CN101522347A - 吸附性金属超微粒子 - Google Patents
吸附性金属超微粒子 Download PDFInfo
- Publication number
- CN101522347A CN101522347A CNA2007800383967A CN200780038396A CN101522347A CN 101522347 A CN101522347 A CN 101522347A CN A2007800383967 A CNA2007800383967 A CN A2007800383967A CN 200780038396 A CN200780038396 A CN 200780038396A CN 101522347 A CN101522347 A CN 101522347A
- Authority
- CN
- China
- Prior art keywords
- metal particle
- resin
- ultrafine metal
- adsorbable
- adsorptive
- 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
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Images
Classifications
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- A61L9/00—Disinfection, sterilisation or deodorisation of air
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供了吸附性金属超微粒子以及含有该吸附性金属超微粒子并且可形成树脂成形品或涂膜的吸附性树脂组合物以及吸附性涂层材料。本发明的吸附性金属超微粒子的特征在于,其是在有机酸成分与金属之间具有键的金属超微粒子,并具有来源于前述有机酸成分与金属之间的键的、在1518cm-1附近的红外吸收峰,该吸附性金属超微粒子不损害树脂的特性和成形性,并且可以显示优异的除臭性和VOC吸附性。
Description
技术领域
本发明涉及吸附性金属超微粒子,更具体地说,本发明涉及在树脂中配合时不损害树脂的特性和成形性并且能显示优异的吸附性能的吸附性金属超微粒子。
背景技术
迄今已经提出了可吸附甲硫醇等恶臭成分或者甲醛等挥发性有机化合物(Volatile Organic Compounds,以下称为“VOC”)的各种除臭剂或者吸附剂,通常使用活性炭、硅胶、沸石等多孔质物质。
还提出了通过配合到热塑性树脂中而赋予成形品可吸附上述成分的性能的各种物质。
例如,如日本特开平9-75434号公报等中所记载那样,活性炭、多孔质沸石、海泡石等无机填料或者利用光催化作用的二氧化钛可以消除各种臭气成分的臭味,且具有可与热塑性树脂熔融混炼的耐热性。
另外,提出了使用金属的超微粒子的除臭剂。日本特开2006-109902号公报提出了以金属超微粒子胶体液作为有效成分的除臭剂,所述金属超微粒子胶体液通过还原含金属离子的液体而获得。
发明内容
然而,利用多孔性物质的材料通过吸附臭的成分或VOC来表现吸附效果(除臭效果),因此,所具有的问题是,在吸附点达到饱和状态时,效果消失。另外,为了提高分散性,在无机填料与热塑性树脂熔融混炼时,需要使用分散剂。因此,所存在的问题是,无机填料表面的吸附点被树脂、分散剂覆盖,吸附效果显著降低。
另外,利用光催化作用的除臭剂所存在的问题是,为了分解臭气成分并除臭,必须在二氧化钛表面经常照射紫外线。
此外,在使用金属超微粒子的除臭剂中,在所述除臭剂与树脂配合和使用时,所存在的问题是,树脂被表面活性高的金属超微粒子分解,成形性显著受损,并且,从处理性的观点来看,需要分散液,对于与树脂配合来说,不是充分令人满意的。
因此,本发明的目的是提供不损害树脂的特性和成形性,并且可以表现优异的吸附效果(除臭效果)的吸附性金属超微粒子。
本发明的另一个目的是提供含有上述吸附性金属超微粒子并且可形成树脂成形品或者涂膜的吸附性树脂组合物和吸附性涂层材料。
本发明的其它目的是提供可有效吸附甲硫醇等恶臭成分等以及VOC的吸附性金属超微粒子。
根据本发明,提供了吸附性金属超微粒子,其特征在于,其为在有机酸成分与金属之间具有键的金属超微粒子,并具有来源于前述有机酸成分与金属之间的键的、在1518cm-1附近的红外吸收峰。
