JP2012102050A - Hair shampoo composition - Google Patents
Hair shampoo composition Download PDFInfo
- Publication number
- JP2012102050A JP2012102050A JP2010252203A JP2010252203A JP2012102050A JP 2012102050 A JP2012102050 A JP 2012102050A JP 2010252203 A JP2010252203 A JP 2010252203A JP 2010252203 A JP2010252203 A JP 2010252203A JP 2012102050 A JP2012102050 A JP 2012102050A
- Authority
- JP
- Japan
- Prior art keywords
- component
- composition
- carbon atoms
- group
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 239000002453 shampoo Substances 0.000 title abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 47
- -1 acyl β-alanine Chemical compound 0.000 claims abstract description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-aminopropionic acid Natural products NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 10
- XOAAWQZATWQOTB-UHFFFAOYSA-N Taurine Natural products NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940000635 beta-alanine Drugs 0.000 claims abstract description 9
- 229960003080 taurine Drugs 0.000 claims abstract description 9
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940015975 1,2-hexanediol Drugs 0.000 claims abstract description 7
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 7
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical group CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 150000001412 amines Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000006260 foam Substances 0.000 abstract description 30
- 229920001296 polysiloxane Polymers 0.000 abstract description 29
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 abstract description 22
- 230000002421 anti-septic effect Effects 0.000 abstract description 13
- 229960003237 betaine Drugs 0.000 abstract description 12
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 abstract 1
- 125000003368 amide group Chemical group 0.000 abstract 1
- 239000004599 antimicrobial Substances 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical group 0.000 description 28
- 238000005187 foaming Methods 0.000 description 27
- 235000014113 dietary fatty acids Nutrition 0.000 description 25
- 239000000194 fatty acid Substances 0.000 description 25
- 229930195729 fatty acid Natural products 0.000 description 25
- 238000005406 washing Methods 0.000 description 19
- 238000004140 cleaning Methods 0.000 description 15
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 14
- 239000003240 coconut oil Substances 0.000 description 12
- 235000019864 coconut oil Nutrition 0.000 description 12
- 239000003760 tallow Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 235000019865 palm kernel oil Nutrition 0.000 description 10
- 239000003346 palm kernel oil Substances 0.000 description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 9
- 235000015278 beef Nutrition 0.000 description 9
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- 239000003599 detergent Substances 0.000 description 8
- 238000011081 inoculation Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000005639 Lauric acid Substances 0.000 description 7
- 230000007794 irritation Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 4
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229960004488 linolenic acid Drugs 0.000 description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 3
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229960002446 octanoic acid Drugs 0.000 description 3
- 235000021313 oleic acid Nutrition 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
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- 239000002649 leather substitute Substances 0.000 description 2
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 210000002374 sebum Anatomy 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は、シリコーンに対する洗浄力に優れ、起泡性と泡のクリーミー性に優れ、洗髪時、すすぎ時の指通りが良く、また、べたつかずサラサラで自然なまとまりに仕上がり、さらには防腐剤等を配合せずとも防腐性に優れる毛髪洗浄剤組成物を提供することを目的とする。 The present invention is excellent in detergency against silicone, excellent in foaming properties and foam creaminess, good in fingering during shampooing and rinsing, and finished in a smooth and natural unit without stickiness, and further, preservatives, etc. An object of the present invention is to provide a hair cleanser composition that is excellent in antiseptic properties even without blending.
近年、毛髪洗浄剤に対して、洗浄性に加えて、低刺激性、優れた起泡性、クリーミーな泡質、すすぎ時の良好な感触、使用後のなめらかさ、まとまりの良さなどの仕上がり感が求められている。 In recent years, in addition to detergency, the hair cleaner has low irritation, excellent foaming properties, creamy foam quality, good feeling when rinsing, smoothness after use, good feeling of unity, etc. Is required.
従来、毛髪洗浄剤基剤用の界面活性剤として、アルキル硫酸エステル塩、ポリオキシエチレンアルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、α−オレフインスルホン酸塩などのアニオン性界面活性剤が広く用いられてきた。ところが、これらの界面活性剤は、洗浄力が比較的高く、近年洗髪の頻度が高まっていることと相まって、時にかさつきや乾燥を感じる場合があり、よりいっそう刺激性の低い毛髪洗浄剤が求められてきていた。また、これらは石油由来の界面活性剤であり、最近のナチュラル志向に反するものであった。 Conventionally, anionic surfactants such as alkyl sulfate salts, polyoxyethylene alkyl sulfate salts, alkylbenzene sulfonates, and α-olefin sulfonates have been widely used as surfactants for hair cleansing bases. It was. However, these surfactants have a relatively high detergency, and coupled with the recent increase in the frequency of hair washing, there are times when they feel dry and dry, and there is a need for a hair washing agent with even less irritation. It has been. These are petroleum-derived surfactants, which are contrary to the recent natural orientation.
これに対し、アルキルベタイン型やアミドベタイン型界面活性剤、β−アラニン型界面活性剤およびアシルタウリン型界面活性剤は、皮膚や眼粘膜に対する刺激性が低く、極めて温和な界面活性剤であり、注目されてきている。 In contrast, alkylbetaine-type and amidebetaine-type surfactants, β-alanine-type surfactants, and acyltaurine-type surfactants are extremely mild surfactants with low irritation to skin and ocular mucosa, Has attracted attention.
アシルタウリン型界面活性剤とβ−アラニン型界面活性剤を主成分として用いた洗浄剤組成物としては、特許文献１に開示された洗浄剤組成物が挙げられる。また、アミドベタイン型界面活性剤を主成分として用いた洗浄剤組成物としては、特許文献２に開示されたシャンプー組成物が挙げられる。しかし、これらの洗浄剤組成物は、いずれも泡立ち、泡のクリーミー性の点で充分とはいえず、特に皮脂汚れや整髪料の存在下では泡立ちや泡のクリーミー性が著しく低下し、さらには洗浄力も不充分であり、満足するものではなかった。 As a cleaning composition using an acyl taurine type surfactant and a β-alanine type surfactant as main components, the cleaning composition disclosed in Patent Document 1 can be mentioned. Moreover, the shampoo composition disclosed in Patent Document 2 is an example of a detergent composition using an amide betaine surfactant as a main component. However, none of these cleaning compositions are sufficient in terms of foaming and foam creaminess, and particularly in the presence of sebum stains and hair styling, the foaming and foam creamy properties are significantly reduced. Detergency was also insufficient and was not satisfactory.
また、特許文献３には、アシルアルキルタウリン型界面活性剤とカチオン性ポリマーを用いた洗浄剤組成物が提示されている。しかし、この洗浄剤組成物は、泡のクリーミー性に乏しく、洗髪時の泡の感触に問題があった。β−アラニン型界面活性剤とポリオキシエチレングリコールとを使用した頭髪用化粧料については、特許文献４に開示されている。しかし、この頭髪用化粧料では、刺激性の点で問題を生じたり、さらには洗髪時、すすぎ時における指通りが悪く、乾燥後の髪に好ましい感触が得られなかった。 Patent Document 3 proposes a cleaning composition using an acylalkyl taurine type surfactant and a cationic polymer. However, this detergent composition has poor foam creaminess, and has a problem with the feel of foam during hair washing. A hair cosmetic using a β-alanine surfactant and polyoxyethylene glycol is disclosed in Patent Document 4. However, this hair cosmetic composition causes problems in terms of irritation, and further, the finger does not pass easily during shampooing and rinsing, and a favorable touch cannot be obtained on the hair after drying.
