TWI468181B - 以聚碳酸酯多元醇類為主且適用於個人保養產品之聚胺基甲酸酯分散液 - Google Patents
以聚碳酸酯多元醇類為主且適用於個人保養產品之聚胺基甲酸酯分散液 Download PDFInfo
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- TWI468181B TWI468181B TW97129973A TW97129973A TWI468181B TW I468181 B TWI468181 B TW I468181B TW 97129973 A TW97129973 A TW 97129973A TW 97129973 A TW97129973 A TW 97129973A TW I468181 B TWI468181 B TW I468181B
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- 229920003009 polyurethane dispersion Polymers 0.000 title claims description 28
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- 239000004417 polycarbonate Substances 0.000 title claims description 13
- 229920005862 polyol Polymers 0.000 title claims description 10
- 150000003077 polyols Chemical class 0.000 title claims description 10
- 150000002009 diols Chemical class 0.000 claims description 23
- 125000003010 ionic group Chemical group 0.000 claims description 23
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
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- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
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- 239000004440 Isodecyl alcohol Substances 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
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- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims 1
- WNEIROYUZJGWIK-UHFFFAOYSA-N 1-(3-ethylpentyl)-2-methylhydrazine Chemical compound C(C)C(CCNNC)CC WNEIROYUZJGWIK-UHFFFAOYSA-N 0.000 claims 1
- 239000004146 Propane-1,2-diol Substances 0.000 claims 1
- ROZLDLJVUNEAFL-UHFFFAOYSA-N [Na].NCCNCCS(O)(=O)=O Chemical compound [Na].NCCNCCS(O)(=O)=O ROZLDLJVUNEAFL-UHFFFAOYSA-N 0.000 claims 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
