JPS628099B2 - - Google Patents
Info
- Publication number
- JPS628099B2 JPS628099B2 JP55132308A JP13230880A JPS628099B2 JP S628099 B2 JPS628099 B2 JP S628099B2 JP 55132308 A JP55132308 A JP 55132308A JP 13230880 A JP13230880 A JP 13230880A JP S628099 B2 JPS628099 B2 JP S628099B2
- Authority
- JP
- Japan
- Prior art keywords
- hair
- weight
- carbon atoms
- general formula
- alkyl group
- 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
- 210000004209 hair Anatomy 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000002537 cosmetic Substances 0.000 claims description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 125000005526 alkyl sulfate group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000002355 alkine group Chemical group 0.000 claims 1
- -1 alkyl quaternary ammonium salt Chemical class 0.000 description 14
- 230000003766 combability Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000003676 hair preparation Substances 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 7
- 230000003020 moisturizing effect Effects 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- 206010044625 Trichorrhexis Diseases 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- DGSZGZSCHSQXFV-UHFFFAOYSA-N 2,3-bis(2-ethylhexanoyloxy)propyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(OC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DGSZGZSCHSQXFV-UHFFFAOYSA-N 0.000 description 1
- GECRRQVLQHRVNH-MRCUWXFGSA-N 2-octyldodecyl (z)-octadec-9-enoate Chemical compound CCCCCCCCCCC(CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC GECRRQVLQHRVNH-MRCUWXFGSA-N 0.000 description 1
- BGRXBNZMPMGLQI-UHFFFAOYSA-N 2-octyldodecyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OCC(CCCCCCCC)CCCCCCCCCC BGRXBNZMPMGLQI-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- YSJGOMATDFSEED-UHFFFAOYSA-M behentrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C YSJGOMATDFSEED-UHFFFAOYSA-M 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- CDIPRYKTRRRSEM-UHFFFAOYSA-M docosyl(trimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C CDIPRYKTRRRSEM-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- SFFVATKALSIZGN-UHFFFAOYSA-N hexadecan-7-ol Chemical compound CCCCCCCCCC(O)CCCCCC SFFVATKALSIZGN-UHFFFAOYSA-N 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- MRAPAFWHXSJNRN-UHFFFAOYSA-M icosyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCC[N+](C)(C)C MRAPAFWHXSJNRN-UHFFFAOYSA-M 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 229940073665 octyldodecyl myristate Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
Description
本発明は、毛髪に対し櫛通り性、なめらかさ、
柔軟性およびしつとり感を付与する上で優れた効
果を有する毛髪化粧料に関する。
通常、毛髪は、ヘアークリームやヘアーオイル
等の動植物油および毛髪自身から分泌される皮脂
等により覆われているが、石鹸や合成洗剤等で洗
髪すると、それらの油脂成分は必要以上に除去さ
れてしまう。そのため洗髪後の毛髪はなめらかさ
が失なわれ、パサパサした硬い感触となり、櫛通
りが悪くなつて裂毛や枝毛が生じ易くなつてしま
う。
このような不都合を解消するため、洗髪後の毛
髪処理剤として各種の毛髪化粧料が開発され、使
用されている。これら毛髪化粧料は、ジアルキル