一方、使用中および使用後の感触の点では、油剤を配合した毛髪洗浄剤が開発されているのに加えて、乾燥時のしっとり感やなめらかさ、まとまり感をさらに高める目的で、油剤を配合した毛髪洗浄剤、例えば、トリートメントやヘアワックス、ヘアオイル、洗い流さないタイプのトリートメントを使用することが一般的となっている。使用される油剤としては、炭化水素、トリグセライド、ワックス、エステル等種々の油剤が挙げられるが、中でもシリコーンが感触の点で特に優れることが知られており、毛髪洗浄剤にシリコーンを配合することが公知の技術となっている。 On the other hand, in terms of feel during and after use, in addition to the development of hair cleansing agents that contain oils, oils are added for the purpose of further enhancing the moist feeling, smoothness and cohesiveness when dried. It has become common to use hair cleansing agents such as treatments, hair waxes, hair oils, and non-washing type treatments. Examples of the oil used include various oils such as hydrocarbons, triglycerides, waxes, esters, etc. Among them, it is known that silicone is particularly excellent in terms of touch. It is a known technique.
シリコーンは、毛髪に優れた感触を付与できる一方で、他の油剤と比較して通常のシャンプーで洗浄されにくく、毛髪表面、及び頭皮に残存しやすいほか、洗髪時にシャンプーの泡立ちを阻害するという問題がある。また、残存したシリコーンは毛髪表面を被膜する状態で存在すると考えられ、染毛やスタイリングの際に、薬剤や熱の作用を阻害し、問題を生じるおそれもあるため、シリコーンに対する洗浄力に優れる毛髪洗浄剤が求められている。シリコーンに対する洗浄力に優れる洗浄剤組成物については特許文献５に開示されているが、起泡性と泡のクリーミー性、洗髪時および乾燥後の感触において満足するものではなかった。 While silicone can give an excellent feel to hair, it is difficult to wash with normal shampoo compared to other oils, and it tends to remain on the hair surface and scalp, and also inhibits foaming of shampoo during hair washing. There is. In addition, the remaining silicone is considered to exist in a state of coating the hair surface, and in hair dyeing and styling, it may interfere with the action of chemicals and heat and may cause problems. There is a need for cleaning agents. A detergent composition having excellent detergency against silicone is disclosed in Patent Document 5, but it is not satisfactory in foaming property and creamy property of foam, feeling during hair washing and after drying.
さらには、いわゆるナチュラル志向の高まりを背景に、植物由来原料の使用、低刺激性原料の使用、防腐剤の不使用または減量に対する要望が高まっている。特許文献６においては、刺激性が高い防腐剤の配合量の低減を目的として、アルカンジオールとグレープフルーツ抽出物とを併用した防腐殺菌剤が開示されているが、これを洗浄剤組成物に用いた場合には、起泡性と泡のクリーミー性が悪化し、乾燥後にべたつきを生じるという問題があった。 Furthermore, against the background of so-called natural orientation, there is an increasing demand for the use of plant-derived materials, the use of hypoallergenic materials, the non-use of preservatives, or weight loss. Patent Document 6 discloses an antiseptic disinfectant that uses an alkanediol and a grapefruit extract in combination for the purpose of reducing the amount of preservatives with high irritation, and this was used in a detergent composition. In some cases, foaming properties and foam creaminess are deteriorated, resulting in stickiness after drying.
このように、シリコーンに対する洗浄力、起泡性と泡のクリーミー性、使用中および使用後の感触、低刺激性をともに満足する毛髪洗浄剤組成物はこれまで提供されていなかった。 As described above, there has not been provided a hair cleanser composition that satisfies the detergency for silicone, foamability and foam creaminess, feel during use and after use, and low irritation.
本発明は、このような従来技術の問題点に鑑み、シリコーンに対する洗浄力に優れ、起泡性と泡のクリーミー性に優れ、洗髪時、すすぎ時の指通りが良く、また、べたつかずサラサラで自然なまとまりに仕上がり、さらには防腐剤等を配合せずとも防腐性に優れる毛髪洗浄剤組成物を提供することを目的とする。 In view of such problems of the prior art, the present invention is excellent in detergency against silicone, excellent in foaming properties and foam creaminess, good in fingering during shampooing and rinsing, and is smooth and smooth. An object of the present invention is to provide a hair cleansing composition that is finished in a natural unit and is excellent in antiseptic properties even without adding a preservative or the like.
本発明者らは、上記課題を解決するために鋭意検討した結果、（ａ）アシルβ−アラニン型界面活性剤、（ｂ）アシルタウリン型界面活性剤、（ｃ）アミドベタイン型界面活性剤及び／又はアルキルベタイン型界面活性剤、（ｄ）ポリオキシエチレングリコール、（ｅ）１，２−ペンタンジオール及び／又は１，２−ヘキサンジオール、（ｆ）カチオン性ポリマーを特定の比率で組み合わせることで、前記の特性を全て満足する毛髪洗浄剤組成物が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that (a) an acyl β-alanine type surfactant, (b) an acyl taurine type surfactant, (c) an amide betaine type surfactant, and By combining an alkylbetaine type surfactant, (d) polyoxyethylene glycol, (e) 1,2-pentanediol and / or 1,2-hexanediol, and (f) a cationic polymer in a specific ratio. The present inventors have found that a hair cleansing composition satisfying all the above-mentioned properties can be obtained, and have completed the present invention.
すなわち、本発明は、下記の（ａ）成分〜（ｆ）成分を含有し、（ａ）成分が組成物中２〜１０質量％、（ｂ）成分が組成物中５〜１５質量％、（ｃ）成分が組成物中１〜５質量％、（ｄ）成分が組成物中０．５〜５質量％、（ｅ）成分が組成物中１〜５質量％、（ｆ）成分が組成物中０．１〜１質量％であることを特徴とする毛髪洗浄剤組成物である。 That is, this invention contains the following (a) component-(f) component, (a) component is 2-10 mass% in a composition, (b) component is 5-15 mass% in a composition, ( c) Component is 1 to 5 mass% in the composition, (d) component is 0.5 to 5 mass% in the composition, (e) component is 1 to 5 mass% in the composition, and (f) component is the composition. It is 0.1-1 mass% in inside, It is a hair cleaning composition characterized by the above-mentioned.
