JPH026732B2 - - Google Patents
Info
- Publication number
- JPH026732B2 JPH026732B2 JP17262186A JP17262186A JPH026732B2 JP H026732 B2 JPH026732 B2 JP H026732B2 JP 17262186 A JP17262186 A JP 17262186A JP 17262186 A JP17262186 A JP 17262186A JP H026732 B2 JPH026732 B2 JP H026732B2
- Authority
- JP
- Japan
- Prior art keywords
- chitin
- chitosan
- titanium oxide
- granules
- particle size
- 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.)
- Expired
Links
- 229920001661 Chitosan Polymers 0.000 claims description 63
- 229920002101 Chitin Polymers 0.000 claims description 56
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000008187 granular material Substances 0.000 claims description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 26
- 239000011859 microparticle Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003637 basic solution Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000002537 cosmetic Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229940073609 bismuth oxychloride Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 101100491263 Oryza sativa subsp. japonica AP2-4 gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229960005196 titanium dioxide Drugs 0.000 description 1
Landscapes
- Cosmetics (AREA)
Description
〓産業上の利用分野〓
本発明は、キチン・キトサン微小粒状体中に無
機物質である極微粉末の酸化チタンを分散包含せ
しめたキチン・キトサン微小粒状体に関する。本
発明による酸化チタンを分散包含した微小キチ
ン・キトサン粒状体は紫外線散乱能が極めて高
く、しかも皮膚に対するなじみがよく、化粧用基
材等の用途に好適なものである。
〓従来の技術〓
本発明者等はキチン・キトサン微小粒状体を化
粧料用に使用することについて研究をなし、特願
昭61−29878号（特開昭62−190109号公報）及び
特願昭61−29879号（特開昭62−190110号公報）
として出願を行つた。該キチン・キトサン粒状体
を使用した化粧料に紫外線防止効果をもたせるた
めには、例えば特公昭47−42502号に記載されて
いるような最大粒径0.1μ以下であり、平均粒径30
乃至40μｍの極微粉末酸化チタンを混合すること
が考えられる。キチン・キトサン粒状体は、の
び・ひろがりに勝れ、酸化チタンは紫外線防止剤
としての効果を有するものであるが、単に両者を
混合し、配合した化粧料では、均一な分散は得ら
れず、また、酸化チタンに起因する皮膚に対する
感触性の劣化、即ち、使用感を悪くする欠点があ
る。
〓発明が解決しようとする問題点〓
本発明は、上述の如く、キチン・キトサン微小
粒状体は、化粧料として使用する際に皮膚に対す
るのび・ひろがりに効果があるものの、紫外線散
乱能が小さく、一方、無機物質である酸化チタン
は、のび・ひろがりの効果は小さいが紫外線散乱
能が大きい。本発明は、この両者の長所、欠点を
相補うことにより勝れた効果を有する新規な化粧
用基材を提供することを目的とする。
〓問題点を解決するための手段〓
本発明は、キチン又はキトサンを再生キチン又
はキトサンの粒状体とした後に極微粉末酸化チタ
ンを添加撹拌して分散懸濁液となし、該分散懸濁
液を高温雰囲気中に噴霧乾燥することによつて得
られる。極微粉末酸化チタンが分散包含されたキ
チン又はキトサン微小粒状体に係るものである。
キトサン粒状体は、低分子量キトサンの酸性溶
液を塩基性溶液中に落下させて得られる。
本発明において用いる低分子量キトサンは、平
均分子量が10000〜230000のものである。フレー
ク状の高分子キトサンは、過硼酸ソーダ水溶液中
で加温処理することによつて所望の分子量を有す
る良質なキトサンが得られる。低分子量キトサン
は、酢酸、ジクロル酢酸、蟻酸の単独又は混合物
の水溶液に溶解させキトサン酸性溶液とする。そ
の濃度は取扱いの容易な範囲を適宜選択出来るが
２〜20％の範囲が好ましい。該キトサン酸性溶液
を孔径0.1〜0.25mmφのノズルより圧力下で塩基
性凝固浴中に一定量ずつ落下させ粒状キトサンを
得る。凝固液の塩基性物質としては、水酸化ナト
リウム、水酸化カリウム、炭酸ナトリウム、炭酸
カリウム、アンモニア、エチンジアミン等のアル
カリ性物質が用いられ、塩基性溶液には、水、又
はメタノール、エタノール等の極性を有するアル
コール類、又は水とアルコールとの混合物に前記
塩基性物質を加えて使用する。得られた粒状キト
サンは極性溶媒を用いて中性になる迄充分に洗浄
を行う。
キチン粒状体は上記のようにして得られた粒状
キトサンをアルコールで水置換後、例えばエタノ
ール中で無水酢酸を用いて反応させてＮ−アセチ
ル化を行つて再生キチン粒状体とすることによつ
て得られるが、その他に
() キチンをアルカリキチン水溶液した後に、
酸性水溶液中で凝固析出させ、これを中性にな
る迄水洗して得られる凝固再生キチン。
() キチンをジメチルアセトアミドと塩化リチ
ウムとの混合溶剤に溶解し、水又はアルコー
ル、アセトン中に落下せしめて凝固析出させた
後、水で充分洗浄して得た凝固再生キチン。
も使用することが出来る。上記（）の方法とし
ては、例えばキチンに水を加え、加圧下で高温処
理後アルカリ水溶液に浸漬膨潤させて凍結解凍を
繰返してアルカリキチン水溶液とし、このアルカ
リキチン水溶液を酸性水溶液中に落下して凝固析
出させて再生キチン粒状体とする方法が挙げられ
る。
上記のようにして得られた粒状キトサン又は再
生キチン粒状体は極微粉末酸化チタンを加えて水
中で撹拌し、必要に応じてホモジナイザー等によ
り微粉砕して分散させ懸濁液とする。該懸濁液を
加圧空気と共に高温雰囲気中に噴霧乾燥すること
によりキチン・キトサン粒状体に極微粉末酸化チ
タンが分散包含されたキチン・キトサン微小粒状
体が得られる。高温雰囲気の温度は、キチン・キ
トサン微小粒状体が乾燥されるに充分な温度であ
つて100〜180℃の範囲で自由に選択出来る。噴霧
されたキチン・キトサン懸濁液は、分散媒である
水の表面張力等によつて高温雰囲気中で乾燥され