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- GFKIUEJKIJMIGA-UHFFFAOYSA-N hexane-1,6-diol;n-propylpropan-1-amine Chemical compound CCCNCCC.OCCCCCCO GFKIUEJKIJMIGA-UHFFFAOYSA-N 0.000 description 1
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- 230000002209 hydrophobic effect Effects 0.000 description 1
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- 230000003472 neutralizing effect Effects 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- AKNQYIXNIUXHFU-UHFFFAOYSA-N propane-1,3-diol;n-propylpropan-1-amine Chemical compound OCCCO.CCCNCCC AKNQYIXNIUXHFU-UHFFFAOYSA-N 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- 235000020679 tap water Nutrition 0.000 description 1
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Description
本發明係關於水性聚胺基甲酸酯分散液、彼等製備方法及彼等於化妝用品上之用途,例如頭髮定型劑。
聚胺基甲酸酯分散液最近已併入化妝品中,例如頭髮定型劑、防曬乳液等,提供數種優於習用技術例如丙烯酸及丙烯醯胺共聚物、聚乙烯吡咯啶酮及PVP/VA共聚物之優點。這些優點包括水相容性、容易調配低VOC噴霧、耐水性及優良的成膜能力。特別是在頭髮保養品上,聚胺基甲酸酯分散液提供極佳的無黏性感之定型效果、優良的造型保持性(因聚合物之彈性記憶)、自然外觀及觸感。所有這些屬性係對消費者具高度價值。設計作為頭髮定型劑及頭髮造型聚合物之市售的聚胺基甲酸酯分散液通常具有良好高濕度捲度保持性、造型保持性以及良好的觸感及亮度。然而,梳整後在頭髮上廣範圍呈片狀證明其對頭髮缺乏黏性。這對消費者明顯造成了美學上的問題。
設計頭髮定型劑聚合物之挑戰包括達成通常為衝突的需求間之平衡:即使在潮濕的情況下,聚合物應具足夠的疏水性以提供捲度保持性,同時其應保有足夠的親水性以便在以水清洗時能由頭髮上移除。又,聚合物必須具有最適的玻璃轉化溫度、彈性及分子量之組合以提供造型強度、彈性、對頭髮之黏性及柔軟觸感。
美國專利第5,626,840號揭示以聚胺基甲酸酯分散液為主之頭髮定型劑,其係利用經2,2-羥基甲基取代之羧酸所製備。其說明如何使用水溶性或水分散性聚胺基甲酸酯達到良好耐濕性及噴霧特性。此等例子證明聚合物之效力僅在於含醇的氣溶膠噴霧調配物。這對環境和頭髮健康二者為有害的。最後,此發明利用在聚胺基甲酸酯分散液中每克聚胺基甲酸酯含0.35-2.25 meq的COOH之二甲基醇丙酸(DMPA)的範圍,其必須觀察而為有效的分散液。
然而,揭示文中並無教導如何藉由達到對頭髮良好黏性避免頭髮上聚合物薄片之常見的問題。再者,其並無教導如何獲得造型保持性,例如聚合物的彈性行為。最後,較佳地應使用較低量的酸,而仍能達到捲度保持性及可清洗性,因為酸有助於加速聚合物之分解。
美國專利第6,613,314號揭示了使用聚胺基甲酸酯分散液之可再造型之頭髮組合物。在製備聚胺基甲酸酯期間,形成了異氰酸官能預聚物。此預聚物併入至少一種可溶於分散液介質之多活性氫化合物。較佳地,使用磺酸化化合物。磺酸基團併入預聚物,而非經由尿素部分。
美國專利第6,106,813號揭示了適用於化妝用品之聚酯聚胺基甲酸酯。其揭示了一新的聚酯聚胺基甲酸酯家族,不僅具有良好成膜性質亦給予良好的硬性以及可藉由水及清潔劑移除之優良抗性。有關頭髮造型/頭髮定型應用,該專利之實例顯示此發明僅用於聲稱良好造型保持性之頭髮造型液。
然而,此參考文獻並無提及對頭髮之黏性或如何達到具良好水可移除性之優良耐濕性。其亦未提及頭髮造型/頭髮定型聚合物之重要屬性,例如自然的觸感及頭髮光澤。
