CN111615382A - 贴附剂 - Google Patents
贴附剂 Download PDFInfo
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- CN111615382A CN111615382A CN201980008891.6A CN201980008891A CN111615382A CN 111615382 A CN111615382 A CN 111615382A CN 201980008891 A CN201980008891 A CN 201980008891A CN 111615382 A CN111615382 A CN 111615382A
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Abstract
一种贴附剂，其具备支持体层及粘着剂层，上述粘着剂层为非水性，上述粘着剂层含有壬酸香草酰胺、萜烯系树脂、松香系树脂、苯乙烯‑异戊二烯‑苯乙烯嵌段共聚物、及液体石蜡，上述粘着剂层中的上述萜烯系树脂的含量与上述松香系树脂的含量的质量比(萜烯系树脂的含量/松香系树脂的含量)为0.45～1.3，上述粘着剂层中的上述苯乙烯‑异戊二烯‑苯乙烯嵌段共聚物的含量与上述液体石蜡的含量的质量比(苯乙烯‑异戊二烯‑苯乙烯嵌段共聚物的含量/液体石蜡的含量)为0.45～1.2。
Description
技术领域
本发明涉及一种贴附剂，更详细而言，涉及一种含有壬酸香草酰胺的贴附剂。
背景技术
作为目的在于缓和腰痛、肩酸等慢性疾病的症状的制剂，自先前以来开发有对局部赋予温感刺激的温感型外用剂。可以认为温感型外用剂是通过温感刺激成分使局部产生温热感而使毛细血管扩张、促进血液流动，从而提高组织的新陈代谢，由此对上述慢性疾病发挥消炎、镇痛效果。
作为上述温感刺激成分，已知有辣椒萃取物、合成辣椒的壬酸香草酰胺、及烟酸酯等，例如在日本专利特开平10-298065号公报(专利文献1)中记载有下述贴附剂：其在含有30～80重量％的水的亲水性基剂层中调配有选自生育酚乙酸酯、聚乙烯磺酸钠、壬酸香草酰胺、辣椒萃取物、辣椒末、辣椒酊、辣椒碱、烟酸苄酯、及壬酸中的至少1种血流促进剂。此外，例如在国际公开第2004/047820号(专利文献2)中公开有一种含有温感赋予物质、l-薄荷醇及聚乙二醇的温感敷剂，作为上述温感赋予物质，记载有辣椒碱、二羟基辣椒碱、辣椒红素、辣椒素、辣椒甙、辣椒萃取物、辣椒酊、辣椒末、烟酸苄酯、烟酸β-丁氧基乙酯、N-酰基香草酰胺、壬酸香草酰胺及香草醇烷基醚等。
现有技术文献
专利文献
专利文献1：日本专利特开平10-298065号公报
专利文献2：国际公开第2004/047820号
发明内容
发明想要解决的课题
为了持续对贴附部位赋予温感刺激，必须使贴附剂的粘着剂层的厚度较厚(优选为250μm以上)，但本发明者等人对含有壬酸香草酰胺作为温感刺激成分的贴附剂、尤其是非水系贴附剂进而进行了研究，结果发现，若在该贴附剂中使粘着剂层的厚度增厚，则存在粘着剂层的凝聚力降低而导致在剥离贴附剂时粘着剂层残留于皮肤、或粘着剂层的粘着性降低的情形。
本发明是鉴于上述课题而完成的，目的在于提供一种粘着剂层的凝聚力及粘着性优异的非水系贴附剂。
用于解决课题的方法
本发明者等人为了达成上述目的而反复进行努力研究，结果发现，在具备支持体层及粘着剂层的贴附剂中，使上述粘着剂层为实质上不含有水的非水性，使上述粘着剂层组合含有壬酸香草酰胺、萜烯系树脂、松香系树脂、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、及液体石蜡，且使上述萜烯系树脂的含量与上述松香系树脂的含量的质量比、及上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与上述液体石蜡的含量的质量比均成为特定范围内，由此，即便在使粘着剂层的厚度较厚的情形时，也能够使该粘着剂层的凝聚力及粘着性良好，从而完成本发明。
即，本发明的贴附剂具备支持体层及粘着剂层，
上述粘着剂层为非水性，
上述粘着剂层含有壬酸香草酰胺、萜烯系树脂、松香系树脂、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、及液体石蜡，
