CN113873989B - 协同抗炎组合物 - Google Patents
协同抗炎组合物 Download PDFInfo
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- CN113873989B CN113873989B CN202080038777.0A CN202080038777A CN113873989B CN 113873989 B CN113873989 B CN 113873989B CN 202080038777 A CN202080038777 A CN 202080038777A CN 113873989 B CN113873989 B CN 113873989B
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- Prior art keywords
- oxide
- cas
- pyridinol
- composition
- azoxystrobin
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Abstract
本发明涉及一种个人护理组合物，该个人护理组合物包含：a)嘧菌酯；b)2‑吡啶酚‑N‑氧化物材料，其中a:b的比率为约4:1至约1:50；其中存在协同抗炎/细胞应激活性。
Description
技术领域
本发明涉及个人护理组合物，该个人护理组合物包含展示出协同抗炎活性的2-吡啶酚-N-氧化物材料和嘧菌酯。
背景技术
毛发、头皮和皮肤的最佳健康取决于细胞应激的控制和通过适当的保护机制抵消或去除侵害的能力。细胞应激可以通过反应性氧物质、污染、毒素、微生物、机械或化学侵害以及几种其它外在或内在因素来触发。延长、未解决或高水平的细胞应激表现出具有可见的损伤迹象(例如，毛发损失、毛发或皮肤色素沉着损失、头皮或皮肤干燥、片落、瘙痒)的毛发、头皮或皮肤健康的下降，以及加速和时程衰老两者。对病理性应激的细胞应答会在炎症上汇聚，因为主要的常见机制和过度炎症促成减少健康和几种应激相关病症。皮肤的慢性炎性病症(如头皮屑和痤疮)具有广泛的患病率，并且两者均涉及皮肤上的微生物，所述微生物产生触发和加剧炎症的物质。
需要改进的产品，该产品搞定和解决皮肤、头皮和毛发的慢性病症中的炎症和细胞应激。还期望个人护理产品减少细胞应激并提供消费者以更健康、毛发、头皮和皮肤以及增强的抗衰老有益效果。
发明内容
本发明涉及一种个人护理组合物，该个人护理组合物包含：a)嘧菌酯；b)2-吡啶酚-N-氧化物材料，其中a:b的比率为约4:1至约1:50；其中存在协同抗炎/细胞应激活性。
具体实施方式
除非另外指明，否则本文中使用的所有百分比和比率均按总组合物的重量计。除非另外指明，所有测量均被理解为是在环境条件下进行，其中“环境条件”是指在约25℃下，在约一个大气压下，并且在约50％相对湿度下的条件。所有数值范围是包括端值在内的更窄的范围；所描述的范围上限和下限是可组合的，以形成没有明确描述的另外的范围。
本发明的组合物可包含本文所述的基本组分以及任选的成分，基本上由其组成或由其组成。如本文所用，“基本上由...组成”是指组合物或组分可包含附加成分，只要附加成分不在本质上改变受权利要求书保护的组合物或方法的基本特征和新颖特征。
如本文所用，“包括/包含”是指可加入不影响最终结果的其它步骤和其它成分。该术语涵盖术语“由……组成”和“基本上由……组成”。
如本文所用，“混合物”旨在包括物质的简单组合以及由它们的组合所可能产生的任何化合物。
如本文所用，除非另外指明，否则“分子量”是指重均分子量。分子量使用工业标准方法、凝胶渗透色谱法(“GPC”)测量。
在给定含量范围的情况下，这些应当被理解为组合物中所述成分的总量，或在多于一种物质落入成分定义的范围内的情况下，组合物中所有成分的总量符合所述定义。
除非另外说明，否则所有百分比、份数和比率均基于本发明的组合物的总重量。所有涉及所列成分的这些重量均基于活性物质的含量，并且因此不包括可能包含在可商购获得的物质中的载体或副产物。
除非另外指明，否则所有组分或组合物水平均是就该组分或组合物的活性部分而言，且不包括可能存在于此类组分或组合物的可商购获得的来源中的杂质，例如残余溶剂或副产物。
应当理解，贯穿本说明书给出的每一最大数值限度包括每一较低数值限度，如同此类较低数值限度在本文中明确写出。贯穿本说明书给出的每一最小数值限度将包括每一较高数值限度，如同此类较高数值限度在本文中明确写出。贯穿本说明书给出的每一数值范围将包括落在此类较宽数值范围内的每一较窄数值范围，如同此类较窄的数值范围全部在本文中明确写出。
嘧菌酯和其它嗜球果伞素
嘧菌酯，CAS号：131860-33-8，IUPAC：甲基-(E)-(2-{2[6-(2-氰基苯氧基)-嘧啶-4-基氧]-苯基}-3-甲氧基丙烯酸酯是属于嗜球果伞素类的农业杀真菌剂。嗜球果伞素是通过各种担子菌诸如嗜球果伞(Strobilurus tenacellus)和粘小奥德蘑(Oudemansiellamucida)生物合成的，或者在天然的嗜球果伞素之后进行建模并且用保留关键的β-甲氧基丙烯酸酯毒簇合成。一些合成的嗜球果伞素具有经修饰的毒簇，例如甲氧基亚胺乙酸甲酯或甲基-N-甲氧基氨基甲酸酯。一些合成的嗜球果伞素是嘧菌酯(CAS号：131860-33-8)、丁香菌酯(CAS号850881-70-8)、醚菌胺(CAS号149961-52-4)、烯肟菌酯(CAS号238410-11-2)、氟嘧菌酯(CAS号193740-76-0)、醚菌酯(CAS号143390-89-0)、mandestrobin(CAS号173662-97-0)、苯氧菌胺(CAS号133408-50-1)、肟醚菌胺(CAS号248593-16-0)、啶氧菌酯(CAS号117428-22-5)、唑菌酯(CAS号862588-11-2)和肟菌酯(CAS号141517-21-7)。