（a）式（１）で表わされるアシルβ−アラニン型界面活性剤 (A) Acyl β-alanine type surfactant represented by the formula (1)
（式中、Ｒ1は炭素数７〜１９のアルキル基、又はアルケニル基、Ｒ2は水素原子、又は炭素数１〜３のアルキル基、Ｍ1はアルカリ金属、又は有機アミンを示す） (In the formula, R 1 represents an alkyl group having 7 to 19 carbon atoms or an alkenyl group, R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M 1 represents an alkali metal or an organic amine)
（b) 式（２）で表わされるアシルタウリン型界面活性剤 (B) Acyl taurine type surfactant represented by the formula (2)
（ここでＲ3は、炭素数７〜１９のアルキル基、又はアルケニル基、Ｒ4は水素原子、又は炭素数１〜３のアルキル基、Ｍ2はアルカリ金属、又は有機アミンを示す。） (Here, R 3 represents an alkyl group having 7 to 19 carbon atoms or an alkenyl group, R 4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M 2 represents an alkali metal or an organic amine.)
（c) 式（３）で表されるアミドベタイン型界面活性剤及び／又は式（４）で表されるアルキルベタイン型界面活性剤
（Ｒ5は炭素数７〜１９のアルキル基、又はアルケニル基、Ｒ6，Ｒ7はそれぞれ独立して炭素数１〜３のアルキル基、ｎは２〜４の整数を示す。） (R 5 is an alkyl group having 7 to 19 carbon atoms or an alkenyl group, R 6 and R 7 are each independently an alkyl group having 1 to 3 carbon atoms, and n is an integer of 2 to 4)
（Ｒ8は炭素数８〜２０のアルキル基、又はアルケニル基、Ｒ9，Ｒ10はそれぞれ独立して炭素数１〜３のアルキル基を示す。） (R 8 represents an alkyl group having 8 to 20 carbon atoms or an alkenyl group, and R 9 and R 10 each independently represents an alkyl group having 1 to 3 carbon atoms.)
（d）式（５）で表されるポリオキシエチレングリコール (D) Polyoxyethylene glycol represented by formula (5)
（ここでＲ11は炭素数１４〜２２のアルキル基、又はアルケニル基、ｍは４０〜８０、Ｒ12は炭素数１０〜１８のアルキル基、又はアルケニル基を示す） (Here, R 11 represents an alkyl group having 14 to 22 carbon atoms or an alkenyl group, m represents 40 to 80, and R 12 represents an alkyl group having 10 to 18 carbon atoms or an alkenyl group.)
（e）１，２−ペンタンジオール及び／又は１，２−ヘキサンジオール (E) 1,2-pentanediol and / or 1,2-hexanediol
（f）カチオン性ポリマー (F) Cationic polymer
本発明の毛髪洗浄剤組成物によれば、シリコーンに対する洗浄力に優れ、起泡性と泡のクリーミー性に優れ、洗髪時、すすぎ時の指通りが良く、また、べたつかずサラサラで自然なまとまりに仕上がり、さらには防腐剤等を配合せずとも防腐性に優れるという効果が得られる。 According to the hair cleansing composition of the present invention, it has excellent detergency against silicone, excellent foaming properties and foam creaminess, good fingering during shampooing and rinsing, and is smooth and natural. In addition, an effect of excellent antiseptic properties can be obtained without adding a preservative or the like.
以下、本発明の実施形態を説明する。本発明の毛髪洗浄剤組成物は、下記（ａ）成分〜（ｆ）成分を含有する。 Embodiments of the present invention will be described below. The hair cleansing composition of the present invention contains the following components (a) to (f).
〔（ａ）アシルβ−アラニン型界面活性剤〕
本発明に用いられる（ａ）成分は、前記式（１）で表わされるβ−アラニン型界面活性剤である。式（１）においてＲ1は炭素数７〜１９のアルキル基、又はアルケニル基である。すなわち、式中のＲ1ＣＯはアシル基であり、炭素数８〜２０の直鎖あるいは分岐の脂肪酸残基である。脂肪酸としてはカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸等の飽和脂肪酸、パルミトオレイン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸等の不飽和脂肪酸、およびこれらの混合物であるヤシ油脂肪酸、パーム核油脂肪酸、牛脂脂肪酸、硬化牛脂脂肪酸が挙げられる。これらのうち好ましくは、ラウリン酸、ミリスチン酸、オレイン酸、ヤシ油脂肪酸、パーム核油脂肪酸、牛脂脂肪酸が挙げられる。アシル基の炭素数が８未満の場合は起泡性が悪くなり、炭素数が２０を超える場合は安定性が悪くなる。
[(A) acyl β-alanine type surfactant]
The component (a) used in the present invention is a β-alanine type surfactant represented by the formula (1). In the formula (1), R 1 is an alkyl group having 7 to 19 carbon atoms or an alkenyl group. That is, R 1 CO in the formula is an acyl group, which is a linear or branched fatty acid residue having 8 to 20 carbon atoms. As fatty acids, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, unsaturated fatty acids such as palmitooleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, And coconut oil fatty acid, palm kernel oil fatty acid, beef tallow fatty acid, and hardened tallow fatty acid, which are mixtures thereof. Of these, lauric acid, myristic acid, oleic acid, coconut oil fatty acid, palm kernel oil fatty acid, and beef tallow fatty acid are preferable. When the carbon number of the acyl group is less than 8, the foaming property is deteriorated, and when the carbon number exceeds 20, the stability is deteriorated.
式（１）においてＲ2は、水素原子、又は炭素数１〜３のアルキル基である。また式（１）においてＭ1はアルカリ金属、又は有機アミンである。アルカリ金属としては、ナトリウムやカリウムが挙げられる。有機アミンとしては、炭素数２〜３のヒドロキシアルキル基を有するアミンが挙げられ、具体的には、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンが挙げられる。（ａ）成分として１種又は２種以上を用いることができる。 In the formula (1), R 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In formula (1), M 1 is an alkali metal or an organic amine. Examples of the alkali metal include sodium and potassium. Examples of the organic amine include amines having a C2-C3 hydroxyalkyl group, and specific examples include monoethanolamine, diethanolamine, and triethanolamine. (A) 1 type (s) or 2 or more types can be used as a component.
式（１）で示されるアシルβ−アラニン型界面活性剤の具体例としては、Ｎ−ラウロイル−β−アラニン塩、Ｎ−ミリストイル−β−アラニン塩、Ｎ−ココイル−β−アラニン塩、Ｎ−ラウロイルグルタミン酸塩、Ｎ−ココイルグリシン塩、Ｎ−ラウロイル−Ｎ−メチル−β−アラニン塩、Ｎ−ミリストイル−Ｎ−メチル−β−アラニン塩などが挙げられる。 Specific examples of the acyl β-alanine type surfactant represented by the formula (1) include N-lauroyl-β-alanine salt, N-myristoyl-β-alanine salt, N-cocoyl-β-alanine salt, N- Examples include lauroyl glutamate, N-cocoyl glycine salt, N-lauroyl-N-methyl-β-alanine salt, and N-myristoyl-N-methyl-β-alanine salt.