る際に、微小な球状体に形成される。得られる球
状体の球径は、高温雰囲気中に噴霧する際の吐出
速度を適宜調節することによつて自由に制御する
ことが出来る。化粧用基材として使用する場合
は、酸化チタンが分散されたキチン・キトサンの
粒状体の粒径は、１〜100μｍ程度であることが
好ましい。配合される無機物質である極微粉末酸
化チタンは、密度が高く、粒子径が0.01〜1μｍ、
化粧料用としては0.01〜0.05μｍが好ましく、配
合比はキチン・キトサン粒状体１重量部に対し、
0.01〜１重量部の範囲で適宜に選定される。極微
粉末酸化チタンをキトサン酸性溶液に予め分散し
ておく方法も考えられるが、工程中での酸化チタ
ンの損失等歩留りを考慮すると好ましくない。
本発明はキチン・キトサン微小粒状体に極微粉
末酸化チタンを配合させたものであるが、他の目
的、用途によつては亜鉛華、酸化亜鉛、酸化鉄、
チタン酸鉄、γ酸化鉄、黄酸化鉄、黒酸化鉄、酸
化クロム、水酸化クロム、チタン酸コバルト、コ
ーテツド雲母、酸化チタンコーテツドオキシ塩化
ビスマス、オキシ塩化ビスマス、酸化チタンコー
テツドタルク、着色酸化チタンコーテツド雲母、
アルミニウムパウダー、カツパーパウダー等を配
合したキチン・キトサン微小粒状体を同様な方法
で得ることが可能であることは勿論である。
〓実施例〓
以下実施例により本発明を説明するが、本発明
はこの範囲に限定されないことは勿論である。
実施例 １
脱アセチル化度85％、平均分子量142000のキト
サン25ｇを酢酸12.5ｇを含む水975ｇに加えて溶
解させてキトサン酸性溶液を得た。
該酸性溶液の20℃における粘度は回転粘度計で
測定したところ2100Cpであつた。該キトサン酸
性溶液を５％のアンモニア水溶液中に落下させ平
均粒径1.2ｍ／ｍの粒状キトサン凝固再生させて
得た。該凝固物を中性になるまで充分水洗した
後、粒径0.05μｍのルチル型極微粉末酸化チタン
12.5ｇを加え、水中でホモジナイザー（日本精機
株式会社AM−３型）を用いて15000r.p.m.の回転
数で７分間粉砕、分散させ乳状の懸濁液を得た。
充分に分散、混合させた後、４Kg／cm2の加圧空気
と共に17.6ml／minの流速で170〜175℃の高温雰
囲気中に吐出し噴霧、乾燥させた。乾燥された酸
化チタン配合のキトサン微小粒状物30ｇをサイク
ロンコレクターに捕集した。
得られた粒状物の球径を走査型電子顕微鏡（日
本電子株式会社製JSM−T200）で測定した処、
キトサン粒状物の平均粒径5μｍ、粒径分布は１
〜10μｍであつた。そして該粒状物表面にカーボ
ン蒸着（日本電子株式会社製JEE−4X使用）を
し、反射電子検出器（日本電子株式会社製T200
−BEIS）で組成像を観察した処、キトサン粒状
体内に酸化チタンが分散包含されていることが判
つた。又、該粒状体５ｇを触秤し、500℃で強熱
後灰分を測定した処、灰分率は32.6％であつた。
比較として実施例１と同様にキトサン25ｇを酢酸
12.5ｇを含む水975ｇに加え溶解し、５％アンモ
ニア水溶液にて凝固再生させ、充分水洗して得ら
れた粒径1.2mmの粒状キトサンを水と共にホモジ
ナイザーで粉砕させた懸濁液を４Kg／cm2の加圧空
気と共に17.6ml／minの流速で170〜175℃の高温
雰囲気中に吐出、噴霧、乾燥し平均粒径5μ、粒
径分布１〜10μｍのキトサン粒状体19ｇを得た。
この灰分を測定した処、灰分は0.55％であつた。
又、市販粘着テープに上記実施例１の酸化チタン
配合キトサン微小粒状体（試料）と上記比較例
のキトサン微小粒状体（試料）をフイルム上に
塗布し、ガススプレー（応研商事株式会社製）で
接着していない粒状体を吹き落し均一に粒状体の
付いたフイルムを得た。これを電子顕微鏡で観察
した処、粒状体が単一層で付着していた。該フイ
ルム二種を有害紫外線測定器（紫田化学株式会社
製UV−３型）のセンサーヘツド部に付け、殺菌
ランプ（日立株式会社製GL15）の紫外線ランプ
より５cmの距離における紫外線被曝量を測定し
た。コントロールとして極微粉末酸化チタンのみ
を塗付した粘着テープ（試料）を用いて測定し
た。この結果は第１表の通りであり、試料は試
料と殆ど同じ紫外線散乱能があることが判る。
次に皮膚に対する感触を調べる為に被験者20名
によつて、官能検査を行つた。評価には下記の五
段階でのび・ひろがりの項目について判定した。
結果は第１表に記した如くであり、総合的に本発
明の試料が化粧用基材として好適であることが
判る。
〓Field of Industrial Application〓 The present invention relates to chitin/chitosan microparticles in which extremely fine powdered titanium oxide, which is an inorganic substance, is dispersed and included in the chitin/chitosan microparticles. The fine chitin/chitosan particles containing titanium oxide dispersed therein according to the present invention have extremely high ultraviolet scattering ability, are compatible with the skin, and are suitable for applications such as cosmetic base materials. 〓Prior art〓 The present inventors have conducted research on the use of chitin/chitosan microparticles for cosmetics, and have published Japanese Patent Application No. 61-29878 (Japanese Unexamined Patent Publication No. 62-190109) and Japanese Patent Application No. 1987-190109. No. 61-29879 (Japanese Unexamined Patent Publication No. 62-190110)
The application was filed as In order to provide a UV protection effect to cosmetics using chitin/chitosan granules, the maximum particle size should be 0.1 μ or less and the average particle size should be 30
