JP4220752B2 - UV absorber - Google Patents

UV absorber Download PDF

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Publication number
JP4220752B2
JP4220752B2 JP2002300275A JP2002300275A JP4220752B2 JP 4220752 B2 JP4220752 B2 JP 4220752B2 JP 2002300275 A JP2002300275 A JP 2002300275A JP 2002300275 A JP2002300275 A JP 2002300275A JP 4220752 B2 JP4220752 B2 JP 4220752B2
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JP
Japan
Prior art keywords
ultraviolet
rice bran
present
lignin
skin
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Expired - Fee Related
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JP2002300275A
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Japanese (ja)
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JP2004131672A (en
Inventor
加珠子 藤
博行 野田
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Yamagata Promotional Organization for Ind Tech
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Yamagata Promotional Organization for Ind Tech
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Cosmetics (AREA)
  • Medicines Containing Plant Substances (AREA)
  • Compounds Of Unknown Constitution (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、米糠由来のリグニンの350nm〜400nmにおける吸光度を高める方法に関するものである。
【0002】
【従来の技術】
近年、オゾン層の破壊に伴って、地上に降りそそぐ紫外線量が増大しつつあることが指摘されている。このため、紫外線の人体への影響が一段と問題視されるようになっており、皮膚癌など皮膚疾患の増加も懸念されている。このため、紫外線吸収剤の開発研究が活発に行われており、これまでにも種々の商品が実用化されるに至っている。
【0003】
例えば、紫外線吸収能を有する有機化合物が合成されているが(特許文献1〜5参照)、地上に降りそそぐ紫外線波長(UVA及びUVB)全領域で吸収能を有するものがほとんどないことや安全性の点で問題があるものが多い。特に強力な紫外線吸収能を有する合成有機化合物は、皮膚に適用した場合にかぶれや発疹を生じることが多い。このため、紫外線吸収能が高くて安全な紫外線吸収剤を提供することが求められている。
【特許文献1】
特開平05−112487号公報
【特許文献2】
特開平05−201928号公報
【特許文献3】
特開平05−246946号公報
【特許文献4】
特開平06−135985号公報
【特許文献5】
特開2001−200238号公報
【0004】
【発明が解決しようとする課題】
これらの従来技術の現状を考慮して、本発明は、安価に紫外線吸収能を高めることにより安全な紫外線吸収材料を提供することを課題とした。特に本発明は、化粧品等の皮膚外用剤として有用な紫外線吸収材料を提供する方法を開発することを課題とした。
【0005】
【課題を解決するための手段】
本発明者らは上記の課題を解決するため種々の検討を重ねた結果、植物に含まれるリグニンを所定の方法で改質した改質リグニンが良好な紫外線吸収能を有することを見出し、しかも原料として間伐材や食品廃棄物等を利用すれば安価に提供することができることを見出した。
【0006】
すなわち、アルカリ処理を施したリグニン(本明細書ではこれを「改質リグニン」という)を含む紫外線吸収剤が有用であることを見出したの紫外線吸収剤は、280〜400nmの領域における最小吸光度と最大吸光度の比(最小吸光度/最大吸光度)が0.3以上であることが好ましく、0.8以上であることがより好ましい。この紫外線吸収剤皮膚外用剤として有用である
【0007】
発明は、米糠由来のリグニンをアルカリを含む溶媒に溶解することを特徴とする、米糠由来のリグニンの350nm〜400nmにおける吸光度を高める方法提供するものである。
【0008】
【発明の実施の形態】
以下において、本発明の紫外線吸収剤について詳細に説明する。なお、本明細書において「〜」はその前後に記載される数値をそれぞれ最小値および最大値として含む範囲を意味する。
【0009】
本発明では、米糠由来のリグニンを用いる。特に、食品産業廃棄物として大量に排出される脱脂米糠好適に用いることができる。脱脂米糠は食用にも利用されるので、毒性が低く人体にとって安全性が高い。
【0010】
本発明は、米糠由来のリグニンをアルカリを含む溶媒に溶解する処理を行うことを特徴としている。
【0011】
ルカリ処理用の薬剤としては、水酸化ナトリウムや水酸化カリウム、アンモニア、炭酸ナトリウウム、ホウ酸ナトリウムなど種々の塩基性化合物が挙げられる。なかでも、安全性や後処理の容易さなどから水酸化ナトリウムや水酸化カリウム、炭酸ナトリウム、ホウ酸ナトリウムの溶液が好適に用いられる
【0012】
改質リグニンのなかでも、抽出したリグニンをアルカリ処理したアルカリ処理リグニンや、フェノール化合物とリグニンを化学的に結合させたリグノフェノールをアルカリ処理したアルカリ処理リグノフェノールなどを好適に用いることができる。