〔（ｂ）アシルタウリン型界面活性剤〕
本発明に用いられる（ｂ）成分は、前記式（２）で表わされるアシルタウリン型界面活性剤である。式（２）においてＲ3は炭素数７〜１９のアルキル基、又はアルケニル基である。すなわち、式中のＲ3ＣＯはアシル基であり、炭素数８〜２０の直鎖あるいは分岐の脂肪酸残基である。脂肪酸としてはカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸等の飽和脂肪酸、パルミトオレイン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸等の不飽和脂肪酸、およびこれらの混合物であるヤシ油脂肪酸、パーム核油脂肪酸、牛脂脂肪酸、硬化牛脂脂肪酸が挙げられる。これらのうち好ましくは、ラウリン酸、ミリスチン酸、オレイン酸、ヤシ油脂肪酸、パーム核油脂肪酸、牛脂脂肪酸が挙げられる。アシル基の炭素数が８未満の場合は起泡性が悪くなり、炭素数が２０を超える場合は安定性が悪くなる。
[(B) Acyl Taurine Type Surfactant]
The component (b) used in the present invention is an acyl taurine type surfactant represented by the formula (2). In the formula (2), R 3 is an alkyl group having 7 to 19 carbon atoms or an alkenyl group. That is, R 3 CO in the formula is an acyl group, which is a linear or branched fatty acid residue having 8 to 20 carbon atoms. As fatty acids, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, unsaturated fatty acids such as palmitooleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, And coconut oil fatty acid, palm kernel oil fatty acid, beef tallow fatty acid, and hardened tallow fatty acid, which are mixtures thereof. Of these, lauric acid, myristic acid, oleic acid, coconut oil fatty acid, palm kernel oil fatty acid, and beef tallow fatty acid are preferable. When the carbon number of the acyl group is less than 8, the foaming property is deteriorated, and when the carbon number exceeds 20, the stability is deteriorated.
式（２）においてＲ4は、水素原子、又は炭素数１〜３のアルキル基である。式（２）においてＭ2はアルカリ金属、又は有機アミンである。アルカリ金属としては、ナトリウムやカリウムが挙げられる。有機アミンとしては、炭素数２〜３のヒドロキシアルキル基を有するアミンが挙げられ、具体的には、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンが挙げられる。（ｂ）成分として１種又は２種以上を用いることができる。 In the formula (2), R 4 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In the formula (2), M 2 is an alkali metal or an organic amine. Examples of the alkali metal include sodium and potassium. Examples of the organic amine include amines having a C2-C3 hydroxyalkyl group, and specific examples include monoethanolamine, diethanolamine, and triethanolamine. (B) 1 type (s) or 2 or more types can be used as a component.
式（２）で示されるアシルタウリン型界面活性剤として具体的には、Ｎ−ラウロイル−Ｎ−メチルタウリン塩、Ｎ−ココイル−Ｎ−メチルタウリン塩、Ｎ−ミリストイル−Ｎ−メチルタウリン塩、Ｎ−パルミトイル−Ｎ−メチルタウリン塩、Ｎ−オレオイル−Ｎ−メチルタウリン塩などが挙げられる。 Specific examples of the acyl taurine type surfactant represented by the formula (2) include N-lauroyl-N-methyl taurine salt, N-cocoyl-N-methyl taurine salt, N-myristoyl-N-methyl taurine salt, N -Palmitoyl-N-methyl taurate, N-oleoyl-N-methyl taurate, etc. are mentioned.
〔（ｃ）アミドベタイン型界面活性剤及び／又はアルキルベタイン型界面活性剤〕
本発明に用いられる（ｃ）成分は、アミドベタイン型界面活性剤及び／又はアルキルベタイン型界面活性剤である。
（ｃ）成分として用いられるアミドベタイン型界面活性剤は、前記式（３）で表わされ、式中のＲ5は炭素数７〜１９のアルキル基又はアルケニル基である。すなわち、式中のＲ5ＣＯはアシル基であり、炭素数８〜２０の直鎖あるいは分岐の脂肪酸残基である。脂肪酸としてはカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸等の飽和脂肪酸、パルミトオレイン酸、オレイン酸、エライジン酸、リノール酸、リノレン酸等の不飽和脂肪酸、およびこれらの混合物であるヤシ油脂肪酸、パーム核油脂肪酸、牛脂脂肪酸、硬化牛脂脂肪酸が挙げられる。これらのうち好ましくは、ラウリン酸、ミリスチン酸、オレイン酸、ヤシ油脂肪酸、パーム核油脂肪酸、牛脂脂肪酸が挙げられる。アシル基の炭素数が８未満の場合は起泡性が悪くなり、炭素数が２０を超える場合は安定性が悪くなる。
[(C) Amidobetaine surfactant and / or alkylbetaine surfactant]
The component (c) used in the present invention is an amide betaine type surfactant and / or an alkyl betaine type surfactant.
The amide betaine type surfactant used as the component (c) is represented by the formula (3), and R 5 in the formula is an alkyl group or alkenyl group having 7 to 19 carbon atoms. That is, R 5 CO in the formula is an acyl group and is a linear or branched fatty acid residue having 8 to 20 carbon atoms. As fatty acids, saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, unsaturated fatty acids such as palmitooleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, And coconut oil fatty acid, palm kernel oil fatty acid, beef tallow fatty acid, and hardened tallow fatty acid, which are mixtures thereof. Of these, lauric acid, myristic acid, oleic acid, coconut oil fatty acid, palm kernel oil fatty acid, and beef tallow fatty acid are preferable. When the carbon number of the acyl group is less than 8, the foaming property is deteriorated, and when the carbon number exceeds 20, the stability is deteriorated.
式（３）においてＲ6，Ｒ7は、それぞれ独立して炭素数１〜３のアルキル基である。式（３）中のｎは２〜４の整数である。（ｃ）成分としてのアミドベタイン型界面活性剤は１種又は２種以上を用いることができる。 In the formula (3), R 6 and R 7 are each independently an alkyl group having 1 to 3 carbon atoms. N in Formula (3) is an integer of 2-4. As the component (c), one or more amide betaine surfactants can be used.
式（３）で示されるアミドベタイン型界面活性剤として具体的には、ラウリン酸アミドプロピルジメチルアミノ酢酸ベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン等が挙げられる。 Specific examples of the amide betaine type surfactant represented by the formula (3) include lauric acid amidopropyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, and the like.
（ｃ）成分として用いられるアルキルベタイン型界面活性剤は、前記式（４）で表わされ、式中のＲ8は炭素数８〜２０のアルキル基又はアルケニル基であり、例えばオクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、イソオクタデシル基、ノナデシル基、エイコシル基等のアルキル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基、イソオクタデセニル基、エイコセニル基等のアルケニル基およびこれらの混合物であるヤシ油アルキル基、パーム核油アルキル基、牛脂アルキル基等の混合アルキル基などが挙げられ、これらのうち好ましくは、ドデシル基、テトラデシル基、オクタデセニル基、ヤシ油アルキル基、パーム核油アルキル基である。炭素数が８未満の場合は起泡性および泡質が悪くなり、２０を超える場合は安定性が悪くなる。 The alkylbetaine surfactant used as the component (c) is represented by the above formula (4), wherein R 8 is an alkyl group or alkenyl group having 8 to 20 carbon atoms, such as an octyl group or nonyl group. Group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, isooctadecyl group, nonadecyl group, eicosyl group and other alkyl groups, tetradecenyl group, hexadecenyl group, octadecenyl group Groups, alkenyl groups such as isooctadecenyl group, eicocenyl group and the like, and mixed alkyl groups such as coconut oil alkyl group, palm kernel oil alkyl group, beef tallow alkyl group, etc., among these, preferably among these , Dodecyl group, tetradecyl group, octadecenyl group, coconut oil alkyl Group, palm kernel oil alkyl group. When the number of carbon atoms is less than 8, the foamability and foam quality are deteriorated, and when it exceeds 20, the stability is deteriorated.