It is conceivable to mix ultrafine titanium oxide powder with a diameter of 40 μm to 40 μm. Chitin/chitosan granules are excellent in spreading and spreading, and titanium oxide is effective as a UV inhibitor, but if the two are simply mixed and formulated into a cosmetic, uniform dispersion cannot be obtained. In addition, there is a drawback that titanium oxide causes deterioration in tactility on the skin, that is, it makes the feeling of use worse. Problems to be Solved by the Invention As described above, the present invention solves the problem that although chitin/chitosan microparticles are effective in spreading and spreading on the skin when used as cosmetics, they have low ultraviolet scattering ability. On the other hand, titanium oxide, which is an inorganic material, has a small spreading and spreading effect, but has a large ultraviolet scattering ability. The object of the present invention is to provide a new cosmetic base material that has superior effects by compensating for the advantages and disadvantages of both. 〓Means for solving the problem〓 The present invention involves converting chitin or chitosan into granules of regenerated chitin or chitosan, and then adding and stirring ultrafine powder titanium oxide to form a dispersed suspension. Obtained by spray drying in a high temperature atmosphere. This relates to chitin or chitosan microparticles in which ultrafine powdered titanium oxide is dispersed. Chitosan granules are obtained by dropping an acidic solution of low molecular weight chitosan into a basic solution. The low molecular weight chitosan used in the present invention has an average molecular weight of 10,000 to 230,000. High-quality chitosan having a desired molecular weight can be obtained by heating the flaky polymeric chitosan in an aqueous solution of sodium perborate. The low molecular weight chitosan is dissolved in an aqueous solution of acetic acid, dichloroacetic acid, and formic acid alone or in a mixture to form an acidic chitosan solution. The concentration can be appropriately selected within a range that is easy to handle, but a range of 2 to 20% is preferred. A fixed amount of the chitosan acidic solution is dropped into a basic coagulation bath under pressure through a nozzle with a hole diameter of 0.1 to 0.25 mm to obtain granular chitosan. As the basic substance for the coagulation liquid, alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, ethinediamine are used. The basic substance is added to an alcohol or a mixture of water and alcohol. The obtained granular chitosan is thoroughly washed with a polar solvent until it becomes neutral. Chitin granules are obtained by substituting water with alcohol for the granular chitosan obtained as described above, and then reacting it with acetic anhydride in ethanol, for example, to perform N-acetylation to obtain regenerated chitin granules. However, in addition, () After making chitin into an alkaline chitin aqueous solution,
Coagulated regenerated chitin obtained by coagulating and precipitating in an acidic aqueous solution and washing with water until it becomes neutral. () Regenerated coagulated chitin obtained by dissolving chitin in a mixed solvent of dimethylacetamide and lithium chloride, dropping it into water, alcohol, or acetone to coagulate and precipitate it, and then washing thoroughly with water. can also be used. As for the method () above, for example, water is added to chitin, treated at high temperature under pressure, immersed in an alkaline aqueous solution to swell, frozen and thawed repeatedly to obtain an