ジメチルアンモニウムクロライドやアルキルトリ
メチルアンモニウムクロライドに代表される第４
級アンモニウム塩を主要有効成分とするものであ
る。このようなアンモニウム塩には水難溶性のも
のと水易溶性のものとがあり、従つてそれに対応
して、毛髪化粧料には「すすぐタイプ」のものと
「すすがないタイプ」のものとがあつて、それぞ
れその使用形態を異ならしめている。
洗髪後等の毛髪のキシミやもつれを防ぎ、乾い
た状態の仕上り感をよくするためには、上記アン
モニウム塩が毛髪に吸着されていなければならな
い。しかし、従来の毛髪化粧料は、どの使用形態
によつても上記アンモニウム塩の離脱性や吸着性
に問題があり、充分満足すべきものではなかつ
た。特に、毛髪の櫛通り性、なめらかさ、柔軟性
およびしつとり感において未だ不充分であつた。
また、従来、繊維柔軟剤等の各種繊維処理剤が
知られているが、繊維特に動物性繊維は、その化
学的構造において毛髪と類似であるものの、物理
的構造において毛髪とは全く異なつているため、
そのような繊維処理剤の毛髪への適用は困難であ
る。
本発明は、上記事情の下になされたものであつ
て、すすぐタイプおよびすすがないタイプのいず
れのタイプに適用しても優れた櫛通り性、なめら
かさ、柔軟性およびしつとり感を毛髪に付与し得
る性能を発揮する毛髪化粧料を提供することを目
的とする。
即ち、本発明の毛髪化粧料は、下記一般式
（）で表わされる第４級アンモニウム塩0.1ない
し３重量％と、下記一般式（）で表わされる第
４級アンモニウム塩0.1ないし３重量％と、それ
ぞれ下記一般式（）および（）で表わされる
２種の化合物の合計量0.5ないし4.0重量％とを必
須成分として含有し、かつ（）／（）の重量
比は1/3ないし3/1、（）／（）の重量比は2/8
ないし8/2であることを特徴とする。
一般式（）：
（式中、R1は炭素数16〜18のアルキル基、
R2，R3およびR4は炭素数１〜３のアルキル基又
はヒドロキシアルキル基、Ｘはハロゲン原子又は
アルキル基の炭素原子数が１又は２のアルキル硫
酸基を示す。）
一般式（）：
（式中、R5は炭素数20〜22のアルキル基、
R6，R7およびR8は炭素数１〜３のアルキル基又
はヒドロキシアルキル基、Ｘはハロゲン原子又は
アルキル基の炭素数が１又は２のアルキル硫酸基
を示す。）
一般式（）
（式中、ＲはＨ又は炭素原子数１ないし３のア
ルキル基、ｍ＋ｎは５ないし50、ｐは０ないし
３、ａ／ｂは40/60ないし60/40であり、且つ当該
共重合体がポリオキシアルキレン基70ないし80重
量％を含有するような数値である。）
一般式（）
（式中、ａ＋ｂ＋ｃは20ないし25）
以下、本発明の毛髪化粧料について更に詳細に
説明する。
本発明の毛髪化粧料の第１の必須成分は、以下
の一般式（）で表わされるモノ−C16-18アルキ
ル第４級アンモニウム塩である。
一般式（）：
（式中、R1は炭素数16〜18のアルキル基、
R2，R3およびR4は炭素数１〜３のアルキル基又
は、ヒドロキシアルキル基、Ｘはハロゲン原子又
はアルキル基の炭素原子数が１又は２のアルキル
硫酸基を示す。）
第１の必須成分の配合量は、毛髪化粧料全体に
対し0.1ないし3.0重量％、好ましくは0.1ないし
2.0重量％である。0.1重量％未満では本発明の効
果は発揮されず、3.0重量％を越えると毛髪のべ
たつきおよび重みが増加し、好ましくない。
第１の必須成分の代表例として以下の物質があ
る。
パルミチルトリメチルアンモニウムクロリド、
ステアリルトリメチルアンモニウムクロリド、水
素添加牛脂アルキルトリメチルアンモニウムクロ
リド、水素添加牛脂アルキルトリメチルアンモニ
ウムブロミド、水素添加牛脂アルキルトリエチル
アンモニウムメチルサルフエート。
本発明の毛髪化粧料の第２の必須成分は、以下
の一般式（）で表わされるモノ−C20-22アルキ
ル第４級アンモニウム塩である。
一般式（）
（式中、R5は炭素数20〜22のアルキル基、
R6，R7およびR8は炭素数１〜３のアルキル基又
はヒドロキシアルキル基、Ｘはハロゲン原子又は
アルキル基の炭素数が１又は２のアルキル硫酸基
を示す。）
第２の必須成分の配合量は、毛髪化粧料全体に
対し0.1ないし3.0重量％、好ましくは0.1ないし
2.0重量％である。0.1重量％未満では本発明の効
果は発揮されず、3.0重量％を越えると毛髪のべ
たつきおよび重みが増加し、好ましくない。
第２の必須成分の代表例として以下の物質があ
る。
エイコシルトリメチルアンモニウムクロリド、
ヘンエイコシルトリメチルアンモニウムクロリ
ド、ドコシルトリメチルアンモニウムクロリド、
ドコシルトリメチルアンモニウムブロミド、ドコ
シルトリエチルアンモニウムクロリド、ドコシル
トリメチルアンモニウムメチルサルフエート。
本発明の毛髪化粧剤においては、上述の一般式
（）の第４級アンモニウム塩と一般式（）の
第４級アンモニウム塩との重量比（）／（）
が1/3ないし3/1の範囲にある必要がある。特に好
ましくは（）／（）＝１／2.5〜2.5／１であ
る。（）／（）が1/3未満であるか又は3/1を
越える場合には、本発明の効果を得ることができ
ず、好ましくない。
本発明の第３の必須成分は、以下の一般式
（）で表わされるポリオキシアルキレン変性オ
ルガノポリシロキサンである。
一般式（）
（式中、ＲはＨ又は炭素原子数１ないし３のア
ルキル基、ｍ＋ｎは５ないし50、ｐは０ないし
３、ａ／ｂは40/60ないし60/40であり、且つ当該
共重合体がポリオキシアルキレン基70ないし80重
量％を含有するような数値である。）
一般式（）において、ａ／ｂは40/60ないし6
０／４０であるが、特に好ましくは50／50である。
ａ／ｂが40/60未満では、油性感、及びべたつき
が増し、櫛通り、及びなめらかさが劣り、好まし
くない。ａ／ｂが60/40を越えると、水溶性が増
し、毛髪に対する残存率が小さく、効果を得る事
ができない。
更に、本発明の第３の必須成分として用いられ
るポリシロキサンとしては、ポリオキシアルキレ
ン基含有量が70ないし80重量％のものが好まし
く、特に好ましくは70ないし7.5重量％のものが
よい。ポリオキシアルキレン基含有量が70重量％
未満では、油性感が増し、なめらかさが劣る。80
重量％を越えると、水溶性が増し、毛髪に対する
残存率が少なく効果が出ない。
本発明の第４の必須成分は、下記の一般式
（）に示すポリオキシエチレングリセリールモ
ノピログルタメートモノイソステアレートであ
る。
一般式（）
（式中、ａ＋ｂ＋ｃは20ないし25）
一般式（）において、ａ＋ｂ＋ｃは20ないし