【0013】
本発明で得られる改質リグニンは、280〜400nmの紫外線を吸収することを特徴としている。地上に到達する紫外線は、その波長によりUV−A領域の紫外線とUV−B領域の紫外線に分類されている。UV−A領域は波長が320〜400nm程度の紫外線であり、地上に到達する紫外線の9割程度を占めている。UV−A領域の紫外線を長期間にわたって浴びると、皮膚深部において慢性的な皮膚疾患を生じる危険性が高い。一方、UV−B領域は波長が280〜320nm程度の紫外線であり、地上に到達する紫外線の1割程度を占めている。UV−A領域の紫外線に比べると皮膚に対する影響が強いため、UV−B領域の紫外線はソバカスやシミの原因となることが多い。
【0014】
本発明で得られる改質リグニンを含む紫外線吸収剤(以下、本発明の紫外線吸収剤という)は、これらのUV−A領域とUV−B領域の紫外線をともに吸収し、280〜400nmの紫外線を比較的満遍なく吸収する。本発明の紫外線吸収剤の280〜400nmの領域における最小吸光度と最大吸光度の比(最小吸光度/最大吸光度)0.3以上であることが好ましく、0.65以上であることがより好ましく、0.8以上であることがさらにより好ましい。未改質のリグニンを含む紫外線吸収剤に比べると、改質リグニンを含む本発明の紫外線吸収剤は、特に350〜400nmの領域の吸収が高い。
【0015】
本発明の紫外線吸収剤の形態は特に制限されない。本発明の紫外線吸収剤は、たとえば、粉末状やスラリー状、液状で紫外線吸収能を発揮させることが可能である。
【0016】
本発明の紫外線吸収剤は皮膚外用剤として有効に用いられる。
例えば、本発明の紫外線吸収剤は化粧品や医薬品として使用することができる。具体的には、日焼け止めオイル、日焼け止めローション、日焼け止めクリーム、クリーム・乳液、化粧水、香水、おしろい、化粧油、頭髪用化粧品、染毛料、練香水、パウダー、パック、ファンデーション、粉末香水、頬紅、アイライナー、アイクリーム、アイシャドー、マスカラ、眉墨、爪クリーム、マニキュア、口紅、リップクリームなどとして使用することができる。また、本発明の皮膚外用剤は、軟膏剤として使用することもできる。
【0017】
本発明の皮膚外用剤には、紫外線吸収剤以外のさまざまな成分をさらに添加させておくことができる。例えば、エモリエント効果改善、使用感改善、使用後のかさつき軽減、可溶性改善、乳化性改善、乳化安定性改善、油剤成分との相溶性改善、使用後のつっぱり感軽減、肌への馴染み改善、皮膚上におけるのびの改善、べたつきの軽減、肌荒れ防止、美肌効果改善、皮膚保護効果改善、角質改善、表皮角化正常化、老人性乾皮症などの乾皮症軽減、ひび割れや落屑などの皮膚乾燥状態改善、しわ発生抑制、しわ消滅、創傷治療、色素沈着予防及び改善、老化防止、ふけやかゆみの軽減、脱毛軽減、頭皮疾患予防及び治療、保存性改善、柔軟性改善、弾力性改善、艶付与、メラニン色素産生抑制、日焼け防止などを目的として適当な成分を添加させることができる。
【0018】
本発明の皮膚外用剤に添加しうる成分として、例えば、油脂成分、リン脂質、UV吸収剤、IR吸収剤、乳化剤、界面活性剤、防腐剤、棒黴剤、酸化防止剤、美白剤、ビタミン、アミノ酸、ホルモン、ペプチド、生理活性植物抽出物、蛍光材料、顔料、色素、香料、スクラブ剤、金属イオン封鎖剤、バインダー、増量剤、増粘剤、糖類、栄養成分、pH調節剤、キレート剤、殺菌剤、角質改善剤、角質溶解剤、抗生物質、皮膚透過促進剤、血行促進剤、消炎剤、細胞賦活剤、抗炎症剤、鎮痛剤、皮膚軟化剤、皮膚緩和剤、創傷治療剤、新陳代謝促進剤などを使用目的に応じて適宜配合することができる。
【0019】
これら以外の材料についても、用途に応じて本発明の皮膚外用剤に添加することができる。各成分の添加量や添加方法については、本技術分野に周知の方法に従うことができる。
当業者は、上記の一般的な説明及び実施例の具体的開示を基にして、または必要に応じてそれらに適宜修飾や改変を加えることにより、本発明の好ましい態様の紫外線吸収剤を容易に製造することができよう。改質リグニンの量は特に限定されず、紫外線吸収剤の用途などに応じて適宜選択することができる。
【0020】
【実施例】
以下に実施例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。
【0021】
例1:本発明の紫外線吸収剤1の調製
脱脂米糠からジオキサン:水=8:2で抽出後、濃縮したのち少量の90%酢酸水溶液に溶解し、過剰の水を加えて沈殿させ、これをろ過してリグニンを得た。得られたリグニン1mgを1mlのジオキサン:0.2MNaOH=8:2に溶解して紫外線吸収剤1を得た。
【0023】
:本発明の紫外線吸収剤の評価
例1で得られた紫外線吸収剤1の紫外線吸収能を評価した。具体的には、日立製U−2000紫外可視分光光度計及び光路長10mmの石英セルを用い吸光度により評価した。
図1に、紫外線吸収剤1の280〜400nm領域における吸光度を示す。比較のためリグニンの吸光度も併せて示す。紫外線吸収剤1は、280〜400nmの全領域にわたって紫外線を吸収した。特に、340nmより長波長域の紫外線吸収能がリグニンに比べ増加した
【0024】
【発明の効果】
本発明の紫外線吸収剤は、安全で紫外線吸収能が高い。また、廃棄物を原料に安価に製造することができるために、産業上の利用性も高い。このような性質を有することから、本発明の紫外線吸収剤は化粧品や医薬品を始めとする皮膚外用剤として極めて有用である。
【図面の簡単な説明】
【図1】 紫外線吸収剤1及びリグニンの紫外線吸収特性を示す図である。
[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for increasing the absorbance at 350 nm to 400 nm of lignin derived from rice bran .
[0002]
[Prior art]