嘧菌酯和其它合成的嗜球果伞素控制广谱植物真菌疾病，并且在全球的作物保护中频繁使用。嗜球果伞素通过抑制线粒体呼吸而发挥作用。嘧菌酯和其它嗜球果伞素的特定作用模式是通过结合电子传输链的细胞色素b复合物III中的泛醇氧化位点(Q0位点)和阻断细胞色素b和细胞色素c1之间的电子转移而进行的。具有这种特定作用模式的其它化合物包括：同样首次从粘小奥德蘑分离的被称为小奥德蘑素的关键β-甲氧基丙烯酸酯毒簇的合成和天然存在的衍生物，来自粘细菌诸如Myxococcus flavus的合成和天然存在的粘噻唑，来自粘细菌诸如Stigmatella aurantica的stigmatellin，以及合成农业化学品噁唑菌酮和咪唑菌酮。
嘧菌酯作为农业杀真菌剂具有保护性、治愈性、根除性、跨层转移和全身性质，并且抑制孢子发芽和菌丝体生长，并且还显示抗孢子活性。在标记的应用速率下，嘧菌酯控制许多植物病原体，包括温带禾谷类作物上的小麦白粉病菌(Erysiphe graminis)、柄锈菌属(Puccinia spp.)、Lepiosphaeria nodorum、小麦壳针孢叶枯病菌(Septoria tritici)和圆核腔菌(Pyrenophora teres)；稻上的稻瘟病菌(Pyricularia oryzae)和立枯丝核菌(Rhizoctonia solani)；藤本植物上的霜霉病菌(Plasmopara viticola)和葡萄钩丝壳菌(Uncinula necator)；葫芦科植物上的黄瓜白粉病菌(Sphaerotheca fuliginea)和黄瓜霜霉病菌(Pseudoperonospora cubensis)；马铃薯和番茄上的马铃薯晚疫病菌(Phytophthora infestans)和番茄早疫病菌(Alternaria solani)；花生上的落花生球腔菌(Mycosphaerella arachidis)、立枯丝核菌(Rhizoctonia solani)和齐整小核菌(Sclerotium rolfsii)；桃上的褐腐病菌(Monilinia spp)和嗜果枝孢(Cladosporiumcarpophilum)；草皮上的腐霉属(Pythium spp.)和立枯丝核菌(Rhizoctonia solani)；香蕉上的球腔菌属(Mycosphaerella spp.)；山胡桃上的Cladosporium caryigenum；柑橘上的fawcetii、炭疽菌属(Colletotrichum spp.)和柑橘茎点霉(Guignardiacitricarpa)；咖啡豆上的炭疽菌属(Colletotrichum spp.)和咖啡锈菌(Hemileiavastatrix)。嘧菌酯是具有低水中溶解度的固体材料。
一些用于嘧菌酯的商品名包括ABOUND FLOWABLE FUNGICIDE、Aframe、Azoxystar、Azoxyzone、AZteroid 1.65 SC Fungicide、AZURE AGRICULTURAL FUNGICIDE、Endow、QUADRIS FLOWABLE FUNGICIDE、Satori Fungicide、Strobe 2L和Willowood Azoxy 2SC。嘧菌酯可从例如Sigma-Aldrich(St.Louis,MO)和Ak Scientific,Inc(Union City,CA)商购获得。
在本发明中，所述个人护理组合物可包含约0.02％至约10％的嘧菌酯；约0.05％至约2％的嘧菌酯；约0.1％至约1％的嘧菌酯。
在本发明中，所述个人护理组合物可包含约0.02％至约10％的嗜球果伞素；约0.05％至约2％的嗜球果伞素；约0.1％至约1％的嗜球果伞素。
2-吡啶酚-N-氧化物材料
适用于本发明的2-吡啶酚-N-氧化物材料包括取代或未取代的2-吡啶酚-N-氧化物材料或其盐。该材料的互变异构体例如1-羟基-2(1H)-吡啶酮包括在本发明范围内。取代或未取代的2-吡啶酚-N-氧化物材料及其对应的互变异构形式1-羟基-2(1H)-吡啶酮示于下文中：
其中R1、R2、R3、R4基团独立地选自H、Cl、Br、I、F、NO、NO2和(CH2)nG，其中每个G独立地选自(O)mSO3M3、(O)mCO2M3、(O)mC(O)(R5)、(O)mC(O)N(R5R6)、(O)mCN、(O)m(R5)和N(R5R6)，其中m为0或1，n为0至4的整数，R5和R6独立地选自H以及取代或未取代的C1-C12有机基团，并且M3选自H、取代或未取代的C1-C12有机基团、+N(R7R8R9R10)和1/q M’q+，其中M’选自带电荷q的碱金属和带电荷q的碱土金属，其中R7、R8、R9和R10独立地选自H以及取代或未取代的C1-C12有机基团，并且其中任何一对邻位基团R1与R2、R2与R3、R3与R4可结合在一起，以形成任选地被选自Cl、Br、I、F、NO、NO2、CN、(CH2)nG、以及它们的混合物的一个或多个基团所取代的另一个五-或六-元芳族或脂族环。合适的有机基团包括(C1-C12)烷基、(C2-C12)烯基和(C2-C12)炔基。有机基团可任选是取代的，并且合适的取代基包括羟基基团、羧基基团和氨基基团。2-吡啶酚-N-氧化物还被称为例如2-羟基吡啶-N-氧化物、2-吡啶酚-1-氧化物、或2-羟基吡啶-1-氧化物。
在某些方面，2-吡啶酚-N-氧化物材料为根据上式的2-吡啶酚-N-氧化物材料或其互变异构体，其中R1、R2、R3、R4独立地选自H、Cl和(CH2)nG，其中G独立地选自(O)mSO3M3、(O)mCO2M3、(O)mC(O)(R5)、(O)mCN和(O)m(R5)，其中m为0或1。在其他方面，2-吡啶酚-N-氧化物材料为根据上式的2-吡啶酚-N-氧化物材料，其中R1、R2、R3、R4独立地选自H、SO3M3和CO2M3。在其他方面，R1、R2、R3、R4独立地选自H、SO3M3和CO2M3，其中不超过一个R1、R2、R3、R4为SO3M3或CO2M3。
在某些方面，2-吡啶酚-N-氧化物材料为取代或未取代的2-吡啶酚-N-氧化物材料的盐。在这些方面，2-吡啶酚-N-氧化物材料中羟基基团的氢可被合适的电荷平衡阳离子取代。在这些方面，取代氢的阳离子的非限制性示例包括Na、Li+、K+、1/2Mg2+或1/2Ca2+、取代的铵(如C1-C6链烷醇铵、单乙醇胺(MEA)、三乙醇胺(TEA)、二乙醇胺(DEA))、或它们的任何混合物。在某些方面，在溶液中，阳离子可与2-吡啶酚-N-氧化物或1-羟基-2(1H)-吡啶酮阴离子解离。
在某些方面，2-吡啶酚-N-氧化物材料为取代或未取代的2-吡啶酚-N-氧化物材料。可用于本文的盐包括由多价金属钡、铋、锶、铜、锌、镉、锆、以及它们的混合物所形成的那些。
在一些方面，2-吡啶酚-N-氧化物材料选自：6-羟基-3-吡啶磺酸，1-氧化物(CAS191672-18-1)；2-吡啶酚-1-氧化物(CAS 13161-30-3)；2-羟基-4-吡啶羧酸，1-氧化物(CAS13602-64-7)；5-乙氧基-2-吡啶酚，2-乙酸根，1-氧化物(CAS 51984-49-7)；1-(3-羟基-2-氧代-4-异喹啉基)-乙酮(CAS 65417-65-4)；6-羟基-3-吡啶羧酸，1-氧化物(CAS 90037-89-1)；2-甲氧基-4-喹啉甲腈，1-氧化物(CAS 379722-76-6)；2-吡啶羧酸，6-羟基-，1-氧化物(CAS 1094194-45-2)；3-吡啶羧酸，2-羟基-，1-氧化物(CAS 408538-43-2)；2-吡啶酚，3-硝基-，1-氧化物(CAS 282102-08-3)；3-吡啶丙腈，2-羟基-，1-氧化物(193605-60-6)；3-吡啶乙醇，2-羟基-，3-乙酸根，1-氧化物(CAS 193605-56-0)；2-吡啶酚，4-溴-，1-氧化物(CAS170875-41-9)；2-吡啶酚，4,6-二溴-，2-乙酸根，1-氧化物(CAS 170875-40-8)；2-吡啶酚，4,6-二溴，1-氧化物(CAS 170875-38-4)；2-吡啶酚，4-(2-氨基乙基)-，1-氧化物(CAS154403-93-7)；2-吡啶酚，5-(2-氨基乙基)-，1-氧化物(CAS 154403-92-6)；3-吡啶丙酸，α-氨基-6-羟基-，1-氧化物(CAS 134419-61-7)；2-吡啶酚，3,5-二甲基，1-氧化物(CAS102074-62-4)；2-吡啶酚，3-甲基-，1-氧化物(CAS 99969-07-0)；2-吡啶酚，3,5-二硝基,1-氧化物(CAS 98136-47-1)；2-吡啶酚，3,5-二溴-，1-氧化物(CAS 98136-29-9)；2-吡啶酚，4-甲基-6-(2-甲基丙基)-，1-氧化物(CAS 91408-77-4)；2-吡啶酚，3-溴-4,6-二甲基-，1-氧化物(CAS 91408-76-3)；2-吡啶酚，4,5,6-三甲基-，1-氧化物(CAS 91408-75-2)；2-吡啶酚，6-庚基-4-甲基-，1-氧化物(CAS 91408-73-0)；2-吡啶酚，6-(环己基甲基)-4-甲基-，1-氧化物(CAS 91408-72-9)；2-吡啶酚，6-溴-，1-氧化物(CAS 89284-00-4)；2-吡啶酚，5-溴-，1-氧化物(CAS 89283-99-8)；2-吡啶酚，3,5-二氯-4,6-二氟-，1-氧化物(CAS 33693-37-7)；2-吡啶酚，3,4,5,6-四氯-，1-氧化物(CAS 32835-63-5)；2-吡啶酚，6-甲基-，1-氧化物(CAS 14420-62-3)；2-吡啶酚，5-硝基-，1-氧化物(CAS 14396-03-3)；2-吡啶酚，4-甲基-5-硝基-，1-氧化物(CAS 13602-77-2)；2-吡啶酚，4-氯-5-硝基-，1-氧化物(CAS 13602-73-8)；2-吡啶酚，4-氯-，1-氧化物(CAS 13602-65-8)；2-吡啶酚，4-硝基-，1-氧化物(CAS13602-63-6)；以及2-吡啶酚，4-甲基-，1-氧化物(CAS 1952-64-3)，以及它们的混合物。这些材料可商购自例如Sigma-Aldrich(St.Louis,MO)和/或Aces Pharma(Branford,CT)。
在某些方面，2-吡啶酚-N-氧化物材料为选自下列的2-吡啶酚-N-氧化物材料：2-羟基吡啶-1-氧化物；3-吡啶羧酸，2-羟基-，1-氧化物；6-羟基-3-吡啶羧酸，1-氧化物；2-羟基-4-吡啶羧酸，1-氧化物；2-吡啶羧酸，6-羟基-，1-氧化物；6-羟基-3-吡啶磺酸，1-氧化物；以及它们的混合物。
在某些方面，2-吡啶酚-N-氧化物材料为选自下列的1-羟基-2(1H)-吡啶酮材料：1-羟基-2(1H)-吡啶酮(CAS 822-89-9)；1,6-二氢-1-羟基-6-氧代-3-吡啶羧酸(CAS677763-18-7)；1,2-二氢-1-羟基-2-氧代-4-吡啶羧酸(CAS l19736-22-0)；1,6-二氢-1-羟基-6-氧代-2-吡啶羧酸(CAS 94781-89-2)；1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2(1H)-吡啶酮(CAS 50650-76-5)；6-(环己基甲基)-1-羟基-4-甲基-2(1H)-吡啶酮(CAS29342-10-7)；1-羟基-4,6-二甲基-2(1H)-吡啶酮(CAS 29342-02-7)；1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2-吡啶酮单乙醇胺(CAS 68890-66-4)；1-羟基-6-(辛基氧基)-2(1H)-吡啶酮(CAS 162912-64-3)；1-羟基-4-甲基-6-环己基-2-吡啶酮乙醇胺盐(CAS41621-49-2)；1-羟基-4-甲基-6-环己基-2-吡啶酮(CAS 29342-05-0)；6-乙氧基-1,2-二氢-1-羟基-2-氧代-4-吡啶羧酸，甲酯(CAS 36979-78-9)；1-羟基-5-硝基-2(1H)-吡啶酮(CAS 45939-70-6)；以及它们的混合物。这些材料可从以下公司商购获得：例如Sigma-Aldrich(St.Louis,MO)、Princeton Building Blocks(Monmouth Junction,NJ)、3BScientific Corporation(Libertyville,IL)、SynFine Research(Richmond Hill,ON)、Ryan Scientific,Inc.(Mt.Pleasant,SC)，和/或Aces Pharma(Branford,CT)。
在某些方面，2-吡啶酚-N-氧化物材料为根据下式的2-吡啶酚-N-氧化物材料或其互变异构体：
其中X是氧或硫部分，R是具有1至20个碳原子的取代或未取代的烃基团。可按照US5,675,013中公开的工序合成这类材料。
在某些方面，2-吡啶酚-N-氧化物材料为根据下式的2-吡啶酚-N-氧化物材料或其互变异构体：
其中R'和R”独立地为氢或具有1至20个碳原子的取代或未取代的烃基团。可按照US 5,675,013中公开的工序合成这类材料。在某些方面，2-吡啶酚-N-氧化物材料为1-羟基-4-甲基-6-(2,4,4-三甲基戊基)-2-吡啶酮单乙醇胺盐，吡罗克酮乙醇胺。
在本发明中，所述个人护理组合物可包含约0.1％至约10％的取代或未取代的2-吡啶酚N-氧化物材料。另选地，所述个人护理组合物可包含约0.3％至约3％的取代或未取代的2-吡啶酚N-氧化物材料。另选地，所述个人护理组合物可包含约0.5％至约2％的取代或未取代的2-吡啶酚N-氧化物材料。
其它抗微生物活性物质
本发明可包含选自吡啶硫酮的多价金属盐的头皮健康剂，并且还可还包含一种或多种抗真菌或抗微生物活性物质。合适的抗微生物活性物质包括煤焦油、硫、怀特菲耳德氏软膏、castellani的颜料、氯化铝、龙胆紫、环已吡酮羟乙胺酮、十一碳烯酸及其金属盐，高锰酸钾、硫化硒、硫代硫酸钠、丙二醇、苦橙油、尿素制剂、灰黄霉素、8-羟基喹啉氯碘羟喹、硫代地巴唑、硫代氨基甲酸盐、卤普罗近、聚烯、羟基吡啶酮、吗啉、苄胺、烯丙胺(诸如特比萘芬)、茶树油、丁香叶油、印楝、胡荽、玫瑰草、小檗碱、百里香红、桂皮油、肉桂醛、香茅酸、日柏酚、磺化页岩油、Sensiva SC-50、Elestab HP-100、壬二酸、溶酶、碘代丙炔基丁基氨基甲酸盐(IPBC)，异噻唑啉酮诸如辛基异噻唑啉酮和唑类、以及它们的组合。在本发明的一个实施方案中，抗微生物剂包括伊曲康唑、酮康唑、硫化硒和煤焦油。
b.硫化硒
硫化硒是适用于本发明抗微生物组合物中的粒状头皮健康剂。硫化硒通常被认为是具有一摩尔硒和两摩尔硫的化合物，尽管它也可为符合通式SexSy的环状结构，其中x+y＝8。如通过前向激光散射装置(例如Malvern 3600仪器)测量的硫化硒的平均粒径通常小于15μm，并且在本发明的一个实施方案中小于10μm。硫化硒化合物描述于例如美国专利2,694,668；美国专利3,152,046；美国专利4,089,945；和美国专利4,885,107中。
c.硫
硫也可用作本发明的抗微生物组合物中的粒状抗微生物/头皮健康剂。
d.角质层分离剂
本发明还可包含一种或多种角质层分离剂，诸如水杨酸。
本发明还可包含表面活性剂可溶性头皮健康剂和粒状头皮健康剂的组合。在一个实施方案中，抗微生物活性物质的组合选自由以下组成的组合：吡罗克酮乙醇胺和吡啶硫酮锌、松焦油和硫、水杨酸和吡啶硫酮锌、水杨酸和新康唑、吡啶硫酮锌和新康唑、吡啶硫酮锌和氯咪巴唑、吡罗克酮乙醇胺和氯咪巴唑、水杨酸和吡罗克酮乙醇胺、以及它们的混合物。
e.附加抗微生物活性物质
本发明的附加抗微生物活性物质可包括白千层属灌木(茶树)和木炭的提取物。本发明还可包含抗微生物活性物质的组合。此类组合可包括吡罗克酮乙醇胺和吡啶硫酮锌组合、松焦油和硫组合、水杨酸和吡啶硫酮锌组合、吡罗克酮乙醇胺和氯咪巴唑组合、以及水杨酸和吡罗克酮乙醇胺组合、吡啶硫酮锌和氯咪巴唑组合、以及它们的混合物。
在一个实施方案中，所述头皮健康剂可以如下量存在：约0.01％至10％，在另一个实施方案中约0.1％至9％，在另一个实施方案中约0.25％至8％，在另一个实施方案中约0.5％至6％。
在一个实施方案中，组合物包含有效量的含锌层状物质。含锌层状材料可为主要在二维平面上具有晶体生长的那些。常规上将层状结构描述为不仅其中所有原子均掺入良好限定的层中的那些，而且其中在层之间存在称为隧道离子(A.F.Wells，“StructuralInorganic Chemistry”Clarendon Press，1975)的离子或分子的那些。含锌层状物质(ZLM)可具有掺入层中的锌和/或可作为隧道离子的组分。以下类别的ZLM代表了总类别中相对常见的示例，并且不旨在对范围更广的符合此定义的材料作出限制。
许多ZLM在自然界以矿物的形式出现。在一个实施方案中，ZLM选自：水锌矿(碳酸锌氢氧化物)、碱式碳酸锌、绿铜锌矿(碳酸锌铜氢氧化物)、斜方绿铜锌矿(碳酸铜锌氢氧化物)、以及它们的混合物。相关的含锌矿物质也可包含于组合物中。天然ZLM也可存在，其中阴离子层物质诸如粘土型矿物质(例如页硅酸盐)含有离子交换的锌隧道离子。所有这些天然物质也可通过合成获得，或在组合物中或在生产过程期间原位形成。
另一种通常但不总是合成获得的常见类别ZLM为层状二元氢氧化物。在一个实施方案中，ZLM为符合式[M2+ 1-xM3+ x(OH)2]x+Am- x/m·nH2O的层状二元氢氧化物，其中二价离子(M2 +)中的一些或全部为锌离子(Crepaldi，EL，Pava，PC，Tronto，J，Valim，JB J.ColloidInterfac.Sci.2002，248，429-42)。
可制备另一类别的ZLM，称为羟基复盐(Morioka，H.，Tagaya，H.，Karasu，M，Kadokawa，J，Chiba，K Inorg.Chem.1999，38，4211-6)。在一个实施方案中，ZLM为符合式[M2 + 1-xM2+ 1+x(OH)3(1-y)]+An- (1＝3y)/n·nH2O的羟基复盐，其中两个金属离子(M2+)可相同或可不同。如果它们相同并且由锌表示，则该式简化为[Zn1+x(OH)2]2x+2x A-·nH2O。后一式代表了(其中x＝0.4)材料诸如羟基氯化锌和碱式硝酸锌。在一个实施方案中，ZLM为羟基氯化锌和/或碱式硝酸锌。这些也涉及水锌矿，其中二价阴离子替换一价阴离子。这些材料还可在组合物中或在生产过程中或生产过程期间原位形成。
在一个实施方案中，组合物包含碱式碳酸锌。碱式碳酸锌的可商购获得的来源包括碱式碳酸锌(Cater Chemicals：Bensenville，IL，USA)、碳酸锌(Shepherd Chemicals：Norwood，OH，USA)、碳酸锌(CPS Union Corp.：New York，NY，USA)、碳酸锌(ElementisPigments：Durham，UK)和碳酸锌AC(Bruggemann Chemical：Newtown Square，PA，USA)。碱式碳酸锌，商业上还可以称作“碳酸锌”或“碳酸锌碱性物”或“羟基碳酸锌”，为合成型式，由与天然存在的水锌矿类似的材料组成。理想的化学计量表示为Zn5(OH)6(CO3)2，但实际化学计量比可稍有不同，并且晶格中可掺有其它杂质。
在一个实施方案中，组合物包含有效量的含锌层状物质。在一个实施方案中，组合物包含按组合物的总重量计约0.001％至约10％、或约0.01％至约7％、或约0.1％至约5％的含锌层状物质。
在具有含锌层状物质和吡啶硫酮或吡啶硫酮的多价金属盐的实施方案中，含锌层状物质与吡啶硫酮或吡啶硫酮的多价金属盐的比率为约5:100至约10:1、或约2:10至约5:1、或约1:2至约3:1。
PGE-2测定
抑制对应激源的细胞炎症应答-前列腺素E2(“PGE2”)测定。
该示例展示了在一定比率下嘧菌酯和吡罗克酮乙醇胺(PO)组合以协同方式抑制PGE2激活的能力。PGE2是已知参与调节炎症的激素样物质。细胞炎症与多种毛发、皮肤和头皮病症相关，并且因此抑制PGE2激活相对于细胞炎症可以有助于处理这些类型的毛发、皮肤和头皮病症。
方法
TERT角化细胞(tKC)是人角化细胞，其已经用人端粒酶逆转录酶基因转染以使细胞永生化。它们获自Jerry Shay,University of Texas,Southwestern，并将它们以40,000个细胞/孔铺板到1ml/孔体积中的24孔板中。将补充有角化细胞生长补充剂(生命技术目录号S-001-5)的EpiLife培养基(生命技术目录号MEPICFPRF500)用作测定培养基。使细胞生长至融合/接近融合(通常在24孔板中铺板40,000个细胞/孔之后24小时)，然后进行15mJ/cm2 UVB-应激(通常在BioSun中14-16暴露时间)。添加测试组合物(嘧菌酯(Sigma)、吡罗克酮乙醇胺、嘧菌酯+吡罗克酮乙醇胺、以及阳性对照10uM艾地苯醌)以替换培养基(具有0.1％最终浓度的DMSO的EpiLife培养基-简要地，1000X活性物质原液以及制备于100％DMSO且1至1000稀释于Epilife培养基的组合)，并且将板温育18-24小时。从每个孔中去除上清液，并且用2ml/孔培养基(无补充剂)冲洗细胞。使用Cell Titer-Glo测定(Promega目录号G7571；Madison WI)来测量ATP活性，其在细胞上进行以归一化。根据制造商的说明书，在PGE2测定中测试上清液(前列腺素E2测定试剂盒，来自Cisbio Bioassays目录号62P2APEB)。将PGE2结果归一化为ATP活性。将来自上清液的PGE2定量(pg/mL)除以归一化因子(处理ATP/对照ATP)。