上述粘着剂层中的上述萜烯系树脂的含量与上述松香系树脂的含量的质量比(萜烯系树脂的含量/松香系树脂的含量)为0.45～1.3，
上述粘着剂层中的上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与上述液体石蜡的含量的质量比(苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量/液体石蜡的含量)为0.45～1.2。
在本发明的贴附剂中，优选为上述粘着剂层中的壬酸香草酰胺的含量相对于上述粘着剂层的总质量为0.005～0.1质量％。此外，优选为上述粘着剂层实质上不含有水。进而，也优选为上述粘着剂层含有选自水杨酸甲酯、乙二醇水杨酸酯、l-薄荷醇、dl-樟脑、薄荷油、及百里酚中的至少1种消炎镇痛剂，更优选为上述粘着剂层中的上述消炎镇痛剂的含量相对于上述粘着剂层的总质量为1～10质量％。
此外，在本发明的贴附剂中，优选上述粘着剂层的厚度为250～400μm，进而，也优选通过B型粘度计在115℃的温度下测得的上述粘着剂层的粘度为100～2500dPa·s。
发明的效果
根据本发明，可提供一种粘着剂层的凝聚力及粘着性优异的非水系贴附剂。
具体实施方式
以下，针对本发明，基于其适当的实施形态详细地进行说明。本发明的贴附剂是具备支持体层及粘着剂层的贴附剂，
上述粘着剂层为非水性，
上述粘着剂层含有壬酸香草酰胺、萜烯系树脂、松香系树脂、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、及液体石蜡，
上述粘着剂层中的上述萜烯系树脂的含量与上述松香系树脂的含量的质量比(萜烯系树脂的含量/松香系树脂的含量)为0.45～1.3，
上述粘着剂层中的上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与上述液体石蜡的含量的质量比(苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量/液体石蜡的含量)为0.45～1.2。
本发明的贴附剂具备支持体层及粘着剂层。作为上述支持体层，只要为能够支持下述粘着剂层的支持体层，则并无特别限制，可适当采用公知的支持体层作为贴附剂的支持体层。作为本发明的支持体层的材质，例如可列举：聚乙烯、聚丙烯等聚烯烃；乙烯-乙酸乙烯酯共聚物、乙酸乙烯酯-氯乙烯共聚物、聚氯乙烯等；尼龙等聚酰胺；聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯；纤维素衍生物；聚氨基甲酸酯等合成树脂、铝等金属。其中，就药物非吸附性、药物非透过性的观点而言，优选为聚酯、聚对苯二甲酸乙二酯。作为上述支持体层的形态，例如可列举：膜；片材、片状多孔质体、片状发泡体等片材类；织布、编织布、无纺布等布帛；箔；及它们的叠层体。此外，作为上述支持体层的厚度，并无特别限制，就贴附贴附剂时的操作容易性及制造容易性的观点而言，优选为5～1000μm的范围内。
本发明的贴附剂也可以在上述粘着剂层的与上述支持体层相反的面上进而具备剥离衬垫。作为该剥离衬垫，可列举：聚乙烯、聚丙烯等聚烯烃；乙烯-乙酸乙烯酯共聚物、乙酸乙烯酯-氯乙烯共聚物、聚氯乙烯等；尼龙等聚酰胺；聚对苯二甲酸乙二酯等聚酯；纤维素衍生物；聚氨基甲酸酯等合成树脂、或包含铝、纸等材质的膜、片材及它们的叠层体。作为这样的剥离衬垫，优选为对与该粘着剂层接触的侧的面实施含硅化合物涂布或含氟化合物涂布等脱模处理，使得能够从上述粘着剂层容易地剥离。
本发明的贴附剂为非水系贴附剂，本发明的粘着剂层必须为非水系的粘着剂层。在本发明中，所谓“非水系的粘着剂层”，是指粘着剂层实质上不含有水，作为上述水，可列举：纯化水、灭菌水、天然水、及它们的混合物等。在本发明中，所谓实质上不含有水，是指在制造步骤中不存在意图在上述粘着剂层中调配水的步骤，并不排除制造步骤中所含有的空气中等的水分及将贴附剂应用于皮肤的过程中吸收汗等而成的水分。作为此种粘着剂层中的水的含量，更具体而言，相对于上述粘着剂层的总质量，优选为小于1质量％，更优选为0.99质量％以下，进而优选为0～0.5质量％。
