにより、分子量分散度が１．３
以下のシロキサン重合体を得る。なお、重合の停止は弱
酸性の化合物、例えば固形二酸化炭素を添加することに
より行われ得、重合度は反応条件を適宜変化させること
により選択され得る。次に、得られたシロキサン重合体
の一方の分子鎖末端に所望の反応性末端基を慣用の方法
に従って導入することにより、本発明に使用し得る反応
性アルキルポリシロキサンとすることができる。[Chemical 1] Ring-opening polymerization is carried out using a pentavalent silicon complex catalyst represented by The one-end silanol compound is, for example, living polymerization using an anionic polymerization catalyst, nitric acid, trifluoromethanesulfonic acid, a sulfonic acid group-containing ion exchange resin,
Acid-catalyzed polymerization using hydrochloric acid, activated clay, etc., alkali-catalyzed polymerization using potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, tetrabutylphosphonium hydroxide, etc. are known. However, even if a small amount of both-end silanol compound is present as an impurity in the one-end silanol compound, the methacryl-functional dialkyl polysiloxane of the final product contains a difunctional methacrylate-substituted siloxane. When a methacryl-functional dialkyl polysiloxane containing such a bifunctional methacrylate-substituted siloxane is copolymerized with a vinyl-based monomer,
It tends to cause gelation. Therefore, in the present invention, ring-opening polymerization using the above-mentioned pentavalent silicon complex catalyst is preferable as a method for producing a silanol compound having one terminal. That is, the method using the pentavalent silicon complex catalyst provides a reactive alkylpolysiloxane having a specific degree of polymerization and molecular weight dispersity and having a hydroxyl group at the end of the molecular chain, which is suitable for use in the present invention. Derivatization of Other Reactive End Group The one-terminal silanol compound obtained in the preceding section is converted into an organosilane capable of forming a desired reactive end group, for example, organosilazane, organohalogensilane, or organoalkoxysilane (eg, triethoxysilane). Etc.) according to a conventional method to produce a reactive alkyl polysiloxane having a reactive end group other than a hydroxyl group. Other Methods First, the corresponding cyclic trisiloxane or cyclic tetrasiloxane is prepared from alkali metal silanolates and siloxanolates, quaternary ammonium and quaternary phosphonium silanolates and siloxanolates, and lithium alkyl, alkenyl or allyl compounds. Proceeding ring-opening polymerization in an organic solvent such as toluene or xylene in the presence of a basic catalyst selected from the group consisting of, and terminating the polymerization when 50% by weight or less of the starting material is converted into a polymer. Therefore, the molecular weight dispersity is 1.3
The following siloxane polymer is obtained. The termination of the polymerization can be carried out by adding a weakly acidic compound such as solid carbon dioxide, and the degree of polymerization can be selected by appropriately changing the reaction conditions. Next, a desired reactive terminal group is introduced into one end of the molecular chain of the obtained siloxane polymer by a conventional method to obtain a reactive alkyl polysiloxane usable in the present invention.

【００１２】本発明において顔料または体質顔料とは、
無機顔料例えば酸化チタン、酸化亜鉛、酸化ジルコニウ
ム、黄色酸化鉄、黒色酸化鉄、ベンガラ、群青、紺青、
酸化クロムまたは水酸化クロム等、真珠光沢顔料例えば
雲母チタンまたはオキシ塩化ビスマス等、有機色素例え
ばタール色素または天然色素等、粉体例えばシリカビー
ズまたはナイロンもしくはアクリル等のプラスチックビ
ーズ等、タルク、カオリン、白雲母、絹雲母、その他の
雲母類、炭酸マグネシウム、炭酸カルシウム、ケイ酸ア
ルミニウム、ケイ酸マグネシウム、ケイ酸カルシウム、
クレー類等を包含する。中でも、粒径１μｍ以下の微粒
子いわゆる超微粒子酸化チタン、微粒子酸化チタンまた
は着色顔料（例えば黄色酸化鉄、黒色酸化鉄、ベンガ
ラ、群青、紺青、酸化クロム、水酸化クロムまたはター
ル色素等）が滑らかさ、付着性および展色性の点で非常
に良好であり、本発明における使用に好適である。In the present invention, the pigment or extender pigment means
Inorganic pigments such as titanium oxide, zinc oxide, zirconium oxide, yellow iron oxide, black iron oxide, red iron oxide, ultramarine blue, dark blue,
Chromium oxide or chromium hydroxide, pearlescent pigments such as mica titanium or bismuth oxychloride, organic pigments such as tar pigments or natural pigments, powders such as silica beads or plastic beads such as nylon or acrylic, talc, kaolin, white clouds Mother, sericite, other mica, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, calcium silicate,
Including clays and the like. Among them, fine particles having a particle size of 1 μm or less, so-called ultrafine particle titanium oxide, fine particle titanium oxide or color pigments (for example, yellow iron oxide, black iron oxide, red iron oxide, ultramarine blue, navy blue, chromium oxide, chromium hydroxide or tar pigment) are smooth. It is very good in terms of adhesion and color developability and is suitable for use in the present invention.