用于计算嘧菌酯的PGE2抑制的示例计算：
ATP测定中溶媒对照的发光＝704567
ATP测定中嘧菌酯处理的发光＝678903
嘧菌酯处理的归一化因子＝1.038
溶媒对照的PGE2定量＝2458pg/mL PGE2
嘧菌酯处理的PGE2定量＝2347pg/mL PGE2
归一化PGE2值
对照＝2458/1＝2458
嘧菌酯＝2347/1.038＝2261
嘧菌酯的抑制％＝[100x(2458-2347)/2458]＝8％
学生T检验(相等方差，2侧)用于计算观察到的组合与预期组合之间的p值，其中p值<0.05被认为是统计学上显著的。通过将单独嘧菌酯和单独吡罗克酮乙醇胺的PGE2抑制值相加来计算预期组合值。协同因子仅仅是观察到的组合/预期组合的比率。其中p值<0.05的大于1.0的协同因子被认为是协同的。
比率优化(重量/体积％比率)
*表示统计显著性(观察到的和预期的之间p值<0.05)
PGE2实验的结论是，即使嘧菌酯和吡罗克酮乙醇胺是单独抑制PGE2从角化细胞释放的相对弱的材料，但是嘧菌酯和吡罗克酮乙醇胺的组合实际上令人惊讶地抑制PGE2释放。已经测试了嘧菌酯与吡罗克酮乙醇胺的多个比率，以定义如下比率，在这些比率下发生PGE2释放的协同抑制，并且在嘧菌酯:吡罗克酮乙醇胺的比率为1:1和1:10时存在统计学上显著的协同作用。在嘧菌酯:吡罗克酮乙醇胺的比率为4:1和1:50时，不存在统计学上显著的协同作用，但在这些比率下的组合实际上显示出减少PGE2释放的相加性。
在本发明中，另一种嗜球果伞素和吡罗克酮乙醇胺可以展示嗜球果伞素和吡罗克酮乙醇胺或2-吡啶-N-氧化物材料的组合，该组合实际上同样令人惊讶地抑制PGE2释放，并且可发生PGE2释放的协同抑制并且该协同抑制可在嗜球果伞素:吡罗克酮乙醇胺的比率为1:1和1:10或者嗜球果伞素:2-吡啶-N-氧化物的比率为1:1和1:10时发生。
去污表面活性剂
本发明能够以洗发剂、调理剂、或免洗型处理物的形式存在。洗发剂组合物可包含一种或多种去污表面活性剂，该去污表面活性剂向组合物提供清洁性能。一种或多种去污表面活性剂继而可包括阴离子表面活性剂、两性表面活性剂或两性离子表面活性剂、或它们的混合物。去污表面活性剂的各种示例和描述示于美国专利6,649,155；美国专利申请公布2008/0317698；和美国专利申请公布2008/0206355中，这些文献全文以引用方式并入本文。
去污表面活性剂组分在洗发剂组合物中的浓度应足以提供期望的清洁和发泡性能，并且一般在约2重量％至约50重量％、约5重量％至约30重量％、约8重量％至约25重量％、约10重量％至约20重量％、约5重量％、约10重量％、约12重量％、约15重量％、约17重量％、约18重量％、或约20重量％的范围内。
适用于组合物中的阴离子表面活性剂为烷基硫酸盐和烷基醚硫酸盐。其它合适的阴离子表面活性剂为有机硫酸反应产物的水溶性盐。其它合适的阴离子表面活性剂为用羟乙磺酸酯化并且用氢氧化钠中和的脂肪酸的反应产物。其它类似的阴离子表面活性剂描述于美国专利2,486,921；2,486,922；和2,396,278中，这些文献全文以引用方式并入本文。
用于洗发剂组合物中的示例性阴离子表面活性剂包括月桂基硫酸铵、月桂基聚氧乙烯醚硫酸铵、月桂基硫酸三乙基胺、月桂基聚氧乙烯醚硫酸三乙基胺、月桂基硫酸三乙醇胺、月桂基聚氧乙烯醚硫酸三乙醇胺、月桂基硫酸单乙醇胺、月桂基聚氧乙烯醚硫酸单乙醇胺、月桂基硫酸二乙醇胺、月桂基聚氧乙烯醚硫酸二乙醇胺、月桂酸单甘油酯硫酸钠、月桂基硫酸钠、月桂基聚氧乙烯醚硫酸钠、月桂基硫酸钾、月桂基聚氧乙烯醚硫酸钾、月桂基肌氨酸钠、月桂酰肌氨酸钠、月桂基肌氨酸、椰油酰肌氨酸、椰油酰硫酸铵、月桂酰硫酸铵、椰油酰硫酸钠、月桂酰硫酸钠、椰油酰硫酸钾、月桂基硫酸钾、月桂基硫酸三乙醇胺、月桂基硫酸三乙醇胺、椰油酰硫酸单乙醇胺、月桂基硫酸单乙醇胺、十三烷基苯磺酸钠、十二烷基苯磺酸钠、椰油酰羟乙磺酸钠以及它们的组合。阴离子表面活性剂可为月桂基硫酸钠或月桂基聚氧乙烯醚硫酸钠。
适用于本文洗发剂组合物中的两性表面活性剂或两性离子表面活性剂包括已知用于洗发剂或其它个人护理清洁的那些。此类两性表面活性剂的浓度在约0.5重量％至约20重量％，和约1重量％至约10重量％的范围内。合适的两性离子表面活性剂或两性表面活性剂的非限制性示例描述于美国专利5,104,646和5,106,609中，这些文献全文以引用方式并入本文。
适用于洗发剂组合物中的两性去污表面活性剂包括被广义描述为脂族仲胺和叔胺的衍生物的那些表面活性剂，其中脂族基团可为直链或支链的，并且其中脂族取代基之一包含约8至约18个碳原子，并且一个脂族取代基包含阴离子基团诸如羧酸根、磺酸根、硫酸根、磷酸根、或膦酸根。用于本发明洗发剂组合物中的示例性两性去污表面活性剂包括椰油酰两性基乙酸盐、椰油酰两性基二乙酸盐、月桂酰两性基乙酸盐、月桂酰两性基二乙酸盐、以及它们的混合物。
适用于所述洗发剂组合物中的两性离子去污表面活性剂包括被广泛地描述为脂族季铵、鏻和锍化合物的衍生物的那些表面活性剂，其中脂族基团可为直链或支链的，并且其中脂族取代基之一包含约8至约18个碳原子，并且一个脂族取代基包含阴离子基团诸如羧基、磺酸根、硫酸根、磷酸根或膦酸根。另外，可选择两性离子化物，诸如甜菜碱。
适用于洗发剂组合物中的其它阴离子表面活性剂、两性离子表面活性剂、两性表面活性剂或任选的附加表面活性剂的非限制性示例描述于McCutcheon的《Emulsifiersand Detergents》，1989年鉴，由M.C.Publishing Co.)出版和美国专利3,929,678、2,658,072；2,438,091；2,528,378中，这些文献全文以引用方式并入本文。
洗发剂组合物还可包含洗发剂凝胶基质、含水载体和本文所述的其它附加成分。
含水载体
洗发剂组合物包含第一含水载体。因此，洗发剂组合物的制剂可为可倾倒液体的形式(在环境条件下)。因此，此类组合物通常将包含第一含水载体，所述第一含水载体以至少20重量％，约20重量％至约95重量％，或约60重量％至约85重量％的含量存在。第一含水载体可包含水，或水与有机溶剂的可混溶混合物，并且在一个方面可包含水和最小限度的或不显著浓度的有机溶剂，除了另外作为其它组分的微量成分附带地掺入组合物中的那些。
可用于洗发剂组合物中的第一含水载体包含水以及低级烷基醇和多元醇的水溶液。可用于本文的低级烷基醇是具有1至6个碳的一元醇，在一个方面，为乙醇和异丙醇。可用于本文的多元醇包括丙二醇、己二醇、甘油、和丙烷二醇。
A.含水载体
调理剂组合物的调理剂凝胶基质包含第二含水载体。因此，调理剂组合物的制剂可为可倾倒液体的形式(在环境条件下)。因此，此类组合物通常将包含第二含水载体，所述第二含水载体以约20重量％至约95重量％，或约60重量％至约85重量％的含量存在。第二含水载体可包含水，或水与有机溶剂的可混溶混合物，并且在一个方面可包含水和最小限度的或不显著浓度的有机溶剂，除了另外作为其它组分的微量成分附带地掺入组合物中的那些。
可用于调理剂组合物中的第二含水载体包括水以及低级烷基醇和多元醇的水溶液。可用于本文的低级烷基醇是具有1至6个碳的一元醇，在一个方面，为乙醇和异丙醇。可用于本文的多元醇包括丙二醇、己二醇、甘油、和丙烷二醇。
附加组分
本文所述洗发剂组合物、调理剂组合物和/或免洗型处理物可包含一种或多种已知用于毛发护理或个人护理产品的附加组分，前提条件是该附加组分与本文所述基本组分物理和化学地相容，或不会不适当地损害产品的稳定性、美观性或性能。此类附加组分最典型为描述于参考书诸如“CTFA Cosmetic Ingredient Handbook”第二版(The Cosmetic,Toiletries,and Fragrance Association，Inc.1988，1992)中的那些。按个人护理组合物的重量计，此类附加组分的各个浓度可在约0.001重量％至约10重量％的范围内。
用于个人护理组合物中的附加组分的非限制性示例包括调理剂、天然阳离子沉积聚合物、合成阳离子沉积聚合物、去头皮屑剂、颗粒、悬浮剂、石蜡烃、推进剂、粘度调节剂、染料、非挥发性溶剂或稀释剂(水溶性和水不溶性)、珠光助剂、泡沫促进剂、附加表面活性剂或非离子辅助表面活性剂、灭虱药、pH调节剂、香料、防腐剂、蛋白质、皮肤活性剂、防晒剂、紫外线吸收剂、以及维生素。
1.调理剂
个人护理组合物可包含一种或多种调理剂。调理剂包括用于向毛发提供特定调理有益效果的材料。可用于本发明的个人护理组合物中的调理剂通常包括水不溶性、水分散性、非挥发性、可形成乳化的液体颗粒的液体。可用于个人护理组合物中的合适的调理剂为特征通常为硅氧烷、有机调理油或它们的组合的那些调理剂，或者在含水表面活性剂基质中以其它方式形成液体、分散颗粒的那些调理剂。
按所述组合物的重量计，一种或多种调理剂以约0.01重量％至约10重量％，约0.1重量％至约8重量％，和约0.2重量％至约4重量％的含量存在。
硅氧烷调理剂
本发明的组合物可包含一种或多种硅氧烷调理剂。硅氧烷的示例包括聚二甲基硅氧烷、聚二甲基硅氧烷醇、环状硅氧烷、甲基苯基聚硅氧烷、和具有各种官能团的改性硅氧烷，该官能团诸如氨基基团、季铵盐基团、脂族基团、醇基团、羧酸基团、醚基团、环氧基团、糖或多糖基团、氟改性的烷基基团、烷氧基基团、或此类基团的组合。此类硅氧烷可溶于或不溶于含水(或非水)产品载体。在不溶性液体硅氧烷的情况下，聚合物可为乳化形式，其具有约10纳米至约30微米的液滴尺寸。
有机调理材料
本发明的组合物的调理剂还可包含单独或与其它调理剂诸如上述硅氧烷组合的至少一种有机调理材料诸如油或蜡。有机材料可以是非聚合的、低聚的或聚合的。它可为油或蜡的形式，并且可以纯制剂或以预乳化形式添加。有机调理材料的一些非限制性示例包括但不限于：i)烃油；ii)聚烯烃；iii)脂肪酯；iv)氟化调理化合物；v)脂肪醇；vi)烷基葡糖苷和烷基葡糖苷衍生物；vii)季铵化合物；viii)具有至多约2,000,000的分子量的聚乙二醇和聚丙二醇，包括具有CTFA名称PEG-20 200、PEG-400、PEG-600、PEG-1000、PEG-2M、PEG-7M、PEG-14M、PEG-45M的那些、以及它们的混合物。
有益剂
个人护理组合物还可包含一种或多种附加有益剂。有益剂包括选自以下的材料：去头皮屑剂、抗真菌剂、抗痒剂、抗菌剂、抗微生物剂、保湿剂、抗氧化剂、维生素、脂溶性维生素、香料、增白剂、酶、感觉剂、诱虫剂、染料、颜料、漂白剂、以及它们的混合物。
本发明的个人护理组合物可呈现为典型的个人护理制剂形式。它们可为溶液、分散体、乳液、粉剂、滑石、封装体、球体、海绵、固体剂型、泡沫、以及其它递送机制的形式。本发明的组合物可为毛发滋补剂、免洗型毛发产品诸如处理物、以及定型产品、洗去型毛发产品诸如洗发剂、以及处理产品；以及可施用到毛发的任何其它形式。