式（４）においてＲ9，Ｒ10は、それぞれ独立して炭素数１〜３のアルキル基である。（ｃ）成分としてのアルキルベタイン型界面活性剤は１種又は２種以上を用いることができる。 In the formula (4), R 9 and R 10 are each independently an alkyl group having 1 to 3 carbon atoms. As the component (c), one or more alkylbetaine surfactants can be used.
式（４）で示されるアルキルベタイン型界面活性剤として具体的には、ドデシルジメチルアミノ酢酸ベタイン、ヤシ油アルキルジメチルアミノ酢酸ベタイン等が挙げられる。 Specific examples of the alkylbetaine surfactant represented by the formula (4) include dodecyldimethylaminoacetic acid betaine, coconut oil alkyldimethylaminoacetic acid betaine, and the like.
〔（ｄ）ポリオキシエチレングリコール〕
本発明に用いられる（ｄ）成分は、前記式（５）で示され、式中のＲ11は炭素数１４〜２２のアルキル基またはアルケニル基であり、例えばテトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、イソオクタデシル基、ノナデシル基、エイコシル基等のアルキル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基、イソオクタデセニル基、エイコセニル基等のアルケニル基およびこれらの混合物であるヤシ油アルキル基、パーム核油アルキル基、牛脂アルキル基等の混合アルキル基などが挙げられる。炭素数が１４未満の場合は起泡性が悪くなり、炭素数が２２を超える場合は安定性が悪くなる。ｍは４０〜８０である。Ｒ12は炭素数１０〜１８のアルキル基又はアルケニル基であり、例えばデシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、イソオクタデシル基等のアルキル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基、イソオクタデセニル基等のアルケニル基およびこれらの混合物であるヤシ油アルキル基、パーム核油アルキル基、牛脂アルキル基等の混合アルキル基などが挙げられる。（ｄ）成分として１種又は２種以上を用いることができる。
[(D) polyoxyethylene glycol]
The component (d) used in the present invention is represented by the above formula (5), wherein R 11 is an alkyl group or alkenyl group having 14 to 22 carbon atoms, such as a tetradecyl group, a pentadecyl group, a hexadecyl group, Coconut oil which is an alkyl group such as heptadecyl group, octadecyl group, isooctadecyl group, nonadecyl group, eicosyl group, alkenyl group such as tetradecenyl group, hexadecenyl group, octadecenyl group, isooctadecenyl group, eicocenyl group and a mixture thereof Examples thereof include mixed alkyl groups such as alkyl groups, palm kernel oil alkyl groups, and beef tallow alkyl groups. When the number of carbon atoms is less than 14, the foaming property is deteriorated, and when the number of carbon atoms exceeds 22, the stability is deteriorated. m is 40-80. R 12 is an alkyl group or alkenyl group having 10 to 18 carbon atoms, such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, isooctadecyl, etc. Alkenyl groups such as alkyl groups, tetradecenyl groups, hexadecenyl groups, octadecenyl groups, isooctadecenyl groups, isooctadecenyl groups and the like, and mixed oil groups such as coconut oil alkyl groups, palm kernel oil alkyl groups, beef tallow alkyl groups, etc. It is done. (D) 1 type (s) or 2 or more types can be used as a component.
式（５）で示されるポリオキシエチレングリコールとして具体的には、ポリオキシエチレンセトステアリルヒドロキシミリスチレンエーテルが挙げられる。 Specific examples of the polyoxyethylene glycol represented by the formula (5) include polyoxyethylene cetostearyl hydroxymyristyl ether.
〔（ｅ）１，２−ペンタンジオール及び／又は１，２−ヘキサンジオール〕
本発明に用いられる（ｅ）成分は、１，２−ペンタンジオールおよび１，２−ヘキサンジオールから選ばれる一種又は二種である。上記１，２−ペンタンジオールおよび１，２−ヘキサンジオールに代えて、１，３−ブチレングリコールや１，２−プロピレングリコール等の炭素数４以下の炭素鎖のジオールを使用した場合には、シリコーンに対する洗浄力、シリコーン存在下での起泡性、泡のクリーミー性が低下する。
[(E) 1,2-pentanediol and / or 1,2-hexanediol]
The component (e) used in the present invention is one or two selected from 1,2-pentanediol and 1,2-hexanediol. In place of 1,2-pentanediol and 1,2-hexanediol, when a diol having a carbon chain of 4 or less carbon atoms such as 1,3-butylene glycol or 1,2-propylene glycol is used, silicone Detergency against water, foaming property in the presence of silicone, and creamy property of foam are reduced.
〔（ｆ）ポリオキシエチレングリコール〕
本発明に用いられる（ｆ）成分であるカチオン性ポリマーは、カチオン性を示す第４級窒素含有基を有する高分子化合物であり、例えば、カチオン化セルロース、カチオン化グァーガム、アクリル系カチオン化ポリマー（例えば、塩化ジメチルジアリルアンモニウムアクリルアミド共重合体）等が挙げられる。これらの内、すすぎ時の指通りの点でカチオン化セルロースが好ましい。カチオン性ポリマーとして具体的には、塩化o-〔2-ヒドロキシ-3-（トリメチルアンモニオ）プロピル〕ヒドロキシエチルセルロース、アクリルアミド・アクリル酸・塩化ジメチルジアリルアンモニウム共重合体、グァーガムヒドロキシプロピルトリメチルアンモニウムクロリドエーテル等が挙げられる。（ｆ）成分として１種又は２種以上を用いることができる。
[(F) Polyoxyethylene glycol]
The cationic polymer as the component (f) used in the present invention is a polymer compound having a quaternary nitrogen-containing group that exhibits cationic properties. For example, cationized cellulose, cationized guar gum, acrylic cationized polymer ( Examples thereof include dimethyldiallylammonium chloride acrylamide copolymer). Of these, cationized cellulose is preferred from the viewpoint of fingering during rinsing. Specific examples of the cationic polymer include o- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, guar gum hydroxypropyltrimethylammonium chloride ether, and the like. Is mentioned. (F) 1 type (s) or 2 or more types can be used as a component.
〔各成分の含有率〕
本発明において、上記の（ａ）成分の含有量は、組成物全体の２〜１０質量％、好ましくは３〜８質量％、さらに好ましくは３〜７質量％であるのが好適である。２質量％未満となると起泡性と泡のクリーミー性に乏しくなり、１０質量％を超えると洗髪時とすすぎ時の指通りや、洗浄後のまとまりとさらさら感が悪くなる。
[Content of each component]
In the present invention, the content of the component (a) is 2 to 10% by mass, preferably 3 to 8% by mass, and more preferably 3 to 7% by mass, based on the entire composition. If it is less than 2% by mass, the foamability and foam creaminess will be poor, and if it exceeds 10% by mass, the fingering during shampooing and rinsing, and the cohesion and smoothness after washing will be poor.
