JP3798762B2 - Cosmetics - Google Patents

Description

【００１２】
これらのオリゴマーの単独または両者を主成分とする混合物の数平均分子量の範囲は、下記の方法で測定した結果、およそ２０００〜８０００を示すものである。
【００１３】
数平均分子量の測定法は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の相対分子量分布の測定であり、下記の条件による。
測定機種 東ソー（株）製 ＳＣ−８０１０システム
カラム Ｓｈｏｄｅｘ ＫＦ−８００Ｄ＋ＫＦ−８０５Ｌ ×２本
溶離液 ＴＨＦ
温 度 カラム恒温槽 ４０℃
流 速 １．０ｍｌ／ｍｉｎ
濃 度 約０．２ｗｔ／ｖｏｌ％
注入量 １００μｌ
溶解性 完全溶解
検出器 示差屈折計（Ｒ１）
【００１４】
以下に合成例を記載する。
【合成例１】
撹拌機、温度計、還流装置、窒素ガス供給ノズルを備えたガラス製５Ｌの４つ口フラスコに、ＣＯＯＨ基とＯＨ基の比率（ＣＯＯＨ基／ＯＨ基比）が０．５（硬化ヒマシ油：ダイマー酸＝７０．８：２９．２）になるように硬化ヒマシ油１５００ｇ（１．４４ｍｏｌ）、ダイマー酸６１８ｇ（１．０８ｍｏｌ）、トルエン１８０ｍｌ、パラトルエンスルホン酸６．９ｇを加え窒素気流下２２０℃に加熱し、酸価が２以下になるまで反応した。
【００１５】
【合成例２】
撹拌機、温度計、還流装置、窒素ガス供給ノズルを備えたガラス製５Ｌの４つ口フラスコに、ＣＯＯＨ基／ＯＨ基比が０．４１７（硬化ヒマシ油：ダイマー酸＝７４．６：２５．４）になるように硬化ヒマシ油１５００ｇ（１．４４ｍｏｌ）、ダイマー酸５１１ｇ（０．８９ｍｏｌ、トルエン１８０ｍｌ、パラトルエンスルホン酸６．６ｇを加え窒素気流下２２０℃に加熱し、酸価が２以下になるまで反応した。
【００１６】
【合成例３】
撹拌機、温度計、還流装置、窒素ガス供給ノズルを備えたガラス製５Ｌの４つ口フラスコに、ＣＯＯＨ基／ＯＨ基比が０．３３３（硬化ヒマシ油：ダイマー酸＝７８．４：２１．６）になるように硬化ヒマシ油２０００ｇ（１．９２ｍｏｌ、ダイマー酸５４９．６ｇ（０．９６ｍｏｌ）、トルエン２００ｍｌ、パラトルエンスルホン酸８．２ｇを加え窒素気流下２２０℃に加熱し、酸価が２以下になるまで反応した。
【００１７】
【合成例４】
撹拌機、温度計、還流装置、窒素ガス供給ノズルを備えたガラス製５Ｌの４つ口フラスコに、ＣＯＯＨ基／ＯＨ基比が０．２５（硬化ヒマシ油：ダイマー酸＝８２．９：１７．１）になるように硬化ヒマシ油５００ｇ（０．４８ｍｏｌ）、ダイマー酸１０３．１ｇ（０．１８ｍｏｌ）、トルエン５０ｍｌ、パラトルエンスルホン酸２．０ｇを加え窒素気流下２２０℃に加熱し、酸価が２以下になるまで反応した。
【００１８】
以下に合成例１〜４で得られた硬化ヒマシ油とダイマー酸のオリゴマーの特性値を記載する。