因此,本發明之目的係提供能增進對頭髮之黏性及亦顯示優良捲度及造型保持性、自然觸感及外觀之聚合物組合物。
本發明係提供展現對頭髮之優良黏性之組合物。相較於市售的頭髮定型聚胺基甲酸酯分散液,本發明組合物明顯地較不會或不會形成薄片。此外,相較於上述的聚胺基甲酸酯分散液,本發明提供增進的耐濕性、較高光澤及自然觸感。
本發明係關於製備適用於個人保養品之水性聚胺基甲酸酯分散液之方法,包括:1)製備下式之預聚物:
其中R1
代表聚碳酸酯多元醇之二價基,R2
代表脂族或環脂族聚異氰酸之基,R3
代表低分子量二醇之基,視需要經離子基團取代,n為1至5,及m係>1;
藉由下列反應:1a)至少一聚碳酸酯多元醇,1b)一或多個脂族或環脂族多異氰酸酯,及1c)至少一低分子量二醇(視需要經離子基團取代);2)將該預聚物與至少一種數目平均分子量低於約3,000之單羥基-官能聚環氧烷反應,3)有機溶劑存在下,使用下列鏈延長劑延長該預聚物之鏈以形成聚胺基甲酸酯:3a)至少一種下式之鏈延長劑:H2
N-R4
-NH2
其中R4
代表未經離子基團或視需要離子基團取代之伸烷基或環氧烷,及3b)視需要至少一種下式之鏈延長劑:H2
N-R5
-NH2
其中R5
代表經離子基團或潛在離子基團取代之伸烷基,4)將該聚胺基甲酸酯分散於水中;及5)移除有機溶劑,產生水性聚胺基甲酸酯分散液;其中該單羥基-官能聚環氧烷組成介於約0.1重量%至約5重量%之聚胺基甲酸酯。
如用於文中及下列申請專利範圍,除非另有指出,否
則術語「分子量」應係指數目平均分子量。
適合提供二價基R1
之聚碳酸酯多元醇為具有至少二個羥基團及具有平均分子量從約700至約16,000之聚碳酸酯多元醇,以及較佳為約750至約5000。
含羥基團之聚碳酸酯包括本身已知之聚碳酸酯,例如取自如丙二醇-(1,3)、丁二醇-(1,4)及/或己二醇-(1,6)、二乙二醇、雙酚-A、三乙二醇或四乙二醇之二醇類與例如二苯基碳酸酯、二甲基碳酸酯、二乙二醇碳酸酯或光氣(phosgene)之碳酸二芳酯類反應之產物。
適合提供烴基R2
之聚異氰酸酯包括具有分子量從約112至1,000,及較佳地從約140至約400之有機二異氰酸酯。較佳的二異氰酸酯為以上述所指之通式R2
(NCO)2
表示之異氰酸酯,其中R2
代表具有4至18個碳原子之二價脂族烴基團、具有5至15個碳原子之二價環脂族烴基團、具有7至15個碳原子之二價芳脂族烴基團或具有6-15個碳原子之二價芳香烴基團。適合的有機二異氰酸酯之實例包括四亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、環己烷-1,3-及-1,4-二異氰酸酯、1-異氰酸基-3-異氰酸基-甲基-3,5,5-三甲基環己烷(異佛爾酮二異氰酸酯或IPDI)、雙-(4-異氰酸酯環己基)-甲烷、4,4'-二異氰酸基二環己基丙烷-(2,2')、1,3-及1,4-雙(異氰酸甲基)-環己烷、雙-(4-異氰酸基-3-甲基-環己基)-甲烷、甲苯二異氰酸酯(TDI)之異構物例如2,4-二異氰酸基甲苯、2,6-二異氰酸基甲苯、這些異構物之混合物、氫化TDI、4,4'-二異
氰酸基二苯基甲烷及其帶有2,4'-和視需要2,2'-二異氰酸基二苯基甲烷之異構混合物,以及1,5-二異氰基萘。當然可使用二異氰酸酯之混合物。較佳的二異氰酸酯為脂族及環脂族二異氰酸酯。特佳地為1,6-六亞甲基二異氰酸酯及異佛爾酮二異氰酸酯。
低分子量二醇使用時通常產生聚合物鏈的硬化。「低分子量二醇」係指具有分子量從約62至700,較佳地62至200之二醇。至少一種低分子量二醇含有離子或潛在離子基團。含離子或潛在離子基團之適合的低分子量二醇為該等揭示於美國專利第3,412,054號之二醇。較佳的化合物包括二甲基醇丁酸(DMBA)、二甲基醇丙酸(DMBA)及含羧基的己內酯聚酯二醇。含離子或潛在離子基團之低分子量二醇係以使在聚胺基甲酸酯分散液中每克聚胺基甲酸酯存有<0.30meq的COOH之量來使用。
