JP2007008881A - Skin cleansing agent - Google Patents
Skin cleansing agent Download PDFInfo
- Publication number
- JP2007008881A JP2007008881A JP2005192944A JP2005192944A JP2007008881A JP 2007008881 A JP2007008881 A JP 2007008881A JP 2005192944 A JP2005192944 A JP 2005192944A JP 2005192944 A JP2005192944 A JP 2005192944A JP 2007008881 A JP2007008881 A JP 2007008881A
- Authority
- JP
- Japan
- Prior art keywords
- skin
- general formula
- alkyl group
- present
- skin cleansing
- 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
- 239000003599 detergent Substances 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N Taurine Natural products NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 229960003080 taurine Drugs 0.000 claims description 6
- 239000011538 cleaning material Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 15
- 238000005406 washing Methods 0.000 abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- -1 acyl taurine salt Chemical class 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001815 facial effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229940119423 ultracare Drugs 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 230000001953 sensory effect Effects 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- AVBJHQDHVYGQLS-UHFFFAOYSA-N 2-(dodecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCC(=O)NC(C(O)=O)CCC(O)=O AVBJHQDHVYGQLS-UHFFFAOYSA-N 0.000 description 1
- DABQDIXIAXPQFG-UHFFFAOYSA-N 2-[dodecanoyl(methyl)amino]ethanesulfonic acid Chemical compound CCCCCCCCCCCC(=O)N(C)CCS(O)(=O)=O DABQDIXIAXPQFG-UHFFFAOYSA-N 0.000 description 1
- QFYLRFIMCRPARN-UHFFFAOYSA-N 2-[methyl(tetradecyl)amino]ethanesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCCCN(C)CCS(O)(=O)=O QFYLRFIMCRPARN-UHFFFAOYSA-N 0.000 description 1
- HXFCUMCLVYNZDM-UHFFFAOYSA-N 2-aminoacetic acid;sodium Chemical compound [Na].NCC(O)=O HXFCUMCLVYNZDM-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 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-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-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
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- 229930186217 Glycolipid Natural products 0.000 description 1
- BIVBRWYINDPWKA-VLQRKCJKSA-L Glycyrrhizinate dipotassium Chemical compound [K+].[K+].O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@H]1CC[C@]2(C)[C@H]3C(=O)C=C4[C@@H]5C[C@](C)(CC[C@@]5(CC[C@@]4(C)[C@]3(C)CC[C@H]2C1(C)C)C)C(O)=O)C([O-])=O)[C@@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O BIVBRWYINDPWKA-VLQRKCJKSA-L 0.000 description 1
- 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 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 229940101029 dipotassium glycyrrhizinate Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940124274 edetate disodium Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 229940100242 glycol stearate Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- WNEHWYCWKDNRFW-UQKRIMTDSA-M potassium;(4s)-4-(dodecanoylamino)-5-hydroxy-5-oxopentanoate Chemical compound [H+].[K+].CCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC([O-])=O WNEHWYCWKDNRFW-UQKRIMTDSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Abstract
Description
本発明は泡立ちに優れ、すすぎ時のぬるつき、及び洗浄後の突っ張り感が無く、肌に柔らかな感触を与える皮膚洗浄料に関する。 The present invention relates to a skin cleansing agent that is excellent in foaming, has no stickiness during rinsing, and has no feeling of tension after washing, and gives a soft feel to the skin.