尚、イソステアリン酸硬化ヒマシ油の特性値は、酸価：０．６、けん化価：１８５．０、ヨウ素価：１．９、水酸基価：８４．０、粘度（６０℃）：２１０、色相（Ｇ）：５である（比較例に用いた。）。
【００１９】
以上記載のごとく本発明に利用する前記硬化ヒマシ油とダイマー酸のオリゴマーは、上記のごとく特に水酸基価、粘度が相違するオリゴマーで、本発明では数平均分子量は２０００〜８０００のものが適用される。
これらは目的とする化粧料に対し、オリゴマーの油性感、粘着性、エモリエント性などの特性の相違に応じて適宜選択し、その化粧料に利用する。
またその化粧料における含有量は化粧料の総量を基準として０．１〜２０重量％、好ましくは０．２〜１０重量％である。（以下重量％を％と省略記載する）
【００２０】
本発明の化粧料には、リップクリーム、ファンデーション（サンカット）、シャンプー、トリートメントリンス、ヘアワックス、などが挙げられる。
【００２１】
以下に本発明を実施例により具体的に説明するが、本発明はこれらの記載に限定されるものではなく、通常に利用される化粧料原料を本発明の目的を達成する範囲で適宜含有することが可能である。
【００２２】
【実施例】
実施例１〜５、比較例１〜５を調製し、下記に示す評価方法にて実用特性、保存安定性、及び皮膚安全性を評価した。
【００２３】
（評価方法）
＜１＞ 実用特性
被試験者男子１０名、女子１０名、合計２０名によって、１０日間で５回、各々の実施例、比較例を使用し評価した。油性感、粘着性、エモリエント性などの各々の評価項目に対して化粧料の、良好−普通−悪い、との評価を最大点５から最小点０で示し、評価点の平均値が
３．５〜５．０→ 「○」
２．５〜３．４→ 「△」
０〜２．４ → 「×」
の記号でそれぞれ記載した。
＜２＞ 保存安定性
実施例及び比較例を４５℃の恒温室に３ヶ月間保存した後、また、−５℃と４５℃を往復する恒温室に５回往復する期間保存した後に、固形物では発汗、変色、乳化物では乳化状態（分離の有無）、液状物では分離、着色などの外観を観察した。評価結果は、異常が認められない場合を良好とし「○」で示し、やや異常が認められる場合で実用上問題がない場合は「△」で示し、異常が認められる場合を不良とし「×」で示した。
＜３＞ 皮膚安全性
被試験者男子１０名、女子１０名、合計２０名の前腕屈側部皮膚に、試料０．０５ｇを、直径１．０ｃｍのリント布のついた円型パッチテスト用絆創膏を用いて２４時間閉塞貼付する。絆創膏除去１時間後及び２４時間後の被試験者２０名の皮膚状態を、下記の評価基準に従い判定評価する。評価には、絆創膏除去１時間後及び２４時間後のうち反応の強いほうを採用することとし、（−）が２０名のときは「○」、（±）が１〜２名のときは「△」、（±）が３名以上または（＋）〜（＋＋＋）が１名以上の場合は、「×」で示した。
尚、シャンプー、トリートメントリンスは０．５％の水溶液を試料とした。
（評価基準）
（皮膚状態） （評価）
紅斑、浮腫、水泡 ： （＋＋＋）
紅斑、浮腫 ： （＋＋）
紅斑 ： （＋）
軽微な紅斑 ： （±）
無紅斑、無浮腫 ： （−）
【００２４】
実施例１ リップクリーム
合成例２の硬化ヒマシ油とダイマー酸のオリゴマーを利用して、下記の組成のリップクリームを通常の方法にて、全成分を９５〜１００℃に均一に溶かし、金型に流し込み冷却してリップクリームを調製した。

【００２５】
比較例１ リップクリーム
実施例１の成分である合成例２のオリゴマーに替えて、前記硬化ヒマシ油イソステアリン酸エステルを用いる他は、実施例１と同様にしてリップクリームを調製した。
（評価）

【００２６】
実施例２ ファンデーション（サンカット）
通常の製法にて成分１〜５を９０〜９５℃で加熱、混合した後、成分６〜１２を加え、混合して容器に充填する。

【００２７】
比較例２ ファンデーション（サンカット）
実施例２の成分である合成例４のオリゴマーに替えて、前記硬化ヒマシ油イソステアリン酸エステルを用いる他は、実施例２と同様にしてファンデーション（サンカット）を調製した。
（評価）