可視需要使用不含離子基團或潛在離子基團之其他低分子量二醇。其可含脂族或脂環族或芳香族基團。較佳的化合物僅含有脂族基團。每個分子具有高至20個碳原子之低分子量二醇包括乙二醇、二乙二醇、1,2-二醇、丙1,3-二醇、丁1,4-二醇、丁烯1,3-二醇、新戊二醇、丁基乙基丙二醇、環己二醇、1,4-環己基二甲醇、己1,6-二醇、雙酚A(2,2-雙(4-羥基-苯基)丙烷)、氫化雙酚A(2,2-雙(4-羥基環己基)-丙烷)及其混合物。
適用於本發明之單羥基-官能聚環氧烷化合物包括以環氧乙烷或環氧丙烷或二者為主之任何具有數目平均分子量低於約3,000之單羥基-官能聚酯,較佳為300至3,000。
適合的化合物包括Desmophen®LB-25,一種來自賓州匹茲堡拜耳材料科技公司之環氧乙烷/聚環氧乙烷一醇、來自密西根州密特蘭市陶氏化學公司之甲氧基聚乙二醇CARBOWAX SENTRY線、以及同樣來自陶氏化學公司之UCON LB液及UCON 50-HB液。單羥基-官能化合物之使用量為使經由胺基甲酸酯段併入預聚物之聚環氧烷基佔聚胺基甲酸酯之約0.1重量%至約5重量%之間。
預聚物可使用至少一種,視需要二種鏈延長劑將鏈延長。第一,使用具有下式之化合物:H2
N-R4
-NH2
其中R4
代表未經離子或潛在離子基團取代之伸烷基或環氧烷基。伸烷基二胺類包括肼、乙二胺、丙二胺、1,4-丁二胺及哌、2-甲基-1,5-戊二胺(來自杜邦公司之Dytek A)、己二胺、異佛樂酮二胺及4,4-亞甲基二(環己胺)。環氧烷二胺類包括二丙胺二乙二醇(賓州阿靈頓空氣產品公司之Ancamine®1922A)以及空氣產品公司之ANCAMINE系列醚胺類,包括二丙胺丙二醇、二丙胺二丙二醇、二丙胺三丙二醇、二丙胺聚(丙二醇)、二丙胺乙二醇、二丙胺聚(乙二醇)、二丙胺1,3-丙二醇、二丙胺2-甲基-1,3-丙二醇、二丙胺1,4-丁二醇、二丙胺1,3-丁二醇、二丙胺1,6-己二醇及二丙胺環己-1,4-二甲醇。亦可使用所列的二胺類之混合物。第一類鏈延長劑可具有從約100至1500之分子量,較佳為約170至1000。
視需要第二類的鏈延長劑為具有下式之化合物:
H2
N-R5
-NH2
其中R5
代表經離子或潛在離子基團取代之伸烷基。此等化合物具有一離子或潛在離子基及二個與異氰酸酯基團反應之基團。此等化合物含有二個異氰酸酯反應性基團及一個離子集團或能形成離子基團之基團。離子或潛在離子基團可由下列組成之群中選出:三級或四級銨基團、可轉變為此基團之基團、羧基團、羧酸鹽基團、磺酸基團及磺酸鹽基團。至少部分可轉化為所提及類型鹽基團之基團的轉化可在與水混合之前或混合期間進行。特定的化合物包括二胺基磺酸鹽類,例如N-(2-胺基乙基)-2-胺基乙烷磺酸之鈉鹽或N-(2-胺基乙基)-2-胺基丙酸之鈉鹽。第二類的鏈延長劑可具有從約32至600之分子量,較佳為約32至200。
本發明之聚胺基甲酸酯亦可包括各別位於鏈末端及終止該鏈(鏈終止劑)之化合物。這些鏈終止劑可衍生自具有下式之化合物:
其中R6
為H原子或視需要具有羥基末端之伸烷基,而R7
為視需要具有羥基末端之伸烷基。適合的化合物包括例如單胺類,特別是單二級胺類或單醇類。實例包括:甲胺、乙胺、丙胺、丁胺、辛胺、月桂胺、硬脂胺、異壬基氧基-丙基胺、二甲胺、二乙胺、二丙胺、二丁胺、N-甲基胺
基-丙基胺、二乙基(甲基)胺基丙基胺、嗎啉、哌啶、二乙醇胺及其適合的經取代衍生物、二初級胺類及單羧酸類之醯胺胺類、二初級胺之單酮胺(monoketime)、初級/三級胺類例如N,N-二甲基胺基-丙基胺及其類似物之化合物。同樣適合的除了鏈終止醇類,例如,C1
-C10
或高級醇類,包括甲醇、丁醇、己醇、2-乙基己基醇、異癸醇及其類似物和甚至其混合物,還有胺基-醇類,例如胺基甲基丙醇(AMP)。鏈終止劑可具有從約31至600之分子量,較佳為約31至200。
在本發明一實施例中,二乙二醇係經由使用二丙胺-二乙二醇("DPA-DEG")併入聚胺基甲酸酯分散液中,作為低分子量二醇或非離子鏈延長劑之部分。若二乙二醇用作為低分子量二醇,則較佳地該DPA-DEG不作為非離子鏈延長劑使用。同樣地,若該DPA-DEG用作為非離子鏈延長劑,則二乙二醇較佳地不作為低分子量二醇使用。當聚胺基甲酸酯分散液併入頭髮定型劑時,特別希望使用二乙二醇或DPA-DEG,因為二乙二醇明顯地增加對頭髮的黏性。