In recent years, it has been pointed out that the amount of ultraviolet rays falling on the ground is increasing with the destruction of the ozone layer. For this reason, the influence of ultraviolet rays on the human body is increasingly regarded as a problem, and there is concern about an increase in skin diseases such as skin cancer. For this reason, research and development of ultraviolet absorbers have been actively conducted, and various products have been put into practical use so far.
[0003]
For example, although an organic compound having ultraviolet absorbing ability has been synthesized (see Patent Documents 1 to 5), there is almost no absorption ability in the entire ultraviolet wavelength range (UVA and UVB) that falls on the ground. There are many problems in terms. In particular, synthetic organic compounds having a strong ultraviolet-absorbing ability often cause rashes and rashes when applied to the skin. For this reason, it is required to provide a UV absorber that has a high UV absorbing ability and is safe.
[Patent Document 1]
Japanese Patent Laid-Open No. 05-112487 [Patent Document 2]
JP 05-201928 A [Patent Document 3]
JP 05-246946 A [Patent Document 4]
Japanese Patent Laid-Open No. 06-135985 [Patent Document 5]
Japanese Patent Laid-Open No. 2001-200288
[Problems to be solved by the invention]
Taking into account the current state of these prior art, the present invention has an object to provide a safe UV-absorbing material inexpensively by the ultraviolet absorbing ability high Mel. In particular, an object of the present invention is to develop a method for providing an ultraviolet absorbing material useful as an external preparation for skin such as cosmetics.
[0005]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventors have found that a modified lignin obtained by modifying a lignin contained in a plant by a predetermined method has a good ultraviolet-absorbing ability, and is a raw material. As a result, it was found that if thinned wood, food waste, etc. are used, it can be provided at low cost.
[0006]
Chi words, and (this is referred to herein as "modified lignin") lignin which has been subjected to alkali treatment found that ultraviolet absorber containing are useful. UV absorbers This is preferably the ratio of the minimum absorbance and the maximum absorbance in the region of 280 to 400 nm (minimum absorbance / maximum absorbance) is 0.3 or more, and more preferably 0.8 or more. UV absorbers of this is useful as a skin external preparation.
[0007]
The present invention provides a method for increasing the absorbance of rice bran-derived lignin at 350 nm to 400 nm, which comprises dissolving rice bran-derived lignin in a solvent containing alkali .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the ultraviolet absorbent according to the present invention will be described in detail. In the present specification, “to” means a range including numerical values described before and after that as a minimum value and a maximum value, respectively.