alkaline chitin aqueous solution, and this alkaline chitin aqueous solution is dropped into an acidic aqueous solution. An example of this method is to coagulate and precipitate the regenerated chitin particles. The granular chitosan or regenerated chitin granules obtained as described above are stirred in water to which ultrafine powdered titanium oxide is added, and if necessary, finely pulverized and dispersed using a homogenizer or the like to form a suspension. By spray-drying the suspension in a high-temperature atmosphere together with pressurized air, chitin/chitosan microparticles in which extremely fine powdered titanium oxide is dispersed and included in the chitin/chitosan granules are obtained. The temperature of the high temperature atmosphere is a temperature sufficient to dry the chitin/chitosan microparticles and can be freely selected within the range of 100 to 180°C. The sprayed chitin/chitosan suspension is formed into minute spherical bodies when dried in a high temperature atmosphere due to the surface tension of water, which is a dispersion medium. The spherical diameter of the resulting spherical bodies can be freely controlled by appropriately adjusting the discharge rate when spraying into a high-temperature atmosphere. When used as a cosmetic base material, the particle size of chitin/chitosan particles in which titanium oxide is dispersed is preferably about 1 to 100 μm. The ultrafine powdered titanium oxide, which is an inorganic substance, has a high density and a particle size of 0.01 to 1 μm.
For cosmetics, it is preferably 0.01 to 0.05 μm, and the blending ratio is: 1 part by weight of chitin/chitosan granules.
It is appropriately selected within the range of 0.01 to 1 part by weight. A method of pre-dispersing ultrafine powdered titanium oxide in an acidic chitosan solution is also considered, but this is not preferable in view of the loss of titanium oxide during the process and other yield issues. The present invention combines chitin/chitosan microparticles with ultrafine powdered titanium oxide, but depending on other purposes and uses, zinc white, zinc oxide, iron oxide,
Iron titanate, gamma iron oxide, yellow iron oxide, black iron oxide, chromium oxide, chromium hydroxide, cobalt titanate, coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, colored oxide titanium coated mica,
Of course, chitin/chitosan microparticles containing aluminum powder, cutlet powder, etc. can be obtained by the same method. 〓Example〓 The present invention will be explained below with reference to Examples, but it goes without saying that the present invention is not limited to this scope. Example 1 25 g of chitosan having a degree of deacetylation of 85% and an average molecular weight of 142,000 was added and dissolved in 975 g of water containing 12.5 g of acetic acid to obtain an acidic chitosan solution. The viscosity of the acidic solution at 20°C was 2100 Cp as measured by a rotational viscometer. The acidic chitosan solution was dropped into a 5% ammonia aqueous solution to solidify and regenerate granular chitosan having an average particle size of 1.2 m/m. After thoroughly washing the coagulated material with water until it becomes neutral, rutile type ultrafine powder titanium oxide with a particle size of 0.05 μm is prepared.