実施例２は皮膚に塗布した時、汗により化粧崩れは少なく、またサマー商品として耐水性に優れていた。
【００２８】
実施例３ シャンプー
予め合成例４のオリゴマーと成分６〜８を加熱溶解して加入する他は、通常の製法で全成分を７５〜８０℃で加熱均一にし、溶解分散した後３０℃まで冷却する。

【００２９】
比較例３ シャンプー
実施例の成分である合成例４のオリゴマーに替えて、前記硬化ヒマシ油イソステアリン酸エステルを用いる他は、実施例３と同様にしてシャンプーを調製した。
（評価）

合成例３のオリゴマーはコンディショニング剤として作用し実施例３はすすぎが容易であり、毛髪の油性感も良好である。
【００３０】
実施例４ トリートメントリンス
通常の製法として、成分１〜１３を７５〜８０℃に加熱して均一に溶解し、予め成分１４を７５〜８０℃に加熱した液に加入し、撹拌しながら３０℃まで冷却する。

【００３１】
比較例４ トリートメントリンス
実施例４の成分である合成例３のオリゴマーに替えて、前記硬化ヒマシ油イソステアリン酸エステルを用いる他は、実施例４と同様にしてトリートメントリンスを調製した。
（評価）

実施例４は比較例４と比較して明らかに毛髪の油性感、艶、くし通り性及び毛髪のまとまりに優れている。
【００３２】
実施例５ ヘアワックス
成分１〜９を７５〜８０℃で加熱均一に溶解したものを、予め成分１０〜１４を７５〜８０℃で加熱して均一に溶解分散したものに加入、撹拌した後３０℃まで冷却する。

【００３３】
比較例５ ヘアワックス
実施例５の成分である合成例１のオリゴマーに替えて、前記硬化ヒマシ油イソステアリン酸エステルを用いる他は、実施例５と同様にしてヘアワックスを調製した。
（評価）

実施例５は適度な油性感を有し整髪力に優ている。
【００３４】
実施例６ プレストパウダー（サンカット）
成分１〜９を均一の混合した物に、成分１０〜１４を加熱、均一に分散混合した物を加え、全成分を均一に混合した物を金皿に充填し、プレス成型する。

【００３５】
比較例６ プレストパウダー（サンカット）
実施例６の成分である合成例１のオリゴマーに替えて、前記硬化ヒマシ油イソステアリン酸エステルを用いる他は、実施例６と同様にしてプレストパウダー（サンカット）を調製した。
（評価）

実施例６は皮膚への付着性が良く、化粧もちが良かった。
【００３６】
【発明の効果】
本発明は、特定の硬化ヒマシ油とダイマー酸とのオリゴマーを含有することにより、適度な油性感、粘着性、エモリエント性等を有し、実用特性、保存安定性、皮膚安全性の全てに優れた化粧料を明らかに提供する。[0001]
[Industrial application fields]
The present invention relates to a cosmetic that is excellent in storage stability, practical characteristics, and skin safety, containing an oligomer of hydrogenated castor oil and dimer acid.
[0002]
[Prior art]
Conventionally, hardened castor oil derivatives have been used as raw materials for cosmetics. In particular, an esterified product of hydrogenated castor oil and isostearic acid is known as an adhesive oily material that is familiar to skin or hair and has an appropriate oily feeling (see Patent Document 1).
Further, esterified products of dimer acid and various alcohols are known, but alcohols constituting these esterified products are clearly different from the hardened castor oil constituting the esterified product of the present invention ( (See Patent Document 2).
[0003]
[Patent Document 1]
JP-A-55-11526 [Patent Document 2]
Japanese Patent Laid-Open No. 2001-199937
This cosmetic containing an oligomer of hydrogenated castor oil and isostearic acid has problems in practical properties such as a satisfactory oiliness or tackiness cannot be obtained when applied to the skin or hair. .
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a cosmetic having an appropriate oily feeling and adhesiveness or emollient when applied to the skin or hair, and excellent in practical properties, storage stability and skin safety.
[0006]
[Means for Solving the Problems]
As a result of intensive research to solve the above problems, the present inventors have found that a cosmetic containing an oligomer composed of a specific hardened castor oil and dimer acid described below has an appropriate oily feeling and adhesiveness or emollient. The present invention was completed by finding excellent practical properties, storage stability and skin safety.
[0007]
That is, the present invention comprises a cosmetic comprising an oligomer having a number average molecular weight of 2,000 to 8,000, which is reacted with an amount of dimer acid that binds to 25 to 50% of OH groups of hydrogenated castor oil. It is a fee.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hardened castor oil and dimer acid used in the present invention are known substances, and dimer acid is obtained by dimerizing unsaturated fatty acids having 18 carbon atoms (mainly linoleic acid and linolenic acid). Dimer acid has a purity of 95% or more and contains a small amount of monomeric acid and trimer acid. (Uniqema: “PRIPOL 1009”)
[0009]
Hardened castor oil is a substance obtained by hydrogenating castor oil. In the present invention, 99% or more was used. (Manufactured by Kawaken Fine Chemical Co., Ltd .: “Hima Hard P”)
[0010]
The method for producing the oligomer of hydrogenated castor oil and dimer acid of the present invention is not particularly limited, but can be synthesized by a generally used method. For example, para-toluene sulfonic acid, sulfuric acid, hydrochloric acid, methane sulfonic acid, boron trifluoride, hydrogen fluoride, etc. as a catalyst or non-catalyst, and benzene, toluene etc. as a solvent or solvent-free under reduced pressure. What is necessary is just to react at 150-250 degreeC with the dimer acid of the quantity couple | bonded with 25-50% of OH groups of hydrogenated castor oil. The charging ratio of hydrogenated castor oil and dimer acid during the reaction is 70.8: 29.2 to 82.9: 17.1 by weight.
The oligomer of hydrogenated castor oil and dimer acid obtained by the above synthesis method is represented by the following general formula (1) or (2) or a mixture of general formulas (1) and (2).
[0011]
[Chemical 1]