根据本发明的吸附性金属超微粒子,优选具有下列特征:
1.有机酸成分为高级脂肪酸,
2.金属为金、银、铜中的至少一种。
此外,根据本发明,提供了含有上述吸附性金属超微粒子的吸附性树脂组合物。在该吸附性树脂组合物中,含有吸附性金属超微粒子的树脂的透氧系数(coefficient of oxygenpermeation)优选为1.0×10-4cc·m/m2·day·atm以上。
此外,根据本发明,还提供了含有上述吸附性金属超微粒子的吸附性涂料。
本发明的吸附性金属超微粒子的重要特征在于,其是在有机酸成分与金属之间具有键的金属超微粒子,并具有来源于前述有机酸成分与金属之间的键的、在1518cm-1附近的红外吸收峰。
粒径为1000nm以下的金属超微粒子的特性与通常的金属粒子大不相同,尤其,粒径为1000nm以下的金属超微粒子的表面活性高,而且表面积大,因此认为,与臭气成分或VOC的反应性优异,与通常的粒子相比具有大的吸附速度和吸附量,表现了优异的吸附效果,如前所述,这种金属超微粒子由于表面活性非常高,因此将它配合到树脂中时,促进了树脂的分解,严重损害树脂的成形性。
在本发明中,通过在金属超微粒子表面存在有机酸成分,可以减少金属表面与树脂的直接接触,有效抑制树脂的分解,可以减小树脂分子量的降低等,不会损害成形性。
另外,在含有本发明的吸附性金属超微粒子而形成的树脂组合物中,不像在使用以往的金属超微粒子那样需要分散液等,而是在树脂中可以直接纳米粒子化和纳米分散。也就是说,根据本发明,已经发现,在树脂的加热成形加工工序或涂膜形成工序中,有机酸金属盐通过自身还原或热分解形成金属超微粒子,通过将有机酸金属盐与树脂配合,用挤出机等混炼或者进行涂层材料的烘焙,有机酸金属盐由于热分解而纳米粒子化,而且纳米分散,不会再聚集,在成形同时可以有效地在树脂中纳米粒子化和纳米分散。
这可以从后述实施例的结果看出。例如,图3和图4是实施例2和4获得的薄膜的截面的透射型电子显微镜照片,从图3和图4可以看出,在薄膜中形成了金属超微粒子(黑色部分)(纳米粒子化),另外,图5是实施例1获得的薄膜表面的扫描型电子显微镜照片,从图5可以看出,金属超微粒子(白色部分)是均匀微分散的(纳米分散)。
另外,通过纳米粒子的等离子体吸收(plasmon absorption)的存在,可以确认所述金属超微粒子在树脂中是纳米分散的。图1示出了仅由聚对苯二甲酸乙二醇酯构成的薄膜以及在聚对苯二甲酸乙二醇酯中含有0.5重量%的平均粒径为100μm的肉豆蔻酸银并且在270℃下双螺杆挤出而分散有平均粒径为50nm的金属超微粒子而形成的薄膜的光谱透射率曲线,从该图1可以看出,聚对苯二甲酸乙二醇酯单质A不形成峰,而在含有肉豆蔻酸银的聚对苯二甲酸乙二醇酯B中,可以确认,在400~450nm附近获得了峰,银粒子在聚对苯二甲酸乙二醇酯中纳米分散。
另外,在本说明书中,平均粒径是指,将金属和金属之间没有间隙的物质作为一个粒子,并将各粒子粒径平均所得到的值。
根据本发明的吸附性金属超微粒子,不损害树脂的特性和成形性,并且可以显示优异的吸附性能(还包含除臭性能。另外,在本说明书中,“吸附性”是包含“除臭性”的概念)。而且,本发明的吸附性金属超微粒子不需要分散液等,可以通过成形加工时的加热来纳米粒子化和纳米分散,可以显著提高成形性。
另外,含有所述吸附性金属超微粒子并且可形成树脂成形品或涂膜的吸附性树脂组合物和吸附性涂层材料可以在成形加工或者涂膜形成的同时来纳米粒子化和纳米分散,具有优异的生产率,并且所得成形制品或涂膜还具有优异的吸附性能。
根据本发明的吸附性金属超微粒子,可以有效地吸附臭气成分、VOC,可以实现优异的除臭性能或VOC吸附性能。
附图说明
图1表示用于确认纳米分散的光谱透射率曲线的图。
图2表示由甲硫醇浓度和峰面积求得的校准曲线的图。
图3是实施例2中获得的薄膜的截面的透射型电子显微镜照片。
图4是实施例4中获得的薄膜的截面的透射型电子显微镜照片。
图5是实施例11中获得的薄膜的表面的扫描型电子显微镜照片。
具体实施方式
(金属超微粒子)
在本发明的吸附性金属超微粒子中,金属超微粒子的金属成分没有特定限制,可以列举Cu、Ag、Au、In、Pd、Pt、Fe、Ni、Co、Nb、Ru、Rh、Sn等,其中,Au、Ag、Cu、Pt、Sn是优选的。这些金属成分可以是单质、混合物、合金等。
在本发明中,一个重要特征是所述金属与有机酸之间具有键,作为有机酸,可以例举肉豆蔻酸、硬脂酸、油酸、棕榈酸、正癸酸、对甲基苯甲酸、琥珀酸、丙二酸、酒石酸、苹果酸、戊二酸、己二酸、醋酸等脂族羧酸,邻苯二甲酸、马来酸、间苯二甲酸、对苯二甲酸、苯甲酸、环烷酸等芳香族羧酸,环己烷二羧酸等脂环式羧酸等。
本发明中所使用的有机酸尤其优选肉豆蔻酸、硬脂酸、棕榈酸等高级脂肪酸,由于它们具有支链而且碳数多,有机酸成分自身也可以吸附臭气成分或VOC,可以进一步提高吸附效果(除臭效果)。
作为属于金属超微粒子的优选起始物质的有机酸金属盐,尤其可以列举肉豆蔻酸银、硬脂酸银等,另外,平均粒径优选为1~500μm,尤其优选为10~200μm的范围。
本发明的金属超微粒子可以通过在惰性气体氛围下热处理属于金属超微粒子的起始物质的有机酸金属盐而生成金属超微粒子单质来制备,优选的是,将有机酸金属盐与热塑性树脂混合,经过热处理,可以生成在树脂中纳米粒子化和纳米分散了的金属超微粒子。
用于获得本发明的金属超微粒子所需的加热条件根据所使用的有机酸金属盐而不同,不能一概而论,通常,理想的是在120~350℃,尤其在170~300℃的温度下加热1~1800秒,尤其加热10~600秒。
本发明的金属超微粒子的最大粒径小于1μm、平均粒径尤其为1~100nm的范围是理想的。
(吸附性树脂组合物)
本发明的吸附性树脂组合物是含有上述本发明吸附性金属超微粒子并且可以成形树脂成形品的吸附性树脂组合物,如上所述,可以通过将在惰性气氛下热处理有机酸金属盐而得到的金属超微粒子配合到树脂中来获得,尤其优选是含有上述属于金属超微粒子的起始物质的有机酸金属盐的树脂组合物。
也就是说,如前所述,属于本发明的吸附性金属超微粒子的起始物质的有机酸金属盐通过树脂组合物成形加工时的热处理,在树脂成形品中纳米粒子化和纳米分散,使得本发明的吸附性金属超微粒子可以存在于树脂成形品中。
作为含有本发明的吸附性金属超微粒子的树脂,可以全部使用以往公知的树脂,只要其是可熔融成形的热塑性树脂,例如可以列举低密度聚乙烯、中密度聚乙烯、高密度聚乙烯,线性低密度聚乙烯,线性超低密度聚乙烯,全同立构聚丙烯,间规聚丙烯,丙烯/乙烯共聚物,聚1-丁烯,乙烯/1-丁烯共聚物,丙烯/1-丁烯共聚物、乙烯/丙烯/1-丁烯共聚物等烯烃树脂;聚对苯二甲酸乙二醇酯,聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯等聚酯树脂;尼龙6,尼龙6,6、尼龙6,10等聚酰胺树脂;以及聚碳酸酯树脂等。
在本发明的吸附性树脂组合物中,尤其,透氧系数为1.0×10-4cc·m/m2·day·atm以上的树脂是优选的。由此,臭气成分或VOC在吸附性金属超微粒子上的吸附能够变得容易,可以进一步提高吸附性。
在本发明的吸附性树脂组合物中,尤其优选使用聚乙烯。
另外,在本发明的吸附性树脂组合物中,根据用途,可以按照公知的配方配合本身已知的各种配合剂,例如填充剂、增塑剂、流平剂、增粘剂、减粘剂、稳定剂、抗氧化剂、紫外线吸收剂等。
在本发明的吸附性树脂组合物中,每100重量份树脂优选配合0.01~5重量份的有机酸金属盐,在少于上述范围时,不能获得充分的吸附效果,另一方面,在多于上述范围时,金属粒子聚集,有可能难以获得纳米分散,因此是不优选的。
本发明的吸附性树脂组合物通过进行双辊法、注塑成形、挤出成形、压缩成形等目前公知的熔融成形,可以成形为符合最终成形品的用途的形状,例如粒状、颗粒状、薄膜、片材、容器、建筑材料、壁纸等的吸附性(除臭性)树脂成形品。
树脂成形品的成形温度取决于成形方法以及所使用的树脂和有机酸金属盐的种类,不能一概而论,但要求是使所使用的树脂不产生热劣化的温度,而且是在有机酸金属盐可以纳米粒子化和纳米分散的上述温度范围内。
另外,本发明的吸附性树脂组合物可以单独构成吸附性树脂成形品,但也可以与其它树脂组合形成多层结构。
由本发明的吸附性树脂组合物获得的树脂成形品具有优异的除臭性、VOC吸附性,而且在成形加工的同时可以纳米粒子化和纳米分散,具有优异的生产率。
(吸附性涂层材料)
本发明的吸附性涂层材料是含有上述本发明的吸附性金属超微粒子并且可形成涂膜的吸附性涂层材料,如上所述,可以通过将在惰性气氛下热处理有机酸金属盐而得到的金属超微粒子配合到涂料成分中来获得,尤其,优选是含有上述属于金属超微粒子的起始物质的有机酸金属盐的涂层材料。
也就是说,如前所述,通过涂膜烘焙时的热处理,属于本发明的吸附性金属超微粒子的起始物质的有机酸金属盐在涂料成分中纳米粒子化和纳米分散,使得本发明的吸附性金属超微粒子可以存在于涂膜中。
相对于100重量份涂料成分,有机酸金属盐等金属有机化合物优选以0.01~5重量份的量配合,在少于上述范围时,不能获得充分的吸附效果,另一方面,在多于上述范围时,金属超微粒子有可能发生聚集,因此是不优选的。
作为配合有机酸金属盐等金属有机化合物的涂料成分,可以使用各种涂料,只要它能够通过加热形成涂膜。例如,可以使用已知的丙烯酸系涂料、环氧系涂料、酚醛系涂料、尿烷系涂料、聚酯系涂料、醇酸树脂涂料等以往公知的涂料组合物,但不限于这些。
涂层材料的热处理条件可以根据所使用的涂料成分和有机酸金属盐的种类而改变,不能一概而论,但需要在所使用的涂料成分不产生热劣化的温度、而且有机酸金属盐可以纳米粒子化和纳米分散的上述温度范围内加热处理60~600秒。
由本发明的吸附性涂层材料获得的涂膜具有优异的除臭性、VOC吸附性,且在形成涂膜的同时可以纳米粒子化和纳米分散,而且生产率优异。
实施例
1.吹扫捕集型气相色谱-质谱分析仪(P&T-GCMS)中换算为甲硫醇量
采集各为1μL的浓度为65ppm、6.5ppm和0.65ppm的甲硫醇的水溶液,用吹扫捕集型气相色谱-质谱分析仪(P&T-GCMS)测定,确认来源于各甲硫醇的峰面积,该结果在表1中示出。水溶液浓度单位的ppm是ng/μL。另外,由这些甲硫醇浓度(量)(x)与峰面积(y)获得校准曲线。
y=562626x
R=0.9968
该校准曲线在图2中示出。
表1
注入量 | 甲硫醇水溶液浓度(ppm) | 1μL中的甲硫醇重量(ng) | 峰面积 |
1μL | 65 | 65 | 36,726,852 |
1μL | 6.5 | 6.5 | 2,022,414 |
1μL | 0.65 | 0.65 | 387,688 |
2.粒径的测定
将在实施例1~8、10~15和比较例1~12中获得的薄膜或将在实施例9中获得的底漆涂布薄膜的底漆涂膜沿截面方向制成切片,使用透射型电子显微镜(TEM)观察,获得金属超微粒子的TEM照片(另外,实施例2和4的TEM照片作为代表例在图3和图4中示出)。使用图像分析型粒子分布测定软件:mac-view测定照片中显示出的金属超微粒子的平均粒径。
3.甲硫醇量的测定
将在实施例1~8、10~15和比较例1~12中获得的薄膜或将在实施例9中获得的底漆涂布薄膜放入氮气置换了的500mL玻璃瓶内,用橡胶塞密封,然后,用微量注射器在前述瓶内注入5μL作为恶臭物质的浓度为650ppm的甲硫醇,在室温(25℃)下放置1天。在放置1天后,用气密性注射器从瓶内采集5mL的气体,用吹扫捕集型气相色谱-质谱分析仪(P&T-GCMS)测定前述气体中的甲硫醇量。
4.甲硫醇的除臭量的计算
在口部用橡胶塞密封的氮气置换的500mL玻璃制瓶内,用微量注射器注入5μL作为恶臭物质的浓度为650ppm的甲硫醇,然后,用气密性注射器从瓶内采集5mL的气体,用吹扫捕集型气相色谱-质谱分析仪(P&T-GCMS)测定除臭前的前述气体中的甲硫醇量。
由该除臭前的前述气体中的甲硫醇量减去放置1天后的气体中的甲硫醇量,获得甲硫醇量的除臭量。
5.在1518cm-1附近的红外线吸收峰的确认
对于实施例1~8、10~15和比较例1~12中获得的薄膜或实施例9中获得的底漆涂布薄膜的底漆涂膜,用属于常规方法的全反射测定法,通过傅里叶变换型红外分光光度计((株)デジラボ·ジャパン制造),确认来源于有机酸成分与金属之间的键的、在1518cm-1附近的红外吸光峰。
6.臭气感官评价
在前述3的甲硫醇量的测定后,由4人专家小组打开用橡胶塞密封的玻璃瓶,然后依次进行瓶内恶臭的感官评价。感觉不到恶臭、即甲硫醇的臭气的评价为○,而感觉到臭气的则评价为×。
7.外观评价
对于实施例1~8、10~15和比较例1~12中获得的薄膜或实施例9中获得的底漆涂布薄膜,目测确认粒子有无聚集。无聚集、具有优异外观的薄膜评价为○,而有聚集的、外观不良的薄膜评价为×。
8.VOC物质吸附前残留浓度的测定
将属于VOC物质的甲醛制备成1.5%水溶液。用橡胶塞密封氮气置换的50mL玻璃瓶,然后在前述瓶内用微量注射器注入5μL的1.5%甲醛水溶液,在室温(25℃)下放置1天。在放置后,在瓶内插入甲醛检测管(由(株)ガステック制造),测定吸附之前的浓度。还同样地测定乙醛。
9.VOC物质吸附后残留浓度的测定