12.5 g was added, and the mixture was pulverized and dispersed in water using a homogenizer (Model AM-3, Nippon Seiki Co., Ltd.) at a rotational speed of 15,000 rpm for 7 minutes to obtain a milky suspension.
After sufficiently dispersing and mixing, the mixture was discharged into a high temperature atmosphere of 170 to 175° C. at a flow rate of 17.6 ml/min together with 4 kg/cm 2 of pressurized air and dried. 30 g of dried chitosan fine particles containing titanium oxide were collected in a cyclone collector. The spherical diameter of the obtained granules was measured using a scanning electron microscope (JSM-T200 manufactured by JEOL Ltd.).
Chitosan granules have an average particle size of 5 μm and a particle size distribution of 1
It was ~10 μm. Then, carbon vapor deposition (using JEE-4X manufactured by JEOL Ltd.) was performed on the surface of the granules, and a backscattered electron detector (T200 manufactured by JEOL Ltd. was used).
-BEIS), it was found that titanium oxide was dispersed and included in the chitosan granules. Further, 5 g of the granules were weighed and the ash content after ignition at 500°C was measured, and the ash content was 32.6%.
For comparison, 25g of chitosan was added to acetic acid in the same manner as in Example 1.
A suspension of granular chitosan with a particle size of 1.2 mm obtained by adding it to 975 g of water containing 12.5 g, dissolving it, coagulating and regenerating it with a 5% ammonia aqueous solution, and washing thoroughly with water, and pulverizing it with water using a homogenizer was prepared at 4 kg/cm. The mixture was discharged, sprayed, and dried into a high temperature atmosphere of 170 to 175° C. at a flow rate of 17.6 ml/min together with pressurized air (2 ) to obtain 19 g of chitosan granules having an average particle size of 5 μm and a particle size distribution of 1 to 10 μm.
When the ash content was measured, it was found to be 0.55%.
Further, the titanium oxide-containing chitosan microparticles (sample) of the above Example 1 and the chitosan microparticles (sample) of the above comparative example were coated on a commercially available adhesive tape and sprayed with a gas spray (manufactured by Okenshoji Co., Ltd.). The unadhered granules were blown off to obtain a film with uniform granules attached. When this was observed using an electron microscope, it was found that the granules were attached in a single layer. The two types of films were attached to the sensor head of a harmful ultraviolet ray measuring device (UV-3 type, manufactured by Shida Kagaku Co., Ltd.), and the amount of ultraviolet radiation exposure was measured at a distance of 5 cm from the ultraviolet lamp of a germicidal lamp (GL15, manufactured by Hitachi Corporation). did. As a control, measurements were made using an adhesive tape (sample) coated with only ultrafine powdered titanium oxide. The results are shown in Table 1, and it can be seen that the sample has almost the same ultraviolet scattering ability as the sample. Next, a sensory test was conducted on 20 subjects to examine the sensation on the skin. The evaluation was based on the following five levels of growth and expansion.
The results are shown in Table 1, and it can be seen that the samples of the present invention are generally suitable as cosmetic base materials.
【表】
表中：１…悪い、２…やや悪い、３…普通、
４…やや良い、５…良い
実施例 ２
脱アセチル化度95％、平均分子量62000のキト
サン65ｇを酢酸32.5ｇを含む水935ｇに溶解して、
25℃における粘度6000Cpのキトサン酸性溶液を
得た。
該キトサン酸性溶液を10％苛性ソーダ、30％メ
タノール、60％水からなる塩基性溶液中に落下さ
せてキトサン粒状物を凝固再生した。これを中性
になる迄充分水洗し、キトサン粒状物１を得
た。これをエタノールで四回置換し、水を完全に
アルコールに置換した。そして三倍モルの無水酢
酸を用いて室温で24時間反応させた。この操作を
三回繰返した後エタノールで洗浄、水洗いし、
0.5N苛性ソーダでエステル結合切断のため、室
温で１時間反応させ水洗いし粒径1.2ｍｍ／ｍ、
１の再生キチン粒状体を得た。該再生キチン粒
状体100mlに水50mlを加え、ホモジナイザーで
17000r.p.m.四分間撹拌し、粒径0.05μｍのルチル
型極微粉末酸化チタン3.5ｇを含む水100mlを加え
撹拌し、250mlの濃度4.5％の分散液とした。
該分散液を175℃の高温雰囲気中に回転数
29000r.p.m.のデイスクよりフイード量16.7ml／
