CN103459512A - 抗菌性树脂组合物 - Google Patents
抗菌性树脂组合物 Download PDFInfo
- Publication number
- CN103459512A CN103459512A CN2012800166063A CN201280016606A CN103459512A CN 103459512 A CN103459512 A CN 103459512A CN 2012800166063 A CN2012800166063 A CN 2012800166063A CN 201280016606 A CN201280016606 A CN 201280016606A CN 103459512 A CN103459512 A CN 103459512A
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- Prior art keywords
- compound
- resin
- antibacterial
- resin composition
- silver
- Prior art date
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Abstract
在根据本发明的抗菌性树脂组合物中,式(1)表示的金属化合物包含于热塑性树脂或热固性树脂中,以确保具有抗菌特性的金属如银有效溶出并使作为离子的溶出金属稳定化。结果,根据本发明的抗菌性树脂组合物表现出优良的抗菌性能,且使其可以减少含有银等昂贵化合物的含量。其中,M表示Ag、Cu、Zn、Co或Ni,且X表示选自C、O、S和P的原子或原子团。
Description
技术领域
本发明涉及抗菌性树脂组合物,并更具体地,涉及可使得存在于树脂中的抗菌性物质如银等有效地溶出且该溶出的金属作为其离子保持稳定,从而可表现优良的抗菌性能的抗菌性树脂组合物。
背景技术
近年来,已经提出除了用于如医疗用品以及厨房、浴室和盥洗室等高温和高湿条件下使用的容器(其中,细菌和霉菌容易繁殖)的制品之外,还用于公共场所如皮带、用作与房屋相关的材料如墙纸和家具、用作空调的过滤器,并进一步地,用作需要抗菌性的各种制品如文具的各种抗菌性组合物。
例如,下述专利文献1公开了包含溶剂、银纳米粒子和稳定剂的组合物,下述专利文献2公开了包含有机银系抗菌剂和有机系抗菌剂的抗菌性组合物。
作为能使由植物蛋白如杉木花粉等和动物蛋白如蜱、其排泄物和霉菌等组成的变应原物质免疫失活的树脂组合物,本发明人已提出包含在表面上具有有机酸组分的超微金属粒子的树脂组合物(专利文献3)。
现有技术文献:
专利文献:
专利文献1:JP-T-2008-508321
专利文献2:JP-A-2010-248124
专利文献3:国际公布WO2008/69034
发明内容
发明要解决的问题
上述专利文献1中公开的组合物包含通过在溶剂中分散银纳米粒子获得的分散液,并通过使分散液与将赋予其抗菌性的基体表面接触而用于赋予抗菌性。因此,分散液不能足够程度地固定至基体,在维持其效果方面仍不十分满意。
专利文献2和3中公开的组合物与专利文献1不同不是用于涂敷在已预先成形的成形品上的组合物,而是与树脂组合使用以赋予树脂成形品抗菌性能,从生产性和持续性效果的观点提供优势的组合物。
然而,从经济学观点看,已期望以少于目前使用量使用如银等昂贵物质,而这些抗菌性树脂组合物也表现出与常规性质相当或更优的抗菌性能,仍维持优良的抗菌性能。
即,为了抗菌性树脂组合物表现出抗菌效果,重要的是金属离子如银等对细菌起作用。即,金属离子如银离子必须从树脂组合物中溶出。然而,目前很难使存在于抗菌性树脂组合物的成形体的银有效地溶出至成形体表面上,且仍存在不能有效利用存在于成形体中的银化合物的问题。
此外,溶出的金属离子,特别是离子形态的银是不稳定的容易变成金属银或银化合物,并且不能有效获得抗菌效果。
因此,本发明的目的是提供经济和抗菌性优良的抗菌性树脂组合物,使具有抗菌性能的如银等金属有效地溶出且溶出的金属作为金属离子保持稳定,结果,该抗菌性树脂组合物使用减少量的含有银等的昂贵化合物。
本发明的另一个目的是提供不仅在开始使用的初期而且甚至在时间推移后也具有优良抗菌性能的抗菌性树脂组合物。
用于解决问题的方案
根据本发明的第一方面,提供包含含有下式(1)表示的金属化合物(下文中,“金属化合物(1)”)的热塑性树脂或热固性树脂的抗菌性树脂组合物,
其中M是Ag、Cu、Zn、Co或Ni的任一种,和X是选自C、O、S和P的原子,或其原子团。
在上述抗菌性树脂组合物中,期望基于每100重量份热塑性树脂或热固性树脂,以0.001至10重量份的量包含金属化合物(1)。
根据本发明的第二方面,提供包含与选自Ag、Cu、Zn、Co和Ni的至少一种脂肪酸金属盐和下式(2)表示的化合物(下文中,“化合物(2)”)配混的热塑性树脂或热固性树脂的抗菌性树脂组合物,
其中M'是Na、K或H的任一种,且X是选自C、O、S和P的原子,或其原子团。
在上述抗菌性树脂组合物中,期望基于每100重量份热塑性树脂或热固性树脂,以0.001至10重量份的量包含脂肪酸金属盐,且以0.001至30重量份的量包含化合物(2)。
根据本发明的第三方面,提供包含与承载选自Ag、Cu、Zn、Co和Ni的至少一种金属离子的金属承载化合物和上述化合物(2)配混的热塑性树脂和/或热固性树脂的抗菌性树脂组合物。
在上述抗菌性树脂组合物中,期望基于每100重量份热塑性树脂或热固性树脂以0.001至10重量份量包含承载金属离子的金属承载化合物,和以0.001至30重量份的量包含化合物(2)。
此外,根据本发明,提供通过混合、加热和成形上述抗菌性树脂组合物获得的抗菌性树脂成形体。
发明的效果
在根据本发明第一方面的抗菌性树脂组合物中,金属化合物(1)具有优良的亲油性和亲水性。因此,金属化合物(1)对树脂的亲和力优良并优良地分散于树脂中,且因此如银等金属离子从分散的金属化合物溶出至树脂表面从而能有效地表现出抗菌性能。
在本发明第二和第三方面的抗菌性树脂组合物中,热塑性树脂或热固性树脂配混有与选自Ag、Cu、Zn、Co和Ni的至少一种脂肪酸金属盐或承载选自Ag、Cu、Zn、Co和Ni的至少一种金属离子的金属承载化合物组合的化合物(2),使其可提供具有与当将金属化合物(1)直接添加至热塑性树脂或热固性树脂中时相同的抗菌效果的树脂成形体或涂膜。
即,在使脂肪酸金属盐或金属承载化合物与化合物(2)一起存在于树脂中时,从脂肪酸金属盐或金属承载化合物溶出的金属离子可与化合物(2)一起维持稳定性;即,金属离子和化合物(2)从树脂内部同时溶出以表现出优良的抗菌性能。
本发明抗菌性树脂组合物可有效利用包含具有抗菌性能的如银等金属的化合物。这使其可能减少包含如银等金属的化合物的使用量,并提供经济上的优势。
此外,树脂组合物使其可以有效利用存在于其中的金属化合物(1)、金属化合物(2)和脂肪酸金属盐或金属承载化合物。在初始阶段,存在于表面上的化合物表现出抗菌性能,且时间推移后,存在于树脂组合物内部的化合物迁移至表面上以表现出抗菌性能从而长时间地表现出该抗菌性能。
本发明抗菌性树脂组合物的上述作用和效果将从稍后描述的实施例的结果中变得明确。
即,包含本发明抗菌性树脂组合物的膜(实施例1至16)在与特定数量的化合物(与脂肪酸金属盐或金属承载化合物组合的化合物(1)或化合物(2))配混的情况下表现出优良的抗菌效果,用包含与硬脂酸银、2,3-二氮杂萘酮银、苯并三唑银、1,8-萘二甲酰亚胺银或商购可得的抗菌剂配混的树脂组合物的膜(比较例1至20)不能获得足够程度的抗菌效果。因此,显然银离子从本发明树脂组合物中有效地溶出且表现出了优良的抗菌性能。
此外,实施例的结果说明与实施例相似的效果不可通过2,3-二氮杂萘酮银(比较例7至10)也不可通过苯并三唑银(比较例11至14)获得。因此,得知在本发明中,包含金属化合物(1)和化合物(2)中的五元环和苯环的部分能有效地稳定银离子,且具有包含五元环和具有-CO-N-的五元环的杂环对改善抗菌性能是重要的。
附图说明
图1是显示金属化合物的银浓度测定结果的图。
图2是显示实施例2和比较例4和8中溶出的银量的测定结果的图。
具体实施方式
(金属化合物(1))
关于上式(1)表示的且用于本发明第一方面的具体金属化合物,可列举以下化合物尽管本发明绝不仅限于此。在下式中,可用Cu、Zn、Co或Ni替代Ag。
在根据本发明的上述化合物中,可优选使用糖精银。
图1是显示按照JIS Z7260-107测定的在1-辛醇或水中溶出的各种含银化合物的银浓度结果的图。结果说明糖精银具有亲水性和亲油性,两者均优越于硬脂酸银、2,3-二氮杂萘酮银或苯并三唑银的亲水性和亲油性,且使抗菌性树脂组合物表现出与稍后出现的实施例结果一致的优良性能。
(化合物(2))
作为上式(2)表示的化合物(2),可列举以下化合物尽管本发明绝不仅限于此。在下式的化合物中,可用K或H替代Na。
在上述本发明中,糖精银最适宜作为金属化合物(1)。因此,糖精钠、糖精钾或糖精可优选用作上述化合物(2)。
(脂肪酸金属盐)
在本发明的第二方面中,与化合物(2)组合使用的脂肪酸金属盐是选自Ag、Cu、Zn、Co和Ni的至少一种金属的脂肪酸金属盐。作为脂肪酸,可列举肉豆蔻酸、硬脂酸、油酸、棕榈酸、正癸酸、对甲基苯甲酸(paratoluic acid)、琥珀酸、丙二酸、酒石酸、苹果酸、戊二酸、己二酸和醋酸。其中,优选使用硬脂酸。最期望的脂肪酸金属盐将是硬脂酸银。
这里,在组合使用脂肪酸金属盐和化合物(2)时,这两种化合物可依赖于使用的脂肪酸金属盐和化合物(2)的种类而彼此反应,且化合物(2)与脂肪酸金属盐的金属如银配位以形成金属化合物(1),从而使银离子稳定化且常常可获得与当直接配位化合物(1)时相同的构成。
(金属承载化合物)
在本发明的第三方面中,与化合物(2)组合使用的承载金属离子的金属承载化合物将是承载选自Ag、Cu、Zn、Co和Ni的至少一种金属的金属离子的无机离子交换剂或无机系吸附剂。
通常,承载金属离子的金属承载化合物自身通常已用作抗菌剂,且因为金属离子溶出而表现出抗菌作用。在本发明中,认为金属离子和化合物(2)一起存在于树脂中从而导致金属离子的稳定存在,且金属离子和化合物(2)同时从树脂内部溶出从而导致表现出优良抗菌性能。
作为无机离子交换剂,可列举沸石、磷酸锆、磷酸钾、溶解性玻璃(solubilizable glass)、硅酸铝酸镁(magnesium silicate aluminate)、硅酸钙、水滑石和钙磷灰石。作为无机系吸附剂,可列举硅胶和活性氧化铝。然而,在本发明中特别优选使用沸石和磷酸锆。
(热塑性树脂)
作为可用于本发明抗菌性树脂组合物的热塑性树脂,可使用任何已知树脂。例如,可列举烯烃树脂如低-、中-、或高-密度聚乙烯、线状低密度聚乙烯、线状超低密度聚乙烯、全同立构聚乙烯、间同立构聚乙烯丙烯-乙烯共聚物、聚丁烯-1、乙烯-丁烯-1共聚物、丙烯-丁烯-1共聚物,和乙烯-丙烯-丁烯-1共聚物;聚酯树脂如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯和聚萘二甲酸乙二醇酯;聚酰胺树脂如尼龙6、尼龙6,6和尼龙6,10;和聚碳酸酯树脂。
在本发明中,特别优选使用聚乙烯或聚丙烯。
(热固性树脂)
作为可用于本发明抗菌性树脂组合物的热固性树脂,可使用任何已知的树脂。例如,可列举酚醛树脂、环氧树脂、聚氨酯树脂、三聚氰胺树脂、尿素树脂、醇酸树脂、不饱和聚酯树脂和硅酮树脂。
在本发明中,特别优选使用硅酮树脂。
(抗菌性树脂组合物)
在根据本发明第一方面的抗菌性树脂组合物中,金属化合物(1)的期望使用量为0.001至10重量份,并特别地为0.005至1重量份,基于每100重量份的热塑性树脂或热固性树脂。如果金属化合物(1)的量小于上述范围,不能获得足够程度的抗菌效果。通过提高该量至大于上述范围可增强抗菌效果,但从经济和成形性的观点看这是不期望的。
这里,抗菌表示在制品的表面抑制细菌增殖的状态,且抗菌效果是根据JIS Z2801或JIS L1902规定的抗菌活性值或抑菌活性值(bacteriostaticallyactive value)来判断的抗菌处理制品的效果。
在根据本发明第二方面和第三方面的抗菌性树脂组合物中,脂肪酸金属盐或金属承载化合物的期望使用量为0.001至10重量份,并特别地为0.005至1重量份,基于每100重量份热塑性树脂或热固性树脂,且化合物(2)的期望使用量为0.001至30重量份,并特别地为0.02至10重量份,基于每100重量份热塑性树脂或热固性树脂。
此外,根据用途,本发明的抗菌性树脂组合物可与各种本身已知的配混剂,如填料、增塑剂、流平剂、增粘剂、减粘剂、稳定剂、抗氧化剂、紫外线吸收剂和颜料根据已知配方来配混。
通过将热塑性树脂与金属化合物(1)配混,或者与脂肪酸金属盐或金属承载化合物和化合物(2)的组合来配混而获得的抗菌性热塑性树脂组合物,依赖于双辊成形法、注射成形法、挤出成形法或压缩成形法可进行已知熔融成形以制造满足最终成形品用途的形状如粒状、丸状、纤维状、膜、片和容器等的抗菌性成形品。
树脂成形品的成形温度根据成形法或所使用的热塑性树脂、金属化合物(1)、脂肪酸金属盐、金属承载化合物和化合物(2)的种类而变化,且不能明确地限定,但可在所使用的热塑性树脂可成形的温度范围内。
此外,树脂成形品可通过单独使用本发明的抗菌性热塑性树脂组合物来构成,但也可通过组合使用任意其它树脂而构成为多层结构。
通过将热固性树脂与金属化合物(1)配混,或者与脂肪酸金属盐或金属承载化合物和化合物(2)的组合来配混而获得的抗菌性热固性树脂组合物,可优选以惯常方式用作涂料组合物、涂布剂或粘接剂组合物,此外可形成树脂成形品如膜和片。
形成的涂膜或树脂成形品的加热和固化条件可取决于所使用的热固性树脂、金属化合物(1)、或脂肪酸金属盐或金属承载化合物和化合物(2)的种类而变化,且不能明确限定,但可基于所使用的热固性树脂的固化温度和固化时间来设定。
实施例
(实施例1)
将均聚丙烯(由Prime Polymer Co.制造的F-704NP)与0.01重量%的糖精银配混,并通过在挤出成形机设定温度为180℃以及Q(吐出量)/N(螺杆转数)=4/150=0.027的成形条件下使用双轴挤出机(由Toyo Seiki Seisaku-sho,Ltd.制造)来挤出以制备厚度为100μm的膜。
(实施例2至4和7至16,比较例1至20)
除了如表1所示变更银化合物的种类和其添加量以外,以与实施例1同样的方式来制备膜。表中的抗菌剂A是锆系抗菌剂(商品名:Novaron(AQ1100),由Toa Gosei Co.制造)。
(实施例5和6)
硅酮树脂(由Momentive Performance Materials Japan Godo Co.制造的YSR3022)与量为0.01重量%或0.1重量%的糖精银配混,然后用整体约5倍量的甲苯稀释,随后混合并搅拌。此后,向其添加以硅酮树脂重量计为4%的量的催化剂(由Momentive Performance Materials Japan Godo Co.制造的YC6831),在50℃静置该混合物3小时以固化从而制备硅酮膜。
(评价方法)
按照JIS Z2801:2000(抗菌处理制品-抗菌性试验方法)实施抗菌试验。细菌菌株为金黄色葡萄球菌(S.aureus)。抗菌活性值表示通过将未处理膜上培养的细菌数除以抗菌处理膜上培养的细菌数获得的数值的对数值。
(抗菌效果判定)
当两者的添加量为0.1重量%和0.01重量%的抗菌活性值为2.0以上时,判定抗菌效果为○。当添加量为0.1重量%的抗菌活性值为2.0以上但添加量为0.01%的抗菌活性值小于2.0时,判定抗菌效果为Δ。当两者的添加量为0.1重量%和0.01重量%的抗菌活性值小于2.0时,判定抗菌效果为×。
表1
从表1中可明显看出,实施例的膜即使化合物的添加量为0.01重量%也表现出抗菌性。这是因为如上所述银化合物均一分散在树脂中,并因此,银比以前更有效地溶出并作为银离子保持稳定。另一方面,比较例的膜不表现出抗菌性或必须添加0.1重量%的化合物以表现出抗菌性。
(银的溶出性试验)
测试实施例2和比较例4和8制备的膜的银溶出。将5cm×25cm的两片膜投入50mL水中,然后在25℃静置18小时。此后,通过使用发射分光装置(由Thermo Scientific Co.制造的iCAP6500),测定溶于水中的银的量。测定结果如表2所示,从中获悉含有糖精银的膜比含有硬脂酸银或2,3-二氮杂萘酮银的膜的银溶出量更高。
产业上的可利用性
尽管仅含少量能表现出抗菌性的金属化合物如银,但是本发明的抗菌性树脂组合物能有效地表现出优良抗菌性能,经济性优越,且可有利地用于一次性制品和一般制品。
此外,本发明的抗菌性树脂组合物不仅对细菌、致敏物质等而且对真菌,根据氨基酸的排列具有特定立体结构的酶和微蛋白(microproteins)如包含DNA或RNA(核酸)和少量蛋白质分子的粒子状物质的病毒均能够有效地灭活。抗菌性树脂组合物可用于,例如,医疗、生活用品、床上用品、建筑材料、电子工业和水处理设施等领域。具体地,抗菌性树脂组合物可有利地用于医院等使用的制品或医疗用品,高温和高湿条件下如厨房、浴室、盥洗室等使用的制品,用作如地板、墙、窗帘、地毯、墙和地板用涂料、粘接剂和接缝材料(joint mixture)的住宅使用材料,用作如空调、织物和无纺布的纤维制品,和用作如口罩和过滤器等的过滤材料。
Claims (7)
1.一种抗菌性树脂组合物,其包含含有由下式(1)表示的金属化合物的热塑性树脂或热固性树脂,
其中M是Ag、Cu、Zn、Co或Ni的任一种,且X是选自C、O、S和P的原子或其原子团。
2.根据权利要求1所述的抗菌性树脂组合物,其中基于每100重量份所述热塑性树脂或所述热固性树脂,以0.01至10重量份的量包含所述金属化合物。
4.根据权利要求3所述的抗菌性树脂组合物,其中基于每100重量份所述热塑性树脂或所述热固性树脂,以0.001至10重量份的量包含所述脂肪酸金属盐,且以0.001至30重量份的量包含所述上式(2)表示的化合物。
5.一种抗菌性树脂组合物,其包含与承载选自Ag、Cu、Zn、Co和Ni的至少一种金属离子的金属承载化合物和所述上式(2)表示的化合物配混的热塑性树脂和/或热固性树脂。
6.根据权利要求5所述的抗菌性树脂组合物,其中基于每100重量份所述热塑性树脂或热固性树脂,以0.001至10重量份的量包含承载所述金属离子的所述金属承载化合物,且以0.001至30重量份的量包含所述上式(2)表示的所述化合物。
7.一种抗菌性树脂成形体,其通过将根据权利要求1至6任一项所述的抗菌性树脂组合物混合、加热和成形来获得。
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