（ｂ）成分は組成物全体の５〜１５質量％、好ましくは６〜１２質量％、さらに好ましくは７〜１１質量％であるのが好適である。５質量％未満となると、起泡性と泡のクリーミー性に乏しくなり、１５質量％を超えると洗髪時とすすぎ時の指通りや、洗浄後のまとまりとさらさら感が悪くなる。 (B) It is suitable that a component is 5-15 mass% of the whole composition, Preferably it is 6-12 mass%, More preferably, it is 7-11 mass%. When it is less than 5% by mass, foaming properties and foam creamy properties are poor, and when it exceeds 15% by mass, fingering during shampooing and rinsing, and cohesion and smoothness after washing become worse.
（ｃ）成分は組成物全体の１〜５質量％、好ましくは２〜４質量％、さらに好ましくは２〜３質量％であるのが好適である。１質量％未満となると、系を安定して均一に保つことができなくなり、５質量％を超えると、洗浄後のまとまりとさらさら感が悪くなる。 (C) It is suitable that a component is 1-5 mass% of the whole composition, Preferably it is 2-4 mass%, More preferably, it is 2-3 mass%. When the amount is less than 1% by mass, the system cannot be stably and uniformly maintained, and when the amount exceeds 5% by mass, the unity and the smooth feeling after washing are deteriorated.
（ｄ）成分は組成物全体の０．５〜５質量％、好ましくは１〜４質量％、さらに好ましくは１〜３質量％であるのが好適である。０．５質量％未満となると、泡のクリーミー性に乏しくなり、５質量％を超えると起泡性が悪化し、さらには系の粘度が非常に高くなり、調整や使用が困難となる。 (D) It is suitable that a component is 0.5-5 mass% of the whole composition, Preferably it is 1-4 mass%, More preferably, it is 1-3 mass%. If it is less than 0.5% by mass, the creamy property of the foam is poor, and if it exceeds 5% by mass, the foaming property is deteriorated, and the viscosity of the system becomes very high, making adjustment and use difficult.
（ｅ）成分は組成物全体の１〜５質量％、好ましくは１〜４質量％、さらに好ましくは２〜３質量％であるのが好適である。１質量％未満となると、防腐性が低下するほか、泡のクリーミー性が悪化し、さらにはシリコーンに対する洗浄力が低下する。５質量％を超えると起泡性と、洗浄後のまとまりとさらさら感が悪化する。 (E) It is suitable that a component is 1-5 mass% of the whole composition, Preferably it is 1-4 mass%, More preferably, it is 2-3 mass%. When it is less than 1% by mass, the antiseptic property is lowered, the creamy property of the foam is deteriorated, and the detergency against silicone is also lowered. If it exceeds 5% by mass, the foaming property, and the unity and smoothness after washing are deteriorated.
（ｆ）成分は組成物全体の０．１〜１質量％、好ましくは０．１〜０．８質量％、さらに好ましくは０．２〜０．７質量％であるのが好適である。０．１質量％未満となると、洗髪時とすすぎ時の指通りや、洗浄後のまとまりとさらさら感が得られず、１質量％を超えると起泡性が悪くなる。 The component (f) is suitably 0.1 to 1% by mass, preferably 0.1 to 0.8% by mass, more preferably 0.2 to 0.7% by mass of the entire composition. When it is less than 0.1% by mass, it is difficult to obtain a smooth feeling after washing and rinsing, and when the amount exceeds 1% by mass, foaming properties deteriorate.
本発明において、前述の（ａ）成分と（ｂ）成分の含有量は、ａ／ｂが質量比で０．３〜１、好ましくは０．４〜０．８、さらに好ましくは０．４〜０．７であるのが洗髪時とすすぎ時の指通りや、洗浄後のまとまりとさらさら感の点で好適である。 In the present invention, the content of the aforementioned component (a) and component (b) is such that a / b is 0.3 to 1, preferably 0.4 to 0.8, more preferably 0.4 to a by mass. A value of 0.7 is suitable in terms of finger passing during shampooing and rinsing, and a unity and smooth feeling after washing.
本発明の毛髪洗浄剤組成物は、通常の方法に従って製造することができる。本発明の毛髪洗浄剤組成物の形態は、液状、ゲル状等を適宜選択できるが、溶剤として水又は低級アルコール、特に水を用いた液状のものが好ましい。また、使用形態は限定されず、例えばヘアシャンプー、リンスインシャンプーとして用いることができ、特に、シリコーン含有毛髪化粧料を洗浄するためのシャンプー組成物として好適に用いることができる。なお、本発明の毛髪洗浄剤組成物においては、洗浄料に常用されている添加剤を本発明の性能を損なわない範囲で配合することも可能である。 The hair cleansing composition of the present invention can be produced according to a usual method. The form of the hair cleansing composition of the present invention can be appropriately selected from liquid form, gel form, etc., but liquid form using water or lower alcohol, particularly water as a solvent is preferable. Moreover, a usage form is not limited, For example, it can be used as a hair shampoo and a rinse-in shampoo, and can be used suitably especially as a shampoo composition for wash | cleaning silicone containing hair cosmetics. In addition, in the hair cleaning composition of this invention, it is also possible to mix | blend the additive normally used for the cleaning material in the range which does not impair the performance of this invention.
以下、実施例および比較例を挙げて本発明をさらに具体的に説明する。表１に示す毛髪洗浄剤（以下、試料とも言う）を調製し、下記の方法によりその特性を評価した。結果を表１に示す。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Hair cleansing agents (hereinafter also referred to as samples) shown in Table 1 were prepared and their characteristics were evaluated by the following methods. The results are shown in Table 1.
（１）シリコーンに対する洗浄力
直鎖および環状のメチルポリシロキサン（ＫＦ９６−１０００ｃｓおよびＫＦ９９５、ともに信越化学工業（株）製）を１：１の比率で混合し、その０．１ｇを３ｃｍ×３ｃｍ大の人工皮革（出光テクノファイン（株）製）に均一に塗付した。試料を０．１ｇ塗付し、指で１０回、円を描くように擦った後、水で洗い流した。洗浄前と洗浄後の人工皮革の表面を走査型電子顕微鏡で観察し、ケイ素存在部位をマッピング処理（（株）堀場製作所製：ＥＭＡＸ）後その面積を算出し、次の式によりシリコーン洗浄率を求めた。
(1) Detergency for silicone Linear and cyclic methylpolysiloxanes (KF96-1000cs and KF995, both manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed at a ratio of 1: 1, and 0.1 g of the resultant is 3 cm × 3 cm large The artificial leather (Idemitsu Techno Fine Co., Ltd.) was applied uniformly. 0.1 g of the sample was applied, rubbed with a finger 10 times so as to draw a circle, and then washed with water. The surface of the artificial leather before and after washing is observed with a scanning electron microscope, and the area where silicon is present is calculated after mapping processing (HORIBA, Ltd .: EMAX). Asked.