min遠心噴霧し、乾燥物をサイクロンコレクター
で捕集した処、平均粒径10μｍ、粒径分布１〜
20μｍのキチン微小粒状体18.8ｇを得た（試料
）。このキチン粒状体を実施例１と同様の方法
で反射電子の組成像を観察した処、キチン粒子内
に均一に酸化チタンが分散包含していることが確
認出来た。又、灰分率は30.5％であつた。
一方比較として上記方法で得たルチル型極微粉
末酸化チタンが添加されていない再生キチン粒状
体100mlに水50mlを加え、ホモジナイザーで
17000r.p.m.四分間撹拌後、水100mlを加え、250
mlの濃度2.6％の分散液とした。
該分散液を175℃の高温雰囲気中にフイード量
16.7ml／minで遠心噴霧し、乾燥物をサイクロン
コレクターで捕集した処、平均粒径10μｍ、粒径
分布１〜20μｍの球状キチン粒状体5.3ｇを得た
（試料）。この粒状体の灰分率は0.35％であつ
た。
上記二種粒状体を実施例１と同様粘着テープに
塗布し単一粒子層で粒状体が付着しているフイル
ムを得た。また、対照例としてルチル型極微粉末
酸化チタンのみを付着させたものを試料とし
た。該フイルムによる紫外線被曝量を実施例１と
同様の方法で測定した。また、該粒状体の皮膚に
対する感触を官能検査により評価した結果を第２
表に示す。[Table] In the table: 1...poor, 2...slightly bad, 3...fair,
4...fairly good, 5...good example 2 65g of chitosan with a degree of deacetylation of 95% and an average molecular weight of 62000 was dissolved in 935g of water containing 32.5g of acetic acid.
A chitosan acidic solution with a viscosity of 6000 Cp at 25°C was obtained. The chitosan acidic solution was dropped into a basic solution consisting of 10% caustic soda, 30% methanol, and 60% water to solidify and regenerate chitosan granules. This was thoroughly washed with water until it became neutral, and chitosan granules 1 were obtained. This was replaced with ethanol four times to completely replace water with alcohol. Then, the mixture was reacted with three times the molar amount of acetic anhydride at room temperature for 24 hours. After repeating this operation three times, wash with ethanol and water.
To cleave the ester bond with 0.5N caustic soda, react at room temperature for 1 hour, wash with water, and reduce the particle size to 1.2 mm/m.
Regenerated chitin granules of No. 1 were obtained. Add 50 ml of water to 100 ml of the regenerated chitin granules and mix with a homogenizer.
The mixture was stirred at 17,000 rpm for 4 minutes, and 100 ml of water containing 3.5 g of rutile-type ultrafine powder titanium oxide with a particle size of 0.05 μm was added and stirred to form a 250 ml dispersion with a concentration of 4.5%. The dispersion was rotated at a high temperature of 175°C.
Feed amount 16.7ml/from 29000r.pm disk
After centrifugal spraying and collecting the dried material with a cyclone collector, the average particle size was 10 μm, and the particle size distribution was 1 to 1.
18.8 g of chitin microparticles of 20 μm were obtained (sample). When the composition image of reflected electrons of this chitin granule was observed in the same manner as in Example 1, it was confirmed that titanium oxide was uniformly dispersed and contained within the chitin particles. Moreover, the ash content was 30.5%. On the other hand, for comparison, 50 ml of water was added to 100 ml of recycled chitin granules obtained by the above method to which rutile-type ultrafine powdered titanium oxide was not added, and the mixture was heated using a homogenizer.
After stirring for 4 minutes at 17000r.pm, add 100ml of water and
A dispersion solution with a concentration of 2.6% per ml was prepared. Feed the dispersion in a high temperature atmosphere of 175℃.
Centrifugal spraying was performed at 16.7 ml/min, and the dried material was collected with a cyclone collector, yielding 5.3 g of spherical chitin particles with an average particle size of 10 μm and a particle size distribution of 1 to 20 μm (sample). The ash content of this granule was 0.35%. The above two types of granules were applied to an adhesive tape in the same manner as in Example 1 to obtain a film to which the granules were attached in a single particle layer. In addition, as a control example, a sample was prepared in which only rutile type ultrafine powder titanium oxide was deposited. The amount of ultraviolet rays exposed to the film was measured in the same manner as in Example 1. In addition, the results of evaluating the feel of the granules on the skin through a sensory test were evaluated in a second test.
Shown in the table.