[0012]
The range of the number average molecular weight of these oligomers alone or a mixture containing both as a main component is about 2000 to 8000 as a result of measurement by the following method.
[0013]
The method for measuring the number average molecular weight is measurement of relative molecular weight distribution in terms of polystyrene by GPC (gel permeation chromatography), and is based on the following conditions.
Measurement model SC-8010 system column manufactured by Tosoh Corporation Shodex KF-800D + KF-805L x 2 eluents THF
Temperature Column temperature chamber 40 ° C
Flow rate 1.0ml / min
Concentration about 0.2wt / vol%
Injection volume 100 μl
Solubility Complete dissolution detector Differential refractometer (R1)
[0014]
Synthesis examples are described below.
[Synthesis Example 1]
In a glass 5 L four-necked flask equipped with a stirrer, a thermometer, a reflux device, and a nitrogen gas supply nozzle, the ratio of COOH group to OH group (COOH group / OH group ratio) is 0.5 (cured castor oil: Dimer acid = 70.8: 29.2) Hardened castor oil 1500 g (1.44 mol), dimer acid 618 g (1.08 mol), toluene 180 ml, paratoluenesulfonic acid 6.9 g were added, and nitrogen flow was performed. The reaction was continued until the acid value was 2 or less.
[0015]
[Synthesis Example 2]
In a glass 5 L four-necked flask equipped with a stirrer, a thermometer, a reflux device, and a nitrogen gas supply nozzle, the COOH group / OH group ratio was 0.417 (hardened castor oil: dimer acid = 74.6: 25. 4) Hardened castor oil 1500 g (1.44 mol), dimer acid 511 g (0.89 mol, toluene 180 ml, paratoluenesulfonic acid 6.6 g were added and heated to 220 ° C. under a nitrogen stream, and the acid value was 2 or less. It reacted until it became.
[0016]
[Synthesis Example 3]
In a glass 5 L four-necked flask equipped with a stirrer, a thermometer, a reflux device, and a nitrogen gas supply nozzle, the COOH group / OH group ratio was 0.333 (hardened castor oil: dimer acid = 78.4: 21. 6) Hardened castor oil 2000 g (1.92 mol, dimer acid 549.6 g (0.96 mol)), toluene 200 ml, paratoluenesulfonic acid 8.2 g was added and heated to 220 ° C. in a nitrogen stream, so that the acid value was It reacted until it became 2 or less.
[0017]
[Synthesis Example 4]
In a glass 5 L four-necked flask equipped with a stirrer, a thermometer, a reflux device, and a nitrogen gas supply nozzle, a COOH group / OH group ratio was 0.25 (hardened castor oil: dimer acid = 82.9: 17. 1) 500 g (0.48 mol) of hydrogenated castor oil, 103.1 g (0.18 mol) of dimer acid, 50 ml of toluene and 2.0 g of paratoluenesulfonic acid were added and heated to 220 ° C. under a nitrogen stream, It reacted until it became 2 or less.
[0018]
The characteristic values of the hydrogenated castor oil and dimer acid oligomers obtained in Synthesis Examples 1 to 4 are described below.