个人护理组合物一般由常规方法制备，诸如制备组合物的领域已知的方法。此类方法通常包括在一个或多个步骤中将各成分混合至相对均一的状态，可使用或不使用加热、冷却、施加真空等。制备该组合物以便优化稳定性(物理稳定性、化学稳定性、光稳定性)和/或活性材料的递送。个人护理组合物可为单相或单一产品，或者个人护理组合物可为单独的相或单独的产品。如果使用两种产品，则可同时或按顺序一起使用产品。按顺序使用可发生在一个短的时间段内，诸如使用一种产品之后立即，或者它可能会发生在超过数小时或数天的一段时间后。
实施例
非限制性示例
通过常规的配制方法和混和方法可制备以下实施例中举例说明的洗发剂组合物。除非另外指明，否则所有例示量以基于活性物质的重量百分比列出，并且排除微量材料诸如稀释剂、防腐剂、颜色百分比是基于重量计的。
洗发剂实施例
以上所有都均基于活性物质计；例如，11％SLE1S将需要添加44％的25％活性物质SLE1S溶液。下表解释了上表中每个注释。
以下实施例进一步描述并展示了本发明范围内的实施方案。这些实施例仅为了例证目的而给出并且不可被理解为是对本发明的限制，因为在不脱离本发明的实质和范围的情况下可能有许多变型。此处适用的成分均以化学名或CTFA名来识别，除非下文另外限定。
调理剂组合物(重量％)
免洗型处理物实施例
1 SD-40B 200醇，得自Pride Solvents
2 Flexithix，得自Ashland
3 Benecel K200M，得自Ashland
4 Structure XL，得自AkzoNobel
5 ZPT，得自Lonza
6碳酸锌，得自Brueggeman Group
7薄荷醇，得自Kerry Ingredients and Flavors
8吡罗克酮乙醇胺，得自Clariant
9烟酰胺，得自Lonza
10咖啡因，得自Merck
11 D-泛醇，得自BASF
12Cremophor RH-40，得自BASF
13丙二醇，得自Sigma Aldrich
产品形式
本发明的个人护理组合物可呈现为典型的个人护理制剂形式。它们可为溶液、分散体、乳液、粉剂、滑石、封装体、球体、海绵、固体剂型、泡沫、以及其它递送机制的形式。本发明的组合物可为毛发滋补剂、免洗型毛发产品诸如处理物、以及定型产品、洗去型毛发产品诸如洗发剂、预洗产品、共洗产品、以及个人清洁产品和处理产品；以及可施用到毛发或皮肤的任何其它形式。
本文所公开的量纲和值不应理解为严格限于所引用的精确数值。相反，除非另外指明，否则每个此类量纲旨在表示所述值以及围绕该值功能上等同的范围。例如，公开为“40mm”的量纲旨在表示“约40mm”。
除非明确排除或以其它方式限制，本文中引用的每一篇文献，包括任何交叉引用或相关专利或专利申请以及本申请对其要求优先权或其有益效果的任何专利申请或专利，均据此全文以引用方式并入本文。对任何文献的引用不是对其作为与本发明的任何所公开或本文受权利要求书保护的现有技术的认可，或不是对其自身或与任何一个或多个参考文献的组合提出、建议或公开任何此类发明的认可。此外，当本发明中术语的任何含义或定义与以引用方式并入的文献中相同术语的任何含义或定义矛盾时，应当服从在本发明中赋予该术语的含义或定义。
虽然已举例说明和描述了本发明的具体实施方案，但是对于本领域技术人员来说显而易见的是，在不脱离本发明的实质和范围的情况下可作出各种其它变化和修改。因此，本文旨在于所附权利要求中涵盖属于本发明范围内的所有此类变化和修改。
Claims (7)
1.一种协同抗炎组合物，所述协同抗炎包含：
a)嘧菌酯；
b)吡罗克酮乙醇胺；
其中a:b的比率为1:1至1:10；其中存在协同抗炎/细胞应激活性。
2.根据权利要求1所述的协同抗炎组合物，其中所述抗炎有益效果被测量为PGE2抑制活性。
3.根据权利要求1所述的协同抗炎组合物，其中协同PGE2抑制活性比所计算的嘧菌酯和吡罗克酮乙醇胺的单独PGE2抑制活性的总和高至少1.5倍。
4.根据权利要求1所述的协同抗炎组合物，其中所述吡罗克酮乙醇胺为按所述组合物的重量计0.05%至5%。
5.根据权利要求1所述的协同抗炎组合物，其中所述吡罗克酮乙醇胺为按所述组合物的重量计0.3%至3%。
6.根据权利要求1-5中任一项所述的组合物用于制备具有协同抗炎/细胞应激活性的药物的用途，所述组合物包含：
a)嘧菌酯；
b)吡罗克酮乙醇胺；
其中a:b的比率为1:1至1:10。
7.根据权利要求6所述的应用，所述组合物包含：
a)嘧菌酯；
b)吡罗克酮乙醇胺；
其中a:b的比率为1:1至1:10，其中与基线相比，PGE2释放减少至少20%。
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| US20210283131A1 (en) | 2021-09-16 |
| EP3989921A1 (en) | 2022-05-04 |
| JP7288092B2 (ja) | 2023-06-06 |
| WO2020264577A1 (en) | 2020-12-30 |
| US11433070B2 (en) | 2022-09-06 |
| MX2021015385A (es) | 2022-01-24 |
| JP2022536652A (ja) | 2022-08-18 |
| CN113873989A (zh) | 2021-12-31 |
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