【表】
第１表の結果と同様に試料が化粧用基材とし
て勝れた機能を有することが明らかである。
実施例 ３
カニ由来キチンフレーク（20〜60メツシユ）30
ｇを0.3N−HCl500ml中に分散させ、該分散液を
1.2Kg／cm2の圧力下121℃で30分間オートクレーブ
処理した。該処理液を充分水洗した後濾別し、10
℃に保ちながらこれに48゜Be−NaOH100mlを加
え撹拌して充分分散させた後、−80℃に冷却しそ
のまま凍結させた。この状態で４時間放置後これ
を取出し５℃で解凍した。この操作を再び繰返し
た後に濾別しこれに氷水1000ｇを加え撹拌し均一
なアルカリキチン水溶液を得た。該アルカリキチ
ン水溶液を50％酢酸水溶液３中に落下せしめて
キチン再生粒状体を得た。これを濾別し中性にな
る迄充分洗浄した後再度濾別した。これに0.05μ
ｍの酸化チタン10ｇを加えた後、ホモジナイザー
にて1700r.p.m.の条件で撹拌しながら水を加え全
量1000mlの分散液を得た。
該分散液を４Kg／cm2の加圧空気と共に毎分17.6
mlの液量で200〜210℃の高温雰囲気中に吐出し粒
状体30ｇを得た。
実施例１と同様の方法により反射電子の組成像
を観察した処、キチン粒状体に均一に酸化チタン
が分散包含していることを確認した。粒子径は２
〜25μｍでその灰分率は29.5％cm2あつた。又、実
施例１と全様の方法で紫外線被曝量を測定したら
0.98ffμw／cm2であり、皮膚に対する感触官能検査
では、のび・ひろがり共に評価は５であり、化粧
用基材として勝れたものである。
〓発明の効果〓
本発明による極微粉末無機質含有キチン・キト
サン微小粒状体は、キチン・キトサンを分散に望
ましい脆い状態の粒状のキチン・キトサンとして
水中で充分に微粉砕したものと、極微粉末酸化チ
タンとの分散懸濁液を高温雰囲気中に噴霧乾燥し
て得られるものであるので、極微粉末酸化チタン
がキチン・キトサンの微小粒状体中に均一に分散
包含されている。このことは実施例に記載のよう
に、微小粒状体表面へのカーボン蒸着と、反射電
子検出器による観察によつて確認された。本発明
によるキチン・キトサン微小粒状体は、化粧品と
して使用した場合、皮膚に対するのび・ひろがり
に勝れ、しかも紫外線防止効果が極めて大きいも
のであり、化粧用基材として好適なものである。[Table] Similar to the results in Table 1, it is clear that the sample has excellent functionality as a cosmetic base material. Example 3 Crab-derived chitin flakes (20-60 mesh) 30
Disperse g in 500ml of 0.3N-HCl, and add the dispersion to
It was autoclaved at 121° C. for 30 minutes under a pressure of 1.2 Kg/cm 2 . After washing the treated solution thoroughly with water, it was filtered and
While maintaining the temperature at 0.degree. C., 100 ml of 48.degree. Be-NaOH was added and stirred to sufficiently disperse the mixture, and then cooled to -80.degree. C. and frozen as it was. After being left in this state for 4 hours, it was taken out and thawed at 5°C. After repeating this operation again, the mixture was filtered and 1000 g of ice water was added thereto and stirred to obtain a uniform aqueous alkali chitin solution. The alkali chitin aqueous solution was dropped into a 50% acetic acid aqueous solution 3 to obtain chitin regenerated granules. This was separated by filtration, thoroughly washed until it became neutral, and then filtered again. 0.05μ for this
After adding 10 g of titanium oxide (m), water was added while stirring with a homogenizer at 1700 rpm to obtain a dispersion with a total volume of 1000 ml. The dispersion was pumped with 4Kg/ cm2 of pressurized air at a rate of 17.6 minutes per minute.
A liquid volume of ml was discharged into a high temperature atmosphere of 200 to 210°C to obtain 30 g of granules. When the composition image of reflected electrons was observed by the same method as in Example 1, it was confirmed that titanium oxide was uniformly dispersed and included in the chitin granules. The particle size is 2
~25 μm and its ash content was 29.5% cm2 . In addition, if the amount of ultraviolet radiation exposure was measured using the same method as in Example 1,
It was 0.98ffμw/cm 2 , and in the skin sensory test, it was rated 5 for both spreading and spreading, making it an excellent cosmetic base material. 〓Effects of the Invention〓 The ultrafine powder inorganic-containing chitin/chitosan microparticles according to the present invention include chitin/chitosan sufficiently finely pulverized in water as brittle granular chitin/chitosan suitable for dispersion, and ultrafine powder titanium oxide. Since it is obtained by spray-drying a dispersed suspension of chitin and chitosan in a high-temperature atmosphere, ultrafine powder titanium oxide is uniformly dispersed and included in the chitin/chitosan microparticles. This was confirmed by carbon vapor deposition on the surface of the microparticles and observation using a backscattered electron detector, as described in Examples. When the chitin/chitosan microparticles according to the present invention are used as cosmetics, they are excellent in spreading and spreading on the skin, and have an extremely large ultraviolet protection effect, making them suitable as cosmetic base materials.