近年、洗顔料等の皮膚洗浄料においては本来の目的である洗浄性に加えて、起泡性、泡質、すすぎ性、使用後の感触の良さが求められている。従来、皮膚洗浄料において高級脂肪酸のカリウム塩が泡立ちの良さ、洗浄力の良さ、洗い流し後のさっぱり感等に優れることから多用されている。しかしながら、高級脂肪酸のカリウム塩を主成分とした洗浄剤は、泡立ち、洗浄力、洗い流し後のさっぱり感等に関しては優れた性質を有しているものの、クリーミィな泡質が得られなかったり、洗浄中の過度の脱脂や石鹸カス（スカム）が肌に残ることから使用後に肌がつっぱる等の欠点も有していた。 In recent years, skin cleansing materials such as facial cleansers are required to have foaming properties, foam quality, rinsing properties, and good feeling after use in addition to the original cleanability. Conventionally, potassium salts of higher fatty acids have been frequently used in skin cleansing agents because they have good foaming, good detergency, and a refreshing feeling after washing. However, the detergent mainly composed of potassium salt of higher fatty acid has excellent properties in terms of foaming, detergency, refreshing feeling after washing, etc., but no creamy foam quality can be obtained. There were also disadvantages such as excessive degreasing inside and soap residue (scum) remaining on the skin, resulting in the skin becoming stuck after use.
上記のような、高級脂肪酸のカリウム塩を主成分とした洗浄剤の問題点を解決する方法として、従来アシルタウリン塩型、アシルイセチオン酸型、リン酸エステル型、アシルアミノ酸型等の界面活性剤との併用等が検討されている。（特許文献１参照。）
また界面活性剤以外の添加剤として、シリコーン化合物や特定の糖脂質、ラフィノース、植物種子粘性物、高分子化合物等を配合し泡質を改良したり、つっぱり感を解消しようとする試みがなされてきた。（特許文献２〜６参照）
更には高級脂肪酸のカリウム塩を主成分とせず、アシルグリシン型界面活性剤と特定の高分子化合物を組み合わせることにより上記問題点を改良する試みもなされている。（特許文献７参照）
しかしながら、近年消費者の要求の高まりにより、更なる改良が望まれている。
As a method for solving the problems of the detergents mainly composed of potassium salts of higher fatty acids as described above, conventional surfactants such as acyl taurine salt type, acyl isethionate type, phosphate ester type, acyl amino acid type, etc. Concomitant use is being considered. (See Patent Document 1.)
Attempts have also been made to improve the foam quality and eliminate the feeling of tension by adding silicone compounds, specific glycolipids, raffinose, plant seed viscosity, polymer compounds, etc. as additives other than surfactants. It was. (See Patent Documents 2 to 6)
Furthermore, attempts have been made to improve the above problems by combining an acylglycine surfactant and a specific polymer compound without using a higher fatty acid potassium salt as a main component. (See Patent Document 7)
However, further improvements are desired in recent years due to increasing consumer demand.
従って、本発明の目的は、泡立ちに優れ、すすぎ時のぬるつき、及び洗浄後のつっぱり感が無く、肌に柔らかな感触を与える皮膚洗浄料を提供することにある。 Accordingly, an object of the present invention is to provide a skin cleansing material that is excellent in foaming, does not feel sticky at the time of rinsing, and does not have a feeling of tension after washing, and gives a soft feel to the skin.
本発明者は、本発明の目的を達成するために鋭意研究した結果、Ｎ−アシルタウリン型界面活性剤と、特定の高分子化合物と、多価アルコールとを組み合わせた皮膚洗浄料が、
上記課題を解決することを見出し、本発明を完成した。
As a result of diligent research to achieve the object of the present invention, the present inventor has developed a skin cleansing agent comprising a combination of an N-acyl taurine type surfactant, a specific polymer compound, and a polyhydric alcohol.
The inventors have found that the above problems can be solved and have completed the present invention.
すなわち本発明の請求項１は、（Ａ）下記一般式（１）で表わされるＮ−アシルタウリン型界面活性剤、
（Ｂ）下記一般式（２）で表されるビニルピロリドンモノマーと、下記一般式（３）で表される４級化ビニルイミダゾールモノマーとを構成成分に有する高分子化合物、
(B) a polymer compound having as constituent components a vinylpyrrolidone monomer represented by the following general formula (2) and a quaternized vinylimidazole monomer represented by the following general formula (3);
また本発明の請求項２は、洗顔料であることを特徴とする請求項１記載の皮膚洗浄料である。 Moreover, Claim 2 of the present invention is a skin cleanser according to Claim 1, which is a face wash.