The characteristic values of isostearic acid hydrogenated castor oil are as follows: acid value: 0.6, saponification value: 185.0, iodine value: 1.9, hydroxyl value: 84.0, viscosity (60 ° C.): 210, hue ( G): 5 (used for comparative example).
[0019]
As described above, the hydrogenated castor oil and dimer acid oligomers used in the present invention are oligomers having particularly different hydroxyl values and viscosities as described above. In the present invention, those having a number average molecular weight of 2000 to 8000 are applied. .
These are appropriately selected according to the difference in properties of the oligomer such as oiliness, tackiness, emollient and the like, and used for the cosmetic.
The content in the cosmetic is 0.1 to 20% by weight, preferably 0.2 to 10% by weight, based on the total amount of the cosmetic. (Hereinafter, wt% is abbreviated as%)
[0020]
Examples of the cosmetic of the present invention include lip balm, foundation (sun cut), shampoo, treatment rinse, hair wax, and the like.
[0021]
EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these descriptions, and cosmetic materials that are normally used are appropriately contained within a range that achieves the object of the present invention. It is possible.
[0022]
【Example】
Examples 1 to 5 and Comparative Examples 1 to 5 were prepared, and practical properties, storage stability, and skin safety were evaluated by the evaluation methods shown below.
[0023]
(Evaluation methods)
<1> Practical characteristics Evaluation was performed using 10 examples of boys and 10 girls, 20 girls in total, 5 times in 10 days, using each of the examples and comparative examples. For each evaluation item such as oiliness, tackiness, emollient, etc., the cosmetics are evaluated as good-normal-bad from a maximum score of 5 to a minimum score of 0, with an average rating score of 3.5. 〜5.0 → 「○」
2.5-3.4 → “△”
0-2.4 → “×”
It was described with the symbol of each.
<2> Storage stability After being stored in a thermostatic chamber at 45 ° C. for 3 months, and after being stored in a thermostatic chamber that reciprocates between −5 ° C. and 45 ° C. for a period of 5 reciprocations, solids In, the appearance of sweating, discoloration, emulsified state (presence / absence of separation) in the emulsion, separation, coloring, etc. were observed in the liquid. The evaluation result is shown as “Good” when no abnormality is found, “Good”, when there is a slight abnormality and no problem in practical use, “△”, and when bad, “No”. It showed in.
<3> Skin safety test subject 10 males and 10 females, a total of 20 forearm bent side skins, 0.05 g of sample with circular lint cloth with 1.0 cm diameter lint-cloth adhesive bandage Apply occlusion for 24 hours. The skin condition of 20 test subjects 1 hour and 24 hours after removal of the adhesive bandage is judged and evaluated according to the following evaluation criteria. For the evaluation, the stronger reaction is adopted 1 hour after removal of the adhesive bandage and 24 hours later. When (−) is 20 people, “○”, when (±) is 1 or 2 people, When “Δ”, (±) is 3 or more, or (+) to (+++) is 1 or more, “×” is indicated.
In addition, shampoo and treatment rinse used 0.5% aqueous solution as a sample.
(Evaluation criteria)
(Skin condition) (Evaluation)
Erythema, edema, blisters: (++)
Erythema, edema: (++)
Erythema: (+)
Minor erythema: (±)
No erythema, no edema: (-)
[0024]
Example 1 Using the hydrogenated castor oil and dimer acid oligomer of lip cream synthesis example 2, the lip balm having the following composition was uniformly dissolved at 95-100 ° C. by a conventional method, and the resulting mixture was dissolved in a mold. A lip balm was prepared by pouring and cooling.