本发明的粘着剂层含有壬酸香草酰胺(也称为“nonanoic acid vanillylamide”)作为温感刺激成分。在本发明中，作为上述粘着剂层中所含有的壬酸香草酰胺的含量，相对于上述粘着剂层的总质量，优选为0.005～0.1质量％，更优选为0.01～0.02质量％，进而优选为0.01～0.018质量％，进而更优选为0.012～0.016质量％。若壬酸香草酰胺的含量小于上述下限，则有赋予贴附部位的温感刺激变得不充分而导致温热感降低的倾向，另一方面，若超过上述上限，则有赋予贴附部位的温感刺激变得过强、粘着剂层的凝聚力降低或产生难闻气味的倾向。
本发明的粘着剂层含有萜烯系树脂。在本发明中，所谓萜烯系树脂，是将异戊二烯作为结构单元的树脂，作为本发明的萜烯系树脂，例如可列举：蒎烯聚合物(α-蒎烯聚合物、β-蒎烯聚合物等)、萜烯聚合物、双戊烯聚合物、萜烯-酚聚合物、芳香族改性萜烯聚合物、蒎烯-酚共聚物；可单独使用它们中的1种，也可将2种以上组合使用。作为上述萜烯系树脂，可适当使用YS RESIN(YS RESIN PXN、YS RESIN PX1150N、YS RESIN PX1000、YS RESINTO125、YS RESIN TO105等)、Clearon P105、Clearon M115、Clearon K100(以上为商品名，Yasuhara Chemical股份有限公司制造)、Tamanol 901(商品名，荒川化学工业股份有限公司制造)等市售的树脂，可单独使用它们中的1种，也可将2种以上组合使用。其中，作为本发明的萜烯系树脂，就有粘着剂层的粘着性及对皮肤的附着性变得更良好的倾向的观点而言，更优选为蒎烯聚合物。
在本发明中，作为上述粘着剂层中所含有的上述萜烯系树脂的含量(在2种以上的情形时为它们的合计含量，以下相同)，相对于上述粘着剂层的总质量，优选为1～25质量％，更优选为4～22质量％，进而优选为5～11质量％。若上述萜烯系树脂的含量小于上述下限，则有粘着剂层的粘着性及对皮肤的附着性降低的倾向，另一方面，若超过上述上限，则有在剥离贴附剂时粘着剂层残留于皮肤或剥离时的疼痛增大的倾向。
本发明的粘着剂层也含有松香系树脂。在本发明中，所谓松香系树脂，是将松香酸作为主成分的树脂，作为本发明的松香系树脂，例如可列举：氢化松香甘油酯、超淡色松香、超淡色松香酯、酸改性超淡色松香；可单独使用它们中的1种，也可将2种以上组合使用。作为上述松香系树脂，可适当使用PINECRYSTAL(KE-311、PE-590、KE-359、KE-100等)(商品名，荒川化学工业股份有限公司制造)等市售的松香系树脂，可单独使用它们中的1种，也可将2种以上组合使用。其中，作为本发明的松香系树脂，就有粘着剂层的粘着性及对皮肤的附着性变得更良好的倾向的观点而言，更优选为氢化松香甘油酯。
在本发明中，作为上述粘着剂层中所含有的上述松香系树脂的含量(在2种以上的情形时为它们的合计含量，以下相同)，相对于上述粘着剂层的总质量，优选为1～25质量％，更优选为5～22质量％，进而优选为10～14质量％。若上述松香系树脂的含量小于上述下限，则有粘着剂层的粘着性及对皮肤的附着性降低或粘度变得过高的倾向，另一方面，若超过上述上限，则有在剥离贴附剂时粘着剂层残留于皮肤或剥离时的疼痛增大的倾向。
此外，在本发明中，上述粘着剂层中的上述萜烯系树脂的含量与上述松香系树脂的含量的质量比(萜烯系树脂的含量/松香系树脂的含量)必须为0.45～1.3。此外，作为上述质量比，优选为0.45～1.0，更优选为0.50～1.0。若上述萜烯系树脂的含量相对于上述松香系树脂的含量小于上述下限，则有粘着剂层的粘着性及对皮肤的附着性降低的倾向，另一方面，若超过上述上限，则有在剥离贴附剂时粘着剂层容易残留于皮肤的倾向。
本发明的粘着剂层含有苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)。在本发明中，作为上述粘着剂层中所含有的苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量，相对于上述粘着剂层的总质量，优选为15～34质量％，更优选为16～34质量％，进而优选为20～28质量％。若上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量小于上述下限，则有在剥离贴附剂时粘着剂层容易残留于皮肤的倾向，另一方面，若超过上述上限，则有粘着剂层的粘着性及对皮肤的附着性降低或粘度变得过高的倾向。