また本発明の請求項３は、（Ｂ）高分子化合物が架橋されていることを特徴とする請求項１又は２に記載の皮膚洗浄料である。 The third aspect of the present invention is the skin cleanser according to the first or second aspect, wherein the polymer compound (B) is crosslinked.
本発明は、泡立ちに優れ、すすぎ時のぬるつき、及び洗浄後の突っ張り感が無く、肌に柔らかな感触を与える皮膚洗浄料を提供するものである。 The present invention provides a skin cleansing agent that is excellent in foaming, has no stickiness during rinsing, and has no feeling of tension after washing, and gives a soft touch to the skin.
以下、本発明の構成を詳述する。 Hereinafter, the configuration of the present invention will be described in detail.
本発明における成分（Ａ）Ｎ−アシルタウリン型界面活性剤は、下記一般式（１）で表わされ、例えば、Ｎ−ラウロイル−Ｎ−メチルタウリンナトリウム、Ｎ−ミリストイル−Ｎ−メチルタウリンナトリウム、Ｎ−ココイル−Ｎ−メチルタウリンナトリウム等が挙げられる。尚、本発明において（Ａ）Ｎ−アシルタウリン型界面活性剤は、それぞれ単独又は２種以上を混合して使用することができる。
本発明における（Ａ）Ｎ−アシルタウリン型界面活性剤の配合量は、皮膚洗浄料全量中０．１〜３０質量％（以下、単に％と略す）が好ましく、更に好ましくは１〜２５％である。配合量が０．１％未満では十分な泡立ちが得ることができない場合があり、また３０％を超えて配合すると洗浄力が強すぎ過剰に脱脂され洗い上がり後につっぱり感を感じるようになる場合がある。 The blending amount of the (A) N-acyl taurine type surfactant in the present invention is preferably 0.1 to 30% by mass (hereinafter simply referred to as%), more preferably 1 to 25%, based on the total amount of the skin cleanser. is there. If the blending amount is less than 0.1%, sufficient foaming may not be obtained. If the blending amount exceeds 30%, the detergency is too strong and excessive degreasing may cause a feeling of tension after washing. is there.
本発明における成分（Ｂ）は、下記一般式（２）で表されるビニルピロリドンモノマーと、下記一般式（３）で表される４級化ビニルイミダゾールモノマーとを構成成分に有する高分子化合物であり、例えば、Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｓｍｅｔｉｃ Ｉｎｇｒｅｄｉｅｎｔ Ｄｉｃｔｉｏｎａｒｙ ａｎｄ Ｈａｎｄｂｏｏｋ（Ｎｉｎｔｈ Ｅｄｉｔｉｏｎ ２００２、Ｔｈｅ Ｃｏｓｍｅｔｉｃ，Ｔｏｉｌｅｔｒｙ，ａｎｄ Ｆｒａｇｒａｎｃｅ Ａｓｓｏｃｉａｔｉｏｎ）に収載のＰＯＬＹＱＵＡＴＥＲＮＩＵＭ−１６、ＰＯＬＹＱＵＡＴＥＲＮＩＵＭ−４４等が挙げられ、ＬＵＶＩＱＵＡＴ ＦＣ（ＢＡＳＦ社製）、ＬＵＶＩＱＵＡＴ ＣＡＲＥ（ＢＡＳＦ社製）、ＬＵＶＩＱＵＡＴ ＵＬＴＲＡＣＡＲＥ（ＢＡＳＦ社製）等の市販品を用いることができる。尚、本発明において（Ｂ）ビニルピロリドンモノマーと４級化ビニルイミダゾールモノマーとを構成成分に有する高分子化合物は、それぞれ単独又は２種以上を混合して使用することができる。
本発明における（Ｂ）ビニルピロリドンモノマーと４級化ビニルイミダゾールモノマーとを構成成分に有する高分子化合物の配合量は、皮膚洗浄料全量中０．０１〜０．５％が好ましく、更に好ましくは０．０５〜０．３％である。配合量が０．０１％未満では肌がつっぱったり、洗い上がりの肌の柔らかな感触に欠ける傾向にある。また配合量が０．５％を超えると泡立ちを損ねる傾向にある。 In the present invention, the blending amount of the polymer compound having (B) vinylpyrrolidone monomer and quaternized vinylimidazole monomer as constituent components is preferably 0.01 to 0.5%, more preferably 0, based on the total amount of the skin cleanser. 0.05-0.3%. If the blending amount is less than 0.01%, the skin tends to be tight or the soft feel of the washed-out skin tends to be lacking. Further, if the blending amount exceeds 0.5%, foaming tends to be impaired.