【００１３】本発明において、有機ケイ素化合物、すな
わち直鎖状の反応性アルキルポリシロキサンの配合量
は、処理しようとする顔料または体質顔料の粒径や比表
面積により異なるが、顔料または体質顔料に対して０．
１〜３０重量％の範囲で通常用いられる。特に２〜５重
量％の範囲が好ましい。In the present invention, the blending amount of the organosilicon compound, that is, the linear reactive alkylpolysiloxane varies depending on the particle size and the specific surface area of the pigment or extender pigment to be treated, but is different from that of the pigment or extender pigment. 0.
It is usually used in the range of 1 to 30% by weight. Particularly, the range of 2 to 5% by weight is preferable.

【００１４】本発明の有機ケイ素化合物処理顔料または
体質顔料は、上記本発明の直鎖状の反応性アルキルポリ
シロキサン、該ポリシロキサンを溶解する有機溶媒、お
よび顔料または体質顔料を混合し、そしてこの混合物を
加熱処理により乾燥させることにより製造される。上記
有機溶媒は、表面処理しようとする顔料または体質顔料
の表面活性や熱安定性、有機溶媒自体の引火点や発火点
を考慮して選択されるが、例えばエーテル系、ケトン
系、ハロゲン化炭化水素、脂肪族炭化水素、アルコール
類またはそれら相互の、もしくはそれらと別種の溶媒例
えば水との混合物である。この有機溶媒の添加量は顔料
または体質顔料に対して１〜１００重量％が好ましい。
反応性ポリアルキルポリシロキサン、その有機溶媒およ
び顔料または体質顔料の混合は、それらを一緒にして通
常の混合機により行ってもよいし、また、有機溶媒と顔
料または体質顔料との混合物に反応性アルキルポリシロ
キサンを噴霧することにより行うこともできる。また、
混合物の加熱処理は、用いられた顔料または体質顔料の
耐熱性や有機溶媒の種類に応じて適宜行われる。The organosilicon compound-treated pigment or extender pigment of the present invention is a mixture of the above-mentioned linear reactive alkylpolysiloxane of the present invention, an organic solvent which dissolves the polysiloxane, and a pigment or extender pigment. It is produced by drying the mixture by heat treatment. The organic solvent is selected in consideration of the surface activity and thermal stability of the pigment or extender pigment to be surface-treated, the flash point and the ignition point of the organic solvent itself, and examples thereof include ether-based, ketone-based, and halogenated carbonized. Hydrogen, aliphatic hydrocarbons, alcohols or mixtures of these with one another or with another solvent such as water. The amount of the organic solvent added is preferably 1 to 100% by weight based on the pigment or extender pigment.
The reactive polyalkyl polysiloxane, the organic solvent thereof and the pigment or the extender pigment may be mixed together by an ordinary mixer, or may be reactive with the mixture of the organic solvent and the pigment or the extender pigment. It can also be carried out by spraying an alkylpolysiloxane. Also,
The heat treatment of the mixture is appropriately performed depending on the heat resistance of the pigment or extender pigment used and the type of organic solvent.

【００１５】さらに、本発明は、上記有機ケイ素化合物
処理顔料を含む化粧料に関する。ここで化粧料とは、パ
ウダーファンデーション、リキッドファンデーション、
ルージュ、アイシャドー等を意味する。Furthermore, the present invention relates to a cosmetic containing the above organosilicon compound-treated pigment. Here, cosmetics means powder foundation, liquid foundation,
Means rouge, eye shadow, etc.