Claims (1)
タンとの分散懸濁液を、高温雰囲気中に噴霧乾燥
してなる極微粉末酸化チタンが分散包含されてな
るキチン又はキトサン微小粒状体。 ２ キチン又はキトサン粒状体と極微粉末酸化チ
タンとの分散懸濁液が、低分子量キトサンの酸性
溶液を塩基性溶液中に落下させて得たキトサン粒
状体、又は該キトサン粒状体を無水酢酸で処理し
て得た再生キチン粒状体に極微粉末酸化チタンを
添加撹拌して得られたものである特許請求の範囲
第１項に記載のキチン又はキトサン微小粒状体。 ３ 極微粉末酸化チタンの粒径が0.01〜1.0μｍで
ある特許請求の範囲第１項に記載のキチン又はキ
トサン微小粒状体。 ４ キチン又はキトサン微小粒状体の粒径が１〜
100μｍの範囲である特許請求の範囲第１項に記
載のキチン又はキトサン微小粒状体。[Scope of Claims] 1. Chitin or chitosan microparticles containing dispersed micropowder titanium oxide, which is obtained by spray-drying a dispersed suspension of chitin or chitosan granules and micropowder titanium oxide in a high-temperature atmosphere. . 2 A dispersion suspension of chitin or chitosan granules and ultrafine powdered titanium oxide is obtained by dropping an acidic solution of low molecular weight chitosan into a basic solution, or the chitosan granules are treated with acetic anhydride. The chitin or chitosan microparticles according to claim 1, which are obtained by adding and stirring ultrafine powdered titanium oxide to the regenerated chitin granules obtained. 3. The chitin or chitosan microparticles according to claim 1, wherein the ultrafine titanium oxide powder has a particle size of 0.01 to 1.0 μm. 4 The particle size of the chitin or chitosan microparticles is 1~
The chitin or chitosan microparticles according to claim 1, which have a diameter of 100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17262186A JPS6327501A (en) | 1986-07-22 | 1986-07-22 | Chitin or chitosan minute particle containing ultrafine powder of inorganic substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17262186A JPS6327501A (en) | 1986-07-22 | 1986-07-22 | Chitin or chitosan minute particle containing ultrafine powder of inorganic substance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6327501A JPS6327501A (en) | 1988-02-05 |
| JPH026732B2 true JPH026732B2 (en) | 1990-02-13 |
Family
ID=15945267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17262186A Granted JPS6327501A (en) | 1986-07-22 | 1986-07-22 | Chitin or chitosan minute particle containing ultrafine powder of inorganic substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6327501A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2755972B1 (en) * | 1996-11-21 | 2004-04-02 | Merck Clevenot Laboratoires | PROCESS FOR THE PREPARATION OF MICROPARTICLES OF MINERAL PIGMENTS COATED WITH A CHAIN LAYER, MICROPARTICLES OBTAINED AND USE OF SUCH MICROPARTICLES |
| FR2778919B1 (en) * | 1998-05-19 | 2000-08-11 | Merck Sa | NOVEL POLYMERIC MATERIAL FOR MARKING OR ENGRAVING AND METHOD FOR MARKING OR ENGRAVING SUCH A MATERIAL |
| FR2788688B1 (en) * | 1999-01-25 | 2002-12-06 | Merck Sa | COSMETIC ANHYDROUS COMPOSITION ESSENTIALLY FREE OF FAT BINDERS AND PROCESS FOR PREPARING SUCH A COMPOSITION |
| WO2000061109A1 (en) * | 1999-04-12 | 2000-10-19 | Shionogi & Co., Ltd. | Process for producing medicinal composition of basic hydrophobic medicinal compound |
| US6838087B1 (en) * | 1999-11-15 | 2005-01-04 | Cognis Corporation | Cosmetic compositions having improved tactile and wear properties |
-
1986
- 1986-07-22 JP JP17262186A patent/JPS6327501A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6327501A (en) | 1988-02-05 |
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