また本発明においる（Ｂ）ビニルピロリドンモノマーと４級化ビニルイミダゾールモノマーとを構成成分に有する高分子化合物は、架橋されていることが好ましく、具体的には市販品であるＬＵＶＩＱＵＡＴ ＣＡＲＥ（ＢＡＳＦ社製）、ＬＵＶＩＱＵＡＴ ＵＬＴＲＡＣＡＲＥ（ＢＡＳＦ社製）を用いた場合、柔らかな感触の面で特に優れる。 The polymer compound having (B) a vinyl pyrrolidone monomer and a quaternized vinyl imidazole monomer as constituents in the present invention is preferably cross-linked, and specifically, it is a commercially available product LUVIQUAT CARE (BASF). And LUVIQUAT ULTRACARE (manufactured by BASF) are particularly excellent in terms of soft touch.
本発明における成分（Ｃ）多価アルコールとしては、例えば、グリセリン、エチレングリコール、ポリエチレングリコール（平均分子量が１０００以下）、プロピレングリコール、１，３−ブチレングリコール、ジプロピレングリコール、ソルビトール、マンニトール等が挙げられる。尚、本発明において（Ｃ）多価アルコールは、それぞれ単独又は２種以上を混合して使用することができる。 Examples of the component (C) polyhydric alcohol in the present invention include glycerin, ethylene glycol, polyethylene glycol (average molecular weight is 1000 or less), propylene glycol, 1,3-butylene glycol, dipropylene glycol, sorbitol, mannitol and the like. It is done. In addition, in this invention, (C) polyhydric alcohol can be used individually or in mixture of 2 or more types, respectively.
本発明における（Ｃ）多価アルコールの配合量は、皮膚洗浄剤全量中３〜５０％が好ましく、更に好ましくは１０〜３０％である。配合量が３％未満であると肌がつっぱる場合がある。また配合量が５０％を超えると、泡立ちを損ねる場合がある。 In the present invention, the blending amount of (C) polyhydric alcohol is preferably 3 to 50%, more preferably 10 to 30%, based on the total amount of the skin cleanser. If the blending amount is less than 3%, the skin may become tight. Moreover, when a compounding quantity exceeds 50%, foaming may be impaired.
本発明において、発明の効果を損なわない範囲であれば、上記必須成分の他に、必須成分以外のアニオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤、ガム質、油分、その他の高分子化合物、高級アルコール、粉体、噴射剤、防腐剤、キレート剤、酸化防止剤、ｐＨ調整剤、色素、香料等を配合することも可能である。 In the present invention, within the range that does not impair the effects of the invention, in addition to the above essential components, anionic surfactants other than the essential components, amphoteric surfactants, nonionic surfactants, gums, oils, etc. It is also possible to blend a high molecular compound, higher alcohol, powder, propellant, preservative, chelating agent, antioxidant, pH adjuster, dye, fragrance and the like.