本發明亦關於製造適用於個人保養品之聚胺基甲酸酯分散液之方法,包括a)第一步驟將至少聚碳酸酯多元醇與異氰酸酯反應,形成預聚物A),然後b)第二步驟將預聚物溶於有機溶劑中,c)第三步驟中將含異氰酸酯之預聚物溶液與二種鏈延長劑及(視需要)鏈終止劑反應,d)第四步驟藉由加入水形成分散液,及e)第五步驟移除有機溶劑。
將併入的游離磺酸基團及羧酸基團於第二和第三步驟間,或第三和第四步驟間中和。適合的中和劑包括初級、二級、三級胺類。其中以經三烷基取代之三級胺類為較佳的。這些胺類之實例有三甲胺、三乙胺、三異丙胺、三丁胺、N,N-二甲基-環己胺、N,N-二甲基硬脂胺、N,N-二甲基-苯胺、N-甲基嗎啉、N-乙基嗎啉、N-甲基哌、N-甲基哌啶、N-甲基哌啶、N,N-二甲基-乙醇胺、N,N-二乙基-乙醇胺、三乙醇胺、N-甲基二乙醇胺、二甲基胺基丙醇、2-甲氧基乙基二甲基胺、N-羥基乙基-哌、2-(2-二甲基胺基乙氧基)-乙醇及5-二乙基胺基-2-戊酮。最佳的三級胺類為該等不含有如澤爾維季諾夫(Zerewitinoff)試驗所測定之活性氫,因為其能與預聚物之異氰酸酯反應,而造成膠化、形成不溶性粒子或將鏈終止。
本發明之聚胺基甲酸酯分散液可藉由所謂的丙酮法來製造。在丙酮法中,以本發明分散液為基底之水性聚胺基甲酸酯製備物的合成,係以多階段方法來進行。
在第一階段,由聚碳酸酯多元醇、二異氰酸酯及低分子量二醇合成含異氰酸酯基團之預聚物。個別組份之量係以使預聚物中異氰酸酯含量介於1.4至5.0重量%間之方式來計算,較佳介於2.0至4.5重量%間,以及特佳介於2.6至4.0重量%間。以NCO當量為基準,低分子量二醇係以0至80當量%之量存在,較佳為0至10當量%。
產生的預聚物具有下列結構:
其中R1
代表聚碳酸酯多元醇之二價基,R2
代表脂族或環脂族聚異氰酸酯之烴基,R3
代表低分子量二醇之基,視需要經離子基團取代,n為<5,及m係>1;較佳地,n為1至3,而m為1至5。
然後,將預聚物與數目平均分子量低於約3,000之單羥基-官能聚環氧烷反應。
在第二階段,將階段1產生的預聚物溶於不含異氰酸酯反應基團之有機、至少部分可與水混合之溶劑中。較佳的溶劑為丙酮。然而,其他的溶劑,例如2-丁酮、四氫呋喃或二噁烷或這些溶劑之混合物亦可使用。所用之溶劑之量必須以得到25至60重量%之固體含量的方式來計算,較佳30至50重量%,特佳35至45重量%。
在第三階段,將含異氰酸酯預聚物溶液與胺基-官能鏈延長劑及視需要的鏈終止劑之混合物反應,以形成高分子量聚胺基甲酸酯。使用足量的鏈延長劑及鏈終止劑使得產生的聚胺基甲酸酯所計算的數目平均分子量(Mn)介於10,000至100,000道爾頓,較佳地介於10,000至50,000道爾頓。以存在於預聚物中之NCO當量的殘餘量為基準,
該離子或非離子鏈延長劑係以從15至98當量%,較佳為35至80當量%之總量存在。以存在於預聚物中之NCO當量的殘餘量為基準,鏈延長劑係以從0至35當量%之量存在,較佳為10至20當量%。
在第四階段,將高分子量之聚胺基甲酸酯藉由添加水至溶液中或將溶液加入水中以細粒分散液形式分散。
在第五階段,以蒸餾,視需要於減壓下,將有機溶劑部分或全部移除。在階段四中,水量係以使本發明水性聚胺基甲酸酯分散液顯現20至60重量%之固體含量之方式來計算,較佳為28至42重量%。
本發明之聚胺基甲酸酯分散液適用於個人保養品。較佳地,其係用於非氣溶膠頭髮定性劑。此等頭髮定型劑可藉由添加水或乙醇至分散液中容易地製備。同樣地,藉由添加嫻熟本項技藝者所熟知之組份,此等分散液可用於製備其他個人保養品,例如防曬乳、皮膚保養品、口紅、睫毛膏及除臭劑。
Desmophen® C-2200(以己二醇為主之聚碳酸酯,M/wt.2000,OH No.56;賓州匹茲堡拜之耳材料科技公司)。
Desmodur® W(二環己基甲烷-4,4'-二異氰酸酯,NCO含量31.8%,賓州匹茲堡之拜耳材料科技公司)。
Desmodur® I(異佛爾酮二異氰酸酯,NCO含量37.5%,賓
州匹茲堡之拜耳材料科技公司)。
Desmophen® LB-25(環氧乙烷/聚環氧乙烷一醇,M/wt.2220,賓州匹茲堡之拜耳材料科技公司)。
Acclaim® 4200(以環氧丙烷為主之聚醚二醇,M/wt.2,000,賓州匹茲堡之拜耳材料科技公司)。
PPG 425(以環氧丙烷為主之聚醚二醇,M/wt.425,賓州匹茲堡之拜耳材料科技公司).