25である必要があり、この範囲外では本発明の効
果を得ることができない。
以上説明した一般式（）および（）により
それぞれ表わされる第３および第４の必須成分の
重量比は、（）／（）＝2/8〜8/2、好ましくは
４／６〜６／４であり、またそれらの合計量は、
毛髪化粧料組成物全体に対し0.5ないし4.0重量
％、好ましくは1.0〜3.0重量％である。
（）／（）が2/8未満では油性感が増し、
なめらかさが劣る。8/2を越えると、櫛通り、及
び柔らかさが劣り、好ましくない。また、第３お
よび第４の必須成分の合計量が毛髪化粧料組成物
全体に対し0.5重量％未満では、櫛通り、なめら
かさ、柔らかさが劣り、特に柔らかさが著るしく
低下する。4.0重量％を越えると、べたつきが増
し、重くなりなめらかさが劣化する。
本発明の毛髪化粧料中には、他の任意成分を、
本発明の効果に影響のない範囲で配合することが
可能である。そのような任意成分として以下の物
質がある。
流動パラフイン、ワセリン、固形パラフイン、
スクワランおよびオレフインオリゴマー等の炭化
水素；イソプロピルミリステート、イソプロピル
パルミテート、ステアリルステアレート、ミリス
チン酸オクチルドデシル、オレイン酸オクチルド
デシルおよび２−エチルヘキサン酸トリグリセラ
イド等のエステル；セタノール、ステアリルアル
コール、ベヘニルアルコールおよびヘキシルデカ
ノール等の高級アルコール；グリセリルモノステ
アレート、ソルビタンモノパルミテート、ポリオ
キシエチレンセチルエーテル、ポリオキシエチレ
ンステアリン酸エステルおよびポリオキシエチレ
ンソルビタンモノラウレート等の乳化剤；メチル
セルロース、ヒドロキシエチルセルロース、ヒド
ロキシプロピルセルロースおよびカチオン化セル
ロース等のセルロース誘導体；天然高分子類等の
増粘剤；エチレングリコール、プロピレングリコ
ール、１，３−ブチレングリコール、グリセリン
およびソルビトール等の保湿剤；およびその他溶
剤、殺菌剤、香料等の少量成分である。
本発明の毛髪化粧料は、ヘアーリンス剤、スプ
レー型又はデイスペンサー型のヘアコンデイシヨ
ナー、ヘアーローシヨン等の各種用途に利用する
ことができる。
次に、本発明の実施例と比較例を示し、本発明
の効果をより具体的に説明する。なお、各例の説
明に先立つて、試験法について説明する。
試験法
シヤンプー処理された毛束（５ｇ、20cm）に試
料0.5ｇを直接塗布し、手で均一に伸ばしたのち
25℃、65％RHの雰囲気で乾燥させ、一昼夜放置
後の毛束の「櫛通り性」、「なめらかさ」、「柔軟
性」および「しつとり感」について20名のパネラ
ーにより官能評価する。
評価基準は1.0重量％のステアリルトリメチル
アンモニウムクロライド、３重量％のセチルアル
コール、10重量％のプロピレングリコール、およ
び水（残部）からなる試料（比較例１）により得
た評価を基準とした５段階評価である。
◎：良い 〇：やや良い △：同等
×：やや劣る ××：劣る
試験例 １
種々の第４級アンモニウム塩および／または本
発明の第３および第４の必須成分を含む28種の毛
髪化粧料を調整し、それらの毛髪に対する性能
（櫛通り性、なめらかさ、柔軟性、しつとり感）
を試験した。その結果を表１に示す。なお、配合
量は重量％である（他の試験例でも同様）。
The present invention provides hair with combability, smoothness,
The present invention relates to a hair cosmetic that has excellent effects in imparting flexibility and moisturizing feeling. Normally, hair is covered with animal and vegetable oils such as hair creams and hair oils, as well as sebum secreted from the hair itself, but when hair is washed with soap or synthetic detergents, these oils and fats are removed more than necessary. Put it away. As a result, the hair after washing loses its smoothness, feels dry and stiff, and becomes difficult to comb, making it more likely to cause split ends and split ends. In order to eliminate such inconveniences, various hair cosmetics have been developed and used as hair treatment agents after hair washing. These hair cosmetics contain quaternary compounds such as dialkyldimethylammonium chloride and alkyltrimethylammonium chloride.
The main active ingredient is grade ammonium salt. There are two types of ammonium salts: those that are poorly soluble in water and those that are easily soluble in water.Therefore, correspondingly, there are two types of hair cosmetics: ``rinse type'' and ``non-rinse type.'' However, each type of use is different. In order to prevent hair from squeaking and tangling after washing, etc., and to improve the finish when dry, the above ammonium salt must be adsorbed to the hair. However, conventional hair cosmetics have problems with