本发明的粘着剂层也含有液体石蜡。液体石蜡是也被称为液状石蜡(liquidparaffin)、矿物油、白矿物油的链烷烃系加工处理油。作为本发明的液体石蜡，37.8℃的温度下的动态粘度优选为5.8～100mm2/s，更优选为68～96mm2/s。若上述动态粘度小于上述下限值，则有在剥离贴附剂时粘着剂层容易残留于皮肤或粘着剂层的粘着性及对皮肤的附着性降低的倾向，另一方面，若超过上述上限值，则有粘着剂层的粘度变得过高的倾向。
在本发明中，作为上述粘着剂层中所含有的液体石蜡的含量，相对于上述粘着剂层的总质量，优选为20～45质量％，更优选为22～42质量％，进而优选为25～41质量％。若上述液体石蜡的含量小于上述下限，则有粘着剂层的粘度变得过高的倾向，另一方面，若超过上述上限，则有在剥离贴附剂时粘着剂层容易残留于皮肤或粘着剂层的粘着性及对皮肤的附着性降低的倾向。
此外，在本发明中，上述粘着剂层中的上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与液体石蜡的含量的质量比(苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量/液体石蜡的含量)必须为0.45～1.2。此外，作为上述质量比，优选为0.45～1.0，更优选为0.5～1.0。若上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量相对于上述液体石蜡的含量小于上述下限，则有在剥离贴附剂时粘着剂层容易残留于皮肤的倾向，另一方面，若超过上述上限，则有粘着剂层的粘着性及对皮肤的附着性降低的倾向。
就本发明的粘着剂层而言，优选为进而含有选自水杨酸甲酯、乙二醇水杨酸酯、l-薄荷醇、dl-樟脑、薄荷油、及百里酚中的至少1种消炎镇痛剂。通过将这样的消炎镇痛剂与壬酸香草酰胺并用，能够使源自壬酸香草酰胺的温感刺激更良好。其中，作为上述消炎镇痛剂，就有适度的消炎镇痛效果及对贴附部位赋予适度的刺激感的倾向的观点而言，优选为选自水杨酸甲酯、乙二醇水杨酸酯、及l-薄荷醇中的至少1种，更优选为乙二醇水杨酸酯及l-薄荷醇的组合。
在本发明中，在上述粘着剂层含有上述消炎镇痛剂的情形时，作为上述粘着剂层中所含有的消炎镇痛剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，相对于上述粘着剂层的总质量，优选为1～10质量％，更优选为1.5～9质量％，进而优选为2.55～7.66质量％。若上述消炎镇痛剂的含量小于上述下限，则有消炎镇痛效果变得不充分的倾向，另一方面，若超过上述上限，则有不易均匀地包含于粘着剂层中的倾向。
就本发明的粘着剂层的粘着基剂而言，也可以进而含有上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物以外的其他粘着基剂。作为此种粘着基剂，只要实质上不含有水，则并无特别限制，例如可列举：苯乙烯-异戊二烯-苯乙烯嵌段共聚物以外的其他橡胶系粘着基剂、丙烯酸系粘着基剂、及有机硅系粘着基剂。
作为上述其他橡胶系粘着基剂，可列举：聚异丁烯(PIB)、异戊二烯、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-丁二烯橡胶(SBR)、聚丁烯、天然橡胶等；可单独使用它们中的1种，也可将2种以上组合使用。其中，在与上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的组合中，就有粘着剂层的粘着性及对皮肤的附着性变得更良好的倾向的观点而言，优选使用聚异丁烯作为上述橡胶系粘着基剂。在将上述苯乙烯-异戊二烯-苯乙烯嵌段共聚物与聚异丁烯组合使用的情形时，作为苯乙烯-异戊二烯-苯乙烯嵌段共聚物与聚异丁烯的质量比(苯乙烯-异戊二烯-苯乙烯嵌段共聚物的质量：聚异丁烯的质量)，例如更优选为1：0.28～1：0.58(进而优选为1：0.33～1：0.44的范围)。
作为上述丙烯酸系粘着基剂，可列举作为粘着剂收录于“药品添加物辞典2016(日本药品添加剂协会编辑集)”中的丙烯酸-丙烯酸辛酯共聚物、丙烯酸2-乙基己酯-乙烯基吡咯烷酮共聚物、丙烯酸酯-乙酸乙烯酯共聚物、丙烯酸2-乙基己酯-甲基丙烯酸2-乙基己酯-甲基丙烯酸十二烷基酯共聚物、丙烯酸甲酯-丙烯酸2-乙基己酯共聚树脂、丙烯酸2-乙基己酯-丙烯酸甲酯-丙烯酸-甲基丙烯酸缩水甘油酯共聚物、丙烯酸2-乙基己酯-乙酸乙烯酯-丙烯酸羟乙酯-甲基丙烯酸缩水甘油酯共聚物、丙烯酸2-乙基己酯-二丙酮丙烯酰胺-甲基丙烯酸乙酰乙酰氧基乙酯-甲基丙烯酸甲酯共聚物、丙烯酸乙酯-甲基丙烯酸甲酯共聚物、丙烯酸系树脂烷醇胺液中所含有的丙烯酸系高分子等，可单独使用它们中的1种，也可将2种以上组合使用。