本発明の皮膚洗浄料は洗顔料、ハンドソープ、ボディシャンプー等に応用することができ、洗顔料として用いると特に効果を発現する。 The skin cleanser of the present invention can be applied to facial cleansers, hand soaps, body shampoos, and the like, and is particularly effective when used as a facial cleanser.
以下に実施例、比較例を挙げて本発明を説明する。尚、本発明は、これらにより限定されるものではない。 Hereinafter, the present invention will be described with reference to examples and comparative examples. In addition, this invention is not limited by these.
実施例、比較例に示した物性試験、官能試験の試験方法は下記の通りである。尚、以下の表に示す組成物の配合量は、それぞれ％で示す。 Test methods for physical property tests and sensory tests shown in Examples and Comparative Examples are as follows. In addition, the compounding quantity of the composition shown in the following table | surfaces is each shown by%.
（１）泡立ち試験
皮膚洗浄料の試料を４０℃の水道水により２０倍希釈し、ジューサーミキサー（ナショナルＭＸ−Ｘ５３、松下電器産業社製）に５０ｍＬ入れ、１０秒間攪拌し泡立てた。できた泡をメスシリンダーに移し泡量を測定し泡立ちの良さの指標とした。
(1) Foaming test A skin cleansing sample was diluted 20-fold with tap water at 40 ° C., placed in a juicer mixer (National MX-X53, manufactured by Matsushita Electric Industrial Co., Ltd.), 50 mL, and stirred for 10 seconds to foam. The resulting foam was transferred to a graduated cylinder and the amount of foam was measured and used as an index of good foaming.
（２）官能試験
パネル（２０名）により皮膚洗浄料の試料とコントロールを左右半顔それぞれに塗布し、洗顔を行なった際の、すすぎ時のぬるつき、肌のつっぱり感、肌のやわらかさについて官能評価し、平均評価点を求めた。
(2) Sensory test The skin cleanser samples and controls were applied to each of the left and right half-faces using a panel (20 persons). Sensory evaluation was performed to obtain an average evaluation score.
コントロール
ヤシ油脂肪酸カリウム １５．０％
カチオン性高分子 ０．０８
（商品名：ＭＥＲＱＵＡＴ ５５０、オンデオナルコ社製、純分換算）
グリセリン ２０．０
精製水 残部
Control Potassium oil fatty acid potassium 15.0%
Cationic polymer 0.08
(Product name: MERQUAT 550, manufactured by Ondeonalco Co., Ltd.)
Glycerin 20.0
Purified water balance
また、評価の基準を次のように設定した。
◎：コントロールより良いと答えた人数が１６名以上
○：コントロールより良いと答えた人数が１２名以上
△：コントロールより良いと答えた人数が８名以上
×：コントロールより良いと答えた人数が７名以下
The evaluation criteria were set as follows.
◎: More than 16 people answered that it was better than control ○: More than 12 people answered that it was better than control △: More than 8 people answered that it was better than control ×: 7 people answered that it was better than control Below
実施例１〜７、比較例１〜３
表１に示した処方の皮膚洗浄料（洗顔料）を常法により調製し、前記各試験を実施した。その結果を表１に併せて示す。
Examples 1-7, Comparative Examples 1-3
A skin cleanser (face wash) having the formulation shown in Table 1 was prepared by a conventional method, and the above tests were performed. The results are also shown in Table 1.
表１より明らかなように本発明の成分を用いた実施例の皮膚洗浄料はいずれも優れた性能を有していた。一方、必須成分のいずれかを欠いた比較例では、泡立ち、すすぎ時のぬるつきの無さ、つっぱり感の無さ、肌の柔らかさのいずれかの面で劣っており、本発明の
目的を達成できなかった。
As is clear from Table 1, all of the skin cleansing agents of Examples using the components of the present invention had excellent performance. On the other hand, the comparative example lacking any of the essential components is inferior in terms of foaming, no slickness during rinsing, no feeling of tension, and softness of the skin, achieving the object of the present invention. could not.