[0009]
In the present invention, lignin derived from rice bran is used. In particular, it can be suitably used in large quantities degreasing rice bran that is discharged as the food industry wastes. Since defatted rice bran is also used for food, it has low toxicity and high safety for the human body.
[0010]
The present invention is characterized in that a treatment for dissolving lignin derived from rice bran in a solvent containing an alkali is performed .
[0011]
Agents for Hair alkali treatment, sodium hydroxide, potassium hydroxide, ammonia, carbonate Natoriuumu, various basic compounds such as sodium borate and the like. Of these, a solution of sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium borate is preferably used in view of safety and ease of post-treatment .
[0012]
Among the modified lignins, alkali-treated lignin obtained by alkali treatment of extracted lignin, alkali-treated lignophenol obtained by alkali treatment of lignophenol in which a phenol compound and lignin are chemically bonded, and the like can be suitably used.
[0013]
The modified lignin obtained by the present invention is characterized by absorbing ultraviolet rays of 280 to 400 nm. Ultraviolet rays reaching the ground are classified into ultraviolet rays in the UV-A region and ultraviolet rays in the UV-B region according to the wavelength. The UV-A region is an ultraviolet ray having a wavelength of about 320 to 400 nm and occupies about 90% of the ultraviolet ray reaching the ground. When exposed to ultraviolet rays in the UV-A region for a long period of time, there is a high risk of causing chronic skin diseases in the deep part of the skin. On the other hand, the UV-B region is an ultraviolet ray having a wavelength of about 280 to 320 nm, and occupies about 10% of the ultraviolet ray reaching the ground. Since the influence on the skin is stronger than that in the UV-A region, the UV-B region often causes freckles and spots.
[0014]
The ultraviolet absorbent containing the modified lignin obtained in the present invention (hereinafter referred to as the ultraviolet absorbent of the present invention) absorbs both ultraviolet rays in the UV-A region and the UV-B region and absorbs ultraviolet rays of 280 to 400 nm. Absorbs relatively evenly. Preferably the ratio of the minimum absorbance and the maximum absorbance in the region of 280~400nm ultraviolet absorbent of the present invention (minimal absorbance / maximum absorbance) is 0.3 or more, more preferably 0.65 or more, 0 More preferably, it is 8 or more. Compared with the ultraviolet absorber containing unmodified lignin, the ultraviolet absorber of the present invention containing modified lignin has particularly high absorption in the region of 350 to 400 nm.
[0015]
The form of the ultraviolet absorber of the present invention is not particularly limited. The ultraviolet absorbent according to the present invention can exhibit ultraviolet absorbing ability in, for example, powder, slurry, or liquid.
[0016]
The ultraviolet absorber of the present invention is effectively used as a skin external preparation.
For example, the ultraviolet absorber of the present invention can be used as a cosmetic or a pharmaceutical product. Specifically, sunscreen oil, sunscreen lotion, sunscreen cream, cream / milky lotion, lotion, perfume, irresistible, cosmetic oil, hair cosmetics, hair dye, paste perfume, powder, pack, foundation, powdered perfume, Can be used as blusher, eyeliner, eye cream, eye shadow, mascara, eyebrow, nail cream, nail polish, lipstick, lip balm, etc. Moreover, the skin external preparation of this invention can also be used as an ointment.
[0017]
Various components other than the ultraviolet absorber can be further added to the external preparation for skin of the present invention. For example, improvement of emollient effect, improvement of feeling of use, reduction of bulk after use, improvement of solubility, improvement of emulsification, improvement of emulsification stability, improvement of compatibility with oil components, reduction of feeling of tension after use, improvement of skin familiarity, skin Improvement of spreading, reduction of stickiness, prevention of rough skin, improvement of skin effect, improvement of skin protection, improvement of skin, normalization of epidermal keratinization, reduction of dry skin such as senile xerosis, dry skin such as cracks and desquamation Condition improvement, wrinkle generation suppression, wrinkle disappearance, wound treatment, pigmentation prevention and improvement, aging prevention, reduction of dandruff and itching, hair loss reduction, scalp disease prevention and treatment, storage stability improvement, flexibility improvement, elasticity improvement, gloss Appropriate ingredients can be added for the purpose of imparting, inhibiting melanin pigment production and preventing sunburn.