the release and adsorption properties of the ammonium salt, regardless of the form of use, and are not fully satisfactory. In particular, the combability, smoothness, flexibility and moisturizing feel of the hair were still unsatisfactory. In addition, various fiber treatment agents such as fiber softeners have been known, but although fibers, especially animal fibers, have a chemical structure similar to that of hair, their physical structure is completely different from that of hair. For,
Application of such fiber treatment agents to hair is difficult. The present invention was made under the above circumstances, and provides excellent combability, smoothness, flexibility, and moisturizing feeling to hair regardless of whether it is applied to rinsing type or non-rinsing type. The purpose of the present invention is to provide a hair cosmetic that exhibits performance that can be imparted to hair. That is, the hair cosmetic of the present invention contains 0.1 to 3% by weight of a quaternary ammonium salt represented by the following general formula (), 0.1 to 3% by weight of a quaternary ammonium salt represented by the following general formula (), Contains as essential components a total amount of 0.5 to 4.0% by weight of two types of compounds represented by the following general formulas () and (), respectively, and the weight ratio of ()/() is 1/3 to 3/1, The weight ratio of ()/() is 2/8
or 8/2. General formula (): (In the formula, R 1 is an alkyl group having 16 to 18 carbon atoms,
R 2 , R 3 and R 4 represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or an alkyl sulfate group having 1 or 2 carbon atoms in the alkyl group. ) General formula (): (In the formula, R 5 is an alkyl group having 20 to 22 carbon atoms,
R 6 , R 7 and R 8 represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or an alkyl sulfate group having 1 or 2 carbon atoms in the alkyl group. ) General formula () (wherein R is H or an alkyl group having 1 to 3 carbon atoms, m+n is 5 to 50, p is 0 to 3, a/b is 40/60 to 60/40, and the copolymer is The value is such that it contains 70 to 80% by weight of polyoxyalkylene groups.) General formula () (In the formula, a+b+c is 20 to 25) Hereinafter, the hair cosmetic of the present invention will be explained in more detail. The first essential component of the hair cosmetic of the present invention is a mono-C 16-18 alkyl quaternary ammonium salt represented by the following general formula (). General formula (): (In the formula, R 1 is an alkyl group having 16 to 18 carbon atoms,
R 2 , R 3 and R 4 represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X represents a halogen atom or an alkyl sulfate group having 1 or 2 carbon atoms in the alkyl group. ) The blending amount of the first essential ingredient is 0.1 to 3.0% by weight, preferably 0.1 to 3.0% by weight based on the entire hair cosmetic.
It is 2.0% by weight. If it is less than 0.1% by weight, the effect of the present invention will not be exhibited, and if it exceeds 3.0% by weight, the hair will become sticky and heavy, which is not preferable. The following substances are representative examples of the first essential component. palmityltrimethylammonium chloride,
Stearyltrimethylammonium chloride, hydrogenated tallow alkyltrimethylammonium chloride, hydrogenated tallow alkyltrimethylammonium bromide, hydrogenated tallow alkyltriethylammonium methyl sulfate. The second essential component of the hair cosmetic of the present invention is a mono-C 20-22 alkyl quaternary ammonium salt represented by the following general formula (). General formula () (In the formula, R 5 is an alkyl group having 20 to 22 carbon atoms,
R 6 , R 7 and R 8 represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or an alkyl sulfate group having 1 or 2 carbon atoms in the alkyl group. ) The amount of the second essential ingredient is 0.1 to 3.0% by weight, preferably 0.1 to 3.0% by weight based on the entire hair cosmetic.
It is 2.0% by weight. If it is less than 0.1% by weight, the effect of the present invention will not be exhibited, and if it exceeds 3.0% by weight, the hair will become sticky and heavy, which is not preferable. Representative examples of the second essential component include the following substances. eicosyltrimethylammonium chloride,
Heneicosyltrimethylammonium chloride, docosyltrimethylammonium chloride,
Docosyltrimethylammonium bromide, docosyltriethylammonium chloride, docosyltrimethylammonium methyl sulfate. In the hair cosmetic of the present invention, the weight ratio ()/() of the quaternary ammonium salt of the above general formula () to the quaternary ammonium salt of the general formula () is
must be in the range of 1/3 to 3/1. Particularly preferably, ()/()=1/2.5 to 2.5/1. If ()/() is less than 1/3 or exceeds 3/1, the effects of the present invention cannot be obtained, which is not preferable. The third essential component of the present invention is a polyoxyalkylene-modified organopolysiloxane represented by the following general formula (). General formula () (wherein R is H or an alkyl group having 1 to 3 carbon atoms, m+n is 5 to 50, p is 0 to 3, a/b is 40/60 to 60/40, and the copolymer is It is a numerical value that contains 70 to 80% by weight of polyoxyalkylene groups.) In the general formula (), a/b is 40/60 to 6
0/40, particularly preferably 50/50.
If the a/b ratio is less than 40/60, the oily feel and stickiness will increase, and the combability and smoothness will be poor, which is not preferable. When the a/b ratio exceeds 60/40, the water solubility increases, the residual rate on hair is low, and no effect can be obtained. Furthermore, the polysiloxane used as the third essential component of the present invention preferably has a polyoxyalkylene group content of 70 to 80% by weight, particularly preferably 70 to 7.5% by weight. Polyoxyalkylene group content is 70% by weight
If it is less than that, the oily feeling will increase and the smoothness will be poor. 80
If it exceeds % by weight, the water solubility will increase and the residual rate on hair will be low, resulting in no effect. The fourth essential component of the present invention is polyoxyethylene glyceryl monopyroglutamate monoisostearate represented by the following general formula (). General formula () (In the formula, a+b+c is 20 to 25) In the general formula (), a+b+c is 20 to 25.
25, and the effects of the present invention cannot be obtained outside this range. The weight ratio of the third and fourth essential components respectively represented by the general formulas () and () explained above is ()/()=2/8 to 8/2, preferably 4/6 to 6/4. and their total amount is
The amount is 0.5 to 4.0% by weight, preferably 1.0 to 3.0% by weight, based on the entire hair cosmetic composition. If ()/() is less than 2/8, the oily feeling will increase,
Less smooth. If it exceeds 8/2, the combability and softness will be poor, which is not desirable. If the total amount of the third and fourth essential components is less than 0.5% by weight based on the entire hair cosmetic composition, combability, smoothness, and softness will be poor, and in particular, softness will be significantly reduced. If it exceeds 4.0% by weight, stickiness increases, it becomes heavy and smoothness deteriorates. The hair cosmetic of the present invention contains other optional ingredients,
It is possible to mix them within a range that does not affect the effects of the present invention. Such optional ingredients include the following substances. liquid paraffin, vaseline, solid paraffin,
Hydrocarbons such as squalane and olefin oligomers; esters such as isopropyl myristate, isopropyl palmitate, stearyl stearate, octyldodecyl myristate, octyldodecyl oleate and 2-ethylhexanoic acid triglyceride; cetanol, stearyl alcohol, behenyl alcohol and hexyldecanol, etc. higher alcohols; emulsifiers such as glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene cetyl ether, polyoxyethylene stearate and polyoxyethylene sorbitan monolaurate; methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and cationized cellulose cellulose derivatives such as; thickeners such as natural polymers; humectants such as ethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and sorbitol; and other small amounts of ingredients such as solvents, disinfectants, and fragrances. . The hair cosmetic composition of the present invention can be used in various applications such as a hair rinse, a spray-type or dispenser-type hair conditioner, and a hair lotion. Next, Examples and Comparative Examples of the present invention will be shown to explain the effects of the present invention more specifically. Before explaining each example, the test method will be explained. Test method: Apply 0.5g of the sample directly to a shampooed hair bundle (5g, 20cm) and spread it evenly by hand.
After drying in an atmosphere of 25°C and 65% RH, and leaving it overnight, 20 panelists sensory-evaluated the ``combability'', ``smoothness'', ``flexibility'', and ``moisture feeling'' of the hair strands. . The evaluation criteria is a 5-level evaluation based on the evaluation obtained with a sample (Comparative Example 1) consisting of 1.0% by weight stearyltrimethylammonium chloride, 3% by weight cetyl alcohol, 10% by weight propylene glycol, and water (balance). It is. ◎: Good 〇: Slightly good △: Equal ×: Slightly inferior ××: Inferior Test Example 1 28 types of hair cosmetics containing various quaternary ammonium salts and/or the third and fourth essential ingredients of the present invention and adjust the performance of those hairs (combability, smoothness, flexibility, moisturizing feeling)
was tested. The results are shown in Table 1. In addition, the blending amount is weight % (the same applies to other test examples).
【表】【table】
【表】【table】
【表】
表１から明らかなように、モノ−C16-18アルキ
ル第４級アンモニウム塩、モノ−C20-22アルキル
第４級アンモニウム塩、化合物（）および化合
物（）の組合せ（実施例１）以外の配合物（比
較例１〜27）は、櫛通り性、なめらかさ、柔軟性
およびしつとり感のすべてが充分であるものはな
いことがわかる。
試験例 ２
モノ−C16-18アルキル第４級アンモニウム塩と
モノ−C20-22アルキル第４級アンモニウム塩との
重量比を変えた７種の毛髪化粧料を調整し、それ
らの毛髪に対する性能について試験した。その結
果を以下の表２に示す。[Table] As is clear from Table 1, the combination of mono-C 16-18 alkyl quaternary ammonium salt, mono-C 20-22 alkyl quaternary ammonium salt, compound () and compound () (Example 1 It can be seen that none of the formulations other than ) (Comparative Examples 1 to 27) had sufficient combability, smoothness, flexibility, and moisturizing feeling. Test Example 2 Seven types of hair cosmetics with different weight ratios of mono-C 16-18 alkyl quaternary ammonium salt and mono-C 20-22 alkyl quaternary ammonium salt were prepared, and their performance on hair was evaluated. was tested. The results are shown in Table 2 below.
【表】
表２から明らかなように、モノ−C16-18アルキ
ル第４級アンモニウム塩とモノ−C20-22アルキル
第４級アンモニウム塩との重量比が1/3ないし3/1
のときにいずれも優れた櫛通り性、なめらかさ、
柔軟性およびしつとり感の性能を示すことがわか
る。
試験例 ３
モノC16-18アルキル第４級アンモニウム塩、モ
ノC20-22アルキル第４級アンモニウム塩および第
３および第４の必須成分の種類および量を変えた
10種の毛髪化粧料を調整し、それらの毛髪に対す
る性能について試験した。その結果を以下の表３
に示す。[Table] As is clear from Table 2, the weight ratio of mono-C 16-18 alkyl quaternary ammonium salt to mono-C 20-22 alkyl quaternary ammonium salt is 1/3 to 3/1.
Excellent combability, smoothness,
It can be seen that it exhibits flexibility and moisturizing properties. Test Example 3 The type and amount of mono C 16-18 alkyl quaternary ammonium salt, mono C 20-22 alkyl quaternary ammonium salt, and the third and fourth essential components were changed.
Ten types of hair cosmetics were prepared and tested for their performance on hair. The results are shown in Table 3 below.
Shown below.
【表】【table】
【表】
表３から明らかなように、本発明の各必須成分
の量および種類を本発明の範囲内で変化させた毛
髪化粧料はいずれも優れた性能を示すことがわか
る。
試験例 ４
下記の表４に示す配合組成の２種のヘアーリン
ス組成物を製造し、その性能を評価した。性能評
価は、40℃のヘアーリンス組成物の２％希釈液
200mlに毛束（8.5ｇ、20cm）を５秒間浸漬し、40
℃の温水200mlで30秒間づつ２回すすいで乾燥し
た後のものについて行なつた。[Table] As is clear from Table 3, all the hair cosmetics in which the amounts and types of each essential ingredient of the present invention are varied within the range of the present invention exhibit excellent performance. Test Example 4 Two types of hair rinse compositions having the formulations shown in Table 4 below were manufactured and their performance was evaluated. Performance evaluation was performed using a 2% diluted solution of hair rinse composition at 40°C.
Soak a bundle of hair (8.5g, 20cm) in 200ml for 5 seconds,
The samples were rinsed twice with 200 ml of warm water at ℃ for 30 seconds each time and dried.
【表】【table】
【表】
表４から明らかなように、本発明のヘアーリン
ス組成物は、従来のものよりも優れた櫛通り性、
なめらかさ、柔軟性およびしつとり感の性能を有
していることがわかる。
試験例 ５
下記の表５に示す配合組成のヘアークリーム組
成物を製造し、その性能を評価した。[Table] As is clear from Table 4, the hair rinse composition of the present invention has superior combability and
It can be seen that it has the properties of smoothness, flexibility, and moist feeling. Test Example 5 A hair cream composition having the formulation shown in Table 5 below was manufactured and its performance was evaluated.
【表】【table】
【表】
表５に示すヘアークリーム組成物は、従来のヘ
アークリームにない優れた櫛通り性、なめらか
さ、柔軟性およびしつとり感の性能を有してい
た。[Table] The hair cream composition shown in Table 5 had excellent combability, smoothness, flexibility, and moisturizing properties that are not found in conventional hair creams.