シリコーン洗浄率＝〔（Ａ０−ＡＳ）／Ａ０〕×１００
Ａ０：試料によって洗浄する前のケイ素存在部位の面積
ＡＳ：試料によって洗浄した後のケイ素存在部位の面積
シリコーン洗浄率３０％未満：シリコーンに対する洗浄力が弱い。
シリコーン洗浄率３０％以上６０％未満：シリコーンに対する洗浄力が中程度。
シリコーン洗浄率６０％以上８０％未満：シリコーンに対する洗浄力が強い。
シリコーン洗浄率８０％以上：シリコーンに対する洗浄力が非常に強い。
Silicone cleaning rate = [(A0−AS) / A0] × 100
A0: Area of silicon existing site before cleaning with sample AS: Area of silicon existing site after cleaning with sample Silicone cleaning rate of less than 30%: Detergency against silicone is weak.
Silicone cleaning rate of 30% or more and less than 60%: Detergency against silicone is moderate.
Silicone cleaning rate of 60% or more and less than 80%: Strong cleaning power for silicone.
Silicone cleaning rate of 80% or more: Detergency against silicone is very strong.
（２）起泡性−１
試料濃度１質量％の水溶液を調製してロスマイルス法により、２５℃で試料投入直後と５分後の泡高さを測定した。試料投入直後の泡高さが２００ｍｍ以上のもので、次の式より求められる泡の持続率が９０％以上のものを泡立ちの良い洗浄剤と評価した。
泡の持続率＝〔（５分後の泡高さ）／（試料投入直後の泡高さ）〕×１００
(2) Foamability-1
An aqueous solution having a sample concentration of 1% by mass was prepared, and the bubble height was measured immediately after the sample was added and at 5 minutes at 25 ° C. by the Ross Miles method. A foam having a foam height of 200 mm or more immediately after the sample was introduced and having a foam persistence of 90% or more obtained from the following formula was evaluated as a detergent with good foaming.
Bubble persistence = [(bubble height after 5 minutes) / (bubble height immediately after sample introduction)] × 100
（３）起泡性−２
２０名の女性をパネラーとし、シリコーン含有毛髪化粧料を２ｍＬ塗付した状態で、試料（シヤンプー組成物）５ｍＬで洗髪した時の起泡性について評価した。シリコーン含有毛髪化粧料について組成を表２に示す。起泡性がよいと感じた場合を２点、やや起泡性がよいと感じた場合を１点、起泡性がよいと感じず悪いと感じた場合を０点として、２０名の合計点を求めた。合計点が３０点以上であるものを起泡性が良好であると評価した。
(3) Foamability-2
Twenty women were used as panelists, and foaming properties were evaluated when the hair was washed with 5 mL of a sample (Shyanpu composition) in a state where 2 mL of silicone-containing hair cosmetic was applied. The composition of the silicone-containing hair cosmetic is shown in Table 2. 20 points, 2 points for feeling good foaming, 1 point for feeling slightly better, 0 for not feeling good foaming Asked. Those having a total score of 30 or more were evaluated as having good foamability.
（４）泡のクリーミー性
２０名の女性をパネラーとし、試料（シヤンプー組成物）５ｍＬで洗髪した時のクリーミー性について評価した。泡がクリーミーであると感じた場合を２点、ややクリーミーであると感じた場合を１点、泡がクリーミーでなく粗いと感じた場合を０点として、２０名の合計点を求めた。合計点が３０点以上であるものを泡のクリーミー性が良好であると評価した。
(4) Creamy property of foam Twenty women were used as panelists, and the creamy property when the hair was washed with 5 mL of a sample (Shyanpu composition) was evaluated. The total score of 20 people was obtained, with 2 points when the foam felt creamy, 1 point when it felt slightly creamy, and 0 when the foam felt rough rather than creamy. Those having a total score of 30 or more were evaluated as having good creamy properties.
（５）洗髪時およびすすぎ時の指通り性
２０名の女性をパネラーとし、試料（シヤンプー組成物）を５ｍＬで洗髪した時の指通りを評価した。指通りがスムーズで髪がひっかからないと感じた場合を２点、髪がやや指にひっかかると感じた場合を１点、指通りが非常に悪いと感じた場合を０点として、２０名の合計点を求めた。合計点が３０点以上であるものを洗髪時の指通りが良好であると評価した。
(5) Fingering property at the time of shampooing and rinsing Twenty women were used as panelists, and fingering was evaluated when a sample (Shyanpu composition) was washed with 5 mL of hair. A total of 20 people, 2 points when you feel your fingers are smooth and your hair is not scratched, 1 point when you feel your hair is slightly caught, and 0 points when you feel your fingers are very bad I asked for a point. Those having a total score of 30 or more were evaluated as having good fingering during hair washing.
（６）洗髪後のまとまりとさらさら感
２０名の女性をパネラーとし、試料（シヤンプー組成物）５ｍＬで洗髪、乾燥したのちのまとまりとさらさら感を評価した。まとまりとさらさら感がすぐれていると感じた場合を２点、まとまりとさらさら感がやや得られると感じた場合を１点、まとまりとさらさら感が得られないと感じた場合を０点として、２０名の合計点を求めた。合計点が３０点以上であるものを洗髪後のまとまりとさらさら感が良好であると評価した。
(6) Cohesion and smooth feeling after washing hair 20 women were used as panelists, and after washing and drying with 5 mL of sample (Shyanpu composition), the cohesion and smooth feeling were evaluated. 20 points for feeling that the unity and smoothness are excellent, 1 point for feeling that the unity and smoothness is somewhat obtained, and 0 points for feeling that the unity and smoothness is not obtained, 20 The total number of names was determined. Those having a total score of 30 or more were evaluated as having a good unity and smooth feeling after shampooing.
（７）防腐性
下記菌株を用いて、 微生物汚染に対する抵抗性の確認を行なった。
Escherichia coli IFO3972（大腸菌）
Staphylococcus aureus IFO13276（黄色ブドウ球菌）
Pseudomonas aeruginosa IFO13275 （緑膿菌）
Candida albicans IFO1594（カンジダ菌）
Aspergillus niger IFO9455 （黒コウジカビ）
(7) Antiseptic property Resistance to microbial contamination was confirmed using the following strains.
Escherichia coli IFO3972 (Escherichia coli)
Staphylococcus aureus IFO13276 (Staphylococcus aureus)
Pseudomonas aeruginosa IFO13275 (Pseudomonas aeruginosa)
Candida albicans IFO1594 (Candida)
Aspergillus niger IFO9455 (black koji mold)
滅菌水に懸濁して調製した菌液３００μＬを試料３０ｍＬに添加しよく混合することにより接種するものとした。 それぞれの菌の各試料への接種時と接種７日後の生菌数を寒天平板混釈法で測定した。 測定培地は、細菌にはSCDLP 寒天培地を、真菌にはSabouraud LP寒天培地をそれぞれ使用した。培養条件は、細菌については３５℃にて４８〜７２時間、真菌については２８℃にて７２〜１２０時間とした。 300 μL of the bacterial solution prepared by suspending in sterilized water was added to 30 mL of the sample and mixed well to inoculate. The number of viable bacteria at the time of inoculation of each bacterium to each sample and 7 days after the inoculation was measured by an agar plate pour method. As the measurement medium, SCDLP agar medium was used for bacteria and Sabouraud LP agar medium was used for fungi. Culture conditions were set at 35 ° C. for 48 to 72 hours for bacteria and 72 to 120 hours at 28 ° C. for fungi.