[0018]
Examples of components that can be added to the skin external preparation of the present invention include, for example, oil and fat components, phospholipids, UV absorbers, IR absorbers, emulsifiers, surfactants, preservatives, stickers, antioxidants, whitening agents, vitamins , Amino acids, hormones, peptides, bioactive plant extracts, fluorescent materials, pigments, dyes, fragrances, scrub agents, sequestering agents, binders, extenders, thickeners, sugars, nutritional components, pH regulators, chelating agents , Fungicides, keratin improving agents, keratolytic agents, antibiotics, skin permeation enhancers, blood circulation promoters, anti-inflammatory agents, cell activators, anti-inflammatory agents, analgesics, emollients, emollients, wound treatment agents, Metabolism promoters and the like can be appropriately blended depending on the purpose of use.
[0019]
Materials other than these can also be added to the external preparation for skin according to the present invention. About the addition amount and addition method of each component, it can follow the method well-known in this technical field.
Those skilled in the art can easily obtain the ultraviolet absorber of a preferred embodiment of the present invention based on the above general description and the specific disclosure of the examples or by appropriately modifying or modifying them as necessary. Could be manufactured. The amount of the modified lignin is not particularly limited and can be appropriately selected according to the use of the ultraviolet absorber.
[0020]
【Example】
The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
[0021]
Example 1: Preparation of ultraviolet absorber 1 of the present invention Extracted from defatted rice bran with dioxane: water = 8: 2, concentrated, dissolved in a small amount of 90% aqueous acetic acid, precipitated by adding excess water, Filtration yielded lignin. 1 mg of the obtained lignin was dissolved in 1 ml of dioxane: 0.2M NaOH = 8: 2 to obtain an ultraviolet absorber 1.
[0023]
Example 2 : Evaluation of UV absorber of the present invention The UV absorber 1 of the UV absorber 1 obtained in Example 1 was evaluated. Specifically, it was evaluated by absorbance using a Hitachi U-2000 ultraviolet-visible spectrophotometer and a quartz cell having an optical path length of 10 mm.
In FIG. 1, the light absorbency in the 280-400 nm area | region of the ultraviolet absorber 1 is shown. For comparison, the absorbance of lignin is also shown. The ultraviolet absorber 1 absorbed ultraviolet rays over the entire range of 280 to 400 nm. In particular, the ultraviolet absorption ability in the wavelength region longer than 340 nm was increased compared to lignin .
[0024]
【The invention's effect】
The ultraviolet absorbent according to the present invention is safe and has high ultraviolet absorbing ability. Moreover, since waste can be manufactured at low cost from raw materials, industrial applicability is also high. Because of such properties, the ultraviolet absorber of the present invention is extremely useful as a skin external preparation including cosmetics and pharmaceuticals.
[Brief description of the drawings]
FIG. 1 is a graph showing the ultraviolet absorption characteristics of an ultraviolet absorber 1 and lignin.

Claims (7)

米糠由来のリグニンをアルカリを含む溶媒に溶解することを特徴とする、米糠由来のリグニンの350nm〜400nmにおける吸光度を高める方法。 A method for increasing the absorbance at 350 nm to 400 nm of lignin derived from rice bran, comprising dissolving lignin derived from rice bran in a solvent containing an alkali . 前記米糠由来のリグニンが、脱脂米糠からの抽出物を酸を含む水溶液で処理したリグニンであることを特徴とする請求項1に記載の方法。The method according to claim 1, wherein the lignin derived from rice bran is lignin obtained by treating an extract from defatted rice bran with an aqueous solution containing an acid. 前記酸が酢酸であることを特徴とする請求項2に記載の方法。The method of claim 2, wherein the acid is acetic acid. 前記脱脂米糠からの抽出物が、脱脂米糠から水を含む溶媒で抽出した抽出物であることを特徴とする請求項2または3に記載の方法。The method according to claim 2 or 3, wherein the extract from the defatted rice bran is an extract extracted from the defatted rice bran with a solvent containing water. 前記脱脂米糠からの抽出物が、脱脂米糠からジオキサンを含む溶媒で抽出した抽出物であることを特徴とする請求項2〜4のいずれか一項に記載の方法。The method according to any one of claims 2 to 4, wherein the extract from the defatted rice bran is an extract extracted from the defatted rice bran with a solvent containing dioxane. 前記アルカリが水酸化ナトリウムであることを特徴とする請求項1〜5のいずれか一項に記載の方法。The method according to any one of claims 1 to 5, wherein the alkali is sodium hydroxide. 前記アルカリを含む溶媒がジオキサンを含むことを特徴とする請求項1〜6のいずれか一項に記載の方法。The method according to claim 1, wherein the alkali-containing solvent contains dioxane.
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