作为上述有机硅系粘着基剂，可列举：聚二甲基硅氧烷(以依据ASTMD-1418的表示而表示为MQ的聚合物等)、聚甲基乙烯基硅氧烷(以依据ASTMD-1418的表示而表示为VMQ的聚合物等)、聚甲基苯基硅氧烷(以依据ASTMD-1418的表示而表示为PVMQ的聚合物等)等；可单独使用它们中的1种，也可将2种以上组合使用。
在本发明中，在上述粘着剂层含有这样的其他粘着基剂的情形时，作为上述粘着剂层中所含有的其他粘着基剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，相对于上述粘着剂层的总质量，优选为50质量％以下，更优选为5～44质量％。
作为本发明的粘着剂层，也可以进而含有具有有效成分的经皮吸收促进作用的吸收促进剂(经皮吸收促进剂)。作为上述吸收促进剂，可列举：脂肪族醇、碳原子数6～20的脂肪酸、脂肪酸酯、脂肪酰胺、或脂肪族醇醚；芳香族有机酸；芳香族醇；芳香族有机酸酯或醚；POE氢化蓖麻油类；卵磷脂类；磷脂质；大豆油衍生物；三乙酸甘油酯等；可单独使用它们中的1种，也可将2种以上组合使用。
在本发明中，在上述粘着剂层含有上述吸收促进剂的情形时，作为上述粘着剂层中所含有的吸收促进剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，相对于上述粘着剂层的总质量，优选为15质量％以下，更优选为12质量％以下，进而优选为10质量％以下。
此外，本发明的粘着剂层也可以在不损及本发明的效果的范围内进而适当且适量含有壬酸香草酰胺及上述消炎镇痛剂以外的其他有效成分、上述萜烯系树脂及上述松香系树脂以外的其他增粘剂、抗氧化剂、增塑剂、填充剂、溶解剂等。
作为壬酸香草酰胺及上述消炎镇痛剂以外的其他有效成分，例如可列举：黄柏粉末、甘草次酸等源自植物的成分；非类固醇性消炎镇痛剂(双氯芬酸、吲哚美辛、酮洛芬、联苯乙酸、洛索洛芬、布洛芬、氟比洛芬、噻洛芬、阿西美辛、舒林酸、依托度酸、托美汀、吡罗昔康、美洛昔康、安吡昔康、萘普生、阿扎丙宗、伐地考昔、塞来考昔、罗非考昔、氨芬酸等)、解热镇痛药(对乙酰氨基酚等)、抗组胺剂(苯海拉明、氯苯那敏、美喹他嗪、高氯环嗪等)、降压剂(地尔硫卓、尼卡地平、尼伐地平、美托洛尔、比索洛尔、群多普利等)、抗帕金森剂(培高利特、罗匹尼罗、溴麦角环肽、司来吉兰等)、支气管扩张剂(妥洛特罗、异丙肾上腺素、沙丁胺醇等)、抗过敏剂(酮替芬、氯雷他定、氮卓斯汀、特非那定、西替利嗪、阿扎司特等)、局部麻醉剂(利多卡因、地布卡因等)、神经障碍性疼痛治疗药(普瑞巴林等)、非麻药性镇痛药(丁丙诺啡、曲马多、喷他佐辛)、麻醉系镇痛剂(吗啡、羟考酮、芬太尼等)、泌尿器官用剂(奥昔布宁、坦索罗辛等)、精神神经用剂(丙嗪(Promazine)、氯丙嗪等)、类固醇激素剂(雌二醇、黄体酮、炔诺酮、可的松、氢化可的松等)、抗抑郁剂(舍曲林、氟西汀、帕罗西汀、西酞普兰等)、抗痴呆药(多奈哌齐、利凡斯的明、加兰他敏等)、抗精神病药(利培酮、奥氮平等)、中枢神经兴奋剂(哌醋甲酯等)、骨质疏松症治疗药(雷洛昔芬、阿仑膦酸盐等)、乳腺癌预防药(他莫昔芬等)、抗肥胖药(马吲哚、西布曲明等)、失眠症改善药(褪黑素等)、抗风湿药(阿克他利等)等药效成分；可单独使用它们中的1种，也可将2种以上组合使用。
在本发明中，在上述粘着剂层含有上述其他有效成分的情形时，作为上述粘着剂层中所含有的其他有效成分的含量(在2种以上的情形时为它们的合计含量，以下相同)，由于是根据治疗目的而适当调整，因此不可一概而论，但相对于上述粘着剂层的总质量，优选为5质量％以下，更优选为0.5～5质量％，进而优选为0.5～4质量％，进而更优选为1～3质量％。
作为上述萜烯系树脂及上述松香系树脂以外的其他增粘剂，例如可列举石油系树脂(作为脂环族烃单体的均聚物或共聚物的脂环族饱和烃树脂等)、酚系树脂、及二甲苯系树脂，可单独使用它们中的1种，也可将2种以上组合使用。在本发明中，在上述粘着剂层含有上述其他增粘剂的情形时，作为上述粘着剂层中所含有的增粘剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，相对于上述粘着剂层的总质量，优选为30质量％以下，更优选为25质量％以下。
作为上述抗氧化剂，例如可列举：抗坏血酸、没食子酸丙酯、丁基羟基茴香醚、二丁基羟基甲苯、去甲二氢愈创木酸、生育酚、生育酚乙酸酯、亚硫酸氢钠；可单独使用它们中的1种，也可将2种以上组合使用。在本发明中，在上述粘着剂层含有上述抗氧化剂的情形时，作为上述粘着剂层中所含有的抗氧化剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，例如相对于上述粘着剂层的总质量，优选为5质量％以下，更优选为0.1～5质量％，进而优选为3质量％以下，进而更优选为0.1～1质量％。
作为上述增塑剂，例如可列举：硅油；上述液体石蜡以外的其他链烷烃(paraffin)系加工处理油、环烷系加工处理油及芳香族系加工处理油等石油系油；角鲨烷、角鲨烯；橄榄油、山茶油、蓖麻油、妥尔油及花生油等植物系油；邻苯二甲酸二丁酯及邻苯二甲酸二辛酯等二元酸酯；聚丁烯及液状异戊二烯橡胶等液状橡胶；二乙二醇、聚乙二醇、丙二醇、二丙二醇；可单独使用它们中的1种，也可将2种以上组合使用。在本发明中，在上述粘着剂层含有上述增塑剂的情形时，作为上述粘着剂层中所含有的增塑剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，例如相对于上述粘着剂层的总质量，优选为50质量％以下，更优选为40质量％以下。
作为上述填充剂，例如可列举：碳酸钙、碳酸镁等碳酸盐；硅酸镁等硅酸盐；硅酸、硅酸铝、氢氧化铝、硫酸钡、硫酸钙、锌酸钙、氧化锌、氧化钛；可单独使用它们中的1种，也可将2种以上组合使用。其中，作为上述填充剂，优选为选自氧化钛、氢氧化铝、及硅酸铝中的至少1种。在本发明中，在上述粘着剂层含有上述填充剂的情形时，作为上述粘着剂层中所含有的填充剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，例如相对于上述粘着剂层的总质量，优选为7质量％以下，更优选为0.5～7质量％，进而优选为0.5～5.5质量％，进而更优选为1～5质量％。
作为上述溶解剂，例如可列举：苄基醇；吡咯并硫代癸烷(日文原文：ピロチオデカン)；肉豆蔻酸异丙酯；克罗米通；N-甲基-2-吡咯烷酮等吡咯烷酮类；高级醇类；己二酸二乙酯、己二酸异丙酯、己二酸二异丙酯、己二酸二异丁酯、己二酸二辛酯、己二酸二(2-庚基十一烷基)酯、癸二酸二异丙酯、癸二酸二乙酯等多元酸酯类；可单独使用它们中的1种，也可将2种以上组合使用。在本发明中，在上述粘着剂层含有上述溶解剂的情形时，作为上述粘着剂层中所含有的溶解剂的含量(在2种以上的情形时为它们的合计含量，以下相同)，例如相对于上述粘着剂层的总质量，优选为10质量％以下。
作为此种本发明的粘着剂层，优选为利用B型粘度计(布鲁克菲尔德型旋转粘度计)在115℃的温度下所测得的粘度为100～2500dPa·s，更优选为500～2500dPa·s，进而优选为1000～2500dPa·s，进而更优选为1100～2500dPa·s。通过使上述粘度处于此种范围内，能够使粘着剂层的涂布等制造适用性更良好，此外，能够使粘着剂层的凝聚力及粘着性更良好。
作为本发明的粘着剂层的厚度，并无特别限制，优选为80～400μm，更优选为110～380μm。本发明的粘着剂层即便使粘着剂层的厚度较厚也发挥优异的粘着剂层的凝聚力及粘着性，因此例如上述粘着剂层的厚度也可为250～400μm，更优选为280～360μm。
此外，作为本发明的粘着剂层的贴附面的面积，可根据治疗目的及应用对象适当调整，并无特别限制，通常为0.5～200cm2的范围。进而，作为本发明的粘着剂层的贴附面的形状，并无特别限制，可采用圆型、椭圆型、正方形型、长方形型等任意形状。
本发明的贴附剂并无特别限制，可通过适当采用公知的非水系贴附剂的制造方法来制造。例如，首先依据常规方法将壬酸香草酰胺、萜烯系树脂、松香系树脂、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、液体石蜡、及根据需要的上述其他成分进行混合，获得均匀的粘着剂层组合物。继而，将该粘着剂层组合物以成为所需每单位面积的质量的方式涂布于上述支持体层的面上(通常为一面上)后，根据需要剪裁成所需形状，由此可获得本发明的贴附剂。
此外，作为本发明的贴附剂的制造方法，也可进而包含将上述剥离衬垫贴合于上述粘着剂层的与上述支持体层相反的面上的步骤，可以将上述粘着剂层组合物首先以成为所需每单位面积的质量的方式涂布于上述剥离衬垫的一面上而形成粘着剂层后，将上述支持体层贴合于上述粘着剂层的与上述剥离衬垫相反的面上，并根据需要裁剪成所需形状，由此获得本发明的贴附剂。进而，所获得的贴附剂也可以根据需要被封入保存用包装容器(例如铝层压袋)中而制成包装体。
[实施例]
以下，基于实施例及比较例对本发明更具体地进行说明，但本发明并不限定于以下的实施例。再者，在各实施例及比较例中，粘着性/粘着剂层残留评价试验、及粘着剂层粘度测定分别是通过以下所示的方法进行。
<粘着性/粘着剂层残留评价试验>
将各贴附剂切成直径25mm的圆形并将剥离衬垫剥离，分别让6～7名被试验者用手指触碰粘着剂层的表面(粘着面)，并分别依据以下粘着性评价的基准评价粘着剂层对皮肤的粘着性：
[粘着性评价]
0：粘着性极低
25：粘着性较低
50：粘着性略低
75：粘着性略高
100：粘着性极高
此外，分别依据以下粘着剂层残留评价的基准对上述评价粘着性时的粘着剂层(膏体)对手指表面的残留进行评价：
[粘着剂层残留评价]
0：粘着剂层残留于手指表面达到被介意的程度(残留于整个手指表面)
25：粘着剂层残留于手指表面的一部分
50：粘着剂层虽略微残留于手指表面，但将手指从粘着剂层的表面剥离时发现大量拉丝
75：将手指从粘着剂层的表面剥离时发现少许拉丝
100：粘着剂层未残留于手指表面，且也未发现拉丝
此处，所谓“拉丝”，是粘着剂层的凝聚力越低而出现越多的现象，表示粘着剂层的一部分以拉丝的方式剥落而导致粘着剂层变形。
关于从被试验者获得的粘着性评价及粘着剂层残留评价的各评价的值，分别将所获得的值的合计除以被试验者的人数而算出的平均值设为各评价值。再者，关于粘着性评价，认为75～100是粘着剂层对皮肤的粘着性良好而为容许级别，关于粘着剂层残留评价，认为63～100是粘着剂层的凝聚力良好而为容许级别。
<粘着剂层粘度测定>
在室温下从各实施例及比较例中所获得的贴附剂刮取一定量的粘着剂层，将其加热至115℃，将温度保持为115℃并将B型粘度计(装置：Viscotester VT-04F，制造公司：Rion股份有限公司)的转子浸没后使其旋转，测定作用于该转子的粘性阻力(转矩)，并设为上述粘着剂层在115℃的温度下的粘度(dPa·s)。
(实施例1)
首先，将壬酸香草酰胺0.012质量份、黄柏粉末1.70质量份、乙二醇水杨酸酯2.55质量份、l-薄荷醇5.11质量份、萜烯系树脂(TP)(YS RESIN PX1150N，Yasuhara Chemical股份有限公司制造)5.00质量份、松香系树脂(RS)(PINECRYSTAL KE-311，荒川化学工业股份有限公司制造)10.00质量份、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)21.79质量份、聚异丁烯9.40质量份、液体石蜡(LP)40.828质量份、及其他成分(抗氧化剂、填充剂)3.61质量份进行混合，获得粘着剂层组合物。继而，将所获得的粘着剂层组合物涂布于剥离衬垫(实施有脱模处理的聚对苯二甲酸乙二酯制膜)上，以粘着剂层的厚度成为320μm的方式形成粘着剂层。在所获得的粘着剂层的与上述剥离衬垫相反的面上叠层支持体层(聚酯制无纺布)，获得将支持体层/粘着剂层/剥离衬垫依序叠层而成的贴附剂。
(实施例2～5、比较例1～6)
使粘着剂层组合物的组成成为下述表1～2所示的组成，除此以外，以与实施例1相同的方式获得各贴附剂。
(比较例7～8)
使粘着剂层组合物的组成成为下述表3所示的组成，且将粘着剂层的厚度设为260μm(比较例7)或400μm(比较例8)，除此以外，以与实施例1相同的方式获得各贴附剂。
针对实施例1～5及比较例1～8中所获得的贴附剂，分别实施粘着性评价/粘着剂层残留评价试验、以及粘着剂层粘度测定。分别将结果与各实施例及比较例的粘着剂层组合物的组成一并示于下述表1～3中。此外，表1～3中也一并示出粘着剂层中的萜烯系树脂的含量与松香系树脂的含量的质量比(TP/RS)及苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与液体石蜡的含量的质量比(SIS/LP)。再者，在下述表中，粘度中的“N.D.”表示超过粘度测定的测定极限(4000dPa·s)。