Claims (1)
ニウム塩0.1ないし３重量％と、下記一般式
（）で表わされる第４級アンモニウム塩0.1ない
し３重量％と、それぞれ下記一般式（）および
（）で表わされる２種の化合物の合計量0.5ない
し4.0重量％とを必須成分として含有し、かつ
（）／（）の重量比は1/3ないし3/1、（）／
（）の重量比は2/8ないし8/2であることを特徴
とする毛髪化粧料。 一般式（）： （式中、R1は炭素数16〜18のアルキル基、
R2，R3およびR4は炭素数１〜３のアルキル基又
はヒドロキシアルキル基、Ｘはハロゲン原子又は
アルキル基の炭素原子数が１又は２のアルキル硫
酸基を示す。） 一般式（）： （式中、R5は炭素数20〜22のアルキル基、
R6，R7およびR8は炭素数１〜３のアルキル基又
はヒドロキシアルキル基、Ｘはハロゲン原子又は
アルキル基の炭素数が１又は２のアルキル硫酸基
を示す。） 一般式（） （式中、ＲはＨ又は炭素原子数１ないし３のア
ルキン基、ｍ＋ｎは５ないし50、ｐは０ないし
３、ａ／ｂは40/60ないし60/40であり、且つ当該
共重合体がポリオキシアルキレン基70ないし80重
量％を含有するような数値である。） 一般式（） （式中、ａ＋ｂ＋ｃは20ないし25）[Scope of Claims] 1 0.1 to 3% by weight of a quaternary ammonium salt represented by the following general formula (I), 0.1 to 3% by weight of a quaternary ammonium salt represented by the following general formula (), and each of the following: Contains a total amount of 0.5 to 4.0% by weight of two types of compounds represented by general formulas () and () as essential components, and the weight ratio of ()/() is 1/3 to 3/1, () /
A hair cosmetic characterized in that the weight ratio of () is 2/8 to 8/2. General formula (): (In the formula, R 1 is an alkyl group having 16 to 18 carbon atoms,
R 2 , R 3 and R 4 represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or an alkyl sulfate group having 1 or 2 carbon atoms in the alkyl group. ) General formula (): (In the formula, R 5 is an alkyl group having 20 to 22 carbon atoms,
R 6 , R 7 and R 8 represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and X represents a halogen atom or an alkyl sulfate group having 1 or 2 carbon atoms in the alkyl group. ) General formula () (wherein R is H or an alkyne group having 1 to 3 carbon atoms, m+n is 5 to 50, p is 0 to 3, a/b is 40/60 to 60/40, and the copolymer is The value is such that it contains 70 to 80% by weight of polyoxyalkylene groups.) General formula () (In the formula, a+b+c is 20 to 25)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13230880A JPS5758607A (en) | 1980-09-25 | 1980-09-25 | Hairdressing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13230880A JPS5758607A (en) | 1980-09-25 | 1980-09-25 | Hairdressing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5758607A JPS5758607A (en) | 1982-04-08 |
| JPS628099B2 true JPS628099B2 (en) | 1987-02-20 |
Family
ID=15078265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13230880A Granted JPS5758607A (en) | 1980-09-25 | 1980-09-25 | Hairdressing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5758607A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0386495A (en) * | 1989-08-28 | 1991-04-11 | Takahashi Seisakusho:Kk | Work device for food material |
| JPH03123699U (en) * | 1990-03-27 | 1991-12-16 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1196575A (en) * | 1982-05-20 | 1985-11-12 | Michael S. Starch | Compositions used to condition hair |
| DE3581421D1 (en) * | 1984-03-15 | 1991-02-28 | Procter & Gamble | HAIR TREATMENT WITH CONDITIONING PROPERTIES. |
| JPH0615454B2 (en) * | 1985-06-13 | 1994-03-02 | 株式会社資生堂 | Hair cosmetics |
| JPH0613450B2 (en) * | 1990-05-31 | 1994-02-23 | サンスター株式会社 | Cosmetics for hair |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4831900A (en) * | 1971-02-12 | 1973-04-26 | ||
| JPS55108811A (en) * | 1979-02-10 | 1980-08-21 | Lion Corp | Hair-treating composition |
-
1980
- 1980-09-25 JP JP13230880A patent/JPS5758607A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4831900A (en) * | 1971-02-12 | 1973-04-26 | ||
| JPS55108811A (en) * | 1979-02-10 | 1980-08-21 | Lion Corp | Hair-treating composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0386495A (en) * | 1989-08-28 | 1991-04-11 | Takahashi Seisakusho:Kk | Work device for food material |
| JPH03123699U (en) * | 1990-03-27 | 1991-12-16 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5758607A (en) | 1982-04-08 |
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