実施例８（ポンプフォーマー型洗顔料）
Ｎ−ココイル−Ｎ−メチルタウリンナトリウム ３．０％
ヤシ油脂肪酸グリシンナトリウム １．２
（商品名：アミライトＧＣＳ−１１、味の素社製）
ＰＯＲＹＱＵＡＴＥＲＮＩＵＭ−４４ ０．０６５
（商品名：ＬＵＶＩＱＵＡＴ ＵＬＴＲＡＣＡＲＥ、ＢＡＳＦ社製、純分換算）
１，３−ブチレングリコール ５．０
グリセリン １０．０
ポリオキシエチレン硬化ひまし油（６０Ｅ．Ｏ．） ０．３
モノラウリン酸ポリオキシエチレンソルビタン（２０Ｅ．Ｏ．） ０．１
エデト酸ニナトリウム ０．１
パラオキシ安息香酸メチル ０．１
クエン酸 ０．０８
クエン酸ナトリウム ０．０２
サボンソウエキス ０．１
混合果実抽出液 ０．１
（商品名：マルチフルーツＢＳＣ、Ａｒｃｈ Ｐｅｒｓｏｎａｌ Ｃａｒｅ Ｐｒｏｄｕｃｔｓ社製）
香料 ０．２
精製水 残 部
Example 8 (pump former type face wash)
N-cocoyl-N-methyltaurine sodium 3.0%
Palm oil fatty acid glycine sodium 1.2
(Product name: Amilite GCS-11, manufactured by Ajinomoto Co., Inc.)
POLYQUATERNIUM-44 0.065
(Product name: LUVIQUAT ULTRACARE, BASF, pure conversion)
1,3-butylene glycol 5.0
Glycerin 10.0
Polyoxyethylene hydrogenated castor oil (60 EO) 0.3
Polyoxyethylene sorbitan monolaurate (20E.O.) 0.1
Edetate disodium 0.1
Methyl paraoxybenzoate 0.1
Citric acid 0.08
Sodium citrate 0.02
Soap extract 0.1
Mixed fruit extract 0.1
(Product name: Multifruit BSC, manufactured by Arch Personal Care Products)
Fragrance 0.2
Purified water balance
上記組成を常法により調製し、ポンプフォーマー容器（大和製罐社製）に充填し洗顔料を作成し評価したところ、泡立ち、すすぎ時のぬるつきの無さ、つっぱり感の無さ、肌の柔らかさについて、優れた性能を有していた。 The above composition was prepared by a conventional method and filled into a pump former container (manufactured by Daiwa Seisaku Co., Ltd.) to create a facial cleanser and evaluated. As a result, there was no foaming, no stuffiness when rinsing, no feeling of tension, It had excellent performance in terms of softness.
実施例９（クリーム状洗顔料）
Ｎ−ミリスチル−Ｎ−メチルタウリンナトリウム １．５％
（商品名：ＭＭＣ、日光ケミカルズ社製）
Ｎ−ラウロイル−Ｌ−グルタミン酸カリウム ３．０％
（商品名：アミソフトＬＫ−１１、味の素社製）
ＰＯＲＹＱＵＡＴＥＲＮＩＵＭ−４４ ０．１３
（商品名：ＬＵＶＩＱＵＡＴ ＵＬＴＲＡＣＡＲＥ、ＢＡＳＦ社製、純分換算）
グリセリン ２５．０
ラウリン酸 ５．０
ミリスチン酸 １８．０
パルミチン酸 １．０
ステアリン酸 １．５
水酸化カリウム ６．０
ステアリン酸ポリエチレングリコール ０．８
（商品名：ＮＩＫＫＯＬ ＭＹＳ−４５、日光ケミカルズ社製）
ポリオキシエチレンセチルエーテル（２０Ｅ．Ｏ．） ０．８
ステアリン酸グリセリル ０．８
ジステアリン酸グリコール １．０
（商品名：エステパール１０、日光ケミカルズ社製）
サリチル酸 ０．０１
グリチルリチン酸ジカリウム ０．１
Ｎ−ラウロイル−Ｌ−グルタミン酸
ジ（フィトステリル・２−オクチルドデシル） ０．１
香料 ０．１
精製水 残 部
Example 9 (Cream face wash)
N-myristyl-N-methyltaurine sodium 1.5%
(Product name: MMC, manufactured by Nikko Chemicals)
N-lauroyl-L-glutamate potassium 3.0%
(Product name: Amisoft LK-11, manufactured by Ajinomoto Co., Inc.)