将实施例1~8、10~15和比较例1~12中获得的薄膜或将实施例9中获得的底漆涂布薄膜投入氮气置换的500mL玻璃制瓶内密封,然后用微量注射器在所述瓶内注入5μL的1.5%甲醛水溶液,在室温(25℃)下放置1天。在放置后,在瓶内插入甲醛检测管(由(株)ガステック制造),测定吸附后的浓度。还同样地测定乙醛。
10.VOC物质的吸附率计算
以甲醛吸附前残留浓度减去吸附后残留浓度所获得的数值作为吸附量。对乙醛也同样计算。
[实施例1]
将平均粒径100μm的肉豆蔻酸银与5kg低密度聚乙烯树脂配合,使得肉豆蔻酸银的含有率为0.1wt%,用双螺杆挤出机((株)东洋精机制作所制造)在220℃的挤出成形温度下挤出,制备厚度50μm的薄膜,测定前述甲硫醇量,计算甲硫醇的除臭量,确认和评价在1518cm-1附近的红外线吸收峰。结果在表2中示出。
[实施例2]
除了肉豆蔻酸银的含有率为0.5wt%以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例3]
除了肉豆蔻酸银的含有率为1.0wt%以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例4]
除了肉豆蔻酸银的含有率为1.5wt%以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例5]
除了挤出成形温度为190℃以外,与实施例2同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例6]
除了使用平均粒径为100μm的硬脂酸银并且含有率为0.5wt%以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例7]
除了挤出成形温度为250℃以外,与实施例2同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例8]
除了挤出成形温度为270℃以外,与实施例2同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例9]
以46:46:3:5的树脂成分比率将高分子量双酚型环氧树脂、酚醛树脂(甲阶酚醛树脂)溶液、固化催化剂(磷酸)、平均粒径100μm的肉豆蔻酸银搅拌混合,并使用混合溶剂(环己烷:MIBK:MEK=1:1:1)来制备底漆,使得涂料树脂成分浓度为20%。在厚度50μm的双螺杆取向PET/I(对苯二甲酸/间苯二甲酸=88/12)共聚物聚酯薄膜上以0.6g/m2的干燥重量涂布底漆,在180℃下干燥,制备底漆涂布薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[比较例1]
除了以0.5wt%的含有率配合平均粒径2μm的沸石(水泽化学工业(株)制造)以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[比较例2]
除了以0.5wt%的含有率配合平均粒径1μm的市售无机系除臭剂(东亚合成(株):注册商标ケスモン)以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[比较例3]
除了以2.0wt%的含有率配合无机系除臭剂以外,与比较例2同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[比较例4]
除了以0.5wt%的含有率配合平均粒径100nm的银以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[比较例5]
除了以0.5wt%的含有率配合平均粒径4.5μm的银以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[比较例6]
除了以0.5wt%的含有率配合平均粒径100μm的氧化银以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[比较例7]
除了以0.5wt%的含有率配合将用公知方法生产的硬脂酸银在惰性气体氛围下、在250℃的温度下加热而获得的粒径1~100nm的硬脂酸银以外,与实施例1同样地制备薄膜,进行测定、计算、确认、评价。结果在表2中示出。
[实施例10]
将平均粒径100μm的硬脂酸银与5kg低密度聚乙烯树脂配合,使得硬脂酸银的含有率为0.5wt%,用双螺杆挤出机((株)东洋精机制作所制造)在220℃的挤出成形温度下挤出,制备厚度50μm的薄膜,测定作为前述VOC物质的甲醛、乙醛的吸附浓度,测定吸附后残留浓度,计算吸附量,确认和评价在1518cm-1附近的红外线吸收峰。结果在表3中示出。
[实施例11]
除了硬脂酸银的含有率为1.0wt%以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[实施例12]
除了硬脂酸银的含有率为1.5wt%以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[实施例13]
除了平均粒径为100μm的肉豆蔻酸银的含有率为0.5wt%以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[实施例14]
除了挤出成形温度为190℃以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[实施例15]
除了挤出成形温度为250℃以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[实施例16]
除了挤出成形温度为270℃以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[比较例8]
除了以0.5wt%的含有率配合平均粒径2μm的沸石(水泽化学工业(株)制造)以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[比较例9]
除了以0.5wt%的含有率配合平均粒径1μm的市售无机系除臭剂(东亚合成(株):注册商标KESUMON)以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[比较例10]
除了以0.5wt%的含有率配合平均粒径100nm的银以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[比较例11]
除了以0.5wt%的含有率配合平均粒径4.5μm的银以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
[比较例12]
除了以0.5wt%的含有率配合比较例7中获得的粒径1~100nm的硬脂酸银以外,与实施例10同样地制备薄膜,进行测定、计算、确认、评价。结果在表3中示出。
Claims (6)
1.一种吸附性金属超微粒子,其特征在于,其是在有机酸成分与金属之间具有键的金属超微粒子,并具有来源于前述有机酸成分与金属之间的键的、在1518cm-1附近的红外吸收峰。
2.根据权利要求1所述的吸附性金属超微粒子,其中前述有机酸成分为高级脂肪酸。
3.根据权利要求1所述的吸附性金属超微粒子,其中前述金属为金、银、铜中的至少一种。
4.一种吸附性树脂组合物,其含有权利要求1所述的吸附性金属超微粒子。
5.根据权利要求4所述的树脂组合物,其中前述树脂组合物的透氧系数为1.0×10-4cc·m/m2·day·atm以上。
6.一种吸附性涂层材料,其含有权利要求1所述的吸附性金属超微粒子。
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PCT/JP2007/067546 WO2008029932A1 (fr) | 2006-09-01 | 2007-09-03 | Particules ultrafines de métal adsorbables |
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EP (1) | EP2058066A4 (zh) |
JP (1) | JP4820416B2 (zh) |
KR (1) | KR101430776B1 (zh) |
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Cited By (2)
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CN111819018A (zh) * | 2018-01-26 | 2020-10-23 | 日清工程株式会社 | 微粒子的制造方法及微粒子 |
CN112956757A (zh) * | 2021-02-07 | 2021-06-15 | 泉州市锦恒服装实业有限公司 | 一种面料及内裤 |
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WO2008069034A1 (ja) * | 2006-12-08 | 2008-06-12 | Toyo Seikan Kaisha, Ltd. | 微小蛋白質不活性化金属超微粒子 |
JP5629425B2 (ja) * | 2008-02-29 | 2014-11-19 | 東洋製罐グループホールディングス株式会社 | 金属超微粒子形成用脂肪酸金属塩 |
US8637427B2 (en) | 2008-02-29 | 2014-01-28 | Toyo Seikan Kaisha, Ltd. | Adsorptive composition and adsorptive molded article |
JP5629428B2 (ja) * | 2008-11-17 | 2014-11-19 | 東洋製罐グループホールディングス株式会社 | 金属超微粒子形成用脂肪酸金属塩 |
WO2009107721A1 (ja) | 2008-02-29 | 2009-09-03 | 東洋製罐株式会社 | 金属超微粒子形成用脂肪酸金属塩 |
JPWO2011152467A1 (ja) | 2010-06-01 | 2013-08-01 | 東洋製罐グループホールディングス株式会社 | 銀超微粒子含有樹脂組成物 |
JP6012216B2 (ja) * | 2011-05-12 | 2016-10-25 | キヤノン株式会社 | 被検体情報取得装置及び被検体情報取得方法 |
CN105385097B (zh) * | 2015-12-28 | 2018-06-22 | 上海锦湖日丽塑料有限公司 | 自清除甲醛的耐热abs材料及其制备方法 |
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JP2006348213A (ja) * | 2005-06-17 | 2006-12-28 | Tokan Material Technology Co Ltd | 金属超微粒子、同超微粒子を含む樹脂組成物またはその成型物、および同樹脂組成物またはその成型物の製造方法 |
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2007
- 2007-09-03 CN CN200780038396.7A patent/CN101522347B/zh active Active
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111819018A (zh) * | 2018-01-26 | 2020-10-23 | 日清工程株式会社 | 微粒子的制造方法及微粒子 |
CN112956757A (zh) * | 2021-02-07 | 2021-06-15 | 泉州市锦恒服装实业有限公司 | 一种面料及内裤 |
Also Published As
Publication number | Publication date |
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WO2008029932A1 (fr) | 2008-03-13 |
US20130005888A1 (en) | 2013-01-03 |
US8372904B2 (en) | 2013-02-12 |
KR101430776B1 (ko) | 2014-08-18 |
JPWO2008029932A1 (ja) | 2010-01-21 |
CN101522347B (zh) | 2015-08-05 |
KR20090051766A (ko) | 2009-05-22 |
JP4820416B2 (ja) | 2011-11-24 |
US20100010130A1 (en) | 2010-01-14 |
EP2058066A1 (en) | 2009-05-13 |
EP2058066A4 (en) | 2012-01-25 |
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