【００１６】[0016]

【作用】本発明の有機ケイ素化合物処理顔料または体質
顔料は、上記したように、一方に特定の反応性末端基を
有する直鎖状のアルキルポリシロキサンを加熱処理によ
り顔料または体質顔料表面に配向吸着させたものであ
る。この直鎖状の反応性アルキルポリシロキサンは顔料
として使用される各種粉体に対する付着性および反応性
が高く、架橋重合による三次元構造をとらない。従っ
て、表面処理を温和な条件で行うことができるため熱に
弱い顔料も触媒なしで処理でき、得られた処理顔料は滑
らかで感触がよく、皮膚への付着性に優れ、凝集のない
ものであり、しかも、表面処理時に副生するアルコー
ル、アンモニア、塩化水素等は加熱により容易に除去さ
れるので残留することがない。さらに、本発明の上記反
応性アルキルポリシロキサンは特定の分子量範囲で、か
つ分子量分布範囲が狭く、分子鎖長のバラツキが小さい
ものであるため、無機顔料表面との反応性に乏しい高分
子量物や、撥水効果等のシリコーンの特性が出にくい低
分子量物を含まず、顔料または体質顔料の均質な表面処
理が可能となる。また、このように優れた性質を有する
上記処理を施した顔料または体質顔料を含む化粧料は、
のび、付着性等に優れ、特に、化粧料には必須の感触の
滑らかさに優れ、着色顔料を含む化粧料は非常に彩度が
高い色調を有するものである。As described above, the organosilicon compound-treated pigment or extender pigment of the present invention is oriented and adsorbed on the surface of the pigment or extender pigment by heat treatment of a linear alkylpolysiloxane having a specific reactive end group on one side. It was made. This linear reactive alkylpolysiloxane has high adhesion and reactivity to various powders used as a pigment, and does not have a three-dimensional structure due to cross-linking polymerization. Therefore, since the surface treatment can be performed under mild conditions, heat-sensitive pigments can be treated without a catalyst, and the resulting treated pigments are smooth and have a good feel, have excellent adhesion to the skin, and have no aggregation. Moreover, alcohol, ammonia, hydrogen chloride and the like, which are by-products of the surface treatment, are easily removed by heating and do not remain. Furthermore, since the above-mentioned reactive alkylpolysiloxane of the present invention has a specific molecular weight range, a narrow molecular weight distribution range, and a small variation in molecular chain length, a high molecular weight substance having poor reactivity with the surface of the inorganic pigment or Thus, it is possible to perform a uniform surface treatment of a pigment or an extender pigment without including a low molecular weight substance that does not easily exhibit silicone properties such as water repellency. Further, a cosmetic containing a pigment or extender pigment that has been subjected to the above treatment having such excellent properties is
It is excellent in spreadability and adhesiveness, in particular, it is excellent in smoothness of touch which is essential for cosmetics, and a cosmetic containing a coloring pigment has a very saturated color tone.

【００１７】[0017]

【実施例】本発明を実施例に基づいてさらに詳細に説明
する。なお、部は重量部を意味する。 有機ケイ素化合物処理顔料 実施例１ タルク（浅田製粉株式会社製，商品名ＪＡ−１３Ｒ）１
００ｇに対し、クロロホルム７０ｇおよびα−トリエト
キシポリジメチルシロキサン（重合度＝３０，分子量分
散度＝１．１９，片末端基＝トリエトキシ基）を添加
し、ニーダーで５分間混合する。これを６０℃で風乾
し、クロロホルムを完全に除去した後、１１５℃で３時
間加熱し、処理物を得た。EXAMPLES The present invention will be described in more detail based on examples. In addition, a part means a weight part. Organosilicon compound-treated pigment Example 1 Talc (manufactured by Asada Flour Milling Co., Ltd., trade name JA-13R) 1
70 g of chloroform and α-triethoxypolydimethylsiloxane (polymerization degree = 30, molecular weight dispersity = 1.19, one end group = triethoxy group) are added to 00 g, and mixed with a kneader for 5 minutes. This was air-dried at 60 ° C. to completely remove chloroform and then heated at 115 ° C. for 3 hours to obtain a treated product.

【００１８】比較例１ 実施例１におけるポリメチルエトキシシロキサンを重合
度が３０、分子量分散度が１．７１、片末端基がトリエ
トキシ基のものに代えた以外は実施例１と同様の操作を
行い、処理物を得た。Comparative Example 1 The same operation as in Example 1 was carried out except that the polymethylethoxysiloxane in Example 1 was changed to one having a polymerization degree of 30, a molecular weight dispersity of 1.71, and one end group of triethoxy group. , A processed product was obtained.

【００１９】比較例２ 実施例１におけるポリメチルエトキシシロキサンを重合
度が３０、分子量分散度が１．２３、両末端基がトリエ
トキシ基のものに代えた以外は実施例１と同様の操作を
行い、処理物を得た。Comparative Example 2 The same operation as in Example 1 was carried out except that the polymethylethoxysiloxane in Example 1 was changed to have a polymerization degree of 30, a molecular weight dispersity of 1.23 and triethoxy groups at both end groups. , A processed product was obtained.

【００２０】比較例３ 実施例１におけるポリメチルエトキシシロキサンを重合
度が１５０、分子量分散度が１．２１、片末端基がトリ
エトキシ基のものに代えた以外は実施例１と同様の操作
を行い、処理物を得た。Comparative Example 3 The same operation as in Example 1 was carried out except that the polymethylethoxysiloxane in Example 1 had a polymerization degree of 150, a molecular weight dispersity of 1.21 and a triethoxy group at one end. , A processed product was obtained.

【００２１】実施例１、比較例１ないし比較例３で得ら
れた処理物について撥水性、皮膚への付着性および感触
の試験を行った。結果を表１にまとめて示す。なお、そ
れぞれの特性の評価は以下の５点法により行った： ５＝非常に良い，４＝やや良い，３＝普通，２＝やや悪
い，１＝非常に悪い。The treated products obtained in Example 1 and Comparative Examples 1 to 3 were tested for water repellency, adhesion to skin and feel. The results are summarized in Table 1. Each characteristic was evaluated by the following five-point method: 5 = very good, 4 = somewhat good, 3 = normal, 2 = somewhat bad, 1 = very bad.

【表１】 表１に示す結果から、本発明の処理顔料は従来のものに
比べ、撥水性、皮膚への付着性および感触の全てにおい
てすぐれ、特に感触の改善の度合いが極めて高いことが
わかる。[Table 1] From the results shown in Table 1, it can be seen that the treated pigment of the present invention is superior in all of water repellency, adhesion to the skin and feel to the touch, and in particular, the degree of improvement in touch is extremely high.

【００２２】実施例２ セリサイト（三信鉱業株式会社製，商品名ＦＳＥ）１０
０ｇに対し、トルエン１０ｇを添加し、家庭用ミキサー
で５分間混合し、α−モノヒドロキシシロキサン（重合
度＝５０，分子量分散度＝１．２１，片末端基＝モノシ
ラノール基）３ｇを噴霧添加しながら５分間混合する。
これを８０℃で乾燥し、トルエンを完全に除去した後、
１１５℃で３時間加熱し、処理物を得た。得られた処理
物は撥水性が高く、シルキーな感触で、皮膚への付着性
に優れていた。Example 2 Sericite (manufactured by Sanshin Mining Co., Ltd., trade name FSE) 10
To 0 g, 10 g of toluene was added, mixed for 5 minutes with a household mixer, and 3 g of α-monohydroxysiloxane (polymerization degree = 50, molecular weight dispersity = 1.21, one end group = monosilanol group) was added by spraying. While mixing for 5 minutes.
This is dried at 80 ° C. to completely remove toluene,
It heated at 115 degreeC for 3 hours, and obtained the processed material. The obtained treated product had high water repellency, had a silky feel, and had excellent adhesion to the skin.

【００２３】比較例４ 実施例２におけるジメチルポリシロキシシラノールをメ
チルハイドロジェンポリシロキサンに代えた以外は実施
例２と同様の操作を行い、処理物を得た。得られた処理
物は撥水性は良好であったが、粉っぽい感触で、皮膚へ
の付着性が悪かった。Comparative Example 4 A treated product was obtained in the same manner as in Example 2 except that methylhydrogenpolysiloxane was used instead of dimethylpolysiloxysilanol in Example 2. The obtained treated product had good water repellency, but had a powdery feel and poor adhesion to the skin.

【００２４】比較例５ 実施例２におけるジメチルポリシロキシシラノールをジ
メチルポリシロキサン（１００ｃｓ）に代え、トルエン
を完全に除去した後、２５０℃で３０分間加熱し、処理
物を得た。得られた処理物は撥水性が悪く、重い感触
で、滑らかさが全くなかった。Comparative Example 5 After replacing dimethylpolysiloxysilanol in Example 2 with dimethylpolysiloxane (100 cs) and completely removing toluene, the product was heated at 250 ° C. for 30 minutes to obtain a treated product. The obtained treated product had poor water repellency, had a heavy feel, and had no smoothness.

【００２５】実施例２、比較例４および比較例５におい
て得られた処理物に対して以下の試験（Ａ）および
（Ｂ）を行った。 （Ａ）各処理物１０ｇを２００ｍｌのガラスビーカーに
採取し、ジエチルエーテル１００ｍｌを添加し、３０分
間震盪した後、濾過し、濾過残渣を乾燥させ、ＦＴ−Ｉ
Ｒ粉体拡散反射法により、セリサイト粒子表面上に吸着
しているジメチルポリシロキサンを確認した。測定され
たスペクトルを図２に示す。実施例２のものに観察され
る２９６４ｃｍ-1（Ｃ−Ｈ伸縮振動）、１２６１ｃｍ-1
（Ｓｉ−ＣＨ3 伸縮振動）のピークはジメチルポリシロ
キサンの振動に相当する。これに対し、比較例４のもの
には２１６７ｃｍ-1にＳｉ−Ｈの伸縮振動が認められ、
これは残留水素を示すもので好ましくない。また、比較
例５のものにはジメチルポリシロキサンのピークが確認
できず、エーテルによって完全に抽出されてしまってい
ることがわかる。以上の結果は、本発明により得られる
処理物のみが残留水素を含まず、しかもジメチルポリシ
ロキサンが顔料粒子表面に吸着していることを確認する
ものである。The following tests (A) and (B) were conducted on the treated products obtained in Example 2, Comparative Example 4 and Comparative Example 5. (A) 10 g of each treated product was collected in a 200 ml glass beaker, 100 ml of diethyl ether was added, and the mixture was shaken for 30 minutes, filtered, and the filter residue was dried, and FT-I was used.
The dimethylpolysiloxane adsorbed on the surface of the sericite particles was confirmed by the R powder diffuse reflection method. The measured spectrum is shown in FIG. 2964 cm -1 (CH stretching vibration) observed in Example 2, 1261 cm -1.
The peak of (Si—CH 3 stretching vibration) corresponds to the vibration of dimethylpolysiloxane. On the other hand, in Comparative Example 4, stretching vibration of Si—H was observed at 2167 cm −1 ,
This indicates residual hydrogen and is not preferable. Further, in Comparative Example 5, the peak of dimethylpolysiloxane could not be confirmed, and it was found that the sample was completely extracted with ether. The above results confirm that only the treated product obtained by the present invention does not contain residual hydrogen and that dimethylpolysiloxane is adsorbed on the surface of the pigment particles.

【００２６】（Ｂ）前項Ａで得られた粉体について皮膚
上での延び、付着性および撥水性の試験を行った。結果
を表２にまとめて示す。なお、それぞれの特性の評価は
以下の５点法により行った： ５＝非常に良い，４＝やや良い，３＝普通，２＝やや悪
い，１＝非常に悪い。(B) With respect to the powder obtained in the above-mentioned item A, the test for the spread on the skin, the adhesion and the water repellency were conducted. The results are summarized in Table 2. Each characteristic was evaluated by the following five-point method: 5 = very good, 4 = somewhat good, 3 = normal, 2 = somewhat bad, 1 = very bad.

【表２】 表２に示す結果から、本発明の処理顔料は従来のものに
比べ、皮膚上での延び、付着性および撥水性の全てにお
いて顕著にすぐれていることがわかる。[Table 2] From the results shown in Table 2, it can be seen that the treated pigment of the present invention is significantly superior to the conventional pigment in terms of spreading on skin, adhesion and water repellency.

【００２７】化粧料 実施例３ 以下のようにしてパウダーファンデーションを製造し
た。 成分１（顔料および体質顔料，註１） マイカ粉 １５．０ 部 セリサイト ２０．０ 部 タルク ３６．４５部 酸化チタン １５．０ 部 黄色酸化鉄 ２．５ 部 ベンガラ １．０ 部 黒色酸化鉄 ０．５ 部 成分２ メチルフェニルポリシロキサン ５．０ 部 トリオクタン酸グリセリン ２．５ 部 ｋｆ９６（１０００ｃｓ） ２．０ 部 酢酸トコフェロール ０．０５部 註１）それぞれ以下のものを用いた：マイカ粉（三好化
成製，商品名Ｍ−３０２），セリサイト（三信鉱業株式
会社製，商品名ＦＳＥ），タルク（浅田製粉株式会社
製，商品名ＪＡ−１３Ｒ），酸化チタン（石原産業株式
会社製，商品名ＣＲ−５０），黄色酸化鉄（チタン工業
製，商品名ＬＬＸＬＯ），ベンガラ（森下べんがら工業
株式会社製，商品名ベンガラ七宝），黒色酸化鉄（チタ
ン工業製，商品名ＢＬ−１００）Cosmetic Example 3 A powder foundation was produced as follows. Component 1 (Pigment and extender pigment, Note 1) Mica powder 15.0 parts Sericite 20.0 parts Talc 36.45 parts Titanium oxide 15.0 parts Yellow iron oxide 2.5 parts Bengala 1.0 parts Black iron oxide 0 .5 parts Component 2 Methylphenylpolysiloxane 5.0 parts Glycerin trioctanoate 2.5 parts kf96 (1000cs) 2.0 parts Tocopherol acetate 0.05 parts Note 1) Mica powder (Miyoshi Kasei) was used respectively. Made, product name M-302), Serisite (made by Sanshin Mining Co., Ltd., product name FSE), talc (made by Asada Flour Milling Co., product name JA-13R), titanium oxide (made by Ishihara Sangyo Co., Ltd., product name CR -50), yellow iron oxide (manufactured by Titanium Industry, trade name LLXLO), red iron oxide (made by Morishita Bengal Industry Co., Ltd., trade name Bengal Cloisonne), black iron oxide (Chita) Industry Co., Ltd., product name BL-100)

【００２８】まず、成分１の顔料および体質顔料の混合
物をヘンシェルミキサーで混合し、その中から２００ｇ
をバキュームニーダーに移し、クロロホルム１５０ｇに
ジメチルポリシロキシシラザン（重合度３０，分子量分
散度＝１．１５，片末端基＝ＮＨ基）２ｇを溶解させた
溶液を添加し、前記ニーダーを４０℃に維持し、吸引し
ながら２〜３時間混合し、クロロホルムを除去する。得
られた粉体を１１５℃で３時間さらに加熱処理し、処理
物を得る。該処理物をアトマイザーで粉砕し、この中に
成分２の加熱混合物を添加し、さらにヘンシルミキサー
で混合後、再度アトマイザーで粉砕する。この粉砕物を
中皿に充填成形して製品とする。First, the mixture of the component 1 pigment and the extender pigment is mixed with a Henschel mixer, and 200 g of the mixture is added.
Was transferred to a vacuum kneader, and a solution of 2 g of dimethylpolysiloxysilazane (polymerization degree 30, molecular weight dispersity = 1.15, one end group = NH group) in 150 g of chloroform was added, and the kneader was maintained at 40 ° C. And mix with suction for 2-3 hours to remove chloroform. The obtained powder is further heat treated at 115 ° C. for 3 hours to obtain a treated product. The treated product is pulverized with an atomizer, the heated mixture of the component 2 is added thereto, the mixture is further mixed with a Hensyl mixer, and then pulverized again with the atomizer. The crushed product is filled in an inner plate and molded to obtain a product.

【００２９】比較例６ 実施例３における成分１の顔料および体質顔料の混合物
をメチルハイドロジェンポリシロキサン（重合度４０）
で表面処理した以外は実施例３と同様の操作を行い、パ
ウダーファンデーションを製造した。Comparative Example 6 A mixture of the pigment of Component 1 and the extender pigment of Example 3 was treated with methyl hydrogen polysiloxane (degree of polymerization 40).
A powder foundation was manufactured by performing the same operations as in Example 3 except that the surface treatment was carried out in step 1.

【００３０】比較例７ 実施例３における成分１の顔料および体質顔料の混合物
をジメチルポリシロキサン（１００ｃｓ）で表面処理し
た以外は実施例３と同様の操作を行い、パウダーファン
デーションを製造した。Comparative Example 7 A powder foundation was produced in the same manner as in Example 3, except that the mixture of the pigment of component 1 and the extender pigment in Example 3 was surface-treated with dimethylpolysiloxane (100 cs).

【００３１】実施例３、比較例６および比較例７におい
て得られた製品について以下の試験（Ａ）および（Ｂ）
を行った。 （Ａ）各製品について、分光式色差計（日本電色社製，
商品名ＳＺ−ε９０）を用いて明度、色相および色彩を
測定した。測定結果を表３に示し、偏色判定図を図３に
示す。なお、肌色を有する化粧料を作成するための着色
顔料として、黄色酸化鉄、赤色酸化鉄、黒色酸化鉄の３
色が一般に広く用いられているが、この中で、ベンガラ
等の赤色酸化鉄の展色性が悪いことが知られている。こ
のため、従来は数回の展色工程を経ないと彩度・色調の
高い肌色が得られなかった。The following tests (A) and (B) were performed on the products obtained in Example 3, Comparative Example 6 and Comparative Example 7.
I went. (A) For each product, a spectroscopic color difference meter (manufactured by Nippon Denshoku Co.,
The brightness, hue and color were measured using a trade name SZ-ε90). The measurement results are shown in Table 3, and the color change determination chart is shown in FIG. In addition, as a coloring pigment for producing a cosmetic having a skin color, there are three types of iron oxides such as yellow iron oxide, red iron oxide and black iron oxide.
Color is generally widely used, but it is known that red iron oxide such as red iron oxide has a poor color spreading property. For this reason, conventionally, it has been impossible to obtain a flesh color having high saturation and color tone without going through several color development steps.

【表３】 ──────────────────────────── Ｌ* ａ* ｂ* ──────────────────────────── 実施例３ ６８．２１ ８．１９ １９．８０ 比較例６ ６９．０３ ７．６２ １８．９４ 比較例７ ６８．５３ ８．０２ １９．１０ ────────────────────────────[Table 3] ──────────────────────────── L * a * b * ───────────── ──────────────── Example 3 68.21 8.19 19.80 Comparative Example 6 69.03 7.62 18.94 Comparative Example 7 68.53 8.02 19 10 ────────────────────────────

【００３２】以上の結果から、本発明によるパウダーフ
ァンデーションは発色性が良く、鮮やかな色調を示すこ
とがわかる。From the above results, it can be seen that the powder foundation according to the present invention has good color developability and exhibits a vivid color tone.

【００３３】（Ｂ）実施例３、比較例６または比較例７
において得られる製品のいずれかを、パネラーの顔面に
塗布し、使用感、皮膚への付着性、化粧もちを評価し
た。評価結果を表４にまとめて示す。それぞれの特性の
評価は以下の規準で行った：○＝良好，△＝普通，×＝
悪い。(B) Example 3, Comparative Example 6 or Comparative Example 7
One of the products obtained in 1. was applied to the face of a panelist, and the feeling of use, adhesion to skin, and makeup lasting were evaluated. The evaluation results are summarized in Table 4. The evaluation of each property was performed according to the following criteria: ○ = good, △ = normal, × =
bad.

【表４】 [Table 4]

【００３４】[0034]

【発明の効果】以上詳細に説明したように、本発明の有
機ケイ素化合物処理顔料または体質顔料は、加熱処理に
よる顔料または体質顔料へのシリコーンの吸着性が良
く、残留水素がなく、非常に滑らかで、付着性が良く、
微粒子である着色顔料の展色性に優れたものである。特
に、本発明において、顔料を覆う有機ケイ素化合物は、
片末端に反応基を有し、そして特定の重合度で、かつ分
子量分布範囲が極めて狭いものであるので、顔料に対し
て一定の方向に確実に配向吸着し、しかも分子鎖長が揃
っている。従って、本発明の処理顔料は感触が極めて滑
らかなものである。このように優れた性質を有する処理
顔料は、パウダーファンデーション、リキッドファンデ
ーション、ルージュ、アイシャドー等で代表されるメッ
クアップ化粧料に配合され、品質向上に著しく貢献する
ものであり、特に従来の化粧料にはなかった優れた滑ら
かさを付与する。As described in detail above, the organosilicon compound-treated pigment or extender pigment of the present invention has good adsorption of silicone to the pigment or extender pigment by heat treatment, has no residual hydrogen, and is extremely smooth. And has good adhesion,
The color pigment, which is a fine particle, has excellent color spreadability. In particular, in the present invention, the organosilicon compound covering the pigment is
It has a reactive group at one end, and has a specific degree of polymerization and an extremely narrow molecular weight distribution range, so it is surely adsorbed in a fixed direction to the pigment and has a uniform molecular chain length. . Therefore, the treated pigment of the present invention has an extremely smooth feel. Treated pigments having such excellent properties are blended in mech-up cosmetics typified by powder foundations, liquid foundations, rouges, eye shadows, etc., and contribute significantly to quality improvement. It provides excellent smoothness not found in other products.

【図面の簡単な説明】[Brief description of drawings]

【図１】アルキルポリシロキサンのＧＰＣチャートであ
り、ａが本発明の反応性アルキルポリシロキサン（Ｍｗ
／Ｍｎ＝１．１７）のものであり、そしてｂが市販され
ている従来のアルキルポリシロキサン（Ｍｗ／Ｍｎ＝
１．９）のものである。FIG. 1 is a GPC chart of alkylpolysiloxane, where a is a reactive alkylpolysiloxane (Mw) of the present invention.
/Mn=1.17) and b is a commercially available conventional alkylpolysiloxane (Mw / Mn =
1.9).

【図２】実施例２、比較例４および比較例５で得られた
処理顔料のＦＴ−ＩＲ粉体拡散反射法によるスペクトル
図である。FIG. 2 is a spectrum diagram of the treated pigments obtained in Example 2, Comparative Example 4 and Comparative Example 5 by an FT-IR powder diffuse reflection method.

【図３】実施例３、比較例６および比較例７で得られた
製品の偏色判定図である。FIG. 3 is a color change determination chart of the products obtained in Example 3, Comparative Example 6 and Comparative Example 7.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 重合度が２５〜１００、重量平均分子量
（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）
が１．０〜１．３である、一方の分子鎖末端にアミノ水
素基、ハロゲン原子、水酸基またはアルコキシ基を有す
る直鎖状の反応性アルキルポリシロキサンを加熱処理に
より顔料または体質顔料の表面に配向吸着させたことを
特徴とする有機ケイ素化合物処理顔料または体質顔料。1. The degree of polymerization is 25 to 100, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
Is 1.0 to 1.3, and a linear reactive alkylpolysiloxane having an amino hydrogen group, a halogen atom, a hydroxyl group or an alkoxy group at one molecular chain end is heat-treated on the surface of the pigment or extender pigment. An organosilicon compound-treated pigment or an extender characterized by being oriented and adsorbed. 【請求項２】 重合度が２５〜１００、重量平均分子量
（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）
が１．０〜１．３である、一方の分子鎖末端にアミノ水
素基、ハロゲン原子、水酸基またはアルコキシ基を有す
る直鎖状の反応性アルキルポリシロキサン、該ポリシロ
キサンを溶解する有機溶媒、および顔料または体質顔料
を混合し、そしてこの混合物を加熱処理により乾燥させ
ることからなる有機ケイ素化合物処理顔料または体質顔
料の製造方法。2. The degree of polymerization is 25 to 100, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
Is 1.0 to 1.3, a linear reactive alkyl polysiloxane having an amino hydrogen group, a halogen atom, a hydroxyl group or an alkoxy group at one terminal of the molecular chain, an organic solvent dissolving the polysiloxane, and A method for producing an organosilicon compound-treated pigment or an extender pigment, which comprises mixing a pigment or an extender pigment and drying the mixture by heat treatment. 【請求項３】 請求項１記載の有機ケイ素化合物処理顔
料または体質顔料を含む化粧料。3. A cosmetic containing the organosilicon compound-treated pigment according to claim 1 or an extender pigment.
JP35319593A 1993-12-28 1993-12-28 Organosilicon compound-treated pigment or extender, method for producing the same and cosmetics Expired - Lifetime JP3567335B2 (en)

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