[0025]
Comparative Example 1 A lip balm was prepared in the same manner as in Example 1 except that the hardened castor oil isostearate was used in place of the oligomer of Synthesis Example 2 which is a component of lip cream Example 1.
(Evaluation)

[0026]
Example 2 Foundation (Suncut)
Ingredients 1-5 are heated and mixed at 90-95 [deg.] C. by an ordinary production method, then ingredients 6-12 are added, mixed and filled into a container.

[0027]
Comparative Example 2 Foundation (Suncut)
A foundation (suncut) was prepared in the same manner as in Example 2 except that the hydrogenated castor oil isostearate was used in place of the oligomer of Synthesis Example 4 which is a component of Example 2.
(Evaluation)

In Example 2, when it was applied to the skin, there was little makeup collapse due to sweat, and it was excellent in water resistance as a summer product.
[0028]
Example 3 Shampoo In addition to heating and dissolving the oligomer of Synthesis Example 4 and components 6 to 8 in advance, all components were heated and homogenized at 75 to 80 ° C. by ordinary manufacturing methods, dissolved and dispersed, and then cooled to 30 ° C. .

[0029]
Comparative Example 3 Shampoo A shampoo was prepared in the same manner as in Example 3 except that the hydrogenated castor oil isostearate was used instead of the oligomer of Synthesis Example 4 which is a component of the shampoo example.
(Evaluation)

The oligomer of Synthesis Example 3 acts as a conditioning agent, and Example 3 is easy to rinse and the oily feel of the hair is also good.
[0030]
Example 4 Treatment Rinse As a normal manufacturing method, ingredients 1 to 13 are heated to 75 to 80 ° C. to dissolve uniformly, and added to a solution in which ingredient 14 is heated to 75 to 80 ° C. in advance, and stirred to 30 ° C. Cooling.

[0031]
Comparative Example 4 Treatment Rinse A treatment rinse was prepared in the same manner as in Example 4 except that the hydrogenated castor oil isostearate was used in place of the oligomer of Synthesis Example 3 as a component of Example 4.
(Evaluation)

Example 4 is clearly superior to Comparative Example 4 in the oily feel, gloss, combing property and hair unitiness of the hair.
[0032]
Example 5 Hair wax components 1 to 9 were heated and uniformly dissolved at 75 to 80 ° C., added to components 10 to 14 previously heated and uniformly dissolved and dispersed at 75 to 80 ° C., stirred, and then 30 Cool to ° C.

[0033]
Comparative Example 5 Hair Wax A hair wax was prepared in the same manner as in Example 5 except that the hydrogenated castor oil isostearate was used in place of the oligomer of Synthesis Example 1 which is a component of Example 5.
(Evaluation)

Example 5 has a moderate oiliness and is excellent in hair styling power.
[0034]
Example 6 Presto Powder (Suncut)
A product in which components 10 to 14 are heated and uniformly dispersed and mixed is added to a product in which components 1 to 9 are uniformly mixed, and the product in which all components are uniformly mixed is filled in a metal pan and press-molded.

[0035]
Comparative Example 6 Pressed powder (Suncut)
A pressed powder (sun cut) was prepared in the same manner as in Example 6 except that the hydrogenated castor oil isostearate was used in place of the oligomer of Synthesis Example 1 which is a component of Example 6.
(Evaluation)

In Example 6, the adhesion to the skin was good and the makeup was good.
[0036]
【The invention's effect】
The present invention has an appropriate oily feeling, adhesiveness, emollient, etc. by containing an oligomer of a specific hydrogenated castor oil and dimer acid, and is excellent in all practical properties, storage stability, and skin safety. Clearly provide cosmetics.

Claims (2)

  A cosmetic comprising an oligomer having a number average molecular weight of 2,000 to 8,000, which is reacted with an amount of dimer acid that binds to 25 to 50% of OH groups of hydrogenated castor oil. A cosmetic characterized in that the content of the oligomer is 0.1 to 20% by weight based on the total amount of the cosmetic.