[表1]
[表2]
[表3]
根据表1～3所示的结果明确确认到，在本发明的贴附剂中，粘着剂层的粘度(115℃)处于100～2500dPa·s的范围内，此外，粘着性评价及粘着剂层残留的评价均良好，均达成优异的粘着性及凝聚力。另一方面，确认到在萜烯系树脂的含量与松香系树脂的含量的质量比(TP/RS)偏离本发明的范围的情形(比较例1～4)、及苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与液体石蜡的含量的质量比(SIS/LP)偏离本发明的范围的情形(比较例5～6)时，即使满足其中任一条件，也未能如本发明这样实现优异的粘着性及凝聚力。进而，在本发明的贴附剂中，根据比较例7～8的比较也明确确认到，即使粘着剂层的厚度相对较厚为320μm，也均实现了上述优异的粘着性及凝聚力。
(实施例6～7)
使粘着剂层组合物的组成成为下述表4所示的组成，且将粘着剂层的厚度设为250μm(实施例6)或400μm(实施例7)，除此以外，以与实施例1相同的方式获得各贴附剂。
(实施例8～12)
使粘着剂层组合物的组成成为下述表4所示的组成，除此以外，以与实施例1相同的方式获得各贴附剂。
针对实施例6～12中所获得的贴附剂，分别实施粘着性评价/粘着剂层残留评价试验、以及粘着剂层粘度测定。分别将结果与各实施例的粘着剂层组合物的组成一并示于下述表4中。此外，在表4中也一并示出粘着剂层中的萜烯系树脂的含量与松香系树脂的含量的质量比(TP/RS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与液体石蜡的含量的质量比(SIS/LP)、聚异丁烯的含量与苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量的质量比(PIB/SIS)。
[表4]
根据表4所示的结果明确确认到，在本发明的贴附剂中，即使变更贴附剂的厚度(例如实施例6～7)、壬酸香草酰胺的含量(例如实施例8)、作为其他成分的PIB的含量(实施例9～10)或黄柏粉末等的添加的有无(实施例11)，粘着剂层的粘度(115℃)也处于100～2500dPa·s的范围内，此外，粘着性评价及粘着剂层残留评价均良好，而均实现了优异的粘着性及凝聚力。进而确认到，即便降低粘着剂层的粘度(例如实施例12)，粘着性评价及粘着剂层残留评价也均良好，而均实现了优异的粘着性及凝聚力。
产业上的可利用性
根据以上说明，可提供一种粘着剂层的凝聚力及粘着性优异的非水系贴附剂。
Claims (7)
1.一种贴附剂，其具备支持体层及粘着剂层，
所述粘着剂层为非水性，
所述粘着剂层含有壬酸香草酰胺、萜烯系树脂、松香系树脂、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、及液体石蜡，
所述粘着剂层中的所述萜烯系树脂的含量与所述松香系树脂的含量的质量比，即，萜烯系树脂的含量/松香系树脂的含量为0.45～1.3，
所述粘着剂层中的所述苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量与所述液体石蜡的含量的质量比，即，苯乙烯-异戊二烯-苯乙烯嵌段共聚物的含量/液体石蜡的含量为0.45～1.2。
2.根据权利要求1所述的贴附剂，其中，所述粘着剂层中的壬酸香草酰胺的含量相对于所述粘着剂层的总质量为0.005～0.1质量％。
3.根据权利要求1或2所述的贴附剂，其中，所述粘着剂层实质上不含有水。
4.根据权利要求1至3中任一项所述的贴附剂，其中，所述粘着剂层含有选自水杨酸甲酯、乙二醇水杨酸酯、l-薄荷醇、dl-樟脑、薄荷油、及百里酚中的至少1种消炎镇痛剂。
5.根据权利要求4所述的贴附剂，其中，所述粘着剂层中的所述消炎镇痛剂的含量相对于所述粘着剂层的总质量为1～10质量％。
6.根据权利要求1至5中任一项所述的贴附剂，其中，所述粘着剂层的厚度为250～400μm。
7.根据权利要求1至6中任一项所述的贴附剂，其中，通过B型粘度计在115℃的温度下所测得的所述粘着剂层的粘度为100～2500dPa·s。
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