接種７日後の生菌数が、細菌においては接種時の１／１０4未満、かつ真菌においては接種時の１／１０未満に減少したものを防腐性に優れると評価し、表１中に「○」と記載した。接種７日後の生菌数が、細菌において接種時の１／１０4以上、または、真菌において接種時の１／１０以上であるものは、防腐性が不充分と評価し、表１中に「×」と記載した。 It was evaluated that the number of viable bacteria 7 days after inoculation was less than 1/10 4 at the time of inoculation in bacteria and less than 1/10 at the time of inoculation as having excellent antiseptic properties. "". When the number of viable bacteria 7 days after inoculation is 1/10 4 or more at the time of inoculation in bacteria or 1/10 or more at the time of inoculation in fungi, the antiseptic property is evaluated as insufficient. X ".
以上の評価結果から明らかなように、本発明に係る実施例１〜７の毛髪洗浄剤組成物は、いずれも、シリコーンに対する洗浄力が高く、起泡性および泡のクリーミー性に優れており、さらに洗髪時、すすぎ時の指通り性および洗髪後のまとまりとさらさら感にも優れ、さらには優れた防腐性を有していた。また、実施例１〜７の毛髪洗浄剤組成物は、皮膚刺激性の高い界面活性剤や防腐剤を含まず、皮膚に対する刺激性が低い（ａ）成分〜（ｃ）成分の界面活性剤を含んでいるので、安全性が高い。 As is clear from the above evaluation results, the hair cleanser compositions of Examples 1 to 7 according to the present invention all have high detergency against silicone, excellent foaming properties and foam creamy properties, Furthermore, it was excellent in the fingering property at the time of shampooing and rinsing, the unity and smoothness after shampooing, and also had excellent antiseptic properties. In addition, the hair cleansing compositions of Examples 1 to 7 do not contain surfactants or preservatives with high skin irritation, and have low surfactant irritation to skin (a) to (c) surfactants. Because it contains, safety is high.
これに対し、比較例１〜８では十分な性能が得られていない。すなわち、比較例１では（ａ）成分を含有していないため、起泡性と泡のクリーミー性が不足し、洗髪時およびすすぎ時の指通り性、さらに洗髪後のまとまりとさらさら感が不充分であった。比較例２では（ｂ）成分の配合量が本発明規定範囲の下限値よりも少ないため、起泡性と泡のクリーミー性、洗髪時およびすすぎ時の指通り性、さらに洗髪後のまとまりとさらさら感が不充分であった。 On the other hand, in Comparative Examples 1-8, sufficient performance is not obtained. That is, since the component (a) is not contained in Comparative Example 1, the foaming properties and foam creaminess are insufficient, the fingering property at the time of shampooing and rinsing, and the unity and smooth feeling after shampooing are insufficient. Met. In Comparative Example 2, since the blending amount of component (b) is less than the lower limit of the range specified in the present invention, foaming property and foamy creaminess, ease of fingering at the time of rinsing and rinsing, and unity and smoothness after shampooing The feeling was insufficient.
比較例３では（ｃ）成分が本発明規定範囲の上限値を超えて配合されており、洗髪後のまとまりとさらさら感が充分ではなく、また防腐性が不充分であった。比較例４では、（ｄ）成分に代えてジステアリン酸ポリエチレングリコールが配合されていることより、泡の持続性およびクリーミー性が不充分であった。比較例５では、（ｅ）成分に代えて、１，３−ブチレングリコールが含有されていることから、シリコーンに対する洗浄力と泡のクリーミー性、さらには防腐性が不充分であった。また、シリコーンに対する洗浄力が不充分であり、さらにはシリコーン存在下での起泡性、泡のクリーミー性も充分なものではなかった。 In Comparative Example 3, the component (c) was blended in excess of the upper limit of the range specified in the present invention, and the unity and smoothness after washing was not sufficient, and the antiseptic property was insufficient. In Comparative Example 4, since the polyethylene glycol distearate was blended in place of the component (d), the foam persistence and creaminess were insufficient. In Comparative Example 5, since 1,3-butylene glycol was contained instead of the component (e), the detergency against silicone, the creaminess of foam, and the antiseptic properties were insufficient. Moreover, the detergency with respect to silicone was insufficient, and further, the foaming property and the creamy property of foam in the presence of silicone were not sufficient.
比較例６では（ｅ）成分が本発明規定範囲の上限値を超えて配合されており、起泡性および洗髪後のまとまりとさらさら感が不充分であった。比較例７では（ｆ）成分が本発明規定範囲の上限値を超えて配合されており、起泡性において充分なものではなく、また防腐性が不充分であった。比較例８においては（ｆ）成分が含有されておらず、泡のクリーミー性および洗髪時とすすぎ時の指通り性が不充分であった。 In Comparative Example 6, the component (e) was blended in excess of the upper limit of the range specified in the present invention, and the foamability and the unity and smooth feeling after washing were insufficient. In Comparative Example 7, the component (f) was blended in excess of the upper limit of the range specified in the present invention, and the foaming property was not sufficient, and the antiseptic property was insufficient. In Comparative Example 8, the component (f) was not contained, and the creamy property of the foam and the fingering property at the time of washing and rinsing were insufficient.
Claims (1)
（a）式（１）で表わされるアシルβ−アラニン型界面活性剤
（b) 式（２）で表わされるアシルタウリン型界面活性剤
（c) 式（３）で表されるアミドベタイン型界面活性剤及び／又は式（４）で表されるアルキルベタイン型界面活性剤
（d）式（５）で表されるポリオキシエチレングリコール
（e）１，２−ペンタンジオール及び／又は１，２−ヘキサンジオール
（f）カチオン性ポリマー The following (a) component-(f) component is contained, (a) component is 2-10 mass% in a composition, (b) component is 5-15 mass% in a composition, (c) component is a composition. 1 to 5% by mass, (d) component is 0.5 to 5% by mass in the composition, (e) component is 1 to 5% by mass in the composition, and (f) component is 0.1 to 1 in the composition. A hair cleanser composition characterized by being a mass%.
(A) Acyl β-alanine type surfactant represented by the formula (1)
(B) Acyl taurine type surfactant represented by the formula (2)
(C) Amidobetaine surfactant represented by formula (3) and / or alkylbetaine surfactant represented by formula (4)
(D) Polyoxyethylene glycol represented by formula (5)
(E) 1,2-pentanediol and / or 1,2-hexanediol (f) cationic polymer
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| JP2016193886A (en) * | 2015-03-31 | 2016-11-17 | 日油株式会社 | Hair cleansing composition |
| JP2019038859A (en) * | 2018-12-14 | 2019-03-14 | ポーラ化成工業株式会社 | Sunscreen cosmetics and method for producing the same |
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