POLYQUATERNIUM-44 0.13
(Product name: LUVIQUAT ULTRACARE, BASF, pure conversion)
Glycerin 25.0
Lauric acid 5.0
Myristic acid 18.0
Palmitic acid 1.0
Stearic acid 1.5
Potassium hydroxide 6.0
Polyethylene glycol stearate 0.8
(Product name: NIKKOL MYS-45, manufactured by Nikko Chemicals)
Polyoxyethylene cetyl ether (20E.O.) 0.8
Glyceryl stearate 0.8
Glycol distearate 1.0
(Product name: Este Pearl 10, manufactured by Nikko Chemicals)
Salicylic acid 0.01
Dipotassium glycyrrhizinate 0.1
N-lauroyl-L-glutamic acid di (phytosteryl 2-octyldodecyl) 0.1
Fragrance 0.1
Purified water balance
上記組成のクリーム状洗顔料を調製し評価したところ、泡立ち、すすぎ時のぬるつきの無さ、つっぱり感の無さ、肌の柔らかさについて、優れた性能を有していた。 When the creamy facial cleanser having the above composition was prepared and evaluated, it had excellent performance in terms of foaming, no slickness at the time of rinsing, no feeling of tension, and softness of the skin.
尚、上記の実施例８〜９において使用した香料の組成は表２に示す。 In addition, the composition of the fragrance | flavor used in said Examples 8-9 is shown in Table 2.
Claims (3)
（Ｂ）下記一般式（２）で表されるビニルピロリドンモノマーと、下記一般式（３）で表される４級化ビニルイミダゾールモノマーとを構成成分に有する高分子化合物、
(B) a polymer compound having as constituent components a vinylpyrrolidone monomer represented by the following general formula (2) and a quaternized vinylimidazole monomer represented by the following general formula (3);
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005192944A JP4299274B2 (en) | 2005-06-30 | 2005-06-30 | Skin cleanser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005192944A JP4299274B2 (en) | 2005-06-30 | 2005-06-30 | Skin cleanser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007008881A true JP2007008881A (en) | 2007-01-18 |
| JP4299274B2 JP4299274B2 (en) | 2009-07-22 |
Family
ID=37747830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005192944A Active JP4299274B2 (en) | 2005-06-30 | 2005-06-30 | Skin cleanser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4299274B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277140A (en) * | 2006-04-05 | 2007-10-25 | Kao Corp | Skin cleaning agent |
| JP2008247782A (en) * | 2007-03-29 | 2008-10-16 | Naris Cosmetics Co Ltd | Face-cleansing cosmetic composition |
| JP2010209220A (en) * | 2009-03-10 | 2010-09-24 | Nof Corp | Creamy detergent composition |
| JP2020007303A (en) * | 2018-06-27 | 2020-01-16 | 小林製薬株式会社 | Skin cleanser composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031561A (en) * | 1999-07-15 | 2001-02-06 | Sakamoto Yakuhin Kogyo Co Ltd | Skin cleansing preparation |
| JP2002087950A (en) * | 2000-07-12 | 2002-03-27 | L'oreal Sa | Foaming cleansing composition of clear gel form |
| JP2003160797A (en) * | 2001-09-17 | 2003-06-06 | Shiseido Co Ltd | Cleaning material composition |
| WO2004013266A2 (en) * | 2002-07-27 | 2004-02-12 | Beiersdorf Ag | Detergent-dipped cleaning substrate |
| WO2004012698A2 (en) * | 2002-07-27 | 2004-02-12 | Beiersdorf Ag | Soap-containing cleaning substrate |
-
2005
- 2005-06-30 JP JP2005192944A patent/JP4299274B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031561A (en) * | 1999-07-15 | 2001-02-06 | Sakamoto Yakuhin Kogyo Co Ltd | Skin cleansing preparation |
| JP2002087950A (en) * | 2000-07-12 | 2002-03-27 | L'oreal Sa | Foaming cleansing composition of clear gel form |
| JP2003160797A (en) * | 2001-09-17 | 2003-06-06 | Shiseido Co Ltd | Cleaning material composition |