Ancamine® 1922A(二丙胺-二乙二醇,賓州阿靈頓之空氣產品公司)。
Kathon® LX(殺生物劑,賓州費城羅門哈斯公司)。
Microcare® MTG(殺生物劑,英國柴郡之索爾公司)。
將25.74克的Desmophen® C-2200、0.18克新戊二醇及0.62克的DMBA於75℃燒瓶中共同混合,以取得均質的混合物。將4.31克的Desmodur® W及3.65克的Desmodur® I於70℃添加到燒瓶中。在95℃進行反應直到實際的NCO含量變得較低於或等於理論的NCO。然後加入0.7克的Desmophen® LB-25並反應直到實際的NCO變成恆定。將預聚物冷卻至60℃,並將60克丙酮加入反應燒瓶中。將澄清的預聚物溶液混合15分鐘,同時冷卻至40℃。將0.43克的三乙胺於40℃加到預聚物中並混合10分鐘。接著於40℃加入2.65克的Ancamine® 1922A溶於15克蒸餾水之溶液,進行鏈延長步驟。15分鐘後,於室溫
將61.34克的蒸餾水以600 rpm攪拌下加至預聚物中。當分散液變得太黏稠時加入額外的水。分散階段後接著蒸餾丙酮。待蒸餾完全後,加入0.38克的Microcare® MTG。
實例2-5係使用與實例1相同之製程所製備。
使用去離子水及本發明之聚胺基甲酸酯分散液製備非氣溶膠頭髮定型劑調配物。藉由混合10份的聚胺基甲酸酯及90份水,調配物為4份的聚胺基甲酸酯分散液活性樹脂固體。含3%活性樹脂固體之非氣溶膠噴霧調配物(20毫升)係如下製備:((3/%固體PUD)x 20毫升)/100=溶於(20-X)克水之X克的PUD。
捲度保持性試驗依照詳述於美國專利第5,626,840號之試驗方法來進行。使用細霧噴霧瓶來施行。所使用之樣本頭髮為Yaki棕髮,8英吋,顏色4。捲度保持性試驗係如下進行。將頭髮剪成各~2克的樣品並將一端綁在一起。各樣本以潔淨洗髮精之10%溶液清洗30秒並以溫自來水沖洗。將各樣本之頭髮由繫緊端剪成6英吋長度。然後將頭髮再次弄濕並梳整,及將過量的水擠出。將頭髮樣本弄捲及捲在直徑1/2英吋的捲子上,並於49℃乾燥大概1小時。將乾燥的頭髮自捲子移出並將產生的髮捲由綁繫端懸掛。測量各樣本之髮捲高度。
各髮捲每邊一律噴4次。將髮捲放在鋁盤上並置於49℃烘箱中烘約30分鐘至乾。然後將乾燥的髮捲懸掛起,並測量時間0分鐘之髮捲長度,並置入22℃、95% R.H.
之Thermotron高溫震盪培養箱中。24小時後測量髮捲高度。
捲度保持性係如下算式:%捲度保持性=[(L-L 1 )/(L-L o )]x100
其中L為頭髮的全長,6英吋。
Lo
為噴霧及暴露前之髮捲長度,及L1
為噴霧及暴露後之髮捲長度。
造型保持性係如下評估:暴露於高溼度24小時後,將髮捲梳整10次。造型保持性係以髮捲保持其起初的形狀及長度之能力為基準來判別。在大多數的案例中,髮捲仍不受梳整影響。
觸感係如下評估:將未處理的頭髮及以PUD處理之頭髮提出給10位評審之審查團。要求評審將觸感分成1-5,1為無顯示聚合物存在之最自然柔軟觸感。
對頭髮之黏性係以梳子通過經處理的頭髮來評估,並以肉眼觀察梳子及頭髮成片狀及殘留。
如所見,根據本發明實例1,在有關對頭髮黏性及觸感上得到令人驚訝良好之結果,而仍提供有關捲度及造型保持性之優良結果。
防曬乳係使用實例1之聚胺基甲酸酯分散液調配,並具有30+之SPF等級:
此防曬液具有完美的防水性質,使用滑順及具有良好觸感。再者,此防曬液不具有球化效應(balling effect)。
雖然本發明已以說明為目的詳細描述於前文中,但應
了解,此詳細說明僅用做該目的,且除了可能受限於申請專利範圍外,在不悖離本發明精神及範圍下,熟習本項技術者可在其中做變化。
Claims (16)
- 一種製備適用於個人保養品之水性聚胺基甲酸酯分散液之方法,包括:1)製備根據下式之預聚物:
- 如申請專利範圍第1項之方法,其中該方法進一步包含以至少一種根據下式之化合物終止該預聚物之鏈長:
- 如申請專利範圍第2項之方法,其中用於鏈終止之該化合物係由下列組成之群中選出:甲胺、乙胺、丙胺、 丁胺、辛胺、月桂胺、硬脂胺、二甲胺、二乙胺、二丙胺、二丁胺、嗎啉、哌啶及二乙醇胺、N,N-二甲基胺基-丙基胺、胺基甲基丙醇及其混合物。
- 如申請專利範圍第1項之方法,其中用於鏈終止之該化合物係由下列組成之群中選出:異壬基氧基-丙基胺、N-甲基胺基丙基胺、二乙基(甲基)胺基-丙基胺、二初級胺類及單羧酸類之醯胺胺類、二初級胺之單酮胺類(monoketime)、甲醇、丁醇、己醇、2-乙基己基醇、異癸醇及其混合物。
- 如申請專利範圍第1項之方法,其中該一或多種聚異氰酸酯係由下列組成之群中選出:四亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、環己烷-1,4-二異氰酸酯、1-異氰酸基-3-異氰酸基-甲基-3,5,5-三甲基環己烷(異佛爾酮二異氰酸酯)、雙-(4-異氰酸酯環己基)-甲烷、4,4'-二異氰酸基二環己基丙烷-(2,2')及其混合物。
- 如申請專利範圍第1項之方法,其中該分子量為62至700之二醇係由下列組成之群中選出:乙二醇、二乙二醇、丙-1,2-二醇、丙1,3-二醇、丁1,4-二醇、丁烯1,3-二醇、環己二醇、1,4-環己基二甲醇、己1,6-二醇、雙酚A(2,2-雙(4-羥基苯基)丙烷)、氫化雙酚A(2,2-雙(4-羥基環己基)丙烷)及其混合物。
- 如申請專利範圍第1項之方法,其中該分子量為62至700之二醇係由二甲基醇丁酸及二甲基醇丙酸組成 之群中選出。
- 如申請專利範圍第3或4項之方法,其中該分子量為62至700之二醇係由二甲基醇丁酸及二甲基醇丙酸組成之群中選出。
- 如申請專利範圍第1項之方法,其中該鏈延長劑3b)為N-(2-胺基乙基)-2-胺基乙烷磺酸之鈉鹽。
- 如申請專利範圍第1項之方法,其中該單羥基-官能聚環氧烷化合物為具有約2220之數目平均分子量之聚環氧乙烷一醇。
- 如申請專利範圍第1項之方法,其中n為1至3,而m為1至5。
- 如申請專利範圍第1項之方法,其中R3 為二乙二醇之基或R4 為4,7,10-三氧雜-1,13-十三烷二胺之基。
- 一種水性聚胺基甲酸酯分散液,其係藉由申請專利範圍第1項之方法取得。
- 一種頭髮定型劑,其係包含申請專利範圍第13項之聚胺基甲酸酯分散液及水。
- 一種頭髮定型劑,其係包含申請專利範圍第13項之聚胺基甲酸酯分散液及乙醇。
- 一種防曬乳,其係包含申請專利範圍第1項之聚胺基甲酸酯分散液。
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KR20090015842A (ko) | 2009-02-12 |
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US7452525B1 (en) | 2008-11-18 |
CN101361701A (zh) | 2009-02-11 |
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