| WO2004013266A2 (en) * | 2002-07-27 | 2004-02-12 | Beiersdorf Ag | Detergent-dipped cleaning substrate |
| WO2004012698A2 (en) * | 2002-07-27 | 2004-02-12 | Beiersdorf Ag | Soap-containing cleaning substrate |
| JP2005537289A (en) * | 2002-07-27 | 2005-12-08 | バイヤースドルフ・アクチエンゲゼルシヤフト | Cleaning substrate containing soap |
| JP2006512424A (en) * | 2002-07-27 | 2006-04-13 | バイヤースドルフ・アクチエンゲゼルシヤフト | Substrate for cleaning with surfactant |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277140A (en) * | 2006-04-05 | 2007-10-25 | Kao Corp | Skin cleaning agent |
| JP4676915B2 (en) * | 2006-04-05 | 2011-04-27 | 花王株式会社 | Skin cleanser |
| JP2008247782A (en) * | 2007-03-29 | 2008-10-16 | Naris Cosmetics Co Ltd | Face-cleansing cosmetic composition |
| JP2010209220A (en) * | 2009-03-10 | 2010-09-24 | Nof Corp | Creamy detergent composition |
| JP2020007303A (en) * | 2018-06-27 | 2020-01-16 | 小林製薬株式会社 | Skin cleanser composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4299274B2 (en) | 2009-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2006030881A1 (en) | Detergent composition | |
| JP2008285479A (en) | Skin cleansing composition | |
| CN107106436B (en) | Liquid skin cleansing composition | |
| CN107603789B (en) | Conditioning type solid shampoo soap | |
| JP4299273B2 (en) | Skin cleanser | |
| JP4299274B2 (en) | Skin cleanser | |
| JP4724088B2 (en) | Skin cleanser | |
| JP5959659B2 (en) | Skin cleanser composition | |
| JP2002167324A (en) | Detergent composition | |
| JP3694069B2 (en) | Liquid solidification inhibitor | |
| JP2005298455A (en) | Skin cleanser | |
| JP3811168B2 (en) | Skin cleanser composition | |
| JP2021183591A (en) | Liquid skin cleansing composition | |
| JP5192871B2 (en) | Cleaning composition | |
| JP7033768B2 (en) | Body cleansing composition and body cleansing method | |
| JP2008056608A (en) | Cleansing agent composition for skin | |
| JP2006169453A (en) | Detergent composition | |
| JP7422541B2 (en) | skin cleansing composition | |
| JP4381270B2 (en) | Paste face wash composition | |
| JP4676915B2 (en) | Skin cleanser | |
| JP7188320B2 (en) | Liquid cleaning agent | |
| JP2005314614A (en) | Detergent composition | |
| JP7084222B2 (en) | Skin cleansing composition | |
| JP3739082B2 (en) | Cleaning composition | |
| JP5608357B2 (en) | Skin cleanser |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070209 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20070615 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070725 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081210 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20081114 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090113 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090312 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090414 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090416 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4299274 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120424 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120424 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130424 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130424 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140424 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |